Carbon Capture and Storage Update, Fennell, 2013

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Carbon capture and storage update
Published on 13 September 2013. Downloaded on 05/11/2015 11:56:07.
Cite this: Energy Environ. Sci., 2014, 7,

130
M. E. Boot-Handford,a J. C. Abanades,b E. J. Anthony,c M. J. Blunt,d S. Brandani,e

N. Mac Dowell,a J. R. Fernandez,b M.-C. Ferrari,e R. Gross,f J. P. Hallett,g
R. S. Haszeldine,h P. Heptonstall,f A. Lyngfelt,i Z. Makuch,f E. Mangano,e R. T. J. Porter,j
M. Pourkashanian,k G. T. Rochelle,l N. Shah,a J. G. Yaoa and P. S. Fennell*a
In recent years, Carbon Capture and Storage (Sequestration) (CCS) has been proposed as a potential
method to allow the continued use of fossil-fuelled power stations whilst preventing emissions of CO2
from reaching the atmosphere. Gas, coal (and biomass)-red power stations can respond to changes in
demand more readily than many other sources of electricity production, hence the importance of
retaining them as an option in the energy mix. Here, we review the leading CO2 capture technologies,
Received 12th July 2013

Accepted 13th September 2013
available in the short and long term, and their technological maturity, before discussing CO2 transport
and storage. Current pilot plants and demonstrations are highlighted, as is the importance of optimising
the CCS system as a whole. Other topics briey discussed include the viability of both the capture of
DOI: 10.1039/c3ee42350f
CO2 from the air and CO2 reutilisation as climate change mitigation strategies. Finally, we discuss the
www.rsc.org/ees
economic and legal aspects of CCS.
1. Introduction
This paper discusses Carbon Capture and Storage (CCS), as one
method to mitigate climate change. This paper will not assess
the science behind anthropogenic climate change, the overwhelming evidence is presented by publications such as.1 The
rationale for deployment of CCS on fossil-fuelled power stations
(and possibly in the future with biomass-red stations) is that,
when deployed in conjunction with other technologies (such as
renewables and nuclear), the overall cost of electricity supply is
minimised. This is because fossil-fuelled power stations are
a
Department of Chemical Engineering, Imperial College London, South Kensington,

London, SW7 2AZ, UK. E-mail: p.fennell@imperial.ac.uk; Tel: +44 (0)20 7594 6637
Instituto Nacional del Carb

on, (CSIC), Francisco Pintado Fe 26, 33011 Oviedo, Spain
Energy and Resource Technology Centre, Craneld University, Craneld, Bedford,

MK43 0AL, UK
d
Department of Earth Science and Engineering, Imperial College London, South

Kensington, London, SW7 2AZ, UK
e
SCCS Centre, School of Engineering, The University of Edinburgh, The Kings
Buildings, Edinburgh EH9 3JL, UK
f
Centre for Environmental Policy, Imperial College London, South Kensington, London,
SW7 2AZ, UK
g
Department of Chemistry, Imperial College London, South Kensington, London, SW7
2AZ, UK
h
SCCS, School of Geosciences, The University of Edinburgh, The Kings Buildings,
Edinburgh EH9 3JW, UK
i
Chalmers University of Technology, 412 96 Goteborg, Sweden
Energy Technology and Innovation Initiative, University of Leeds, Leeds, LS2 9JT, UK
k
School of Process, Environmental and Materials Engineering, University of Leeds,
Leeds LS2 9JT, UK
l
McKetta Department of Chemical Engineering, The University of Texas at Austin,

Austin, TX 78712, USA
130 | Energy Environ. Sci., 2014, 7, 130189
able to vary their output in response to changes in demand (or

indeed to the supply from intermittent sources such as wind)
and thus CCS reduces the need for large-scale energy storage to
be developed.
Carbon capture and storage refers to a number of technologies which capture CO2 at some stage from processes such as
combustion (most generally for power generation) or gasication. Many industrial processes, most notably cement manufacture, iron and steel making and natural gas treatment also
intrinsically produce CO2 and can be tted with CO2 capture
technologies (and for these industries, CCS oers one of the
very few remaining methods to reduce CO2 emissions where
the best available technology in terms of e.g. energy eciency
is already used). The captured CO2 is then pressurised to 100
bar (or more), prior to being transported to a storage site,
where it is injected into one of a number of types of stable
geological features, trapping it for multiple hundreds or
thousands of years and preventing its subsequent emission
into the atmosphere. All of the individual components of the
CCS chain, from capture all the way through to (and including)
storage, have been demonstrated at or close to industrial scale.
However, their integration into a single process is a signicant
(but ultimately solvable) engineering challenge. There are a
large number of dierent technologies for CCS, some closer to
deployment than others. The purpose of this paper is to review
the most recent developments in the eld, and not to introduce the topics. The interested reader is referred to a previous
review, and a special edition of this journal for introductory
material.2,3
Here, we discuss solvent scrubbing, oxyfuel combustion
(for both pulverised fuel and in a uidised bed), chemical
This journal is The Royal Society of Chemistry 2014
View Article Online
Review
looping and calcium looping, together with low-temperature

sorbents, as exemplars of CCS technologies which might be
commercialised within 1020 years, (solvent scrubbing and
oxyfuel potentially being commercialised towards the beginning of the period, with the other technologies towards the
end, though we have included ionic liquids as a natural
adjunct to solvent scrubbing even though these solvents are
unlikely to be commercialised within 20 years). Of course,
there are other technologies (such as membranes) which
could also be considered, but are not covered here. We then
move on to discuss a number of technologies that are either
more niche or are further away from commercialisation (CO2
utilisation through mineralisation or in direct production of
useful products). Transport of CO2 is then discussed, prior to
storage. We then discuss the critical overarching themes:
systems integration and policy design and implications for
investment.
Throughout this paper, where eciency penalties are
quoted, it should be noted that they are relative to a power
station which will have an underlying thermal eciency of
between 40 and 60%. This means that an eciency penalty of
(say) 5% requires an increase in fuel-burn of 10% in order to
produce the same amount of electricity.
1.1
Current power generation
Despite recent global economic turmoil leading to appreciable

reductions in global demand for oil and gas, demand for coal
has if anything signicantly increased in the period since 2005.
In 2010, world coal demand was approximately 5000 million
tonnes of coal equivalent (Mtce). Under the IEAs Current
Policies Scenario, this is projected to grow to 7500 Mtce by
2035. It is worth noting that the entirety of this growth (in all
scenarios) occurs in non-OECD countries. The share of global
coal market arising from the non-OECD countries is expected to
rise from 66% to 82%.4
Power generation is heavily dependent on coal-red plants
throughout the world; in 2008, 41% of total global electricity
was obtained by coal combustion (corresponding to 8273
TWh). While this share is expected to drop to 32% by 2035
(corresponding to 11 200 TWh), coal remains the dominant
source of energy globally, with non-OECD demand doubling in
the period to 2035. OECD demand for coal is expected to drop
by as much as 33%a result of a renewed dash-for-gas
arising from the exploitation of reserves of shale gas (and other
unconventional sources) and policies encouraging the reduction of the carbon intensity of power generation.4 Conventional
or so called sub-critical coal-red power generating plants
operate with low thermal eciency (3045%), which in turn
incurs signicant fuel costs. This large fuel requirement will in
turn increase exposure to fuel price volatility, thus increasing
the investment risk associated with this technology. For these
reasons, sub-critical power plants are expected to displaced by
super-critical and ultra-supercritical power plants, reducing
their market share from 73% in 2008 to 31% in 2035.4 Supercritical power plants are considered to be a promising option
for future coal-based power generation as they operate with
Energy & Environmental Science
higher base-load eciency in the range of 4852%.5 Supercritical power plants operate with steam parameters in range
of 240 bar/600 C and ultra-super critical plants which operate
in the range of 350 bar/700 C/720 C or higher are under
development.
However, owing to the relatively high-priced materials
required for their construction, the capital cost associated with
supercritical power plants is relatively high6,7 and this is an
active area of on-going research.
For example, Yamamoto et al.8 reported the application of
heat resistant material of high creep rupture strength and high
oxidation resistance up to 650 C, which have already been
developed for boilers and turbines of ultra-supercritical power
plants. Viswanathan5 discussed the materials for ultrasupercritical (USC) plants to withstand operating steam conditions up to 760 C temperature and 35 MPa pressure, which are
under development.
2.
2.1
Developments in amine scrubbing

Thermodynamic context
CO2 capture by post-combustion chemisorption relies on the

separation of CO2 from ue gas using a chemical solvent. Thus,
the thermophysical properties are of paramount importance in
determining the potential of absorption, as it species interfacial phase equilibrium in addition to speciation in liquid phase
and the enthalpy of absorption. Consequently, appropriate
selection of a physical property model is of prime importance
for the correct modelling of CO2 capture processes.
In the context of CO2 capture, aqueous alkanolamine solutions are an extremely complex solution of molecular species,
electrolyte species and reaction products and, on certain time
scales, reaction intermediates. The physical property model
must be applicable to all phases and chemical equilibria for a
wide range of thermodynamic states. Several thermodynamic
models have been used in the literature to represent the
absorption of acid gases in alkanolamine solution, and they can
be classied as one of three types: empirical models, equation
of state approaches and excess Gibbs energy approaches.
Empirical models are based on empirical mathematical
relations, rather than theoretical considerations. Vapour-liquid
equilibria (VLE) and chemical equilibria are represented in
these models by tting numerical parameters on experimental
data. The resulting correlations, such as that of Gabrielsen
et al.9 for the partial pressure of CO2 as a function of the liquid
phase CO2 loading, are oen easy to implement. However, as
with all correlations, owing to their lack of theoretical underpinning, they are typically unsuitable for predictive calculation
or extrapolation.
Equations of state can be used to represent both liquid phase
and gas phases (including electrolytes). Heterogeneous
approaches, using the excess Gibbs energy to obtain activity
coecients in the liquid phase. These models typically need to
be coupled with a separate model to describe the gas phase; this
is oen a cubic equation of state. Homogeneous approaches are
based on the Helmholtz energy; such as the formulation of
Furst and Renon.10,11 Recently, the Statistical Associating Fluid
Energy Environ. Sci., 2014, 7, 130189 | 131
View Article Online
Theory12,13 (SAFT) for potentials of variable range14 (SAFT-VR)

has been applied to aqueous mixtures of amines15 and alkanolamines16,17 and CO2. This new approach provides an implicit
treatment of the chemical reactions and ionic speciation in
these complex mixtures. Importantly, although the reaction
products are also treated in an implicit fashion, it is possible to
obtain an accurate description of the equilibrium carbamate/
bicarbonate products.17 As a consequence, when these thermodynamic models were incorporated in process models3,18 it
was not necessary to describe the reaction products in the
process model, nor was an enhancement factor required to
describe the accelerating eect of the reactions on the mass
transfer. This had the eect of signicantly reducing the size of
the process models and consequently it was possible to use
these detailed dynamic, non-equilibrium models to perform
optimisation19 and control20 studies. It is noteworthy that the
SAFT approach has been coupled with classical density functional theory approaches and has been used to predict vapour
liquid interfacial properties21 and the so-SAFT variant22 has
also been used to describe the thermophysical properties and
phase behaviour of ionic liquids in the context of CO2 capture.23
The third class of models uses the excess Gibbs energy to
compute activity coecients; they are oen based on alreadyexisting models for nonelectrolyte systems and extended with
the DebyeHuckel theory to address electrolyte species. The
model by Deshmukh and Mather24 is one of the simpler models,
and parameters have been regressed for some amines25 it
assumes ideality for water and calculates the activity coecient
for diluted species with a virial term for interaction between
species. The model by Pitzer26 is quite similar and has been used
to represent the solubility of CO2 in aqueous methyldiethanolamine (MDEA) and piperazine (PZ).27 Among the more elaborated
models using the local composition of the mixture, the
electrolyte-NRTL (e-NRTL) and extended UNIQUAC (e-UNIQUAC)
models prevail. The e-NRTL model28,29 has been extensively used
for CO2 absorption characterisation.30,31 The extended UNIQUAC32 provides the same theoretical basis as e-NRTL, with a
simpler formulation, and it has already proved its ability to
represent the alkanolamine system for CO2 absorption.33
The development of amine scrubbing has been focused on its
application to coal-red power plants. Unless otherwise noted,
the data and discussion on amine scrubbing that follows are
based on the application to coal-red power plants. However,
amine scrubbing should be useful for other applications.
2.2
Process owsheet
The process technology using 30 wt% monoethanolamine

(MEA) that has been evaluated by NETL34 to give a baseline for
the solvent scrubbing process can no longer be used as a
representative baseline for post-combustion capture. A number
of vendors, including Fluor35 and MHI36 have developed
processes and completed evaluations that give energy performances substantially better than that reported in the NETL
analyses. In addition, a recent paper by Ahn et al. has illustrated
all the dierent types of owsheet congurations for the amine
scrubbing process.37
Review
Fig. 1 gives an example of a second generation, optimised

process for CO2 capture by amine scrubbing using 8 molal (m)
piperazine (PZ).38,39 Compared to 30 wt% MEA it has twice the
rate of CO2 absorption, 1.8 times the intrinsic working capacity,
5 to 10% lower heat of absorption (a disadvantage), and a
maximum stripper T/P of 150 C/8 bar.40
In addition to the absorber, the process would probably
include SO2 polishing with sodium alkali scrubbing and direct
contact cooling of the ue gas before the PZ absorber. It
would also usually include a water wash and aerosol removal
aer the absorber. Much of this additional ue gas contacting
could be incorporated into the same vessel as the CO2
absorption.
2.3
Overall energy performance
2.3.1 Reboiler heat duty. The measured and projected

reboiler heat duty for CO2 capture from coal-red power plants by
amine scrubbing has improved from as high as 5.5 MJ tCO21 in
2001 to as little as 2.6 in 2012 (Fig. 2). Early estimates used 20 wt%
(MEA) with a simple stripper and absorber. Current systems assume
35 or 40 wt% MEA or other advanced amines with interheated
strippers and intercooled absorbers or other comparable process
improvements. With a Carnot cycle analysis, the minimum heat
duty to separate 12% CO2 in ue gas and produce pure CO2 at 1 bar
is 1 MJ t1. Therefore, the overall thermodynamic eciency of the
separation process is approaching 40%.
2.3.2 Equivalent work. Improvements in solvents and
processes have reduced the estimated equivalent work to
separate CO2 from coal-red ue gas from 450 kW h tCO21
removed in 2001 to as little as 200 kWh t1 in 2012 (Fig. 3).
These values include CO2 compression to 150 bar and usually
include pump work and fan work. The work value of the reboiler
duty was estimated from a: Carnot eciency based on the
reboiler temperature (Treb, C) and assuming a 75% turbine
eciency, a reboiler approach T of 5 C, and a sink temperature
of 40 C:41
Weq 0:75Qreb
Treb 5 40
Treb 5 273
(1)
The compression work was estimated by a regression of

results from Aspen modelling of an multistage compressor with
intercooling to 40 C:41

8
150
>
>
4:572
ln
4:096 Pin # 4:56 bar
>

<
Pin
kJ
Wcomp

>
mol CO2
150
>
>
: 4:023 ln
2:181 Pin . 4:56 bar
Pin
(2)
The improvements include thermally stable solvents such as
piperazine, that can be stripped at 150 C to produce CO2 at 8
bar. Rochelle et al.40 present estimates of thermodynamic eciencies for other common separation processes: desalination
by reverse osmosis 21%, distillation 14 to 35%, and air
separation 25%. Since the minimum work for this separation
is about 110 kWh t1, it is improbable that further improvement
from the current thermodynamic eciency of about 50% will
View Article Online
Review
Fig. 1
Intercooled Absorber/Interheated stripper with 8 m PZ. Stripper bottom at 150 C/7.9 bar. Weq 30.5 kJ mol1 CO2 193 kW h per tonne CO2.
2.4
Fig. 2 Reboiler heat duty for amine scrubbing on coal-red power

plants, taken in part from Rochelle et al.40 MEA monoethanolamine,
KS-1 proprietary MHI solvent, PZ 40 wt% piperazine, H3
proprietary Hitachi solvent,568 LB1 Proprietary BASF/Linde solvent/
process,569 TS-1 proprietary Toshiba solvent.570
Fig. 3 The total energy requirement for amine scrubbing to separate

CO2 from coal ue gas and produce it at 150 bar, taken in part from
Rochelle et al. (2011). MEA monoethanolamine, KS-1 Proprietary
MHI solvent, PZ 40 wt% piperazine, LB-2 case with Proprietary
BASF/Linde process/solvent (Jovanovic et al., 2012).
come easily. A typical coal-red power plant produces about

1000 kWh tCO21 emitted, so CO2 capture by amine scrubbing
will reduce the power output by 20 to 30%.
Features of second-generation processes
2.4.1 Absorber operating T and intercooling. In processes

relying upon temperature swing regeneration, the absorber
should be operated at as low a temperature as possible with the
available heat sink to maximise the rich and lean loading of the
solvent. The design in Fig. 1 includes removing heat to 40 C in
direct contact cooling of the inlet ue gas, intercooling in the
middle of the absorber, and trim cooling of the lean solvent feed
to the absorber.
2.4.2 Stripper operating T. In processes relying upon
temperature swing regeneration, the stripper should be operated at the maximum temperature allowed by solvent degradation or by the available heat supply. This maximises the
pressure of the CO2 in the rst stage of the compressor. Elevated
stripper T also reduces the ratio of water vapour to CO2 in the
simple stripper overhead. The example uses reboiler conditions
of 150 C and 8 bar.
Steam pressure should be reversibly reduced before it is
used in the reboiler. In this example the steam pressure is 6
bar and could be consistent with steam extracted between the
intermediate and low pressure turbine stages of a typical coalred power plant. The reboiler approach temperature should
be minimised consistent with the tradeo of reboiler capital
cost and equivalent work loss, typically 5 to 10 K. The
equivalent work of the stripper and compressor system
should be estimated from the work value of the steam heat
and the compressor work to a nal pressure (typically 150
bar) by equations such as those oered by Van Wagener
(above).41
Eective cross exchange between the cold rich and hot lean
solvent eliminates much of the energy cost of operating with a
large solvent rate. Plate-and-frame exchangers appear to permit
an economic approach T of 5 K. A cold rich bypass41 can be used
to address imbalance between the heat capacities of the rich
and lean streams. With a typical working capacity of 0.8 mol
CO2 kg(H2O + amine)1 and a heat capacity of 3.5 kJ K1
kg(H2O + amine)1, the 5 K approach requires only 22 kJheat mol
CO21 or 3.5 to 4.4 kJequivalent work mol CO21 (with stripper at
120 to 150 C).
View Article Online
Review
2.4.3 Advanced stripper conguration. A number of

stripper congurations are available to minimise the loss of
heat as water vapour. The interheated stripper is the best of
these (Fig. 3).41 Other congurations that work almost as well
include adiabatic ash with compression,41 cold rich bypass,41
matrix,42 two-stage heated ash,41 and multipressure.43 The
interheated stripper uses 10 to 20% less energy than a simple
stripper.38 With an interheated stripper, less than 20% of the
overhead vapour is water. Therefore, anhydrous solvents or
sorbents will not signicantly reduce the heat requirement by
avoiding the vaporisation of water.
2.4.4 Reversible stripping. When the lean loading (or
solvent ow rate) is optimised to minimise energy consumption, there is a tradeo of sensible heat loss at high solvent rate
(high lean loading) and stripping steam use at low solvent rate
(low lean loading). With a close exchanger approach T (5 K), the
stripper typically only removes enough CO2 from the rich
solvent to leave the maximum lean loading that allows for
adequate CO2 removal.40 An intercooled absorber using a
solvent with a fast rate of CO2 absorption (such as 8 m PZ)
should be able to achieve 90% CO2 removal with a lean loading
that gives an equilibrium CO2 partial pressure of 0.5 kPa at 40

C and a rich loading that gives an equilibrium CO2 partial
pressure of 5 kPa at 40 C.44 Therefore, the dierence between
the CO2 loading at these rich (5 kPa CO2 at 40 C) and lean (0.5
kPa at 40 C) conditions will give a useful estimate of the
working capacity of the solution.
2.5
Solvent selection for energy performance
Three aggregated properties of solvents are related to energy

performance. These are summarised in Table 1 for a number of
potential solvents.
2.5.1 Heat of absorption/Tmax/Pmax. Because amine scrubbing relies upon thermal swing regeneration, a greater heat of
CO2 absorption always provides reduced energy consumption.40
Table 1
This eect of thermal swing depends on the temperature of the

reboiler which is limited by the thermal degradation of
the solvent. In previous work Tmax has been dened
as the temperature where the degradation rate constant is
2.9 108 s1, the same as that of 30% MEA at 120 C.45,46 A
quantitative measure of the eects of the heat of absorption and
Tmax is the estimated reboiler pressure with a representative
lean solvent, assumed to be saturated at 40 C to 0.5 kPa CO2
given by the expression:
Pmax PH2O + PCO2
(3)
where PH2O is the vapour pressure of water at Tmax and PCO2 is

given by:
PCO2 0.5 kPa exp((DHabs/R)(1/Tmax 1/313))
(4)
As reviewed by Freeman45 and Rochelle,46 the piperazine or

piperazine derivatives have been identied as solvents with the
greatest value of Tmax, resulting in greater values of Pmax. Many
amines have lower values of Tmax because they degrade by
formation of cyclic urea or by dimerisation through an
oxazolidinone.46
Solvents with a low heat of absorption (<60 kJ mol-1) will not
be competitive.42 These include systems relying on sodium or
potassium carbonate and tertiary or hindered amines with
lower pKa values.
Although vacuum stripping works with solvents that have a
low heat of absorption, it is not energetically competitive
because of the additional compression work for the CO2.41,42
A number of investigators are developing systems that
increase the eective heat of absorption by precipitating solids
out of the rich solution.47,48 One such system uses aqueous
potassium carbonate with precipitation of potassium bicarbonate. These processes will ultimately have to deal with the
reliability issues posed by precipitating slurries.
Energy properties of amine alternatives49
Amine
kg0
Piperazine (PZ)
PZ/bis-aminoethylether
2-Methyl PZ/PZ
2-Methyl PZ
2-Amino-2-methyl propanol (AMP)
PZ/aminoethyl PZ
PZ/AMP
Diglycolamine (registered trademark)
Hydroxyethyl PZ
PZ/AMP
2-Piperidine ethanol
Monoethanolamine (MEA)
MEA
Methydiethanolamine (MDEA)/PZ)
MDEA/PZ
Kglycinate
Ksarconinate
MEA/PZ
8
6/2
4/4
8
5
5/2
5/2.3
10
8
2/4
8
11
7
5/5
7/2
6
6
7/2
8.5
7.3
7.1
5.9
2.4
8.1
7.5
3.6
5.3
8.6
3.5
3.6
4.3
8.3
6.9
3.2
5
7.2
avg
107
Capacity
mol kg1
Habs
kJ mol1
Tmax C
Pmax bar
PH2O/
PCO2
0.79
0.67
0.84
0.93
0.96
0.67
0.7
0.38
0.68
0.78
1.23
0.66
0.47
0.99
0.8
0.35
0.35
0.62
64
69
70
72
73
71
71
81
69
72
73
70
70
70
68
69
54
80
163
162
155
151
140
138
134
132
130
128
127
125
121
120
120
120
120
104
14.3
16.3
10.3
9.9
6.1
5.0
4.5
9.1
2.3
3.4
3.3
2.7
2.2
1.8
1.4
1.08
0.73
0.7
0.33
0.28
0.41
0.37
0.49
0.55
0.54
0.25
0.98
0.63
0.61
0.67
0.81
0.92
1.15
1.46
2.17
1.38
View Article Online
Review
2.6
Normalised capacity capacity/(m/10)0.25
The capacity and viscosity of the solvent are reected in the

sensible heat requirement of the stripper, given by:

kJ
Cp DT
Qsensible
(5)
mol CO2
C
where Cp is the heat capacity of the solvent (kJ kg(H2O +
amine)1 K1), DT is the hot side approach T of the cross
exchanger, and C is the capacity of the solvent (mol CO2
kg(H2O + amine)1).
One quantitative measure of the intrinsic solvent capacity is
the dierence between the equilibrium CO2 concentration at
40 C at 5 kPa CO2 and the equilibrium concentration at 40 C at
0.5 kPa. These values allow for a reasonable driving force to
provide 90% CO2 removal at conditions of coal-red power
plants. These convenient units of capacity reect the generalisation that the eective partial molar heat capacity of CO2
loading is typically near zero.
Greater solvent viscosity reduces the heat transfer coecient
in the cross-exchanger. The optimum exchanger design will
result in a greater approach DT with a greater viscosity. Therefore, it is appropriate to weight the intrinsic capacity by the
viscosity to the 0.25 power, as reected in the normalised
capacity given in Table 1, capacity/(m/10)0.25.49
A number of amine systems provide greater normalised
capacity than 7 M MEA. Hindered and tertiary amines usually
provide greater capacity because their intrinsic stoichiometry
requires only 1 mol amine mol CO21, as opposed to two for the
MEA system. As shown in Table 1, methyldiethanolamine, (a
tertiary amine) with piperazine and aminomethylpiperazine (a
hindered amine) with piperazine are quite competitive. Greater
capacity is also provided by diamines such as piperazine
because more equivalents of amine can be loaded into the
solvent before the viscosity becomes unacceptable.
A number of researchers are investigating systems that
precipitate solids or separate a lean amine organic phase from
the rich solvent.5052 These phase change systems will usually
provide greater capacity, but they must deal with the reliability
issues posed by precipitating slurries or two-phase systems.
2.7
Rate of CO2 absorption, kg0
Because the optimisation of the absorber design will require

lower rich and lean loading to achieve 90% CO2 removal with a
reasonable amount of packing, the rate of CO2 absorption is an
important energy parameter of the solvent. A fast rate of CO2
absorption facilitates reversible absorber performance at high
rich and lean loading that will minimise energy use in an
optimised system. CO2 typically absorbs by the process of
diusion with fast reaction in the boundary layer. The normalised absorption ux of CO2 (kg0 , mol m2 Pa1) is given
approximately by:
p
kam amineDCO2
Flux
0
kg
(6)
HCO2
PCO2 ;i P*CO2 ;b
kg0 is a property of the amine, and not of the absorber contacting
device. It can be measured in a wetted wall column or similar
device. The value of kg0 at an average loading is given for a

number of solvents in Table 1.
Piperazine or piperazine derivatives provide the greatest
values of kg0 . Secondary or primary amines are usually necessary
to provide an acceptable rate of CO2 absorption. Tertiary amines
and hindered amines are usually too slow to be used by
themselves.
Several investigators are developing carbonic anhydrase
enzymes to catalyse the CO2 kinetics in otherwise slower
solvents.53,54 Unfortunately they have not yet developed
enzymes that are eective at elevated T (>100 C). Furthermore,
the enzymes are most eective in tertiary amines and
carbonate solutions with low heats of CO2 absorption. These
systems will probably not be energetically competitive with
other second generation amine solvents that can be regenerated at 120 to 150 C.
2.8
Solvent management
2.8.1 Oxidative degradation. Monoethanolamine oxidises

at absorber conditions with catalysis by dissolved iron and
manganese.55 This oxidation rate seems to have been economically and environmentally acceptable in previous systems.35
However, it is a nuisance and may be environmentally unacceptable in larger systems. Inhibitors have been identied that
are eective at absorber conditions.55 These additives appear to
degrade or are ineective when used in cyclic systems with
elevated T representative of strippers.56
A number of amines are resistant to oxidation at absorber
conditions, including piperazine, tertiary amines, and hindered
amines. Tertiary amines appear to be oxidation inhibitors when
used in blends with other amines. MDEA is eective in inhibiting the oxidation of MEA at absorber conditions.56,57
However, Closmann56 and Voice57 have shown in benchscale experiments that even resistant amines are subject to
reaction with dissolved and entrained oxygen that is carried
into the high temperature of the cross-exchanger. This oxidation rate depends on the solubility of oxygen in the solvent
and can be substantially less than that in MEA solvents. It can
be minimised by stripping the dissolved oxygen from the rich
solution with nitrogen or by a low-temperature ash of
CO2/H2O.
2.8.2 Other ue gas impurities. Coal-red ue gas contains
a number of impurities that impact processes for postcombustion capture. Existing plants that treat coal-red ue
gas include gas pretreating with sodium alkali scrubbing to
remove practically all of the SO2, HCl, and coarser yash. This
pretreating would not be expected to remove NOx, Hg, submicron y ash, and submicron H2SO4 aerosol.
2.8.3 Nitrosamines. Secondary amines will combine with
NO2 in the inlet ue gas to produce nitrosamines that may
create environmental risk in spills of disposal of spent solvent.
It is probable that NO2 in the absorber inlet will be mostly
absorbed by reaction with secondary and tertiary amines to
produce nitrite.58 At 100 to 150 C in the stripper, nitrite reacts
with secondary amines to quantitatively produce nitrosamines.58 At 150 C, nitrosopiperazine thermally decomposes, so
View Article Online
it will reach a steady-state concentration where the rate of

decomposition is equal to the rate at which NO2 enters the
absorber. Pilot plant data with piperazine-based solvent suggest
a steady-state concentration of about 1 mM nitrosopiperazine at
typical power plant conditions using a stripper at 150 C.59 This
steady-state concentration will increase at lower stripper T and
with ue gas containing more NO2, so other solvents and
conditions may experience greater steady-state concentration.
Amine solvents that do not include secondary amines may still
be subject to this reaction with oxidative and thermal degradation product of the primary or tertiary amines that make up
the solvent.60 Nitrosodiethanolamine has been found in monoethanolamine solvent.61 UV treating is being tested as a
method to selectively decompose nitrosamine in amine
solvents.6264 The volatility of the nitrosamine is expected to be
comparable to that of the parent amine.58 Any gaseous emissions of nitrosamine should also be quickly decomposed by UV
exposure in the atmosphere. Therefore, air emission of nitrosamine should pose negligible risk.65
2.8.4 Amine volatility
Vapour losses. Because practical amines usually include at
least two or more hydrophilic groups such as amine, alcohol, or
ether, residual amine volatility at the top of the stripper can be
managed to less than 1 ppm by a water wash. Nguyen66
measured amine volatility in water and showed that two or more
hydrophilic groups usually produce an amine volatility less than
100 ppm at absorber lean conditions. In solutions loaded with
CO2, diamines such as piperazine are substantially less volatile
because of speciation to ions including protonated amine and
carbamate.67 Hindered amines and tertiary amines with methyl
groups tend to have greater volatility. Aliphatic monoamines
without other polar groups have unacceptable volatility.
Several investigators68 have been developing systems with
amino acids (partially neutralised by K+) which should be
nonvolatile ions. Other vendors may be using amines such as
hydroethylpiperazine with three or more hydrophilic groups
that have practically no volatility and may not require a water
wash.
Amine aerosols. Vapour amine may condense in the absorber
on submicron hydrophilic aerosol or particulate to produce
small aerosol drops that are not removed by typical contacting
internals in the absorber or water wash.69 Several pilot plants
have reported amine emissions as high as 200 ppm from pilot
plants with 1 to 3 ppm SO3 in the inlet ue gas.7073 The resulting
aerosol can be eectively removed by a bre lter mist eliminator with a pressure drop of 150 to 250 mmH2O.74 Aker Clean
Carbon and MHI claim solutions to this problem.74 This
problem could also be addressed by using an amine or amino
acid with low or no volatility.
2.9
Development status
Since 1930, hundreds of plants have used amine scrubbing to

remove CO2 from hydrogen, natural gas, and other gases that
contain little oxygen. The plants use monoethanolamine,
diethanolamine, MDEA/PZ, and a number of second and third
generation solvents.
Review
Amine scrubbing for CO2 capture from natural gas is

commercially available. Since 1980, dozens of plants have
captured CO2 from combustion of methane or other clean fuels.
Most are based on technology provided by Fluor (MEA, Economine) or MHI (KS-1). The Fluor applications include a 70 MWe
gas-red boiler and a gas-red turbine with a ue gas rate
equivalent to 80 MW of a coal-red boiler.
Two public databases demonstrate that amine scrubbing is
near commercial on coal-red power plants.75,76 More than 25
pilot plants have tested amine absorption/stripping on coalred ue gas at 0.1 to 5 MWe. Seven prototype systems have
been operated at 10 to 33 MW with coal-red ue gas and
compression of the CO2. There are no larger plants operating on
coal-red gas, but one is under construction at 120 MW and
another eight plants at 140 to 765 MW in various states of
planning, permitting, and FEED.
2.10
Conclusions
Advanced amine systems will capture CO2 with heat duty less
than 2.7 MJ tCO21 and equivalent work less than 250 kWh
tCO21 (including compression to 150 bar).
The innovations contributing to reduced energy use include:
(1) Thermally stable amines such as 8 m piperazine that can
be regenerated at elevated pressure.
(2) Eective plate-and-frame cross exchangers and high
capacity solvents such as PZ/MDEA and PZ/AMP.
(3) Congurations such as the interheated stripper that
eectively recover heat from the stripper overhead.
(4) Fast amines such as piperazine and absorber intercooling
that provide more reversible absorber operation with greater
rich and lean loading.
(5) Amines with high heat of CO2 absorption that maximise
the energy performance of thermal swing regeneration.
Remaining issues of secondary environmental impact with
advanced amines have acceptable solutions:
(1) Amine oxidation can be minimised by using amines such
as piperazine and MDEA that are resistant to oxidation and by
stripping dissolved oxygen at <100 C.
(2) Nitrosamines can be managed by avoiding secondary
amines or by thermal or UV decomposition.
(3) Vapour losses of amine can be avoided by water wash with
volatile amines or by using non-volatile amines.
(4) Amine aerosol losses can be eliminated by a bre lter.
3. Ionic liquids as alternative solvents

for CCS
It has been suggested that the use of ionic liquids (ILs) as
alternative solvents would have many advantages over conventional amine-based CO2 extraction. The general area of IL use
for CCS has been reviewed recently.7784 In addition to a
potentially lower demand for energy in the solvent regeneration
step, ILs have lower volatility, lower vapour pressure, are nonammable, are more thermally stable, and are easier to recycle.
View Article Online
Review
The comparison of ILs with molecular organic solvents has

been discussed in a recent review3 and also discussed the general
implications of changing the cation and anion (see Fig. 4) or
employing mixtures. The recent developments in this eld will
be reviewed here, and the implications of IL physical properties
and functionalisation on CO2 solubility will also be explored.
3.1 Relationship between IL physical properties and CO2

solubility
Henrys constant is a quick and useful measure of CO2 solubility
in ILs. Henrys law constants for CO2 in a range of dierent ILs
are shown in Table 2. The highest solubility of CO2 recently
reported was in [C5C1im][bFAP], which contains a highly uorinated alkylphosphate anion that is exceedingly noncoordinating, resulting in an open uid structure that
dissolves CO2.85 As can be seen from Table 2, increasing the
length of the alkyl side chain on the imidazolium cation
improves CO2 solubility.86 However, the high molar solubility of
CO2 with increasing n-alkyl chain length is largely a function of
the increase in molecular weight of solvent. The volumetric
solubility of CO2 does still decrease with increasing cation alkyl
chain length, but this eect is less dramatic than the molar
solubility change and must be carefully considered when
selecting IL cations, as most physical properties suer when the
alkyl chain length exceeds octyl. Density increases roughly linearly with increasing alkyl chain length87 while viscosity increases
dramatically.88 This increased viscosity causes poor gas diusion
and slow mass and heat transfer, resulting in larger unit operations, including absorption columns and heat exchangers.89,90
While ILs typically have higher viscosities than common organic
solvents and water at the same temperature91 (resulting in slower
CO2 absorption kinetics),80 other IL physical properties are
Fig. 4 Selected IL cation and anion structures. (a) 1,3-dialkylimidazolium [CnCmim]+; (b) N,N-dialkylpyrrolidinium [CnCmpyrr]+;
(c) alkylpyridinium [Cnpyr]+; (d) tetraalkylammonium [CwCxCyCzN]+; (e)
tetraalkylphosphonium [CwCxCyCzP]+; (f) bis(triuoromethylsulfonyl)
imide [NTf2]; (g) triuoromethanesulfonate [OTf]; (h) hexauorophosphate; (i) tetrauoroborate.

Table 2 Henrys Law constants for CO2 in selected ILs. Data is taken
from Muldoon et al.85 [eFAP] tris(pentauoroethyl)triuorophosphate; [pFAP] tris(heptauoropropyl)triuorophosphate;
[bFAP] tris(nonauorobutyl)triuorophosphate; [ace] acesulfamate; [sac] saccharinate
H (bar)
Cation
Anion
25 C
[C4C1im]
[C4C1im]
[C6C1im]
[C6(3C1)py]
[(C6H4F9)C1im]
[(C8H4F13)C1im]
[C6C1im]
[C6C1im]
[C5C1im]
[C6C1im]
[C6C1im]
[Et3NBH2C1im]
[PF6]
[NTf2]
[NTf2]
[NTf2]
[NTf2]
[NTf2]
[eFAP]
[pFAP]
[bFAP]
[ace]
[sac]
[NTf2]
53.4
33.0
31.6
32.8
28.4
27.3
25.2
21.6
20.2
60 C
0.3
0.3
0.2
0.2
0.1
0.2
0.1
0.1
0.1
33.1 1.2
81.3 0.8
48.6 0.9
45.6 0.3
46.2 0.3
48.5 0.4
44.7 0.5
42.0 0.1
36.0 0.3
32.9 0.2
113.1 16.9
132.2 19.7
potentially better than conventional organic solvents, such as

heat capacity, density and surface tension.92 These favourable
properties can result in a low energy requirement for solvent
regeneration.93 Care is necessary to ensure that overall energy
requirements are minimised by the use of any new solvent. As
discussed above in the section on solvent scrubbing, this is not a
case of nding a solvent with a low heat of regeneration.
3.2
Ion selection
Anion eects on most IL-based solvation processes are dominant.94 This not only includes the solubility of CO2 and the
strength of the ILCO2 interactions in solution,95 but also the
solubility and anity of the IL for water.94 Most IL research has
focused on salts with dialkylimidazolium cations ([CnCmim][X]),
enabling an easy comparison of various anion eects. For bulk
liquid CCS applications, prominence is obviously placed on
hydrophobic (water-immiscible) ILs, as many ILs with highly
basic anions absorb very large quantities of water.94 This naturally
leads to selectivity problems when encountering wet ue gases.
The origin of the anion eect on CO2 solubility in ILs has been
investigated through molecular dynamics86 where the anionCO2
interactions were shown to be the strongest solvation forces
present. That study also pointed to mixtures on ILs with molecular solvents providing an optimised hybrid solution for CCS.
The bistriuorosulfonylimide [NTf2] anion generally gives
the best CO2:N2 selectivity and high overall CO2 solubilities with
most IL cations.96 This anion also possesses poor interactions
with water (leading to highly hydrophobic ILs) and generally
favourable physical properties: relatively low viscosities (2050
mPa s), very high thermal stabilities (a measure of the thermal
stability, Tonset of 400500 C) and low melting points (50
0 C). As a general rule, this anion can be employed to test
designer cations (as it is the most likely to yield favourable
physical properties) and yield salts with generally favourable
CCS potential. This opens up the cation for specic tailoring to
include CO2-philic moieties because it is the easiest portion of
an IL to synthetically modify.
View Article Online
3.3
Conventional ILs
Unfortunately, there is currently no comprehensive model for

gas solubility in ILs.97 However, some general trends can be
observed. Increasing the cation alkyl side chain length increases
CO2 solubility, likely by increasing the available volume for CO2
due to a decrease in cationanion interactions.98,99 It is clear that
there are mainly physical phenomena (such as dispersion
forces) dominating CO2IL interactions when unfunctionalised
ILs are employed, with only weak chemical complexes forming.100 The enthalpy of CO2 physical absorption by these ILs is
generally about 20 kJ mol1. This results in a lower energy
requirement than for amine solutions in the regeneration step,
but not overall: as discussed above, a lower heat of absorption
can lead to a higher overall energy requirement. The structural
exibility of ILs allow tuning of the enthalpy of absorption by
employing basic ionic liquids made by neutralising tetraalkylphosphonium hydroxide with weak proton donors with dierent
pKa values.101 These basic ILs have more rapid absorption rates
with little increase in viscosity, though this is likely to be very
sensitive to water as these are hydrophilic anions.
3.4
Task-specic ILs
Conventional ILs mostly use physical absorption to capture CO2

through the space between ions, while functionalised (taskspecic) ILs are usually designed to chemically bond to CO2
in an absorption process, increasing the overall absorption
capacity.80 The synthetic exibility of ILs means that a nearinnite range of functionalisations are possible, though cost
and stability become important considerations. However, only
some functionalisation strategies have increased CO2 capacity.
This eld of task-specic ILs (TSILs) for CCS applications has
recently undergone rapid growth.82
3.4.1 Fluorinated ILs. Incorporation of peruoroalkyl
groups in ILs increases CO2 solubility compared to nonuorinated inorganic anions such as nitrate and dicyanamide.102 This can be attributed to the large anity of CO2 for the
peruoroalkyl chains. The increase in CO2 solubility is minimal
when the peruoroalkyl chains are employed on the cation of the
IL, but very large when added to the anion. However, these
modications are generally avoided due to environmental
concerns surrounding peruorocarbons. Oxygen-containing
functional groups can serve as alternative sources of interaction
with the electron-poor carbon atom of CO2 with similar eect.77
3.4.2 Amine-functionalised and amino-acid ionic liquids
(AAILs). Amino-functionalised ILs provide strong complexation
potential with CO2 by duplicating much of the amine character of
molecular CCS solvents. Amine character can be inserted into
either the cation or the anion of the IL. Amine-functionalised
side chains103,104 provide chemisorption at the stoichiometric
ratio of IL : CO2 of 2 : 1 as with amine-based solvents, though the
nature of the carbamate complex is still under dispute.103
Unfortunately, these ILs generally have poorer thermal stabilities
and higher melting points and viscosities than conventional
ILs.105 A variety of cations (imidazolium, pyridinium, ammonium and phosphonium) have been be functionalised
with amines for CO2 capture, with (3-aminopropyl)-
Review
tributylphosphonium ILs (coupled with amino acid anions)

exhibiting the best physicochemical properties, such as a low
glass transition temperatures (in the range from 69.7 to
29.6 C) and thermal stability to above 200 C.105 The salt (2hydroxyethyl)-trimethyl-ammonium(S)-2-pyrrolidine-carboxylic
acid salt or [Choline][Pro] has been demonstrated to be able to
capture and release CO2, where CO2 is released by bubbling N2 in
the solution106 (of course, further measurements are necessary
under a CO2 atmosphere). There is, however, some concern over
melting point changes when amino acid anions absorb CO2.82
A variety of imidazolium or tetraalkylphosphonium cations
have been combined with amino acid anions to make
AAILs.107109 Potential advantages of using amino acids include
their low cost, biodegradability and low toxicity. Also, AAILs can
increase CO2 capture because they possess both carboxyl and
amine functional groups and the IL can complex CO2 in a 1 : 1
stoichiometric ratio.110 Immobilisation of AAILs into nanoporous PMMA microspheres has recently been shown to
increase CO2 uptake rates and ease regeneration.111
As mentioned above, amine-functionalised ILs tend to be
highly viscous, which leads to problems of measuring CO2
capacity and developing handling strategies, and also results in
the hindrance of CO2 diusion rates.102 These ILs also require
extra synthetic and purication steps to produce, which will
likely increase the expenses.77 One way to overcome the viscosity
problem is to use a solid support. However, this requires solid/
gas exchange, which is quite challenging in practice. The
conventional MEA process solves the viscosity problem by
diluting the MEA with water. However, this is not ideal as a large
amount of water needs to be evaporated to regenerate the IL.102
3.4.3 Carboxylate ILs. Much interest surrounds the use of
ILs containing carboxylate anions for a variety of applications,
primarily in bioenergy.112 [C2C1im][OAc] has been shown to
uptake almost 2 molar equivalents of water,112 aer which the
basic acetate ion absorbs CO2 which reacts with the water to
form bicarbonate salts. Surprisingly, the regeneration step can
still be carried out under mild conditions with an appropriate
stripping gas.80 Under anhydrous conditions, the absorption
capacity is greatly improved due to the acetate anion partially
deprotonating the C2 position of the imidazolium ring, forming
an in situ carbene that reacts with CO2 to make a zwitterionic
carboxylate, conrmed by FTIR and isolated as a crystalline
product (Fig. 5).113 Though this will only occur under strictly
anhydrous conditions, the unprotected N-heterocyclic carbenes
can lead to unstable side reactions.
Fig. 5 Reaction of CO2 at the C2 position with in situ-generated

carbine.113
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Review
3.4.4 Reversible ILs. Reversible ILs, based on amidinium

(i.e. DBU) or guanidinium alkylcarbonate salts, also show good
CO2 reactivity and high absorption capacity.114119 The molecular state of the system consists of a 1 : 1 mixture of a proton
donor (i.e. alcohol) and organic base, and shows excellent CO2
capacity and good CO2 : N2 selectivities (Scheme 1).101,120122
These new ILs are interesting CO2 capture options, though the
higher volatility of the alcohol component may hinder deployment. To avoid this, the alcohol group can be incorporated into
an IL cation side chain.123 CO2 absorbances of 1.04 : 1 (relative
to base) have been reported for this strategy, which is 20 times
higher than the solubility in the neat IL, and can be achieved in
under 10 min.123 CO2 release can be achieved by mild heating
(90120 C) and the IL re-used. It should be noted that for very
strong bases (e.g. MTBD, tetramethylguanidine), CO2 may
actually react with the IL cation,124 which would imply sensitivity of CO2 absorbance to H2O presence. Functionalisation of
the guanidines or amidines, including tethering of the alcohol
group to the base,125 may avert these diculties.
3.4.5 Protic ILs. One way to overcome the high cost of
dialkylimidazolium cation synthesis is to use protic ILs, which
are acidbase complexes.120 If a weak acid is employed, then a
strong CO2 complex can be formed, though these ILs will be very
hydrophilic. Functionalised protic ILs can dissolve large quantities of CO2 under anhydrous conditions; those based on
uorinated alcohols have been shown to capture 2.04 molar
equivalents of CO2, and the viscosities of these salts is relatively
low (8.63 mPa s). Unfortunately, these specic ILs are unlikely to
be stable in the presence of water.
3.4.6 Supported ionic liquid membranes (SILMs). The use
of ILs in membrane separation is a growing eld.126 SILMs can be
used to separate organic compounds, mixed gases, and ions.
SILMs have many potential advantages in CO2 capture, including
very high thermal and chemical stabilities, extremely low volatilities and increased contact area between the gas and ILs, overcoming many of the viscosity limitations on uptake rate.81 CO2 can
be successfully separated from N2 and CH4 by polymer lms of ILs
which are polymerised by styrene and acrylate monomers. The
SILMs based on task-specic TSILs, such as [(3NH2)C3C1im][NTf2]
and [(3NH2)C3C1im][OTf] have also been explored.127 These TSILs
contain functional groups capable of chemically complexing with
CO2. They show higher selectivity in CO2 separation than [C4C1im]
[NTf2] for CO2CH4 gas mixtures because the amine group
Scheme 1
CO2 capture mechanism for reversible ILs.122
facilitates CO2 transport through the membrane.128 AAILs supported on porous silica displays higher eciency then when used
as a bulk liquid phase. These supported TSILs achieve 2 : 1
IL : CO2 capture capacity through carbamate formation.
However, in the presence of small amounts of water (1% by mass),
the capture capacity can reach an equimolar ratio as shown in
Scheme 2.129 A combination of SILMs and TSILs may be a better
choice for CO2 capture at elevated temperatures and pressures.130
However, there remain drawbacks, including leaching of the IL
through membrane pores when the pressure drop is higher than
the liquid stabilising forces within the matrix. In order to overcome this limitation, polymerisable ILs as membranes could be a
possible option for CO2 separation.100
3.4.7 Poly(IL)s. Poly(ionic liquid)s are a new technology for
CO2 capture. The absorption and desorption of CO2 by poly(IL)s
is faster than bulk ILs.131134 Moreover, desorption by vacuuming
is completely reversible, though would not be energetically
viable in a power generation context. It may be that they are a
potential choice for sorbent and membrane material for CO2
separation. Fig. 6 shows CO2 absorption data for three type of
poly(IL)s:
poly[1-(4-vinylbenzyl)-3-butylimidazolium
tetrauoroborate] (PVBIT),
poly[1-(4-vinylbenzyl)-3-butylimidazolium hexauorophosphate] (PVBIH), and poly[2-(1butylimidazolium-3-yl)ethyl methacrylate tetrauoroborate]
(PBIMT), which are roughly analogous to polymerised versions
of [CnCmim][BF4]. PVBIT and PVBIH have been reported to take
only 4 min and PBIMT only 3 min to reach 90% capacity, and
Scheme 2 Proposed mechanisms of CO2 capture by AAILs: (a) and (b)

without water; (c) with water.129
Fig. 6 CO2 absorption of three poly(ILs) (PVBIH, PVBIT, PBIMT) and

their corresponding monomers (VBIH, VBIT, BIMT) and the IL [bmim]
[BF4] as a function of time (592.3 mmHg CO2, 22 C).131
View Article Online
around 30 min to reach their full capacities. By comparison,

monomeric BIMT and [C4C1im][BF4] required more than 400
min to reach their equilibrium capacity. Higher capacities were
also reported for the poly(IL)s, up to 2.1 times higher than
[C4C1im][BF4].131 However, these gures should be taken in
context with the extremely rapid reactions of solvents such as
MEA and PZ, described above. Studies of any new solvent, such
as ILs should compare their rates of uptake to those of standard
solvents, if the aim is to develop a replacement industrial-scale
technology, as opposed to simply investigating interesting
chemistry. They must also regenerate the CO2 under an atmosphere of CO2 to demonstrate reaction reversibility. Surprisingly, the VBIT and VBIH monomers did not absorb CO2
because of their crystalline structure, and the liquid BIMT
monomer had the same absorption capacity as [C4C1im][BF4],131
indicating that the polymeric structure itself conferred greater
CO2 capacity, perhaps by lowering ionion interactions. Poly(IL)
s with [PF6] anions displayed higher eciency than [BF4] or
[NTf2] based polymers and higher absorption and desorption
rates. Interestingly, while increasing the alkyl chain length of
ILs signicantly increases gas permeability and diusivity, the
reverse trend is observed for poly(IL)s, possibly due to steric
hindrance.134 The eciency of polymeric structures can also be
enhanced by modifying the monomers, such as using oligo(ethylene glycol) or nitrile-containing alkyl groups, though this
will complicate synthesis.87 Lower cost options, such as triethylene tetramine lactate, can absorb nearly 1 : 1 CO2.135
Biopolymers (chitin and chitosan) also have been used in the
process of CO2 capture. These biopolymers are environmentally
friendly, renewable, biodegradable and almost non-toxic. There
are two hydroxyl groups in chitin while there is an additional
amine group in chitosan. The IL [C4C1im]Cl has been used as a
solvent to break the strong inter- and intramolecular hydrogen
bonds, but it cannot disrupt the crystalline domains of chitosan.136 The result is that chitinIL and chitosanIL mixtures
have increased CO2 sorption capacity (8.1% higher than the IL)
under mild conditions (30 C, 1 atm CO2 pressure in CO2 xation and release processes). There are many potential environmental and performance benets from using such recyclable,
non-corrosive and non-volatile CO2 absorption media.93,136
3.5
Molecular simulations of CO2 with ILs
There have been a number of molecular simulation studies

focused on the dissolution of CO2 in ILs. A recent review83
highlights the most relevant advances. In conventional ILs, CO2
dissolves in free volume spaces within the IL matrix without
greatly aecting the structure, accounting for the rather
unusual solubility proles.137 This is also likely responsible for
the lower regeneration energy, as the CO2IL interactions are
relatively weak. By contrast, amineTSILs form strong chemical
complexes with CO2, which has been studied by simulation.138
4. Oxyfuel combustion technology

Oxyfuel combustion is one of the most developed technologies
for carbon capture and storage. Oxyfuel combustion refers to
Review
fuel being burned in a mixture of oxygen and recycled ue gas

(RFG). Unlike conventional fossil fuel-red power stations that
use air as the oxidant, an oxy-red plant employs an Air Separation Unit (ASU) to produce an oxygen stream. The oxygen
stream is combined with RFG to produce an oxygen enriched
gas for the oxidant. The recycle is necessary to moderate the
otherwise excessively high ame temperature that would result
from burning in pure oxygen. Aer the removal of water and
other impurities from the ue gas exhaust stream, high-purity
CO2 is produced. The combustion of fuel in an oxygen and
RFG mixture was proposed in the early 1980s for the purpose of
producing a high-purity CO2 stream for use in Enhanced Oil
Recovery (EOR)139 and for simultaneously reducing greenhouse
gas emissions from fossil fuel energy generation.140 Pilot scale
studies were subsequently carried out141143 in the following
decades. During the last decade, the global research activity has
increased to the point where several demonstration phase
projects have begun and the commercial concept is expected
before 2020. Oxyfuel combustion can be applied to several fuels,
including coal (oxy-coal combustion), natural gas or blends of
biomass and coal. Most interest has focused on oxy-coal
combustion due to the abundance, reliability and high carbon
content of the fuel. The following sections refer to oxy-coal
combustion unless otherwise stated.
4.1
Process considerations
In comparison to air-red plants, the implementation of oxyfuel

operation will lead to a number of plant conguration changes
and additional unit operations, i.e. recycle loop, ASU, CO2
purication and compression. The optimum recycle ratio is
generally 0.7; this yields oxygen levels in the oxidant environment that typically range from 25 to 30% because at these
conditions, the ame and heat transfer characteristics reasonably approximate those of air-red pulverised fuel (PF) boilers.
Oxygen excess levels are 1520% for air-ring conditions but are
kept lower for oxyfuel conditions to no more than 10% in order
to minimise ASU operational costs. Flue gas oxygen content is
typically 3%. The ue gas stream should be cooled, scrubbed
and dried before being diverted for the primary recycle. Particulates are removed in order to avoid accumulation of solids in
the boiler and prevent the ue gas recirculation fan and gas
passages from unnecessary wear due to erosion. Several options
for conguration of a secondary recycle stream exist.144
4.2
Energy performance
Oxyfuel combustion induces an energy penalty to the process

caused by the requirements of producing O2 and compressing
CO2. Using current technology, the overall plant eciency is
reduced by 812%.145 However, oxyfuel combustion does allow
for process exibility and improved combustion eciency. One
strategy to reduce the energy penalty is the use of pressurised
oxyfuel combustion cycles. An advantage of pressurised
systems is that the combustion power cycle utilises the higher
heating value of the fuel and produces more gross power
compared to conventional atmospheric oxyfuel combustion
power systems. Elevated dew point and higher available latent
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Review
enthalpy in the ue gases lead to higher thermal energy

recovery from the water in the ue gases. Pilot scale experimental trials by ENEL have shown that pressurised
systems146,147 have increased heat transfer rates in the Heat
Recovery Steam Generator (HRSG), allowing the possibility of
burning cheaper coals and reducing the size of components,
which will lead to a reduction in capital costs. The pressurised
oxyfuel system is achieved by pre-compressing oxygen in the
ASU which leads to high pressure combustion ue gases and a
reduction in the work duty of the CO2 compression unit.
Overall, the amount of compression work between the ASU and
compression unit is reduced in comparison to conventional
atmospheric oxyfuel operation. Sensitivity studies by Massachusetts Institute of Technology have determined that
maximum eciency can be achieved in the vicinity of 10 bar
combustor operating pressure.148
Further studies have been conducted to reduce the energy
consumption of the ASU by investigating the use of hightemperature oxygen transport membrane (OTM) technology
for oxygen production as an alternative to conventional cryogenic distillation methods.149,150 To conduct oxygen, the
temperature of the OTM must be maintained above 800 C and
an oxygen partial pressure gradient must be applied across the
membrane. Membranes for oxygen production can be operated
with a three-end or four-end design. In the four-end concept, a
sweep stream of RFG is applied on the low pressure side of the
membrane, increasing the driving force by removing the
permeating oxygen and maintaining the necessary operating
temperature. In the three-end concept, the driving potential is
sustained by applying vacuum to the permeate side or by an
increased feed pressure, where the membrane temperature is
maintained by preheating the air. Dierent membrane module
types are being investigated: tubular,151 monolithic,152 hollow
bre153 and at.154 Vente et al.155 compared the dierent module
designs and concluded that tubular systems are the optimal
choice for all considered conditions. Current investigations into
OTM technologies are at the conceptual or laboratory scale. The
dierent process conditions encountered in the three- and fourend concepts will have implications for the types of materials
that can be considered for membranes. The membrane used in
the three-end concept is only exposed to air, which allows many
dierent materials to be employed. The membrane in the fourend concept will have direct contact with ue gas, which can
make integration in coal powered plants complicated because
coal derived ue gas contains corruptive components such as
particles and corrosive acid species. Typical membrane materials like Ba0.5Sr0.5Co0.8Fe0.2O3x (BSCF) and Li2NiO4 that have
high permeation rates at the conditions of interest have been
found to be unsuitable for four-end operation due to chemical
instability aer contact with ue gas components.156 Studies of
possible implementation of the OTMs have found that their use
limits the drop in overall net plant eciency by 5.2% for fourend concept and 5.8% for three-end concept. Although the
four-end concept is preferable due to the higher plant eciency,
the three-end concept will be more technically viable in the near
term because no membrane material has yet been identied
that can withstand contact with ue gas.149
4.3
Pollutant emission and removal
An operational benet of oxyfuel combustion is the reduction of

NOx and SOx emissions. Oxyfuel combustion oers highly
reduced NOx emissions, because NOx in the recycled gas can be
reburned by contact with ame-generated hydrocarbons, which
act as a reducing agent to produce N-volatiles, consisting of
ammonia and cyanide species that may subsequently produce
NOx or N2 depending on the conditions. Moreover, as nitrogen
from the air is largely eliminated from the process by substitution with RFG, thermal and prompt-NOx formation rates are
highly reduced. The amount of NOx emitted per unit of energy
generated can be reduced to around a third that of airring.157159 Recent experimental investigations of NOx formation during oxyfuel combustion of pulverised coal160,161 have
concluded that fuel-N conversion to NO in O2/CO2 is lower than
in O2/CO2. However, very high concentrations of oxygen are
oen present locally in oxy-coal ames, which can result in
enhanced production of NOx from fuel-N if the burner is not
suitably designed and operated.162 The reduction in volume
throughput of oxyfuel combustion also leads to higher
concentration of NOx in the system. Conventional primary and
secondary measures can be used for NOx control under oxyfuel
operation. Primary measures that reduce NOx formation in the
furnace by modifying the combustion environment (i.e.
employing low NOx burners, air-staging, fuel staging and ue
gas recirculation) are believed to be sucient for oxyfuel
combustion but this will depend on future legislation for CO2
emission and storage.163 Additionally, the development of deNOx in CO2 compression and purication processes via
conversion of NO to NO2 and removal by absorption in
condensate is in progress.164
The oxyfuel process using RFG results in a higher concentration of SO2 (ppm) in the combustion ue gas due to reduced
volumetric ow and the introduction of the recycle loop,165
which can in turn lead to higher concentrations of SO3.
However, the overall emission rate of SO2 (mg MJ1) is
lower158,166,167 than air ring due to the increased conversion of
SO2 to other species throughout the process. Elevated concentrations of SOx present serious implications for CCS technologies, including boiler and pipeline corrosion, ash deposition
and increased acid dew point.168 Mitigation and control strategies for SOx include the use of low sulphur and/or high calcium
coals, wall soot blowing, limestone injection, sulphur scrubbing
prior to recycle or compression and removal during compression.165 Development of optimal strategies for SOx mitigation
and control requires techno-economic evaluation. The emission
of mercury in oxy-coal combustion is a corrosion concern
because it forms an amalgam with a number of metals,
including aluminium used in CO2 compression units.169
Elemental mercury can speciate to the oxidised form (Hg2+) or
particulate bound forms HgP during post-combustion quenching. Only a few studies have reported the extent of mercury
oxidation or its retention in y ash. While the change of environment from N2/O2 to CO2/O2 may have little eect on the ratio
of Hg0 to Hg2+;170,171 tests in a 30 MW pilot scale facility of
Babcock and Wilcox showed mercury concentration to increase
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in oxy-coal combustion.172 While the increase in Hg concentration is due to the removal of diluent nitrogen, the increase in
Hg oxidation may be explained by increased chlorine concentration in oxyfuel combustion. Strategies to control Hg emissions include injection of activated carbon sorbents or forcing
oxidation to water soluble Hg2+ forms to then be removed by
conventional FGD scrubbing.
Air Products have developed the possibility of co-removal of
SOx, NOx and mercury during compression using their Sour Gas
Compression technology.173 The process relies on the oxidation
of NO to NO2 to convert SO2 to H2SO4174 in the presence of water.
Mercury will dissolve and react in the nitric acid formed as a
condensate. The technology is based on the lead chamber
process. Further investigations are required to determine the
kinetics at higher pressure. Further pilot-scale work in this area
has been performed by CANMET175 and at the laboratory scale (e.g.
Chalmers University, Sweden176 and Imperial College London177).
Little information on the behaviour under oxyfuel conditions
of other pollutants such as particulates, other trace metals (Pb, As,
Cd, Se, etc.), volatile organic compounds (VOCs), polyaromatic
hydrocarbons, dioxins and other chlorinated compounds are
currently available. More investigations of the release and distribution of these substances under oxyfuel conditions are required.
4.4
Computational uid dynamics modelling
Oxyfuel combustion presents numerous opportunities and

challenges for numerical modelling.178 Extensive use of
Computational Fluid Dynamics (CFD) modelling tools for the
scale-up and advanced design of oxy-coal combustion facilities
is expected.179 Utility boilers can be modelled in 3D and the
impact of changing various design parameters on uid ow,
heat transfer and chemical reactions in combustion can be
investigated. CFD modelling for oxyfuel combustion relies on
sub-models that were initially developed for air-ring conditions. While signicant progress has been made in adapting the
CFD sub-models for application to oxyfuel conditions, some of
the models require further modications and validation in
order to be reliably applied in the CO2 rich environment.
Char oxidation and burnout is inuenced by the high
concentrations of CO2 and H2O in oxyfuel combustion. Physical
eects (heat capacity and mass transfer) and Arrhenius
parameters for homogeneous and heterogeneous reactions
must be adapted for accurate prediction of char burnout and
the transition between combustion regimes.
Reduced gas-phase chemical kinetic mechanisms which can
be adopted within CFD codes at acceptable levels of computational cost require development for CO2 rich environments.
The dominant mode of heat transfer in both air and oxyfuel
combustion is radiation. Radiative heat transfer in oxyfuel
combustion is very dierent than air combustion due to altered
gas emission and absorption. To calculate radiation within a
utility boiler, the radiative transfer equation must be solved and
coupled with a radiative properties model that species the
gaseous and particle properties. Eorts have recently been
made to improve the models for gaseous radiative properties by
making them applicable to oxyfuel combustion modelling.180
Review
Accurate turbulence models are required since turbulence

has important eects on mixing, kinetics and heat transfer with
greater signicance under oxyfuel conditions. At present, Reynolds Averaged Navier Stokes (RANS) models are considered an
acceptable compromise between accuracy and computational
cost. Large Eddy Simulations (LES) are more computationally
intensive and have recently been applied to oxyfuel combustion.178 LES was found to be capable of capturing the intermittency eects of the coal ame and the importance of gas
radiative properties was also demonstrated in the calculations.
As computational resources increase, more sophisticated
methods such as LES should replace classical turbulence
models for CFD.
4.5
Recent trials and developments
Pilot-scale and industrial demonstration projects for oxyfuel

combustion are crucial for verifying observations and theories
from laboratory and bench-scale, in addition to proving the
commercial viability of the technology. Until now, all operated
pilot-scale and demonstration projects have been #100 MWth in
size, and are spread out between several countries. The majority
of projects have focused on the CO2 capture process only,
without linking to CO2 transport and storage.181 Nevertheless,
Vattenfalls Schwartze Pumpe 30 MWth plant in Eastern Germany, which began in 2008, became the worlds rst full chain
oxyfuel pilot demonstration,182 designed for 10 tpd of CO2,
transported by refrigerated truck183 to several storage and
industrial sites. The 30 MWth Lacq project by Total in France
uses natural gas as fuel and commenced in 2009. This was the
rst time an oxyfuel project has been coupled to pipeline
transport for geosequestration. The Lacq project does not
include any inerts-removal step,184 so CO2 is transported at 92%
purity and 27 bar along an existing pipeline through a populated area. The CO2 is injected down to a depth of 4500 m into a
depleted gas eld. The largest currently operating integrated
CCS chain involving oxyfuel combustion is the Callide 30 MWe
oxyfuel project which began in 2011 in Australia.185 The Callide
Oxyfuel project is the rst demonstration of retrot to an
existing coal-red boiler with electricity generation supplied to
the open market and includes on-line coal milling.
Future commercial demonstration-scale oxyfuel plants have
recently been announced. Vattenfalls 250 MWth J
aenschwalde
plant in Germany will also generate electricity for the open
market and has an operational aim of 2015. The FutureGen 2
Merediosa project has been announced. This project aims to
convert an oil-red process into an oxycoal-red utility at the
200 MWe scale.181
Next generation technologies will include co-ring with
biomass, sharing of CO2 transport pipelines and boiler designs
optimised for higher O2 concentration. CanmetENERGY are
working on oxyfuel systems that aim to minimise or eliminate
the RFG. This could lead to drastic plant size reductions, eciency increases and cost reductions. To achieve this objective,
very signicant improvements in materials and system design
are needed. Technologies which combust coal in a mixture of
oxygen and steam/or water, known as hydroxy-fuel combustion
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are also being investigated. In this technology, RGF is not used,

so water or steam will act as a temperature moderator. Similarly,
the technology will lead to reduction in equipment size and will
utilise novel turbomachinery that can generate power from the
expansion of steamgas mixtures.186
As oxyfuel combustion approaches the commercial demonstration stage of development, some technical uncertainties
remain, such as those related to ue gas cleaning; however, no
fundamental technical barriers have been encountered with the
operation of pilot and demonstration scale test facilities. The
successes of demonstration projects will provide practical
information and experience needed to push forward oxyfuel
technology to commercial realisation.
5.
Oxyfuel CFBC
Until recently, the obvious route for oxyfuel combustion was via
conventional pulverised coal-red (PC) boiler technology as
discussed above, and there is already one large European oxyfuel PC demonstration plant, with more planned in the future
(see Section 4.5). However, recently oxy-red uidised bed
combustion (FBC) has also become increasingly important as a
potential technology oering both fuel exibility and the
possibility of ring or co-ring biomass with CO2 capture. For
utility applications, a high velocity version of FBC, in which gas
velocities are of the order of 4 to 8 m s1, called circulating
uidised bed combustion (CFBC) is employed, and this technology is available in the supercritical mode at sizes of up to 460
MWe,187 with larger (550 MWe units) currently being built.188
CFBC is now a widely used technology for the power industry
for dicult fuels (e.g. low volatiles content or high sulphur, ash
or moisture content or for almost any waste material). In this
technology, the fuels are burned in a turbulent bed of an inert
material, thus ensuring high heat transfer rates, and good solid
mixing. Furthermore if sulphur capture is required, limestone
can be added to the bed, ensuring SO2 is removed in solid form
(CaSO4, anhydrite), which can be landlled. While this technology was explored 35 years ago189 in its bubbling bed mode
(uidising velocities 1 to 2.5 m s1), it was not until the last
decade that the oxyfuel FBC technology received serious attention, when two large boiler companies, Alstom190 and Foster
Wheeler, began to carry out pilot-scale test work and other
studies to see if it could be developed as commercial CFBC
boiler technology with CO2 capture.
As discussed above, in oxyring, ue gases must be recycled
in order to keep combustion temperatures to manageable levels
(in the case of CFBC, less than 1000 C). However, unlike oxyred PC units, the hot solids which are an integral part of
CFBC technology can also be used for extra heat transfer and
steam production, either in the primary reaction loop and/or in
external uid bed heat exchangers. This means that unlike PC
systems, where perhaps 7080% of the ue gas must be recycled, lower levels of ue gas recirculation are possible, which
would allow oxyfuel CFBCs of any given thermal output to be
built; these can potentially be 30 or 40% smaller than the
equivalent air-red units, and thus improve plant cost savings.
This lower volume of ue gas means that emissions are best
expressed in terms of mg MJ1 or some similar unit, to avoid

misleading comparisons with gas emissions from air-red units
where pollutants are diluted with N2 from the air.
5.1
Pilot plant studies
Although functioning pilot plant units are still limited in

number (as indicated in Table 3), studies are being undertaken
in numerous countries, and oxyfuel CFBC is being considered
in many other industrially important countries such as Russia191 and Australia.192 Also, there is now an international
workshop on oxyfuel FBC, which is held annually.193 To date,
most test work has been done at small scale (in the <100 kW
range), and/or using bottled gases to supply a suitable
combustion gas, instead of recycling ue gas to achieve the
necessary gas velocity and solid circulation rate in terms of heat
transfer requirement. CanmetENERGY in Canada currently has
one of the most detailed and well-reported programs, based on
results from two pilot plants which are capable of being operated in oxyfuel mode, with full ue gas recycle: a nominal
75 kWth unit and a larger 0.8 MWth unit. Successful runs on the
75 kWth unit were achieved and reported in 2007194 and much of
the emissions data195 discussed below come from this unit.
5.2
Gas and other emissions from oxyfuel CFBC
Air-red CFBC technology normally produces low emissions of

SO2 on addition of limestone, low NOx due to its low operating
temperatures, low emissions of organic species in the form of
unburned hydrocarbons, and also low emissions of heavy
metals.196,197 At the moment it is far from clear how pure ue
gases should be to allow the least-cost production of CO2 for
piping and sequestration. However, it is reasonable to assume
that if a technology such as oxyfuel CFBC has inherently low
emissions then this must represent an advantage.
A series of trials194,195 indicated that fuel nitrogen conversions were oen about half that seen from air-red trials, with
fuel nitrogen conversions down to 1.5 to 3.5%. More recently,
Duan et al.198 investigated the eect of operating parameters on
NO formation using a 50 kWth oxy-red CFB, without ue gas
recycle, and also found that NO production with 21% O2/79%
CO2 was lower than for the air-red case.
CFBC can be regarded as a low SO2 emissions technology,
due to its ability to use limestone to trap SO2 in situ. A key
dierence between air- and oxy-ring is that unless the CFBC is
operated above about 870 C, the CaO/CaCO3 equilibrium
indicates that capture will be with CaCO3 directly (so-called
direct sulphation), rather than with CaO produced from the
rapid calcination of limestone at temperatures above 790 C,
due to the much higher partial pressures of CO2 in an oxyfuel
CFBC. The global reactions which describe sulphur capture in a
CFBC are given below:
CaCO3 + SO2 + 1/2O2 CaSO4 + CO2
(7)
CaCO3 CaO + CO2
(8)
CaO + SO2 + 1/2O2 CaSO4
(9)
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Table 3
Review
List of pilot plant oxyfuel FBC facilities (modied from Wall et al.192)
Location
Size
Purpose
Additional information
Alstom, Windsor, CT, USA
3 MWth
Feasibly studies on O2 fuel FBC

technology
Foster Wheeler, VTT and

Lappeenranta University of
Technology, Finland
CanmetENERGY, Canada
0.1 MWth
Provided design and operational

data for oxyfuel CFB, with ue gas
recycle
Support of national Canadian
program on oxy-fuel CFB
Unit did not employ ue gas recycle,

but R&D on the unit, which began in
2001, represents the beginning of
the companys development of oxyfuel FBC technology. Alstom also
operates a number of smaller
facilities including a 400 bench-scale
FBC (see [Marion et al.572] for an
overview of the companys program
in oxyfuel FBC)
Foster Wheeler used VTT, Finland
along with CanmetENERGY
facilities to test numerous fuels and
limestones573 as a prelude to their
demonstration plant at
CIUDEN199,207
0.1 and 0.8 MWth
CIRCE, University of Zaragoza,

Spain
University of Utah, Utah, USA
100 kWth
0.33 MWth
Metso Power, Finland
4 MWth
Bubbling FBC used to generate

fundamental data
Generation of fundamental
knowledge
Developing commercial technology
Czestochowa University of
Technology, Poland
ICB-CSIC Spain
0.1 MWth
Generation of fundamental data
3 kWth
Southeast University, China

Zhejiang University, China
100 kWth
30 kWth
North China Electric Power

University
NA
Bubbling bed facility used for

generation of fundamental data
Generation of fundamental data
Bubbling bed used to generate
fundamental knowledge
Batch pressurised bubbling bed
facility (using 10 g of fuel) capable of
operating up to 4.5 MPa
Typically, limestone conversion in a CFBC is relatively low

with the 3045% utilisation being regarded as acceptable. The
work of Jia et al.194,195 has suggested that limestone utilisations
are comparable or lower for oxyfuel CFBC combustion.
However, to date, insucient studies have been carried out to
determine this issue unequivocally, although recent tests from
the 30 MWth CIUDEN demonstration unit have also suggested
somewhat lower limestone utilisation.199 CanmetENERGY
work200 has suggested that high-temperature steam, at the levels
present when burning any hydrocarbon fuel, enhances the
sulphation in both the air ring and oxyfuel case, but more so
for air ring, so that sulphation is better or comparable in air
ring to oxyfuel combustion (Fig. 7).
The issue of SO3 emissions, given its potential to cause
corrosion, is something which is also of interest for oxyfuel
systems, for two reasons: the use of recycled ue gases will likely
increase SO3 levels; and potentially high oxygen concentrations,
particularly at the base of the bed, might also enhance its
formation. There is currently a dearth of information on this
subject for oxy-FBC systems; however, from preliminary
research done by CanmetENERGY on its 0.8 MWth CFBC, levels
do not seem excessive at 2 ppmv or less,201 albeit that the
bituminous coal used contains only 0.56% sulphur. Ahn et al.202
A co-operation between Metso and

Fortum, with fundamental studies
performed by Chalmers University,
Sweden574
Unit has also been used to support
Foster Wheelers program
have also recently examined SO3 concentrations for a 1.5 MW

pilot-scale PC combustor and a 330 kW pilot-scale CFB test
facility (using a PRB coal with 0.2% S, a Utah coal with 0.5% S
and an Illinois coal with 4% S). Unfortunately, they appear only
to have examined SO3 levels for the Utah coal, for which they
conclude that SO3 levels are similar for both air and oxy-ring
under their conditions. They also point out that the presence
of particles may provide more opportunities for SO3 formation
via catalytic processes, but note again that SO3 concentrations
do not appear to be noticeably aected by the amount of
limestone addition.
Recently, CanmetENERGY has also examined co-ring of up
to 80% wood with a bituminous coal and found that trace
elements in the ue gas are negligible.201 On the question of Hg
emissions, there are still rather limited data. Font et al.203 have
investigated the fate of Hg and other trace elements employing
a 90 kWth oxy-red bubbling FBC. Here the pH of the leachate
for the bed ash was in the range of 10.711.1, and for the cyclone
y ash even lower (pH 8). As expected, most trace elements
tended to report to the overhead streams (i.e. cyclone and y
ash). Interestingly, in this work the bulk of the Hg was found in
the elemental form. By contrast, in some recent work done at
CanmetENERGY on a bituminous coal, Hg emissions were
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Review
unused O2, and thus no energy is expended for the gas separation and no gas separation equipment is needed. However,
the eciency of the baseline technology must also be taken into
account. If CLC were to be used for power production with
gaseous fuels, and not pressurised, CLC would limit the eciency of the underlying thermodynamic cycle to that of a steam
cycle, rather than a more ecient combined cycle. However,
where the aim is to produce steam/heat or hydrogen, or if solid
fuels are used, this is normally not an issue. Potentially promising technologies, such as chemical looping reforming, which
avoid this issue, will also be discussed below. The CLC system is
composed of two reactors, an air and a fuel reactor, see Fig. 8.
The fuel is introduced in the fuel reactor, which contains a
metal oxide, MexOy. The fuel and the metal oxide react
according to:
Fig. 7 Sulphation conversion proles under oxy-red conditions for
varied concentrations of H2O (with air-red proles overlaid).
0.8 mg m3 or less with about 80% of the Hg present in an

oxidised form.204
5.3
Larger-scale tests and industrial plans
Foster Wheeler commissioned 8 months of trials at CanmetENERGY and these trials demonstrated excellent control on CO2
levels and combustion conditions.205 Overall performance was
excellent, which is a very positive sign for the development of
the technology. Foster Wheeler was also the rst to commercialise supercritical CFBC technology (Lagisza power plant,
Poland) and with this technology as the basis, Foster Wheeler is
now working with the power company ENDESA on the development of a 300 MWe supercritical Flexi-Burn CFBC. The
predicted CO2 capture for this technology is 90% of emissions
and it is anticipated that it could be available by 2020.206 Foster
Wheeler also believes that it could oer such technology at the
600800 MWe size with 600 C steam temperature.
Demonstration tests are currently underway at the 30 MWth
CIUDEN pilot CFB demonstration unit, which will provide a full
experimental CCS platform for the demonstration and validation of exible air/oxyfuel CFB combustion.199,207 An interesting
feature of this unit is that it uses NH3 injection into the cyclone
to help maintain NOx at 120 mg Nm3.
Finally, it must be noted that Alstom has also announced its
intention of carrying out a 100 MWe oxyfuel CFB demonstration; although at the time of writing, no further information
appears to be available in the open literature.208 It appears that
oxy-red CFBC technology is making major strides to enter the
commercial arena, and it is highly probable that it will also be
available as a competitive CCS technology along with oxyfuel PC
technology before the end of the decade.
(2n + m)MexOy + CnH2m / (2n + m)MexOy1

+ mH2O + nCO2
(10)
The exit gas stream from the fuel reactor contains CO2 and
H2O, and a stream of CO2 is obtained when H2O is condensed.
The reduced metal oxide, MexOy1, is transferred to the air
reactor where it is oxidised, reaction (11):
MexOy1 + 1/2O2 / MexOy
(11)
The air, which oxidises the metal oxide, produces a ue gas

containing only N2 and some unused O2. Depending on the
metal oxide and fuel used, reaction (10) is oen endothermic,
while reaction (11) is exothermic. The total amount of heat
evolved from reaction (10) and (11) is the same as for normal
combustion, where the oxygen is in direct contact with the fuel.
The metal oxides used for the oxygen transfer are called
oxygen carriers. The reactor system is normally made up by two
interconnected uidised beds, with the oxygen carrier in the
form of particles being circulated between the two beds, Fig. 9.
CLC was rst introduced by Lewis et al. as way to produce
pure CO2 from fossil fuels, using two interconnected uidised
beds.209,210 Much later, Ishida et al. proposed the use of
chemical-looping combustion for climate mitigation and also
started laboratory research on oxygen-carrier materials.211
6. Chemical-looping combustion
6.1
Introduction
Chemical-looping combustion has emerged as an attractive

option for carbon dioxide capture because CO2 is inherently
separated from the other ue gas components, i.e. N2 and
Fig. 8 Chemical-looping combustion. MexOy/MexOy1 denotes

recirculating oxygen carrier material.
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Review
means that CLC with solid fuels will require a dierent design
of the fuel reactor, as well as oxygen carriers with other properties. The following key issues have been identied in relation
to fuel reactor performance: solid fuel conversion, gas conversion and CO2 capture.
6.3
Fig. 9 CLC process, example with two interconnected uidised

reactors. (1) Air reactor and riser, (2) cyclone, (3) fuel reactor, (4) loop
seals.
Ishida also introduced the name of the process, chemicallooping combustion.212 In 2001, a design based on the circulating uidised-bed principle was presented, see Fig. 9, investigating the critical design parameters of a system such as the
solids inventory and recirculation rate of oxygen carriers
between the reactors and identifying the relationship between
these and the oxygen carrier properties.213
6.2
Applications
Most of the work so far has been focused on gaseous fuels.

Gaseous fuels can be used directly as the uidising medium of
the fuel reactor. Important gaseous fuels, e.g. natural gas and
renery gas, contain large amounts of methane. Thus, oxygen
carrier development has had signicant focus on oxygen carrier
materials with high reactivity towards methane.
Liquid fuels would also be a possible fuel, but except for the
operation involving kerosene in a 300 W unit,214,215 little operational experience is presently available with liquid fuels.
Dierent liquid fuels including heavy fuel oil have been studied
in uidised-bed batch reactor tests.216
The pioneering work of Lewis et al.209,210 utilised copper and
iron oxides. Fiy years later, new studies emerged,217219 revisiting the same oxides. Soon aer, Leion et al. investigated
dierent fuels and oxygen carriers in a laboratory uidised
bed,220222 and today there are a number of publications of
laboratory work with solid fuels, as well as from actual operation in smaller pilots.223,224
When using solid fuels, the reaction between the oxygencarrier and the char remaining aer volatiles release is not
direct, but involves an intermediate gasication step. This
Using CLC for hydrogen production with CO2 capture
The chemical-looping technology can also be adapted for the

production of hydrogen with inherent CO2 capture. Chemicallooping processes for hydrogen production from gas include,
(i) autothermal chemical-looping reforming, (ii) chemicallooping steam reforming, and (iii) chemical-looping with
water-splitting.
Autothermal chemical-looping reforming, CLR-a, involves
utilising chemical-looping for partial oxidation to form a
syngas. That, aer watergas shiing, can be separated into CO2
and H2.225228
Chemical-looping steam reforming, CLR-s, or chemicallooping combustion with steam reforming, is a marriage
between conventional steam reforming and CLC.229 Just as in
commercial steam reforming, the reactions take place inside
tubes using suitable catalysts and at elevated pressures. The
steam reforming tubes are placed in a separate uidised-bed
heat exchanger. Hence, the reformer tubes are not heated by
direct ring but by oxygen carrier particles, which means
extracting the heat generated from the CLC process. The feed
gas to the fuel reactor is the ogas from the steam reforming
process, which is a gas mixture of CH4, CO2, CO and H2.
The CLR-s process has a number of important advantages: (i)
only one gaseous component, i.e. H2, needs to be separated,
unlike the CLR-a process, where two essentially pure streams of
CO2 and H2 are needed, (ii) the chemical-looping can take place
at atmospheric pressure, while the reforming can occur at high
pressure, (iii) compared to the gas boilers used in conventional
steam reforming, the temperature around the tubes is considerably lower and more uniform. The lower temperature means
that a greater fraction of the combustion heat is used for steam
reforming, with the consequence that the reforming eciency
is increased. This may well be the only CO2 capture technology
which results in increased eciency (if the eciency loss of CO2
compression is not included).
Chemical-looping with water-splitting, also known as OneStep Decarbonisation, uses three reactors.230 The process
requires an oxygen carrier which is reduced in steps through
dierent oxidation states, e.g. Fe2O3 > Fe3O4 > FeO. In the fuel
reactor, the fuel and oxygen carrier needs to move countercurrently. In the top, Fe2O3 is reduced to Fe3O4, while accomplishing complete combustion of the fuel, and in the bottom,
Fe3O4 is further reduced to FeO. Then, in the water splitting
reactor, the FeO is oxidised to Fe3O4 by steam, yielding
hydrogen. Finally the material is led to the air reactor where it is
oxidised back to Fe2O3. Note that two changes in oxidation state
are needed. Fe2O3 to Fe3O4 is needed to fully oxidise the fuel,
while FeO to Fe3O4 is needed for water splitting. The process
elegantly avoids any gas separation in the hydrogen production
but at the price of an added complexity of the reactor system.
View Article Online
Review
There is also work with chemical-looping of solid fuels

directed towards hydrogen production, rather than complete
combustion, which is similar to the chemical-looping reforming and water-splitting processes proposed for gaseous fuels. A
chemical-looping process for the production of syngas using
solid fuels and two interconnected uidised beds was patented
more than 60 years ago.225 Some more recent processes involve
using lime to enhance fuel conversion to H2 by in situ CO2
removal, e.g. the Alstom Hybrid CombustionGasication
Process and the GE Fuel-Flexible Process.231 With respect to
water-splitting, it should be mentioned that going back 8090
years, the main process for hydrogen production was the socalled steam-iron process. In this process, iron oxide was
reduced by coal to iron, and the iron was then reacted with
steam to form hydrogen.231 Related processes that are concerned with the direct production of hydrogen through watersplitting using Fe/FeO being studied today are the Syngas
Chemical-Looping process (SCL) and the coal direct chemicallooping process.231
6.4
Oxygen carrier materials
More than 900 dierent oxygen carrier materials have been

studied in the laboratory,232 and there are several reviews
covering oxygen carrier materials,223,232,233 and discussing
important criteria and the required thermodynamic properties.234 The rst phase of oxygen carrier development focussed
mainly on four metal oxides: Ni, Fe, Mn and Cu. However, the
development over the last few years has been more diversied;
there has been more work on combined metal oxides, on low-cost
materials for use with solid fuels, and on materials releasing
oxygen, i.e. CLOU materials (see the following section).
Combined metal oxides, i.e. where two or more oxides are
combined not only physically, but also chemically, produce new
oxides, for example, Cu0.95Fe1.05AlO4, Co0.5Ni0.5FeAlO4,
CoFeAlO4, CuFeGaO4, NiFeAlO4.235 Some of these materials have
the perovskite structure, e.g. La1xSrxFe1yCoyO3d, and
Sr(Mn1xNix)O3.236,237 Other types of oxide that should be
mentioned are combined Mn oxides with partial CLOU properties, i.e. with the ability to release some oxygen. This includes Mn
combined with Ca, Mg, Ni and Fe.238240 Many of these combined
materials are promising, but fewer have been successfully tested
during actual operation. An exception is CaMn0.875Ti0.125O3.241
Another is ilmenite, FeTiO3, a naturally occurring low-cost
combined oxide commonly used with solid fuels.
Low-cost materials have been investigated mainly for use
with solid fuels, these studies include iron ore,242244 manganese
ore,245 ilmenite, CaSO4/CaS,246253 industrial waste materials,254,255 as well as comparisons of materials of dierent
sources.256,257 Most of the studies have used ilmenite,258262
because it is a cheap ore, has a reasonably high reactivity
towards syngas and has shown good uidisation behaviour.
Most materials studied have only been investigated in laboratory, but a signicant number of dierent materials have actually
been used in continuous operation in CLC pilots. These include
oxides of nickel, copper, iron, manganese and cobalt, as well as
natural minerals like ilmenite, iron ore and manganese ore.
6.5
Chemical-looping with oxygen uncoupling (CLOU)
Chemical-Looping with Oxygen Uncoupling (CLOU) is closely

related to chemical-looping combustion but diers from CLC
through the spontaneous release of oxygen in the fuel reactor.
For instance, the CuO/Cu2O system has an equilibrium oxygen
partial pressure of 0.02 bar at a temperature of 913 C. This
means that, at this temperature, the O2 concentration could be
reduced down to a minimum of 2% in the air reactor, while
oxygen could be released up to maximum 2% in the fuel reactor.
As the presence of fuel in the fuel reactor will consume oxygen
released, a very rapid release of oxygen is possible. CLOU using
CuO has been shown to work not only in laboratory batch
uidised-bed tests with CuO and solid fuel,263,264 but also in
continuous operation with solid fuel.265 Also, combined
manganese oxides have the ability to release oxygen240 and
successful operation with calcium manganates has been
reported.241
6.6
Fluidised bed reactor system for CLC
In order to investigate uidised systems for CLC, a number of

studies have utilised cold-ow modelling to identify stable and
suitable operating conditions for various designs.266272
Actual operation in 12 CLC units of sizes 0.3 to 140 kW
involving 29 oxygen-carrier materials was reported by Lyngfelt.273
The units are presented in Table 4, including eight additional
units. Thus, more than 4800 h of operation in 20 units of sizes 0.5
to 140 kW, using a number of dierent oxygen-carriers and fuels
have been accomplished. This includes more than 600 h in seven
units using solid fuels. The successful operation in a number of
small units with dierent designs, dierent fuels, and dierent
oxygen carriers, clearly demonstrates that the process works and
is viable, and that there are suitable oxygen-carrier materials for
this new combustion technology.
6.7
Modelling
For gaseous fuels, the main performance criterion is fuel

conversion in the fuel reactor, and the work primarily involves
estimations of the required solids inventory to gain a given
conversion to CO2, and its comparison to actual
achievements.223,274277
For solid fuels, the performance is more complex, and normally three performance criteria are used, (i) solid fuel
conversion, (ii) gas conversion and (iii) CO2 capture eciency.
These can essentially be modelled separately (as seen in publications available).278282
6.8
Conclusions for CLC
Although more development work is needed, it should be

pointed out that the CLC technology provides unique advantages for avoiding the large costs and energy penalties inherent
in gas separation. In the case of gaseous fuels, the following
conclusions can be made:
The technology has been successfully demonstrated in a
number of smaller pilots and the technology should be ready to
scale up to 1 or 10 MW size.
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Review
Table 4 Testing in chemical-looping combustorsa
Location
Unit
Oxides tested
Time
Fuel\references
Year
Chalmers
KIER
CSIC
Chalmers
10 kW
50 kW
10 kW
0.3 kW
1410
28
120
810
Nat. gas\575578
Nat. gas\579,580
Nat. gas\581,582
Nat. gas, syngas\227,241,583591
2004
2004
2006
2006
Chalmers
CSIC
KAIST
Vienna UT
Alstom
Nanjing
KIER
Nanjing
IFP-Lyon
Stuttgart
Xian Jiaotong
CSIC
Chalmers
Chalmers
Hamburg
Ohio
10 kW-SF
0.5 kW
1 kW
140 kW
15 kW
10 kW-SF
50 kW
1 kW-SF
10 kW-GSF
10 kW
10 kW-Pr
0.5 kW-SF
0.3 kW-LF
100 kW-SF
25 kW-SF
25 kW-SF
NiO, Fe2O3
NiO, CoO
CuO, NiO
NiO, Mn3O4, Fe2O3,
ilmenite, CaMnO3
Ilmenite, manganese ore
CuO, NiO, Fe2O3
NiO + Fe2O3
Ilmenite, NiO
NiO
NiO, Fe2O3
NiO, CoO
Fe2O3 (ore)
NiO
Ilmenite
CuO/Fe2O3
Ilmenite, CuO, Fe2O3
NiO, Mn3O4, CuO
Ilmenite
Ilmenite
Fe2O3
149
820
?
390
100
230
300
>10
>90
?
15
164
116
24
21
72
Coal, petcoke\245,259,592595
Nat. gas\228,254,596606
CH4\607
Nat. gas, CO, H2\262,608617
Nat. gas\4
Coal, biom.\618621
Nat. gas, syngas\622
Coal, biomass\244,623
CH4, coal, syngas\624,625
Syngas\261
Coke oven gas\626
Coal\260,265,627,628
Kerosene\214,215
Coal\629632
Coal\633
Coal\634
2008
2009
2009
2009
2009
2009
2010
2010
2010
2010
2010
2011
2011
2012
2012
2012
SF solid fuel, GSF gaseous & solid fuel, Pr pressurised, LF liquid fuel.
The presently studied technology, i.e. systems that operate

under atmospheric conditions and temperatures of 800950 C,
would have signicantly lower eciency in power production as
compared to natural gas combined cycle (NGCC) plants. CLC for
higher pressures and temperatures need signicant development eorts. However, there are a number of applications
where gaseous fuel CLC could be used for steam/heat
production.
The following conclusion can be made for CLC with solid
fuels:
The technology is similar to established combustion of coal
in circulating uidised beds.
There is a unique potential for dramatic reduction in cost
and energy penalty for CO2 capture.
CLC operation with low-cost mineral ilmenite works well,
but to reach high performance, additional development is
needed, either with regards to reactor system or the oxygen
carrier material used.
Oxygen carrier materials other than ilmenite could provide
signicant improvement of performance, but it is not clear if
are they available at reasonable costs.
The following options to have a complete conversion of the
gas to CO2/H2O in the fuel reactor are available: (i) oxygen
polishing, (ii) separation/recycling of unconverted gas (iii) using
two fuel reactors in series and (iv) CLOU oxygen carriers.
For scale-up, a more detailed understanding of the
processes in the fuel reactor is needed to design and optimise
the fuel reactor system, in order to assess how the performance
will be aected by the properties of the oxygen carrier and the
reactor design.
The optimisation of the fuel reactor system will primarily
need to consider three costs, i.e. costs for oxygen carrier, costs
for the fuel reactor system, and costs downstream of the fuel
reactor to accommodate for incomplete conversion, e.g. oxygen
polishing. Consequently, a good understanding of these costs is
needed to nd the optimal solution and realise the great
potential of this technology.
7. Calcium looping, CaL

Calcium looping is a family of CO2 capture technologies that
use CaO as a regenerable sorbent of CO2:
CaO(s) + CO2(g) $ CaCO3(s), DH298K 178.8 kJ mol1 (12)
Both the carbonation and calcination reactions are carried
out at high temperatures (650700 C and 900 C, respectively),
allowing for ecient heat recovery in the process or steam cycle
of a power generation system. The technology has attracted, in
the last 10 years, a great deal of attention, and several
comprehensive reviews have been recently published.283287 Only
the main aspects and newest developments are discussed in
this section.
The use of this chemical loop was rst attempted in the 19th
century as it was noted that gasication gases would have a
higher heating power when coal was gasied in the presence of
CaO. This idea was exploited in the acceptor gasication
process, which tested the principle in a continuous pilot rig
using an interconnected uidised bed coal gasier and a
combustor operated at high pressure.288 Other hydrogen
generation processes have been investigated from the 90s,
focusing on the sorption enhanced reforming principle.289 The
rst application of Ca-looping as a post-combustion CO2
capture process was patented by Hirama et al.290 They also
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Review
proposed a practical solution for the calcination problem: the

oxy-combustion of an additional ow of fuel in a uidised-bed
calciner to provide the Heat arrow of Fig. 10, that can be
eectively recovered in a steam cycle to generate more power.291
This section briey reviews the status of these two main groups
of CO2 capture processes. A third subsection reviews recent
developments on sorbent performance issues that are common
for both process routes.
7.1
Post-combustion CO2 capture by CaL
For large scale novel energy processes such as the CaL system, it
is essential to carry out detailed process simulation and thermal
integration exercises to assess the viability of the full system
under expected operating conditions, evaluate power generation eciencies and conduct a transparent benchmarking
exercise against more mature CO2 capture technology options. A
variety of research groups have recently conrmed the inherent
thermodynamic advantages of the post-combustion Ca-looping
concept using oxyfuel combustion, with eciency penalties
between 6 and 8% points with respect to reference plants
without CO2 capture.292295 The calcination of the fresh make up
ow of limestone can take up to 310% of the total energy input
to the Ca looping system. But this may be considered not to be
an energy penalty if the solid purge is used for cement applications, desulphurisation, or other large scale uses of CaO. The
synergy between CaL and cement industry has long been recognised, but only recently detailed specic process proposals
and experimental investigations have been reported.284,296
Energy penalties can be further reduced in advanced CaL
concepts that avoid the need of an air separation unit, by
transferring heat from a high-temperature source to the
calciner, which may be operated with lower partial pressures of
CO2 by introducing steam. Although the basic idea is not
new,297,298 only recently there have been works investigating in
detail these processes.299,300 Recent work has also included
experimental studies.301
Several projects have been running in order to prove experimentally the concept of post-combustion CaL using interconnected carbonator and calciner reactors. INCAR-CSIC
designed and operated a 30 kWth test facility made up of two
interconnected circulating uidised-bed reactors (0.1 m ID) that
reported capture eciencies between 70 and 97% under realistic
ue gas conditions in the carbonator reactor. This reactor functioned as an eective absorber of CO2 as long as there was a
Fig. 10 General scheme of calcium looping cycle for CO2 capture in

postcombustion or precombustion (between brackets) applications.
sucient bed inventory (400 kg m2) and solids circulation rate

(0.52.2 kg m2 s1), even with highly deactivated calcium
oxide.302,303 This test facility was also used to test the principle of
low-temperature combustion of biomass (700 C) for in situ CO2
capture.304,305 Capture rates were limited in this rig to 4 mol CO2
m2 s1 because of the need to limit gas velocities to ensure
sucient holdup of solids in the 6 m riser. This limitation was
removed at IFK, University of Stuttgart that designed and operated a 10 kWth pilot plant, consisting of a CFB carbonator (12.4 m
height) and a bubbling uidised-bed calciner. Experimental
results showed capture rates close to those expected in large scale
commercial systems (up to 10 mol m2 s1).306 A 200 kWth pilot
plant was also recently completed at IFK, with three interconnected circulating uidised-bed reactors, which were
designed to accommodate a wide range of solid looping and
make-up ow rates307 and test a variety of process routes. The
CANMET Energy and Technology Centre designed and constructed a 75 kWth dual uidised-bed combustion system able to
test CaL and oxy-combustion conditions. The reactors (5 m of
total height) have an ID of 0.1 m and can be operated at up to 1000

C at atmospheric pressure. Their most recent studies have been
focused on evaluating the eect of steam and SO2 during calcium
looping cycles.308 Ohio State University developed a 120 kWth
plant to perform the CarbonationCalcination Reaction (CCR)
process, which consists of a CaL system with an intermediate
hydration stage to prevent the decay in sorbent reactivity over
multiple carbonationcalcination cycles. The pilot test rig
involves an entrained bed carbonator, a rotary kiln calciner and a
bubbling uidised-bed hydrator. The CCR process has been
demonstrated to be highly eective and ecient in removing
both carbon dioxide (over 90%) and sulphur dioxide (near 100%)
under realistic conditions.309,310 In Taiwan, ITRI has plans to build
(in the near term) a 1 MW pilot plant specially adapted for cement
application (rotary kiln calciner).311
In Spain, the largest pilot globally for post-combustion CaL
testing (1.7 MWth) has been completed and successfully operated. The plant includes two CFB reactors interconnected (15 m
height) and is able to treat up to 2400 kg h1 of ue gas from an
existing 50 MWe CFBC power plant. The CFB calciner has been
operated in air-combustion and in oxy-red mode. Eective CO2
capture (8090% capture eciency) with a conservative value of
calcium conversion to CaCO3 in the carbonator (10%) has been
achieved.312 Fig. 11 shows the evolution of the CO2 carrying
capacity (Xave), sulphation conversion (XCaSO4) and total sorbent
utilisation (sum of both) measured on solid samples from a
long duration experiment in La Pereda pilot plant. The trend is
consistent but slightly better than expected from lab scale
testing.313 Capture eciencies over 80% were obtained even
with low activity and highly sulphated material, as shown on the
right hand side of the plot. Also, successful commissioning and
positive initial results have been reported in a 1 MWth test
facility (11.35 m height) located at Darmstadt University.
Experimental campaigns using propane and pulverised coal as
fuels to supply the heat for sorbent calcination provided CO2
capture eciencies above 90%.314,315 Finally, a new 300 kWth
facility for biomass combustion with in situ CO2 capture with
CaO is being commissioned in Spain.316
View Article Online
Fig. 11 Evolution of sorbent utilisation with the average number of

carbonationcalcination cycles of particles in the 1.7 MWth pilot plant
of la Pereda (see Arias et al.312 for details).
This stream of new experimental data from increasing scales

should provide a strong basis for improved models at the
particle, reactor and process level. Simple CFB reactor models
have been used to interpret results from a test facility at CSIC
and IFK.302,303,317 More elaborated carbonator models have been
recently reported that take into account basic hydrodynamics in
the riser and including the eect of SO2 co-capture and ash
presence in the reactor.318320 Hypp
anen and co-workers319,321
have recently adapted their comprehensive model for CFB
combustors to the carbonation reactor. These will be essential
tools for future scaling up of the technology.
7.2
Pre-combustion CO2 capture by CaL
As noted above, calcium looping can be combined with reforming and/or gasication processes to produce a hydrogen-rich gas,
high fuel conversions and minimal CO formation. These
processes oer signicant potential for eciency and economic
improvements, but they usually involve higher technical
complexity. For natural gas, the benets of the sorption
enhanced reforming process, SER, and the main experimental
results investigating the concept at laboratory scale are reviewed
by Harrison.289 In principle, the overall process is reduced to a
single reaction step, close to thermal neutrality, that can be
operated at intermediate temperatures (around 650 C) and can
yield over 90% of H2 purity on a dry basis. Several studies have
been recently reported on mathematical modelling of natural gas
SER processes322324 and the SER concept has been also proposed
for alternative fuels, such as propane, methanol or ethanol.325327
Romano et al.328 investigated the potentiality of a SER process
coupled to a combined cycle, calculating a net eciency of 50.2%
with a carbon capture ratio of 88%, which are comparable with
those values obtained for a competitive technology based on
autothermal reforming, but with higher plant simplicity and
lower plant cost. Meyer et al.329 evaluated the feasibility of a novel
ZEG power concept, featuring the production of electrical power
via a close integration of the SER process with a hightemperature Solid Oxide Fuel Cell (SOFC), obtaining eciencies close to 77% with 100% CO2 capture and no NOx emissions.
As mentioned above, CO2 capture with CaO during solid fuel
gasication can be considered the rst application of CaL. In
Review
the gasier, the presence of CaO drives the WGS equilibrium

towards H2 formation and the heat released from the carbonation reaction provides heat for the endothermic gasication
reactions. Furthermore, CaO and CaCO3 catalytically enhance
the benecial destruction of tars.330 Dierent congurations for
the gasication of coal have been proposed in order to improve
thermal and CO2 capture eciencies, such as the HyPr-RING
process,331 the LEGS process332 or the Calcium Looping
Process (CLP).333 The gasication of biomass in the presence of
CaO has also been investigated as sustainable path for the
production of hydrogen.334 In the AER process, a biomass
gasier of 8 MWth interconnected with a circulating uidisedbed combustor has been successfully operated,335 yielding a
product gas with a high H2 content of 3540% (dry basis) and
low content of condensable higher hydrocarbons, tar, below 5 g
m3. However, it must be noted that this is not designed as a
CO2 capture system since the CO2 captured by CaO is released
in the air-combustor. In general, the calcination step of CaCO3
in a rich atmosphere of CO2 remains a serious challenge for CaL
practical applications, especially for those that require highpressure operation to access higher eciencies. On the basis
of the unmixed reforming concept,336 a novel process has
recently been proposed that employs the exothermic reduction
of CuO with a fuel to supply the heat required for CO2 sorbent
calcination, obtaining a ue gas rich in CO2 and readily separable H2O. By coupling an endothermic and an exothermic
reaction in the same solid matrix, a higher eciency and lower
equipment cost can be achieved, since the heat is directly
transferred from the metal to the carbonate.337,338 Recent works
have demonstrated the theoretical viability of the novel Ca/Cu
looping process,339,340 and suitable materials are also being
developed.341,342
7.3
CaO performance as a CO2 sorbent
In CaL processes, particles of CaO will experience repeated

cycles of carbonation and calcination. Although particles or
pellets can continuously be replaced by fresh (low cost) material, it is obvious that the design and operation of any CaL
system is highly sensitive to the quality (in terms of CO2 carrying
capacity, reaction rate, mechanical resistance, etc.) of the
functional material in the system. The carbonation reaction is
characterised by a fast chemically-controlled rate followed by a
slower reaction stage controlled by the diusion through the
CaCO3 layer. It has also been observed that the transition
between the fast and slow regimes takes place quite suddenly at
a given level of conversion and that this level of conversion
decreases when the number of carbonationcalcination cycles
is increased. It is generally accepted that a fast decay in CO2
carrying capacity in the rst 20 cycles is almost unavoidable for
natural sorbents, following a similar tendency for a wide range
of particle sizes and reaction conditions. Sorbent capacity tends
to stabilise at very high cycle number at a residual conversion,
which is around 810% for natural limestones.313 The observed
loss in sorbent reactivity has been attributed to the drop in
internal surface area and associated increase in pore size by
sintering, competing sulphation/sulphidation reactions,
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attrition of the sorbent and the subsequent elutriation of nes,

and by ash fouling. It is noteworthy that even when fully
degraded in reactivity, CaO from natural limestone still takes up
0.16 g CO2 per gram, a high value compared to many other
potential sorbents. The thickness of the carbonate layer formed
on the free internal surfaces of CaO is a critical parameter to
explain the end of the fast reaction period. However, some
important phenomena are not well explained by this simple
theory, such as the temperature dependency of the CO2 carrying
capacity and steam eects,343 which can be very signicant.344 Li
et al.345 have recently provided an elegant carbonation reaction
rate model that seems to be able to explain most observations
using a mechanism well established for other gassolid reactions: they model the CaCO3 growth as islands on the CaO
surface. The fast carbonation stage is completed when these
islands merge. With the increase of reaction temperature, the
sizes and heights of the CaCO3 product island increases while
the island density decreases. Only a few parameters are needed
to t the observed carbonation rate curves in a wide range of
temperatures. The calcination reaction of highly cycled particles
in a CaL is assumed to be very fast, but this has only recently
been conrmed experimentally.346 Sulphation rates of CaO in
CaL reactors (carbonator or calciner) are also a recent subject of
investigation. The large make-up ow of fresh limestone characteristic of most CaL systems allows for lower CaSO4 content in
the system than in equivalent desulphurisation units using
CaO. Open pore structures of the sorbent in a CaL can also alter
the rate and the extent of sulphation. Arias et al.347 reported
sulphation kinetics of CaO particles at low levels of conversion
to CaSO4, whilst Anthony and co-workers348 focused their
investigations on the performance of synthetic Ca-based
sorbents. Attrition is another important issue in CaL because
it aects capture eciency, sorbent cost and operational cost.
Particles have been shown to break up mainly during the rst
calcination. In addition, attrition has been found to be highly
sensitive to limestone choice.349,350
Several approaches have been investigated to improve initial
sorbent properties and/or reactivate spent sorbents, but many
still require detailed studies at the process level to ensure their
viability for large-scale commercial applications. Lisbona
et al.351 studied the integration of the sorbent cost and its
carrying capacity and mechanical performance for dierent
options applied to an existing coal-red power plant. They
demonstrated that the optimum CO2 carrying capacity that
involves minimal heat requirements in the calciner is relatively
modest (at around 20% of Ca conversion). However, for precombustion applications higher activities may be desirable. In
general, R&D activity continues on the main techniques
explored
for
sorbent
improvement:
hydration,352354
283,284,287,355
283,286
doping,
thermal pre-activation,
and synthetic
sorbents.286,287 Low cost methods based on co-precipitation can
yield synthetic sorbents with high melting points and a
carbonation conversion above 75% aer 50 cycles.356,357 The use
of supports like alumina358 or cements containing CaO and
Al2O3359, 360 have recently been shown to improve the durability
of CaO sorbent (some of them above 0.50 g g1 sorbent aer 30
carbonationcalcination cycles under severe calcination
conditions).361 A dierent method for reactivation has also been

proposed recently:362 a small regeneration reactor (recarbonator) is added between the carbonator and calciner vessels to recarbonate the particles leaving the carbonator (calcination
carbonationrecarbonation cycles) using a small ow of pure
CO2 from the calciners o-gas. The slight increase in the
carbonate conversion in each cycle sustains the residual activity
at around 0.15 to 0.2, which is close to the optimum design
target for post-combustion systems.
8. Low temperature adsorbents

A large number of adsorbents have been recently proposed and
investigated as possible candidates for carbon capture at low
temperature. The selection of the best samples cannot be based
only on their adsorption properties (i.e. capacity, heat of
adsorption, kinetics) because other factors may play a crucial
role in the overall process. For this reason, economic criteria
have to always be taken into account, not only with regards to
the costs of synthesis but also to the size of the equipment (i.e.
the volume of the adsorbent needed); the regeneration energy
demand (i.e. the heat of adsorption); the cycle time (i.e. equilibrium and kinetic properties and process selected, pressure or
vacuum swing adsorption (PSA or VSA) vs. temperature swing
adsorption (TSA)); the hydrothermal stability; the loss of
performances due to the presence of impurities in the feed
stream.
Based on these observations the best adsorbent should have
high CO2 capacity at low pressure, high selectivity for CO2, fast
adsorption/desorption kinetics, good mechanical properties,
high hydrothermal and chemical stability, as well as low costs of
synthesis.
Zeolites, as well as carbon-based materials, are the most
widely investigated classes of adsorbents. In recent years a
considerable research eort has been put in the development of
a new class of adsorbent, MOFs (metalorganic frameworks), as
promising candidates for CO2 separation. In addition, a large
variety of functionalised (mostly amine-based) adsorbents has
been recently produced. The very encouraging results obtained
are opening a new eld for the investigation of new possible
adsorbents for carbon capture applications.
8.1
Zeolites
Zeolites are crystalline aluminosilicates characterised by a highly

ordered open structure. They can dier greatly for the framework
type, the size and shape of the channels and cages as well as the
Si/Al ratio. With regard to carbon capture applications, type X
and A zeolites have been widely investigated.363 They are generally characterised by a relatively high CO2 capacity at low pressure, which makes them very promising candidates for CO2
separation from ue gases.364371 Generally 13X is indicated as the
best candidate for post combustion PSA applications with values
of the CO2 uptake between 2 and 3 mol kg1 at 0.1 bar, at
temperatures between 15 and 35 C. Despite the relative high
heat of adsorption (3637 kJ mol1),364,368 the high working
capacity and selectivity make zeolite 13X one of the best choice
View Article Online
for CO2 capture from ue gas streams.364,365,368,369 For this reason

13X is generally used as a benchmark material for lowtemperature adsorbents for carbon capture applications.
Despite the good adsorption properties for CO2, zeolites are
generally highly hydrophilic; the presence of water induces an
alteration of the electric eld reducing the strength of interaction between the quadrupole of CO2 and the cations, resulting
in a lower uptake.372,373 Detailed studies on the eect of the
presence of small amounts of water on the CO2 uptake of
zeolites were presented by Brandani and Ruthven372,373 and,
more recently by Li et al.374 and Lee et al.,375 concluding that the
presence of even very small amount of water greatly reduces the
adsorption performance of zeolites.
The nature and the distribution of the cations inside the
zeolite framework play a crucial role in the nal CO2 adsorption
properties. Their presence not only induces modications of the
electrical eld inside the pores, but it can also change the
morphological structure of the zeolites, inuencing the
adsorption kinetics. Ideally, the higher charge density of the
smaller cations should increase the electrostatic interaction
between the CO2 and the cations, resulting in a higher uptake.
This trend of the CO2 uptake with the increasing charge density
has been observed by several authors.375379 Deviations from the
expected trend have also been reported for some types of
zeolites due to the high basicity of the framework, which has a
predominant role relative to the strength of the quadrupole
interaction.380,381 On the other hand, the size, the position and
the grade of occupancy of the extra-framework cations may be
responsible for hindering diusion of CO2 due to the blockage
of the windows of the structure by the cations.376 In this regard,
an interesting case is represented by the Rho zeolites, for which
the presence of extra-framework cations has been proved to
induce considerable distortions in the structure.382387 A recent
study of Lozinska et al.379 reported that the combination of the
framework distortion and the hindering eect of the cations
resulted in an extremely slow diusion of CO2 (measured using
the ZLC technique). In addition, a gating eect was detected for
the Na-Rho type due to the presence of CO2, similarly to what
reported by Palomino et al.378
8.2
MOFs
The structure of MOFs consists of organicinorganic hybrid

networks formed by metal ligand bonds.388 One of their main
attractive features is the possibility to modify their structures
and functional properties by changing the building blocks used
in their construction: this gives the incredible advantage of
nely controlling pore dimension, shape of the channels, and
chemical potential of the surface, which ultimately gives the
possibility to build adsorbents with the desired adsorption
properties.389 MOFs generally show higher CO2 capacity at high
pressures compared to zeolites, but, despite their relatively low
capacity at low partial pressures, their high thermal stability
and the fully reversible CO2 adsorption make them very promising materials for pressure-swing processes.390,391 With regard
to the low pressure applications, MOF-74 and its politypes have
shown attractive features for carbon capture. The trend of the
Review
CO2 uptake follows the sequence, Mg > Ni Co > Zn, with

values of the CO2 capacity for Mg-MOF-74 being almost double
than that for 13X.389,392394 Mg-MOF-74 is characterised by a high
selectivity for CO2395 and the heat of adsorption is generally
higher than the one of zeolites with values of about 47 and 41 kJ
mol1 for the Mg and Ni form respectively.389,393,396,397 The higher
ionic character of the MgO bond improves the anity with
CO2, but on the other hand, it makes the Mg form more
hydrophilic than the analogous Ni form. Studies to compare the
eect of water on CO2 adsorption for Ni-MOF-74 and commercial zeolites were performed by LeVan et al.;391 although the CO2
capacity was found to reduce in presence of water for all the
materials, the eect was less pronounced for Ni-MOF-74. Liu
et al.398 reported that the H2O molecules interact specically
with the strong adsorption sites of Ni-MOF-74, causing a nonrecoverable loss of CO2 capacity. An extensive study on
dierent MOF-74 samples (Zn-, Co-, Ni- and Mg-MOF-74) was
carried out by Hu394 at the conditions of interest for postcombustion carbon capture at 38 C and 0.1 bar using the
ZLC method. Tests in the presence of impurities (water, SOx and
NOx) showed a signicant deactivation of the samples with the
Ni-MOF-74 demonstrating a greater resistant to degradation.
8.3
Carbon-based adsorbents
Carbon-based adsorbents are synthesised by the thermal

decomposition of carbonaceous materials and have been
investigated and used for a wide range of gas separations.
Siriwardane et al.,399 compared the adsorption properties of
commercial activated carbon with 13X and 4A. From the study,
it emerged that, relative to the zeolites, activated carbon
showed a lower uptake and selectivity at lower pressures, but
they maintained higher hydrothermal stability. Values of the
heat of adsorption are generally lower for the activated carbons
than for other adsorbents with values in the range from 15 to
30 kJ mol1.399402
Shen et al.403,404 investigated the use of activated carbon in a
VPSA process to capture CO2 from ue gas, obtaining relatively
high values for the recovery and purity of CO2. The possibility of
application of carbon molecular sieves in a PSA process for CO2
from ue gas was recently investigated by Carruthers et al.402
The study concluded that despite the lower capacity relative to
other adsorbents the low heats of adsorption and the stability of
carbon-based adsorbents make them competitive for CO2
capture from ue gas.
The adsorption properties of activated carbon can be
signicantly improved by the incorporation of amine functional
groups into their porous structure. The CO2 chemically reacts
with the amine groups forming bicarbonate and/or carbamate,405,406 which is promoted at higher temperatures. As a
result, an increase of the CO2 capacity is observed at higher
temperatures while at lower temperatures, physisorption is
predominant and the loss of porosity due to the amine functionalisation has a crucial role in the nal CO2 uptake.406
Moreover, relatively slow kinetics are generally observed.405
As part of the carbon based materials new developments are
in progress with regard to the carbon nanotubes (CNT) for
View Article Online
Review
low-pressure carbon capture. Multi-walled CNT functionalised

with APTES have shown a signicant improvement of the CO2
uptake compared to the pristine sample.407409
8.4
Mesoporous silicas
Mesoporous silicas are generally characterised by low CO2

uptake due to the weak surface interaction with CO2 molecules.
What makes them attractive for carbon capture is the possibility
to introduce functional groups (usually amine-based groups) to
increase the anity with CO2. The advantage of having large
and uniform pores is that it is possible to introduce surface
modication, reducing possible steric hindrance of the
adsorption sites. As a result of the introduction of functional
groups, a signicant increase of CO2 uptake at low pressure has
been shown compared to the pure silica; very promising results
have been obtained recently, but the increased complexity of the
adsorption process may, in some cases, lead to an overestimation of the adsorption capacity.410 The adsorption properties are mostly inuenced by the density of amine active sites
and by the accessibility to the sites (pore size).411
Belmabkhout et al.412414 induced a series of modications on
MCM-41: they synthesised a pore-expanded form (PE-MCM-41)
and successively introduced amine groups in the expanded
form (TRI-PE-MCM-41). The PE-MCM-41 exhibited a higher CO2
uptake at high pressure than the non-modied MCM-41;
however, there was not a signicant improvement in the low
concentration region. On the other hand, the TRI-PE-MCM-41
sample, which combined the advantages of a large pore structure due to the presence of amine groups, showed a dramatic
improvement of the adsorption capacity, especially in the low
pressure region. The value of the CO2 uptake at 0.1 bar and
25 C was comparable with the one of a typical zeolite, 13X
(2.2 mol kg1). Even though the capacity is comparable with
13X, the amine-modied sample exhibited a signicant
increase of the CO2 uptake in presence of water, which is a very
important advantage for the possible application of the sample
for CO2 capture applications. Xu et al.415,416 studied the
adsorption performances of PEI-impregnated MCM-41 under
dierent conditions, reporting an increase of the CO2 capacity
with the PEI loading and temperature (with a maximum at 75 C
for the sample with 75 wt% of PEI), while the adsorption
process was found to be strongly kinetically controlled.
8.5
Pilot-plants development and testing
At present, a few pilot scale demonstrations are investigating

the eectiveness of low temperature adsorbents for CO2
capture. One of the rst pilot plant projects was the CO2CRC H3
project417 lignite-red power plant based at International
Powers Hazelwood Power Plant, and was commissioned in
2009 Latrobe Valley, Victoria, Australia. The research project
was completed in 2011 and the performance of commercial and
novel adsorbents was investigated at high humidity levels in the
presence of SOx and NOx with a 3-bed multi-layered vacuum
swing adsorption process. Multi-layered adsorbents were used
to remove, rst, the water and subsequently SOx/NOx from the
ue gas. A layer of CO2-selective materials was then added. A
purity of about 71% and a recovery of about 60% were achieved

aer continuous running of the process using a simple 6-step
cycle (without purge) for a week.
The Science and Engineering Research Council (SERC) of
Singapore in 2009 launched a research programme on Carbon
Capture and Utilisation (CCU), which includes a collaborative
project418 between the adsorption and process systems research
groups at National University of Singapore (NUS), Nanyang
Technological University (NTU) and Institute of Chemical and
Engineering Sciences (ICES). A pilot plant that was designed
based on the results from a detailed simulation study, has been
constructed. 1 m long columns with 0.3 m internal diameter
were used and the plant is expected to capture around 3 tCO2
madsorbent3 per day using a simple 4-step Vacuum Swing
Adsorption (VSA) with Zeochem 13X and synthetic dry ue gas.
Special attention is focused on the power consumption by the
vacuum pumps so that a reliable estimate of the energy penalty
may be obtained.
Based on a lab scale 1 kW plant with supported amine
sorbents in a circulating uidised bed developed by ADA Environmental Solutions, the US DOE419,420 has funded a 1 MW pilot
plant. The pilot plant will be located in the Southern Company
Alabama power Co. plant and should be completed by the end
of 2013.
Inventys claims that their VeloxoTherm421 process can
capture CO2 for 15 US$ t1. The technology involves an intensied temperature swing adsorption process with structured
adsorbent and steam regeneration in a rotating adsorbent
wheel. ETI422 just announced the award of 20 million funding
for a 5 MW project that can be used for a new-build CCGT or
retrotted onto one. The consortium will be led by Inventys with
Howden, MAST Carbon International and Doosan Power
Systems as partners, as well as Rolls Royce for specialist engineering support. The initial stage of the project is lab scale
studies, but the nal aim is to have a commercial technology
by 2020.
The ATMI/SRI BrightBlack423 microporous carbon was
recently tested at a coal-red steam production facility operated
by the University of Toledo in Ohio, USA. The test results were
presented in Pittsburgh, Pennsylvania, USA at the 2012 NETL
CO2 Capture Technology Meeting. The material exceeded the
DOE targets of >90% CO2 capture with >90% CO2 purity during
tests with 200 standard l min1 of ue gas. Additionally, the
column operated for approximately 7000 adsorptionregeneration cycles with no loss in process or adsorbent performance
and no signs of adsorbent degradation. The project partners are
now looking at scaling up to pilot scale testing.
Not much information is available at the moment on the
pilots due to the early stages of development of most of them;
the availability of data on these projects in the future will
represent a crucial step towards the deployment of adsorption
processes at commercial scale.
Having reviewed a number of technologies for carbon
capture from industrial and power station sources, this article
will now focus on more long-term options. This will include
carbon capture from the ambient atmosphere, CO2 utilisation
and mineralisation.
View Article Online
9. Direct air capture technology
9.1
Introduction
Direct air capture is the process of removing CO2 from the air
and generating a concentrated stream of CO2 for sequestration
or re-use. It belongs to a group of technologies referred to as
negative emissions, or carbon dioxide removal (CDR) technologies. Other negative emissions technologies include bioenergy
enhanced carbon capture and storage (BECCS); augmented
ocean disposal (or ocean liming); biochar production and utilisation; the dispersion of naturally occurring bases such as
serpentine and olivine across the land; and the enhancement of
biological CO2 sinks such as reforestation, aorestation and
aquatic biomass via ocean fertilisation. These technologies are
beyond the scope of this paper, though the interested reader
may refer to a recent techno-economic analysis of negative
emissions technologies by McGlashan et al. for more information.424 In fact, we will only very briey review recent developments in air capture technologies here.
Compared with traditional CO2 capture from concentrated
point sources; direct air capture oers a number of purported
advantages. Firstly, air capture provides a means of adjusting
the atmospheric CO2 concentration in the increasingly more
likely event that mitigation eorts fall short of targets and the
atmospheric greenhouse gas inventory reaches dangerous levels
or takes a trajectory towards stabilisation at dangerous levels.
Air capture could also oer an option for addressing CO2
emissions from mobile and distributed sources, such as vehicles, fuel use in buildings and geographically isolated industry,
where direct capture and integration into a centralised CCS
network would be either impractical and/or uneconomical.
Furthermore, direct air capture technology could be installed by
storage site operators to manage fugitive emissions from the
CCS network and leakage from geological formations. In addition, it has been suggested that direct air capture technology
could potentially be situated anywhere, such as deserts, wasteland and the ocean, provided there is access to an available
energy source and sequestration sites. However, there are also
signicant disadvantages to the technology. Removing and
concentrating CO2 from air at 390 ppm to a pure stream
(>90%) implies a greater energy input, and treatment of a vastly
greater volume of gas than CO2 capture from concentrated
point sources. For example, the thermodynamic minimum
energy required to extract CO2 from ambient air is 20 kJ mol1
compared with 8.4 kJ mol1 and 5.3 kJ mol1 to capture and
concentrate CO2 from the ue gases of natural gas-, and coalred power stations containing 5% and 15% CO2 respectively
at 65 C. Furthermore, the actual energy consumed by air
capture technology will be signicantly larger than the thermodynamic minimum, as is the case for CCS systems. Zeman
et al. estimated that the energy demand of a large-scale MEAbased process for CO2 capture from concentrated sources
would be 181 kJ mol1, which is far greater than the thermodynamic minimum energy requirement.425
Direct air capture has been practiced on a small scale for
decades for the purpose of maintaining safe levels of CO2 in
Review
submarines426 and spaceships427 though it is important to note

that the concentration of CO2 is in these locations is signicantly higher than that within the atmosphere. CO2 must also
be removed from air prior to air liquefaction to avoid operational issues associated with dry ice formation.428 However, the
volume of air that must be handled to capture comparable
amounts of CO2 to traditional CCS technologies is far greater.
This has signicant implications on energy consumption and
the required plant size. As a consequence, capture technologies
that require pre-processing of air, such as drying, heating,
cooling or pressurising will not be economical.429 This rules out
technologies typically used for small-scale air capture such as
membrane separation (large pressure gradients and multiple
passes required to achieve a high-purity CO2 stream);430 cryogenic separation (cooling and compression required); and
zeolite, activated carbon and alumina-based molecular sieves
(adversely aected by moisture and low adsorption capacities at
ambient conditions). Two main approaches have been
proposed for direct air capture (i) wet air capture systems and
(ii) dry air capture systems. Whilst both capture processes
require energy to regenerate the sorbent, the energy demand
scales proportionally to the mass of CO2 captured as opposed to
the volume of air processed. For those seeking more information than this brief overview, the reader is encouraged to read a
recent review by Goeppert et al.431
9.2
Wet air capture systems-the soda/lime process
The most developed approach for wet air capture is the soda/
lime process.431 This uses aqueous sodium hydroxide (NaOH)based solutions to extract CO2 from ambient air in a packedcolumn,432 convection tower433 or spray-tower contactor
system.434 Aer the contactor, the NaOH solution is regenerated
via caustic recovery (or causticisation), where slaked lime (an
aqueous solution of Ca(OH)2) is reacted with the dissolved
sodium carbonate (Na2CO3) product to form a calcium
carbonate (CaCO3) precipitate mud. The CaCO3 mud is ltered,
dried and transferred to a rotary kiln where it is calcined at
temperatures in excess of 900 C to produce a concentrated
stream of CO2 and a calcium oxide (CaO) powder. The CaO
powder is then dissolved in water to regenerate the slaked lime
solution.
The requirement of substantial thermal energy for lime
regeneration represents a signicant drawback of this process.
Baciocchi et al. estimated that process energy demands are
likely to range between 7.6 and 11.6 GJ tCO21 (334510 kJ mol
CO21) with drying, pre-heating and calcining of the CaCO3
accounting for the majority of the total energy demand.435 Other
energy intensive processes considered in the Baciocchi et al.
estimates were CO2 compression and air separation to produce
O2 for an oxyfuel kiln. As a consequence, CO2 abatement costs
for this process are high, typically quoted as 240500 US$ tC1
(65136 US$ tCO21);436 much higher than some estimated cost
of CCS at 3050 US$ tCO21 437 (some authors of this paper
might suggest a more conservative range of costs, from $50
$120 tCO21 depending upon source and capture technology).
Recent papers by the American Physical Society438 and House
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Review
et al.439 have stated costs may be even higher, in the region of

US$600 and US$1000 per ton of CO2 respectively, though it
should be noted that these costings are disputed by researchers
within the air capture community.429,440
9.3
Alternative wet air capture systems
In attempts to eliminate the energy intensive lime regeneration

step, the paper and pulping industry have been developing and
piloting an alternative approach that involves direct causticisation with titanates.441 The energy required to regenerate titananates is much lower than for CaO; 90 kJ mol1 compared to
179 kJ mol1.
9.4
Dry air capture systems
Dry air capture systems typically employ solid organoaminebased adsorbents where amine functional groups are either
physically or chemically bound to the surface of a porous-silica;
carbon, metal oxide; or polymer support.442 Much of the work to
date has focused on developing sorbents with high CO2 capacities and has neglected to use realistic desorption conditions,
opting instead for desorption at elevated temperatures in an
inert gas stream generating a dilute CO2 stream. Lackner et al.
have developed an alternative material for extracting CO2 from
ambient air, comprising of an anionic ion-exchange resin with
quaternary amine functionality dispersed onto a polypropylene
membrane.443 The positive charge associated with the quaternary amines is balanced by mobile hydroxyl or carbonate
counter-ions, which adsorb CO2 when dry, and release CO2
when wet. Desorption can be achieved via either contacting the
material with a humidied gas stream or directly with water. Air
capture costs for a system employing this adsorbent have been
estimated by the purveyors as 15 US$ tCO21 with initial costs
including infrastructure and maintenance costs of 200 US$
tCO21. It is considered by a number of the authors of this
article that these costs are unrealistic, on the basis of highly
contentious assumptions concerning mass production and
autonomous operation. A simple analysis by Brandani indicates
that the cost of air capture relative to CO2 capture from a power
station should be around a factor of ten higher.444
9.5
Conclusions and future scope
Laboratory scale research has demonstrated that direct air

capture is technically feasible. Wet air capture is the most
developed approach. However, the high energy requirements
for sorbent regeneration, particularly in the case of the soda/
lime process, has led to very high estimated mitigation costs.
Some progress has been made towards reducing the energy
demand associated with sorbent regeneration through the use
of alternative causticising agents and other improvements;
however, further work is required to address and manage issues
associated with high energy requirements, heat integration,
large evaporative losses during liquidair contacting and the
high corrosivity of the strong-base absorbents solutions.
At present, the future of large-scale direct air capture as a
climate change mitigation technology remains uncertain. Air
capture R&D is still in its infancy, far behind the more
conventional climate change mitigation technologies. Cost

estimates vary substantially ranging from as low as 20 US$
tCO21 to as high as 1000 US$ tCO21 and it is highly likely that
air capture will oer one of the most expensive options for
mitigating climate change. For this reason, other, cheaper
options for addressing climate change such as reducing the
carbon intensity of electricity generation through eciency
savings in existing power plants, increased deployment of
renewable energy technologies, nuclear power and CCS should
be aggressively pursued before air capture is considered. Ultimately, commercial deployment of air capture technology will
depend on whether the technology can be proven on a large
scale and at a cost that makes it protable to do so. For this to
be realised, the future carbon price must also be high, i.e. more
than the cost of extracting and storing atmospheric CO2.
10. Retrotting CCS to power

stations the case for exible
operation
10.1
Introduction
The aim of this section is to review the recent literature pertaining to the retrotting of post-combustion CO2 capture
technology to fossil fuel-red power stations and then discuss
the impact of this retrot on the merit order of such a decarbonised power station. The temporal, economic and policy
context of this discussion is in that of the UK in the 2030s where
the current electricity market reform445 (EMR) discussion has
been completed and there are signicant amounts of intermittent renewable power446 in the UK energy system. One
important target is that of having 15% of the UKs energy
supplied by renewable resources by 2020.446
At the time of writing (early 2013), the UK is undergoing an
EMR exercise which is intended to create a policy environment
conducive to suciently de-risk the capital investment associated with the installation of new power generation capacity to
support investment by the international capital markets in UK
power generation, and avoid the foreseen energy gap if this
investment is not made.
From the perspective of a potential investor, risk is associated with the probability and magnitude of an unfavourable
outcome (e.g. prot below expectations). Taking prot as simply
the dierence between annualised revenue and cost, in the
context of a power station, and it is a function of:
Electricity price (feeding into a revenue stream).
Load factor and dispatch frequency (how much and how
oen a power plant can sell energy to the grid).
Annualised capital cost (a function of the initial installed
cost, payback time and discount rate).
Fuel cost.
Carbon cost.
However, given that one will typically select a payback time
and discount rate such that 80% of the original investment is
paid back within 10 years,447,448 carbon prices are likely to be
mandated by the EMR (at least in the UK, although there may be
some market element to this as well) and electricity prices are
View Article Online
essentially pegged to fuel prices (gas in the UK), the main

sources of risk associated with investing in a power plant, with
or without CCS, are the load factor, dispatch frequency, fuel and
carbon costs. It is, therefore, evident that the least risky option
will be to invest in a power station that is fuel exible, has low
greenhouse gas (GHG) emission per unit of output and can
operate in a exible (i.e. load following) manner. The authors
would emphasise that this rationale (fuel and operational exibility) should hold for investment into any fungible energy
network, i.e. the arguments presented herein are held to be
equally applicable to any energy system comprising diverse
generation sources.
The remainder of this section is laid out as follows; we rst
provide a high level description of post-combustion CO2 capture
processes, sub- and super-critical coal-red power stations and
of a gas-red power station. We then go on to describe the
optimal means for the integration of the capture and power
plants and discuss some operational strategies that are held to
minimise the operational risk associated with these systems.
10.2
Description of sub-systems
In this section, we provide high-level descriptions of the various

unit operations and sub-processes which come together to
compose a decarbonised power plant.
10.2.1 Post-combustion CO2 capture process. In this
section, by post-combustion CO2 capture, we refer exclusively to
amine-based chemical absorption processes. These gasliquid
separating processes are very well known and have been
described in detail in a number of previous contributions.
Consequently, only a high-level overview is provided here. We
exclusively consider this technology option as it has the
inherent advantage that it is an end-of-pipe technology,
similar to those already in place for the mitigation of SO2
emissions, e.g. ue gas desulphurisation (FGD) processes.
Amine-based CO2 capture processes comprise two distinct
unit operationsabsorption and desorption (or solvent regeneration), for further details, see the section above on solvent
absorbtion.
10.2.2 Coal-red power station. In this section, we highlight the main relevant characteristics of coal-red power
stations for exible operation.
10.2.3 Sub-critical power-station. Conventional sub-critical
coal-red power plants typically have three stages; high pressure (HP), intermediate pressure (IP) and low pressure (LP) and
they operate on a Rankine cycle. In addition to the HP, IP and LP
turbines, the steam cycle has one steam reheater in addition
regenerative heating of condensate through a train of feed water
heaters. The steam conditions at the inlet to and outlet from
each of the HP, IP and LP turbines are typically specic to a
given plant, but representative numbers are presented in Table
5. It is important to note that there are typically multiple steam
extraction points in a given turbine (Fig. 12).449,450
It is evident that the specic enthalpy in the steam in the HP,
IP and LP are not equal (DHIP > DHLP > DHHP). This is important
when calculating the opportunity cost associated with steam
extraction for solvent regeneration.19
Review
10.2.4 Future coal-red power stations. It is interesting to

note that, despite their improved eciency, super-critical power
plants are less exible in their operation than their sub-critical
counter parts. The reason for this is the lack of steam drum in
the power plant, meaning that the rate at which they can ramp
up (or down) their power output is relatively low. In this context,
the addition of a post-combustion CO2 capture process could
actually be an advantage. One can envision a scenario in which
the degree of steam extraction for the solvent regeneration can
be manipulated to instantly provide more steam for power
generation when circumstances dictate. This concept is
explored further below.
10.3
Integration strategy
In integrating the power and capture plants, at the simplest level

of integration, one simply needs to connect the exhaust gas
stream from the FGD process with the inlet to the absorption
process. This will require passing the exhaust gas through a fan,
in order to add a small amount of pressure (>0.02 MPa), to ensure
that the exhaust gas has sucient mechanical energy to overcome the pressure drop associated with the absorption column.
As discussed previously, the CO2 rich solvent needs to be
heated in order to recover the CO2 and reuse the solvent. This
requires the application of appreciable quantities of energy,
QRegen. This energy may be, in turn, partitioned into contributions required to heat the solvent, QSens, and that required to
break the chemical bonds between the CO2 and the amine
solvent, QChem. In part, this energy penalty is oset via heat
exchange between the hot, lean solvent exiting the reboiler and
the cold, rich solvent exiting the absorber. This occurs in the socalled rich-lean heat exchanger, or RLHX. The temperature of
the rich solvent stream exiting the RLHX is clearly a function of
the available heat transfer area, thermal driving force and the
eciency with which the RLHX operates. However, an average
exit temperature for the rich solvent stream would be approximately 87 C.451 This stream will still require 3.84.2 GJ tCO21
recovered as energy input.
Some of the early integration studies proposed the addition
of a separate natural gas ancillary boiler to provide steam for
solvent regeneration on a post-combustion capture retrot on a
coal power plant,452 as is common practice for natural gas
treating plants. However, this option was found to have a relatively low eciency and was subsequently abandoned as a
Table 5 Representative steam cycle conditions for a sub-critical

power plant. Adapted from Asthana and Panigrahi.449 This paper did
not supply temperature data for the IP out/LP in streams
HP in
HP out
IP in
IP out
LP in
LP out
Pressure,
P, (bar)
Temperature,
T, ( C)
Enthalpy, H,
(kJ kg1)
130.00
38.00
35.00
2.50
2.50
0.08
535.0
351.2
535.0
41.5
3430
3100
3530
2861
2861
2366
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Review
Fig. 12
Schematic of sub-critical power station. From Asthana and Panigrahi.449
viable option in decarbonising power plants. Subsequently,

direct extraction of steam from the steam cycle of the main
power plant has become the preferred option. Owing to the
desired conditions within the reboiler (T 120 C, P 0.2 MPa),
this energy is best obtained via condensation of saturated steam
at P z 0.25 MPa. In the case of a sub-critical coal-red power
station, it has been shown that the optimal location for the
extraction of this steam from the steam cycle is between the IP
and LP turbines.453 As before, one can partition the contributions to QRegen into that obtained by the condensation of steam,
QCond, and that obtained by sensible heat transfer by subcooling the condensate, QSub-cool. Once this steam has been
condensed, the resulting condensate is then returned to the
steam cycle. It has been shown19 that the fraction of QRegen
obtained from QSub-cool is negligible. Thus, the condensate
should, therefore, be returned with the minimum degree of subcooling in order to avoid an additional penalty on the power
plant associated with returning large quantities of sub-cooled
liquid to steam cycle. Specically, the condensate should be
returned to the condensate heating train, as opposed to the
power cycle condenser.453 More sophisticated approaches to
heat integration between power and capture plants and the CO2
compression train have also been investigated, for example, a
recent contribution by Duan et al.454 shows how this can
appreciably reduce the total energy penalty associated with the
decarbonisation of the power plant. In particular, the recovery
of heat from the inter-coolers of the compression train was
found to be especially important. The vast majority of integration studies concentrate on the modication of the solvent
phase, either by designing new solvents or by carrying out heat
integration and recovery studies. However, a recent paper
illustrates how the humidity of the inlet exhaust gas stream at
the base of the absorber will play an important role in the
process operation. It would appear that a dry exhaust gas will
require a shorter column than a wet gas, leading to an appreciable reduction in capital cost.18
generate power in a exible way. Furthermore, we suggest that

the position of fossil fuel-based power plants in the power
generation merit order is changing. With the increasing intermittency associated with the diverse energy network envisioned
for the UK in the 2030s and beyond, this capacity for exible
operation will command a special premium.
The concept of storing CO2-rich solvent on-site was originally
proposed by Chalmers and Gibbins.455 This concept has recently
been quantitatively proven456 to provide an important reduction
in operating cost456 and as a buer between the dynamic behaviour of the power plant and the required steady state operation of
a CO2 transport network. In particular, Arce et al. have shown that
adjusting the degree of solvent regeneration in sympathy with
prevailing market prices for energy, fuel and carbon (i.e.
increased solvent regeneration or a lower lean solvent loading at
times of low energy prices, and reduced levels of solvent regeneration at times of high energy prices) can lead to an appreciable
reduction in operating cost. Furthermore, allowing CO2 to accumulate in an on-site solvent inventory can enhance this eect. As
alluded to above, this idea can be used in conjunction with supercritical power plants to enhance their exibility, and, therefore,
their protability in a diverse energy generation system.
11. CO2 transport

11.1
Introduction
CO2 can be transported by pipeline, ship, rail or road. The

choice of transport will depend on the quantity of CO2 that
needs to be transported, the distance and terrain to be travelled,
and the specications of the CO2 stream produced at the
capture facility.457 In most cases, transporting CO2 via pipeline
will be the most cost eective mode of transport. The instances
where transport by ship may prove more economical would be if
CO2 needs to be moved over very large distances (>1000 km) or
over large bodies of water. Transport via rail or road is only
expected to be feasible for moving CO2 on a small scale for
specialist applications.
10.4 Flexible operation of decarbonised power plants

towards risk mitigation
11.2
As discussed in the introduction, in any power generation

network, there are clear benets associated with being able to
Prior to pipeline transport, CO2 is compressed to a supercritical

uid (sc-CO2) or liquid state (i.e. a dense-phase uid). CO2 exists
Basic operation
View Article Online
as a supercritical uid above its critical point, 31.1 C and 74

bar. This is the most ecient phase for transporting CO2 by
pipeline as it has both the high density of a liquid and the
favourable ow characteristics of a gas. However, it is not
possible to maintain pipeline temperatures above the critical
temperature in all situations. It is, therefore, important to
ensure pressures drops are managed and pipeline pressures are
kept above vapourliquid equilibrium conditions to maintain a
single-dense-phase ow and avoid liquid slugs and other
operational problems that may eventuate if conditions fall
within the region where a two-phase (gasliquid) ow may
occur. Operating pressures of existing CO2 pipelines are in the
range of 85 to 210 bar where CO2 is a dense-phase uid over a
wide range of temperatures. To maintain suciently high
pressures over long distances, intermediate pumping (or
booster) stations are required at certain intervals along the
pipeline. For shorter distances, booster stations may be avoided
by increasing the pipeline inlet pressure; however, more energy
would be consumed for compression and thicker walled pipeline would be required.
In terms of CO2 transport by ship, it is most ecient to
transport CO2 as a cryogenic liquid. Aspelund et al. has calculated optimum conditions for CO2 transport by ship of 6.5 bar
and 51.2 C.458 Large scale liquefaction would primarily
involve cooling via compression and expansion of the feed gas.
Some loss of CO2 is expected as a consequence of boil o and
the ships emissions would be in the region of 3 to 4% per 1000
km.457 Losses can be minimised by utilising a refrigerated
container ship or by re-capturing and liquefying the boil-o gas.
Ship-based transport systems require intermediate storage
facilities, and the equipment and infrastructure for loading and
unloading CO2 at the loading docks, and storage sites to link
continuous production of CO2 at capture facilities with discrete
transport of CO2 by ship.
Ships are more exible than pipelines as they are able to
transport CO2 in volumes far below the design capacity. Ships
therefore oer the potential to collect CO2 from multiple sites
on the way to the storage site and can better adapt to uctuations in the CO2 production rate of the emitter.
11.3
Existing experience
Globally, there is approximately 6000 km of pipeline infrastructure in operation for CO2 transportation purposes, most of
which is based in the US and Canada for transporting CO2 to
sites for enhanced oil recovery (EOR).459 At present, most of the
CO2 used for EOR is sourced from natural deposits, though
there are a few projects utilising CO2 from anthropogenic
sources. Table 6 provides a summary of the major long-distance
CO2 pipelines currently operating. There is also limited operational experience of onshore and oshore pipelines transporting CO2, derived from natural gas production, for
sequestration in saline aquifers at the Snhvit LNG facility,
Sleipner, and In Salah.
Ship-based CO2 transport experience is far more limited. At
present, there are only four small ships, transporting food-grade
CO2 in northern Europe.457 Anthony Veder Group operates the
Review
rst purpose-built CO2 tanker, which can ship up to 1825

tonnes of CO2 at 40 C and 18 barg. Yara International charters the other three ships which have capacities between 900
and 1200 tCO21.191,460 Work is on-going to develop ships with
the capacities required for large-scale CCS deployment. Maersk
are currently working on pressurised, semi-refrigerated CO2
tankers with capacities up to 45 000 tonnes.461
11.4
Pipeline design and operation considerations
CO2 pipelines must be designed and constructed at an optimal

cost in such a way that they are reliable and safe to operate,
posing minimal risk to local populations and the environment.462 Pipeline design is primarily inuenced by the required
throughput and hydrodynamic properties of the CO2, such as
density, phase behaviour, viscosity and compressibility. Therefore, factors aecting the hydrodynamic properties of CO2,
including temperature, pressure, ow rate and composition,
need to be modelled and characterised as part of the design
process. The presence of impurities, particularly water, may also
lead to operational problems concerning corrosion, gas hydrate
and ice formation. As a consequence, pipeline entry specications are set in order to minimise or even avoid these problems.
11.4.1 CO2 specications. CO2 from natural sources is
saturated with water and typically composed of 98.37298.350%
CO2; 1.5210.136% N2; 0.1071.514% CH4 and trace amounts of
H2S.462 Therefore apart from dehydration, minimal gas treatment is required. Anthropogenic CO2 on the other hand, tends
to be much less pure, containing other impurities such as CO,
O2, H2S, SOx, NOx and H2. Amines, NH3, methanol and glycols
may also be present as a consequence of CO2 capture, dehydration and corrosion control. The exact levels will vary
depending on the source, capture process and gas treatment
steps.
The level of impurities that can be tolerated will depend on
the storage method (or end use) and the transportation method.
EOR specications tend to be strict (Table 7) as certain impurities will have detrimental eects on the process. In the case of
EOR, there is an economic incentive to remove certain impurities down to very low levels and design CO2 specications for
optimum oil recovery eciency. However, transporting CO2 for
storage purposes does not share this relationship and removing
impurities in anthropogenic CO2 down to very low levels
imposes a signicant energy and cost penalty on the process.
Therefore, CO2 specications for storage purposes will most
likely be determined on the basis of cost-benet analyses,
regulatory and legislative requirements, and health and safety
considerations.
A few studies have attempted to dene CO2 specications for
transport and storage purposes. The Dynamis project463 updated specications that were initially proposed for precombustion CO2 capture technologies as part of the ENCAP
project464 to take into account safety and toxicity limits. As a
consequence, allowable levels of H2S, CO, SOx and NOx gases
have been lowered in accordance with their short term exposure
limits (STELs). To meet these specications, additional gas
treatment measures such as regenerative absorption columns
View Article Online
Review
Table 6

Major long-distance CO2 pipelines465,467
Capacity
[Mt per year]
Pipeline
Operator
Location
Canyon Reef
(SACROC)
Bati Raman
Sheep Mountain
North
Cortez
Bravo
Central Basin
Bairoil
Snhvit
Weyburn
Kinder Morgan
USA
Turkish Petroleum
BP AMOCO
Turkey
USA
Kinder Morgan
Kinder Morgan
Kinder Morgan
Statoil
North Dakota
Gasication Co.
BP
Statoil
USA
USA
USA
USA
Norway
USA & Canada
In Salah
Sleipner
Algeria
Norway
Length
[km]
Pressure
[bar]
Source
Purpose
Start
year
4.4
352
140
Gasication Plant
EOR
1972
1.1
9.2
90
772
170
132
Dodan Field
Sheep Mountain
EOR
EOR
1983
1983
19.3
7.3
20
8.3
1
5
803
350
278
180
160
328
186
165
170
186 & 204
McElmo Dome
Bravo Dome
Denver City Hub
Gas manufacturing plant
Separation from natural gas
Gasication Plant
EOR
EOR
EOR
EOR
Storage
EOR
1984
1984
1985
1986
1996
2000
1.0
0.7
17
153
185
100

Storage
Storage
2004
2006
Table 7 Typical entry specication for CO2 pipelines serving EOR

operations635
Constituent
Specication
Reason
CO2
N2
Hydrocarbons
H2O
O2
H2S
Glycol
Temperature
>95%
4%
5%
480 mg m3
10 ppm
10200 ppm
0.4 ml m3
65 C
MMP
MMP
MMP
Corrosion
Corrosion
Safety
Operations
Material integrity
may be required in addition to the standard SOx and NOx

removal (FGD, low NOx burners and SCR), increasing gas
treatment energy and infrastructure costs.
Ecofys have also produced CO2 transport/storage specications based on impurities that are likely to be present in CO2
from a coal-red power plant.465 The Ecofys specications are
similar to those dened by the Dynamis project, although they
did not dene tolerance limits for SOx and NOx based on their
assumption that these impurities will not cause operational
problems in the absence of a separate water phase. Both the
Dynamis and Ecofys specications recommend a maximum
water level of 500 ppm to avoid precipitation of a separate water
phase, which has been identied as the main factor inuencing
corrosion, gas hydrate and ice formation.
11.4.2 Impact of impurities on pipeline capacity and
operating pressure. Impurities aects the physical and transport properties of dense-phase CO2 in a number of ways. Firstly,
the presence of impurities opens out the range of pressures
where vapour and liquid CO2 exist in equilibrium. Impurities
with lower critical temperatures and pressures than CO2, such
as H2, N2, CH4, O2, CO and Ar, are the most problematic as these
impurities open out the range of pressures above the vapour
liquid equilibrium boundary of pure CO2.465 This impacts the
minimum operating pressure of a CO2 pipeline, which must be
increased with increasing impurity content to avoid two-phase
ows.
The presence of impurities also reduces the density of densephase CO2, particularly at conditions close to the vapourliquid
equilibrium boundary.465,466 As a consequence, pipelines transporting CO2 containing large amounts of impurities must be
operated at higher inlet pressures to achieve the desired
throughput. A thicker walled pipeline or tougher pipeline
material may also be required at a higher infrastructure cost.
Pressure and temperature drops within pipelines are also
aected by the CO2 composition. The presence of impurities
with lower critical temperatures and pressures than CO2
enhance pressure and temperature drops whilst impurities
with higher critical temperatures and pressures, such as H2S,
SO2 and NO2, reduce pressure and temperature drops along a
set length of pipeline.467 To account for increased pressure
drops, more booster stations would be required at shorter
intervals to keep the pressure suciently high to maintain a
dense-phase ow. However, adding more booster station
substantially increases pipeline infrastructure costs, and in any
case, this option is not feasible for subsea pipelines. Alternatively, the pipeline would have to be operated at a higher inlet
pressure.
Yan et al. carried out a cost-benet analysis to determine the
eect of removing typical non-condensable impurities found in
anthropogenic CO2 (N2, H2, O2 and CH4) to dierent levels (1%,
4% and 10%).468 They found that limiting the amount of noncondensable compounds to <4% was optimal in terms of
balancing gas treatment and compression costs, although a
higher limit of <10% may be acceptable for short distances.
11.4.3 The role of impurities in pipeline corrosion. Internal
pipeline corrosion issues are primarily caused by the presence
of an aqueous phase. CO2 dissolves in free water leading to
the formation of carbonic acid, which is highly corrosive to
carbon steel (the material typically used for natural gas and
existing CO2 pipelines). This type of corrosion is termed sweet
corrosion. An aqueous phase may form if the water vapour
content exceeds the saturation vapour level at any point within
the pipeline. Alternatively, accidental ingress of water may
occur due to a malfunction at the gas conditioning facility or
during a maintenance shutdown.
View Article Online
A reasonable amount of work has been published on the

corrosive properties of CO2H2O systems at conditions relevant
to natural gas pipelines; however, there is far less published
research at conditions relevant to CO2 pipeline transport.
Corrosion rates are dependent on the operating conditions,
including pressure, temperature, water vapour content, ow
rate, steel composition and exposure time. The presence of
other impurities will also inuence corrosion rates. Corrosion
rates as high as 20 mm per year have been reported for carbon
steel exposed to water-saturated CO2 at relatively high temperatures and pressures, although the literature is not in general
agreement, with dierent authors reporting signicantly
dierent corrosion rates at quite similar conditions.469,470 The
primary cause of these discrepancies is most likely due to the
dierences in the ow rates, exposure time, material-to-water
surface areas, and steel composition used by dierent
research institutions.
Investigations into the corrosion mechanisms have found
that under stagnant conditions, corrosion rates are initially fast
but decrease with increasing exposure time.471 This is due to
formation of a protective iron carbonate (FeCO3) product layer/
scale that precipitates out of the aqueous phase once it becomes
supersaturated with iron. Product layer formation is inhibited
under free owing conditions as mobile aqueous phases are
less likely to become supersaturated with iron. Furthermore, in
the case where a protective layer has formed, the frictional
forces of the owing gas are likely to cause destabilisation or
removal of the protective lm, which could lead to severe
localised corrosion.
Corrosion can still occur in the absence of a distinct aqueous
phase; however, rates are much lower due to the rapid precipitation of a protective FeCO3 scale. In this case, corrosion and
scale formation is most likely due to the formation of residual
or transient aqueous phases, or stabilised aqueous surface
lms.
The presence of other impurities complicates matters
somewhat as certain impurities will interact in the presence of
an aqueous phase to enhance, or in a few cases hinder, internal
corrosion within a CO2 transport system.472 Of particular
concern are SOx, NOx and O2, which react with water to form
sulphuric or nitric acid. O2 will also react with FeCO3 scales to
form oxides and hydroxides which are not protective. These
acids along with other acidic impurities that may be present in
anthropogenic CO2 such as HCl (a common impurity in ue
gases from coal power stations), will act to further reduce the
pH of any aqueous phases that have formed. The solubility of
FeCO3 is increased at the lower pH values, rendering the
formation of an iron carbonate protective layer unlikely, thus
enhancing the induced corrosion rate. Furthermore, sulphuric
and nitric acids can form in the vapour phase, even at very low
water vapour contents of <200 ppm, causing notable corrosion
in the absence of a distinct aqueous phase.471 Ruhl et al. found
that HNO3 and HCl were the most mobile in supercritical CO2,
causing the highest corrosion rates. H2SO4 on the other hand,
appeared to be much less mobile and did not cause signicant
corrosion in the absence of an aqueous phase.473 On the other
hand, the presence of basic impurities such as glycols, NH3 and
Review
amines such as MEA will have the opposite eect on the pH of

an aqueous phase and thus hinder corrosion. In fact, glycols are
commonly used corrosion inhibitors in natural gas pipelines.
Experience from the petrochemical industry has found that
H2S will also cause corrosion. At partial pressures <0.0035 bar,
H2S interacts with carbon steel in the presence of an aqueous
phase to form iron sulphide.465 As is the case with FeCO3, FeS
can precipitate onto the surface of the carbon steel, forming a
protective layer that inhibits further corrosion. However, H2S at
partial pressures >0.0035 bar can cause sour corrosion (or
sour cracking), primarily via sulphide stress induced cracking
(SSIC) and hydrogen induced cracking (HIC). It has also been
reported that the presence of CO in CO2H2O mixtures can
cause transgranular stress cracking corrosion. Cracking corrosion is particularly problematic as it can lead to material failure
within a timescale of days.
Impurities may also aect the solubility of water in CO2. A
few accounts suggest that the presence of CH4 and other
hydrocarbons reduce the water solubility of CO2,474 whilst H2S
has the opposite eect.463 At present, published research concerning the eect of impurities on the water solubility of densephase CO2 is very limited. More work is required to investigate
the eects of anthropogenic CO2 impurities on corrosion and
the water solubility of dense-phase CO2 at a greater range of
conditions relevant to CO2 transport.
11.4.4 Gas hydrate and ice formation. In addition to
corrosion, the presence of water may also lead to operational
problems concerning gas hydrate and ice formation. Gas
hydrates are solids with similar properties to ice that can cause
blockages in the pipeline and compressors. The published
research concerning hydrate formation in CO2 transport
systems is limited. It is generally reported that hydrates can
form at CO2 pipelines conditions; however, the extent of hydrate
formation is minimal if water levels are controlled in line with
industry accepted standards.463 Chapoy et al. determined that
hydrate formation in a pure CO2H2O system could be avoided
by limiting the water content to <250 ppm at conditions of 2 to
30 C and up to 200 bar.474 Further work is required to determine the eects other common impurities have on gas hydrate
formation.
11.4.5 Dening water level specications for CO2 transport. Current industry-accepted water level specications typically range between 288 and 480 mg m3 (150250 ppm),475
but many operators are opting for an even more conservative
specications of <50 ppm, in which CO2 is considered fully
dehydrated.463 To meet these specications, a two-stage drying
process is required, in which water is rst removed down to
400500 ppm using standard vapourliquid separator drums,
followed by secondary drying on regenerative amine or glycolbased absorption columns.476 Corrosion data from 12 years of
operational experience on the SACROC pipeline showed that
corrosion rates were limited to between 0.5 and 2.5 mm year1
by imposing a <50 ppm water level entry specication.475
Rogers and Mayhew dened the threshold water vapour
limit, below which corrosion and other water related issues are
deemed negligible, as <60% relative humidity.477 Others have
dened threshold water limits between 300 and 600 ppm.463,475
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Review
Kinder Morgan, the largest CO2 pipeline operator, species a

maximum water level of 640 ppm.465 Considering water can be
removed down to 400500 ppm in vapourliquid separator
drums, a 400600 ppm water level limit seems appropriate.
Furthermore, this is well below the 60% relative humidity
threshold at typical pipeline operating conditions (050 C and
85200 bar), where the minimum water solubility of densephase CO2 is 1500 ppm.478 However, it is likely that more
conservative water level requirements may have to be specied
when transporting CO2 containing high concentrations of NOx,
H2S and CH4. Furthermore, water level specications for ship
transport will be less exible owing to the lower operating
temperature. Water level specications will most likely remain
at <50 ppm to avoid gas hydrate and ice formation during
compression and liquefaction.476
11.4.6 Material considerations. Operational experience to
date, which amounts to over 40 years, has demonstrated that
carbon steels are suitable pipeline materials for transporting
dry, dense-phase CO2.479 For wet or sour service, or sections of
the pipeline and compressors where there is a risk of aqueous
phase formation or water ingress, corrosion-resistant alloyed
steel would be more appropriate. Alloyed steels, however, are
much more expensive than carbon steels, so their use should be
minimised to keep infrastructure costs down.
Supercritical CO2 is known to be detrimental to polymers
and lubricants used in pipeline components, such as valves, orings, gaskets and coatings. It diuses into the polymer, which
expands when the pressure is reduced, blistering the material.
As the blistering worsens, components may fail, which in the
case of seals could lead to rapid release of CO2 into the
surrounding atmosphere. The polymeric components used in
smart pigs are also aected, making in situ monitoring and
cleaning of CO2 pipelines very dicult. In the period up until
2008, there were only two instances in North America where
smart pigs survived in situ monitoring and/or cleaning operations in CO2 pipelines.459 Alternatively, more durable polymers
such as Teon and Viton can be used to reduce the problem;
however, the costs are greater and degradation is not eliminated
completely. Further research is required to develop polymeric
materials and lubricants that are resistant to the super-solvent
eects of supercritical CO2.
injected at high pressures deep underground; the principal

storage sites are saline aquifers, depleted oil and gas elds, and
deep coal seams. Most assessments of storage capacity consider
that saline aquifers have the largest storage potential, while oil
and gas elds oer the economic incentive of additional
hydrocarbon recovery when the CO2 is injected. CO2 injection is
routine in the oil industry for improved recovery with many
projects around the world, while CO2 storage itself has been
successfully implemented at several sites. The best publicised
example is at Sleipner, oshore in the Norwegian North Sea,
where around 1 Mt per year of CO2 separated from produced
condensate hydrocarbon has been injected each year since
1996, to avoid the payment of a carbon tax.
There are four principal mechanisms by which the CO2
remains underground: physical trapping below impermeable or
low-permeability rock, such as shale; dissolution trapping,
where the CO2 dissolves in brinethis CO2-laden brine is dense
and tends, slowly, to sink through the storage aquifer; mineral
trapping, where CO2 reacts with the host rock precipitating
carbonate; and capillary trapping whereat the trailing edge of
the CO2 plumeCO2 can be trapped as pore-space bubbles in
the pore space. Fig. 13 illustrates this process schematically:480
at the regional scale, several tens of Mt of CO2 will be injected
each year, leading to a plume in the subsurface that will extend
many km. The injection has to be carefully monitored and
controlled to prevent excessive rises in uid pressure that could
fracture the rock and produce leakage pathways to the surface.
At the small scale, capillary and dissolution trapping leadover
timeto increased storage security.
The main research in the storage area has been principally
devoted to three types of study: investigating in detail the
dierent trapping mechanisms outlined above, understanding
through analytical or simplied models the likely migration of
CO2 injected into the subsurface, and detailed assessments of
safe storage capacity in dierent geological and industrial
settings. Rather than attempt to list this vast literature in a very
brief overview, we will highlight some important work on these
topics to illustrate recent activity and highlight the progress that
is being made towards the understanding and design of eective CO2 storage.
12.1
12. Geological storage of CO2 by

injection into deep porous rock
While CO2 capture is likely to represent the major costin both
money and energyof the whole CCS process, CO2 storage
poses a great deal of uncertainty. This is uncertainty in the
quantication of storage potential, in the conrmation of
outline assessments to a standard suitable for investment, the
tracking verication and monitoring of injected CO2, and nally
the fail-safe retention of CO2, so that a storage site can be
transferred to government as a low-risk proposition for longterm care and maintenance. There are signicant engineering
challenges to ensure that the injected CO2 remains in the
subsurface for hundreds or thousands of years. The CO2 is
Capillary trapping and multiphase ow
12.1.1 Pore-scale properties. Capillary trapping is a

familiar concept in petroleum engineering: when water is
injected to displace oil, typically around half of the oil remains
underground, trapped in the pore space. While this is bad for
hydrocarbon recovery, the same physical process is advantageous for CO2 storage: here, CO2 could be trapped in the pore
space as it migrates and is displaced by brine. However, CO2 has
very dierent properties than oileld uids, leading to a debate
in the literaturebased on direct contact angle measurements
of CO2-brine-mineral systemsover the potential eectiveness
of this trapping mechanism.
Fig. 14 shows the results of micro-ow experiments at typical
aquifer storage conditions (9 MPa uid pressure and a temperature of 70 C) where the CO2 is a supercritical uid. Trapped CO2
View Article Online
A schematic of CO2 storage and trapping mechanisms.480

Here extensive storage of tens of Mt of CO2 per year from several
power stations and other industrial plants is considered. The CO2 is
injected through an array of wells that penetrate deep in the
subsurface. The CO2 and the associated pressure increase has a
footprint underground that may extend 100 km or more. The
eectiveness of long-term storage is controlled by limiting the
pressure increase to avoid fracturing of the rock that could lead to
leakage, and the interplay of trapping mechanisms at the small scale.
Capillary trapping (A: residual CO2 in the pore space at the scale of
around 100 mm) and dissolution (B) are illustrated here. Capillary
trapping occurs at the trailing edge of the CO2 plume, where brine
displaces CO2. This limits the spread of CO2 in its own phase.
Dissolution occurs throughout the plume: the CO2-saturated brine is
dense and sinks. Both processes prevent the escape of CO2 to the
surface.
Fig. 13
Fig. 14 Pore-scale images of trapped CO2 in sandstone.571 (a) This is

a two-dimensional cross-section of a three-dimensional image
showing in grey scale the rock (grey), CO2 (light) and brine (dark).
The segmented image, used to identify the uid phases, is shown
in (b). The trapped CO2 ganglia in three dimensions are shown in
(c). The colours indicate the size of the clusters. A collection of
trapped clusters, illustrating the wide range of size and shape is
shown in (d).
Review
is imaged in the pore space with a resolution of approximately 10

mm. The experiments conrm that indeed a signicant fraction
of the pore space (25% in this case) can contain disconnected
ganglia of CO2 surrounded by water that cannot move further.
These results have been conrmed by traditional core ood
experiments on larger rock samples.481483 Over time the CO2 may
dissolve, but it cannot escape. At the eld scale, this mechanism
severely limits the spread of the CO2 plume.
It is not just the amount of trapping, but also the multiphase
ow of CO2 in the presence of brine that is important when
attempting to predict and design CO2 injection. This is quantied through the relative permeability: it measures the ow
conductance of a phase as a function of the fraction of the pore
space it occupies (the saturation). Fig. 15 shows a compilation
of relative permeability measurements of a supercritical CO2
brine system.482 It shows the relative permeabilities for CO2
injection (CO2 displaces brine) to some maximum CO2 saturation, followed by CO2 displacement by brine, leaving a trapped
saturation of CO2that is, the relative permeability of CO2 is
zero even though the CO2 saturation is nite.
These curves can then be used for a quantitative, predictive
assessment of the extent and speed of CO2 movement in the
subsurface.
12.1.2 Natural analogues. Storage of CO2 has occurred in
many natural situations. This can be as pure CO2 gas, or densephase CO2; or as CO2 mixtures within methane, which grade
into associated CO2 with natural gas deposits, requiring separation for commercial purposes. The more concentrated natural
CO2 deposits can produce additional information, which can
inform predictions on the performance of engineered CO2
storage. Particular aspects which can benet from this long-term
view, over 104 to 106 years, are leakage rates, environmental and
Fig. 15 Relative permeability curves the fractional conductance for

ow as a function of brine saturation.482 A compilation of experiments are shown for CO2 injection into brine to a given saturation,
followed by displacement of CO2 by brine. The curves have a zero
value even for nite CO2 and brine saturations, indicating trapping.
These curves are used to predict the movement of CO2 at the large
scale in the subsurface.
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Review
human health impacts at the surface, and chemical interactions

with reservoir and caprock. Three geographical regions are
providing most of the additional information; these are the
Colorado Plateau of USA, onshore southern Italy and Tyrrhenian
sea adjacent to Sicily, and the North Sea. Some brief highlights of
this expanding literature include that CO2 uids do react with
sandstone reservoirs, albeit slowly via oxidationreduction
pathways.484,485 However, these can oen remain out of equilibrium for several million years.486 CO2 uids in oil elds do not
react strongly with mud caprocks, and so form secure retention
for tens of millions years.487 An important stabilisation mechanism is for CO2 to come into contact with large volumes of
formation water, greatly enhancing dissolution for long-term
stability.488 In a worst-case scenario, CO2 can leak slowly to the
surface for many millennia489 without monitoring or safety
precautions. Around such natural leakage sites, the excess
human death rate is extremely low, at less than one in 30 million
per year.490 The current information thus shows that geochemical factors in reservoirs and caprocks for CO2 storage need not
be adverse, if factored into site choice.
12.2
Regional assessments of storage capacity
To make a signicant contribution to reducing atmospheric

emissions, it will be necessary to store several Gt of CO2 each
year worldwide, and many Mt in large regional aquifers in areas
with signicant industry and fossil-fuel power generation.
Assessment of the storage capacity takes into account the
factors mentioned above: the likely increase in pressure, CO2
movement and trapping processes. These are normally incorporated into analytical or numerical models to estimate how
much CO2 can be safely stored and the likely extent of CO2
migration in the subsurface.
As an example, Fig. 16 shows the estimated storage capacity

in large regional aquifers in the continental US.480 A total
capacity of over 100 Gt is calculated, sucient to make a major
contribution to mitigating CO2 emissions in North America.
The methodology combines an assessment of both the storage
capacity and how fast the CO2 can be injected. However, the
actual capacity in CO2 storage reservoirs at present remains
essentially unvalidated, as we discuss next.
12.2.1 Dening the storage reservoirs and storage complex.
The rst step towards CO2 storage for many nations has been
the evaluation of potential storage volumes beneath their
national territory. Prominent leaders in such assessments have
been Australia, followed by USA and Canada, and subsequently
an overall appraisal for all European-27 states. These initial
estimates demonstrated much more than adequate storage
capacity for the next 100 years of emissions, and are now being
rened through second and third generation compilations.
There is no standardisation of these methods. It is likely that
global nance will require improved standardisation of denition for reserves, to enable valuation of assets. Consequently
dierent states currently approach storage dierently. USA
assessments typically assume that all available storage volume
can be utilised within a reservoir, and can tend to optimism. By
contrast, some European states consider only discrete closed
structures and ignore the intervening connections of saline
formations. Several European states have calculated their entire
storage volume, but have reduced its upper limit by assuming
generic eciencies of CO2 emplacement within the reservoir,
and by calculating maximum permitted injection pressures,
which avoid fracturing caprocks. Some states, notably Norway,
have now started to undertake dynamic reservoir simulations,
which also tend to reduce proposed storage capacities. None of
these assessments consider engineering interventions to
Fig. 16 A US-wide assessment of CO2 storage capacity.480 Analytical models have been combined with regional geological models to estimate a
total storage capacity of over 100 Gt in the continental US.
View Article Online
increase storage tonnages, for example, by systematic extraction

of groundwater, even though engineering optimisation will be
an essential part of any commercial project. As the CCS
endeavour starts to enter into development of the rst pilot
projects, it is likely that much more intense scrutiny of candidate site information on storage will occur, around each
commercial injection location. That will start to provide information to test the predictions made during generic assessments
of regional storage formations, which although are expected to
be accurate, they areas we have commented alreadystill
unvalidated.
Additional complexities can arise when licensing and regulation activities collide with natural subsurface geometries of
reservoir and seal.491 Regulators and lawyers are concerned to
avoid damage or trespass into adjacent subsurface property,
whilst also attempting to ensure maximum certainty in identifying injected CO2. In many states of the USA, this may be
resolved by the acquisition of rights to pore space utilisation
across surrounding properties, although it remains unclear if
this will be to protect against a simple case of physical CO2
movement, or will the much greater geographical area of pressure increase be regarded as adversely aected? Dierent
European states have dierent historical approaches. For
example, in Germany, dierent regions are bound by ancient
mining rights, such that even the federal state cannot interfere.
By contrast, the UK has taken a centralised approach where the
rights to all pore space are managed for the Crown Estate.
However, federal European law has not helped, in that the
European Emissions Allowance Directive denes a very local
storage site, consisting of the dened reservoir and caprock. By
contrast, the European CCS Directive allows denition of a
much greater subsurface volume, which can contain multiple
layers of reservoirs and multiple seals. Unplanned CO2 migration from a European Emissions Allowance reservoir need not
be a leakage from a CCS Directive complex. These legal
approaches will need to be harmonised during the progress of
early CCS injection demonstrations.
12.2.2 Challenges to the concept of large volume storage.
Although the practise of injecting dense-phase liquid CO2 is
well established and although the assumed progress is towards
multi-million-tonne-per-year injection sitessome objectors
still raise potential uncertainty in fundamental processes.
These are on subsurface pressure, induced seismicity, aquifer
contamination, and reservoir evaluation. Firstly, we discuss the
pressure management of subsurface injection. Adding large
tonnages of CO2 into the subsurface usually implies adding
additional uid volume, and in a conned reservoir or aquifer,
that will inevitably tend towards an increase of uid pressure.
Economides & Economides492 suggest that nite poor volumes
below ground will limit CO2 injection to 1% of pore space whilst
also reducing rates of injection. Countering this, Cavanagh,
Blunt and Haszeldine493 point out that, although pressure
buildup needs to be specically managed, perfect containment
of pressure by reservoirs below ground is exceptional, and that
the rate of pressure dissipation over a large area is the important factor. If pessimistic assumptions are made of compartmentalised storage reservoirs, with impermeable boundaries,
Review
that leads to pessimistic outcomes. Existing test injections of

CO2494 show that 19 of 20 pilots have not experienced adverse
pressure buildup with the exception of terminating injection at
Snhvit. In a related piece of modelling prediction Cavanagh495
states that the boundary conditions of permeability of the
enclosing seal are important and should lie between 1018 m2
for pressure bleed-o and 1020 m2, or less to retain pressure.
This range coincides with good quality hydrocarbon caprocks.
Zoback and Gorelick496 inferred an increased risk that seismicity will be induced, especially onshore, by injection of large
volumes of CO2. These earthquakes, it is claimed would cause
multiple storage sites to rupture and leak CO2. However, this
has been widely critiqued on the basis that (i) licensing of a
storage site before injection and monitoring aer injection will
eliminate known tectonic sites and (ii) will detect anomalous
small tremors before buildup to larger events, (iii) that a pressure anomaly can be managed by water production, (iv) that
physical leakage of CO2 as a consequence of seismicity would
only occur if the tremor site coincided in space and depth with
the physical CO2which is very unlikely, (v) the pressure pulse
anomaly will decay within 50 years from the time of peak CO2
injection rate.
From a practical point of view, it still remains very unclear
how large-scale CCS storage reservoirs may be evaluated and
tested. Initial experimental projects, even on industrial scale,
inevitably choose high-quality reservoirs; assessing the regional
impact of injection, and assessing the interaction of multiple
injections into the same reservoir remains a problem with no
clear solution. This causes some analysts to propose that largescale, high-quality investigations of saline aquifer regional
geology will be required before any licensing can occur.497
Clearly this can take 5 or even 10 years, and may cost many tens,
probably hundreds, of millions of dollars. If undertaken in a
failsafe and stage-gated process, such investigations could act
as a terminal slowing of the rollout for commercial CCS. This
remains a real problem, as there are numerous unpublished
examples of commercial investigations worldwide for CO2
storage which have failed to meet the required performance
targets and have resulted in the cancellation of project developments. Determination of adequate storage, suitable for the
CO2 tonnages envisaged during the entire power-plant lifetime,
is likely to be the rate determining step for CCS worldwide.
Innovation is badly needed in the technical evaluation of
storage, linked to suitable business models and regulatory
permissions.
12.2.3 CO2-enhanced oil recovery. CO2 has been injected
into the subsurface for many decades for the purpose of
improving oil recovery, as mentioned in the beginning of this
section. This is overwhelmingly in the USA in southern states of
west Texas, Mississippi and Louisiana; although the longest
duration project is at Rangely and the best-known project for
CCS is Weyburn in Saskatchewan. Most of these 70 or so
projects have been and are supplied with CO2 from natural
accumulations of volcanic derivation, so provide some information on subsurface behaviour but less as an analogue for the
CCS techno-economic system. Four CO2 injection projects are
currently in operation, with a further nine planned to be
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operating by 2016. Of these, about 75% intend to undertake

CO2-EOR where, using conventional injection and production
plans, 3 tonnes of CO2 produce one additional barrel of oil. The
primary purpose of those projects is to produce oil rather than
to dispose of CO2. This can have a benet in that such projects
encourage and enable the development of ecient and low-cost
CO2 capture technology, and such projects may fund the
building of pipeline transportation networks for CO2. However,
viewed from the objective of CCS, such projects have two
signicant disadvantages: the rst problem is that CO2-EOR
objects fall under industrial legislation; consequently there is
no mandate to undertake details or extensive CO2 monitoring
through the lifetime of the project to demonstrate and predict
secure long-term retention. Second, the carbon budget overall
becomes conicted by double counting. CO2 captured from
combustion of coal or gas at a power station cannot be regarded
as free from emissions, available to be used to release additional fossil fuel, which itself will produce CO2 upon combustion.498 In North America the additional oil is not conventionally
regarded as producing an emission, because oil production is
regarded as free of emission, until the end user undertakes
combustion. By contrast in Europe these additional emissions
will be explicitly counted as part of the carbon budget and if CO2
emissions credits are to be claimed, then monitoring validation
of CO2 storage will be required.
Even with these practical diculties of emissions osetting,
it may still be worth undertaking CO2-EOR as a stepping stone
to rapid building of large numbers of capture plants connected
to pipeline networks, connected to multiple storage sites which
will reach their full potential aer the additional oil production
is exhausted.
12.3
Conclusions (CO2 storage)
The overwhelming consensus is that large-scale storage of CO2

is feasible, with storage security increasing over time. The main
concern is to ensure that the uid pressure does not increase
suciently to induce fracturing, and to ensure that the mobile
CO2 does not nd a permeable path to the surface. Over time
with capillary, dissolution and mineral trappingstorage
becomes more secure and the CO2 less likely to escape. It is
wrong to think of the CO2 as having some typical storage time or
leakage rate: the (low) risk of leakage occurs mainly during the
injection period and declines with time as pressure dissipates
and the CO2 becomes less mobile. Even if natural seals are
breached, then leakage rates in natural examples are slow and
impact at the surface is small. The development of CO2-EOR
projects may accelerate the development of ecient capture
engineering but will do little for net CO2 reduction over the life
cycle of a project. Benets from those projects may be a legacy of
pipeline to access abundant proven storage sites.
CO2 storage can be engineered to deal with potential problems. If injectivity is poor, new wells can be drilled; water can be
abstracted from the subsurface to relieve pressure, or reinjected to promote capillary trapping. Diverse objections
raised against storage, suggesting uncontrolled pressure
increase, or induced seismic tremors leading to extensive
leakage, are potential diculties which can be managed with

known techniques. CO2 storage is not a passive process but one
that with responsive monitoring and engineering can be achieved at scale, eciently and securely. More work is needed on
how to provide sucient condence in storage site evaluation,
to positively inform the process of starting a CCS power-plant
development. Additionally, there is a need to produce greater
certainty in the fail-safe retention of CO2, which is shown both
by trapping processes measured at laboratory scale and by
calculations from natural analogues.
13. CO2 sequestration via ex situ

mineral carbonation
13.1
Background
Ex situ mineral carbonation is a suggested CO2 sequestration

option for geological storage. The process involves carbonating
materials containing alkali or alkaline earth metal oxides or
hydroxides, xing captured CO2 as thermodynamically stable
and environmentally benign carbonate minerals (eqn (13) and
(14)). Storage is considered permanent so no post-storage
monitoring would be required.457,499 In addition, the carbonation process is exothermic, so the theory is that the process
could be utilised to produce useful energy if heat is released at
high enough temperatures. There is enough alkaline earth
metal oxide-containing material on earth to sequester all of the
CO2 that could ever be emitted from fossil fuel use.457 Mineral
carbonation also provides an option for storing CO2 at locations
without access to geological storage sites.
CaO(s) + CO2(g) / CaCO3(s), DH 179 kJ mol1
(13)
MgO(s) + CO2(g) / MgCO3(s), DH 118 kJ mol1
(14)
13.1.1 Mineral feedstocks. MgO and CaO are the most

naturally abundant of the alkali and alkaline earth metal oxides,
making up approximately 2.0 and 2.1 mol% of the earths crust
respectively.500 However, in nature, MgO and CaO do not exist as
binary oxides and are typically bound up as silicates. Mgsilicates, such as serpentine and olivine, are considered the
most important mineral carbonation feedstock. They are widely
available, particularly serpentine, and rock deposits bearing
these minerals tend to contain them in high concentrations
(typically containing in the region of 3060 wt% MgO).500
Carbonation of magnesium and calcium silicate ores occurs
naturally (known as natural weathering); however, they are less
reactive than their corresponding metal oxides and the kinetics
under ambient conditions are far too slow to form the basis of a
commercial process.501 The carbonation of Mg- and Ca-silicates
is still exothermic, although to a lesser extent. Improving the
carbonation kinetics is one of the most signicant challenges
facing the development of a commercial mineral carbonation
process.501 Furthermore, extracting and processing the large
amounts of raw material required for an industrial scale operation is very energy intensive. It is estimated that 38 tons of
mineral needs to be mined (and ground to <75 mm) to store the
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CO2 released from the combustion of 1 ton of coal in a coal-red

power plant.502,503
A feasibility study carried out by OConnor et al.504 estimated
that an industrial-scale mineral carbonation operation based
on the NETL process would impose a 3050% energy penalty on
the power generation process; 75% of this penalty was attributed to grinding the feedstock to <37 mm. On the basis of these
calculations, sequestration costs alone were estimated at 50
100 US$ tCO21, an order of magnitude higher than the current
cost of geological storage at 510 US$ tCO21.437 OConnors
costings are still used as the ocial best-case scenario estimated costs for mineral carbonation by many of the important
organisations and agencies advising on climate change and
mitigation strategies, such as the IEA and IPCC.437,457
13.1.2 Indirect mineral carbonation. Over the last few
years, there has been a growing interest in developing indirect
aqueous carbonation processes where metal extraction and
carbonate precipitation is carried out in two or more stages.
Whilst indirect processes are more complex, conditions can be
optimised for each stage individually. Furthermore, indirect
processes oen generate separate streams of the dierent
reaction products (typically magnesium or calcium carbonate,
silica, and iron oxides), which are of commercial value when
obtained at sucient purities. A comprehensive analysis of
potential applications for mineral carbonation products is
provided by Sanna et al.505 The sale of such materials might help
to subsidise process costs, particularly if the technology reaches
the demonstration or early-stage industrial deployment phase.
However, wide-scale deployment would saturate any potential
high value market, and low-value applications will not support a
signicant market.505
13.1.3 Carbonation of alkali waste streams. Alkali and
alkaline earth metal-rich waste streams such as iron and steel
slags, ash from fossil fuel combustion, waste concrete and
cement kiln dust oer a number of advantages as feedstocks for
CO2 mineralisation applications. They are cheap and widely
available; they tend to be much more reactive than naturally
occurring Mg and Ca-silicates; and in most cases, they require
minimal preparation. Furthermore, their use helps to address
issues and costs associated with waste disposal, particularly if
the process generates marketable by-products. In some
instances, mineral carbonation may also serve as a means for
treating environmentally hazardous waste streams. For
example, mineral carbonation reduces the mobility of heavy
metal trace elements such as Pb, Cd and Ni found in some
wastes, which can leach into the surrounding environment aer
disposal.506 CO2 mineralisation can also be used to neutralise
highly caustic waste streams such as red mud produced from
bauxite processing for aluminium production.507
Pilot-scale testing of this technology is likely to follow in the
near future.508 However, like y ash and indeed most other
potential waste-derived feedstocks, the CO2 storage potential of
iron and steel slags is lowestimated at up to 170 MtCO2 per
year509 compared with total global CO2 emissions from the iron
and steel sector of 2.3 Gt per year.510
13.1.4 Future scope. Further development of ex situ CO2
mineralisation processes that utilise waste feedstocks (or
Review
wollastonite) and generate valuable by-products may help to

progress technologies to the pilot and demonstration phases.
Furthermore, it is likely that CO2 mineralisation of waste
streams will nd niche applications for hazardous waste
remediation and as a means for some industries to produce
valuable by-products from their waste whilst reducing their CO2
emissions. However, if CO2 mineralisation technologies are to
oer the kind of CO2 storage capacities required for climate
change mitigation applications, economically feasible
processes utilising naturally occurring Mg- and Ca-silicates
must be developed; and the energy required to grind materials to the required size distribution, together with the low
value of the produced material will make this an exceptionally
challenging proposition.
14.
14.1
Carbon dioxide re-use

Background
Carbon dioxide re-use (CDR) is a purported alternative to

storage that involves the production of saleable products from
captured CO2. CDR includes the use of CO2 as a technological
uid and as a reagent for the production of chemicals (CO2-tochemicals), plastics (CO2-to-plastics), or fuels (CO2-to-fuels).
The combined system of CO2 capture with CO2 re-use is typically referred to as carbon capture and utilisation (CCU). In a
few cases, CDR can result in some permanent storage and
removal of CO2 from the carbon cycle (e.g. enhanced oil recovery
or mineral carbonisation); however, in most cases, CDR will
result in re-emission further down the line (e.g. the use of CO2
as a technological uid or as a precursor for fuel production). In
the latter case, the lifetime in which CO2 is removed from the
carbon cycle will vary: some uses, such as the use of CO2 as a
fuel precursor, are very short term (days to months); whilst
others, such as its use as a precursor for plastics, have a longer
term. In fact, the use of CO2 as a precursor for some plastics may
result in the CO2 being xed away from the atmosphere for
decades and can, therefore, be considered a form of storage.
The primary advantage of CDR compared with CCS is that its
end product is of value. It has been argued that increased
deployment of CDR processes will therefore drive up the market
price of CO2, incentivising development and deployment of CO2
capture technologies. CCS on the other hand requires market
intervention by governments through the application of strict
penalties or economic support and subsidies to achieve the
same result. However, the argument that CDR will meaningfully
increase the price of CO2 fails to take into account the vast
supply of CO2 and the comparatively small demand for CO2.
14.2
Current status of CDR technology
Despite the fact that CO2 is a renewable, widely available, lowcost and low-toxicity C1 feedstock, current industrial demand
is relatively low, amounting to around 232 Mt per year, with
only a few commercial processes currently using CO2 as a raw
material (Table 8). Most of the current demand is met by
naturally derived CO2 with only 40 Mt obtained from anthropogenic sources of which 70% is used for EOR purposes and
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another signicant fraction used for urea production.511 At

present, the market for CO2 is several orders of magnitude
smaller than the amount of CO2 released into the atmosphere
each year from anthropogenic sources and approximately 60
times smaller than the amount of CO2 emitted from large
point sources (14 000 Mt per year).512 The following sections
provide a brief overview of the current status of CDR
technology.
14.2.1 CO2 as a technological uid. CO2 has a number of
commercial applications as a technological uid, including
enhanced oil recovery (EOR), enhanced gas recovery (EGR),
enhanced coal bed methane (ECBM) and numerous food and
beverage applications. CO2 is also used as a coolant in air
conditioning units, as a fumigant, for controlling the pH of
process water in water treatment applications, and as a green
solvent (including its use in dry cleaning).513 At present, most of
the CO2 used for EOR (50 Mt per year) and by the food and
beverage industry (8 Mt per year) is sourced from natural CO2
reservoirs;512 therefore minor emissions reductions could be
achieved by utilising captured CO2 instead.
EOR oers one of the largest potential markets for CO2. In a
recent report, Advanced Resources International estimated
that at least 8 billion tons of CO2 could be sequestered using
EOR in the US alone.511 This, in turn, would produce between 4
and 47 billion barrels of additional domestic resources. Given
that the US has only 1.6% of the Worlds proven oil reserves,
there is potential for signicant growth in CO2 use and
subsequent sequestration via EOR, particularly as oil production declines in existing wells in the Gulf States. Despite this,
the future of EOR is uncertain. High CAPEX and OPEX costs
and uncertainty over long-term oil prices, unclear and illdened regulations governing EOR activities, and wavering
public support have all impeded deployment of EOR.514
Furthermore, oshore EOR has yet to be proven. Over recent
years, a number of elds in the North Sea have been assessed
as potential sites for EOR by Shell, BP and Norsk-Hydro and
have failed commercial hurdles due to high oshore platform
retrot costs, cash ow issues, and alternative, cheaper options
for maintaining oil production in depleting reservoirs, such as
by drilling additional targeted and deviated bore-holes. EOR

also competes with other methods of enhanced resource
production, such as unconventional gas and tight oil, coal-toliquids (CTL) and gas-to-liquid (GTL) technologies.
CO2 to chemicals. There are a vast amount of dierent
chemicals that in theory could be produced using CO2 as a C1
feedstock; however, many would either prove impractical to
produce from CO2 on an industrial scale or have limited
market potential. Scheme 3 outlines a number of promising
CO2-derived synthetic targets and their current global market.
Of particular interest are alkylene carbonates and polycarbonates, which have current global markets of several
hundred kt per year515517 and 4 Mt per year3 respectively,
inorganic carbonates (60 Mt per year),518,519 urea (160 Mt per
year);520 polyurethane (18 Mt per year),521 and acrylic acid and
acrylates (10 Mt per year).522
14.2.2 Urea. Urea has been produced from CO2 on an
industrial scale for many years and currently represents the
largest market for CO2 outside of EOR.3 Urea is manufactured
via a two-step process that involves the exothermic reaction of
liquid ammonia and dry ice (solid CO2) to form ammonium
carbonate, followed by the endothermic decomposition and
dehydration of ammonium carbonate to yield urea. The overall
process is exothermic and no catalyst is required.
According to the International Fertiliser Association, current
global production of urea is 159.4 Mt per year.520 Given that
between 0.735 and 0.75 tonnes of CO2 are consumed per tonne
of urea, CO2 consumption as a consequence of urea production
is around 119.6 Mt per year. The overwhelming market for urea
is that of the fertiliser industry, which consumes over 80% of
total global urea production.3
Table 8 Current CO2 consuming industrial processes3,520,636638
Process
Urea
Methanol
Inorganic
carbonates
Organic
carbonates
Technological
Food
EOR
Total
Industrial
volume
Mt per year
Global
CO2 usage
Mt per year
159.4
55
80
119.6
14
30
4
10
8
50
0.2
10
8
50
232 Mt
Lifetime of
storage
Months
Months
Decades
permanent
Decades
Days to years
Days to years
Permanenta
Whilst EOR oers the potential of permanent storage, most of the CO2
used for EOR is currently not stored.
Scheme 3 Chemical transformations of CO2 into synthetic targets

with large current or potential markets (adapted and updated from
Mac Dowell et al.3
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The climate change mitigation potential of ramping up urea

production is poor. As discussed by Fennell,503 the storage of
CO2 within urea is short, since the chemical breaks down upon
application as fertiliser, releasing the CO2 into the atmosphere.523 In addition, N2O emissions, of which fertiliser use is
the main source, correspond to around a third of anthropogenic
N2O emissions, further reducing the case for increasing urea
production as a means for stimulating the development and
deployment of CCS/CCU technology.
14.3
CO2-to-fuels
The production of fuels from CO2 is ostensibly an attractive

goal, given that the global fuels market is roughly two orders of
magnitude greater than that of chemicals. In order for the
production and use of CO2-derived fuels to contribute to climate
change mitigation eorts, the energy requirements must be
supplied from non-fossil sources, i.e. RETs or nuclear. The idea
is that the application of such technology may provide a way of
storing excess electrical or intermittent electricity production.
The fuels produced could be used to re a power plant, generator or fuel cell during periods when RETs relying on intermittent energy sources (such as the sun or wind) are not able to
meet demand; alternatively, the fuels could be used for mobile
or distributed applications. Furthermore, the production of
easy to transport fuels from CO2, utilising renewable energy at a
remote location (such as geothermal or solar) might prove a
more convenient and cost-eective way of delivering otherwise
stranded resources to market than constructing transmission
lines or nding other potential uses for such resources.
CO2 is the lowest energy state of any binary neutral carbon
species and the ultimate product of energy-releasing hydrocarbon
combustion and metabolic pathways. Therefore, a signicant
energy input is required to overcome the substantial thermodynamic and kinetic barriers of converting CO2 into a useable fuel.
When considering the energetics of CO2 activation, only a very few
synthetic fuel targets can possibly be considered viable, these
targets include syngas, methane, methanol and formic acid.3
Methanol can be produced via the catalytic hydrogenation of
CO2 utilising similar conditions catalysts to those used for the
production of methanol in the conventional commercial
approach.524 In this case, the use of hydrocarbons can be avoided by using H2 from renewable sources, i.e. water splitting via
electrolysis. However, the drawbacks with this approach are that
equilibrium yields are much lower compared with methanol
production from syngas. In addition, a third of the hydrogen is
converted to water; this process is inecient, particularly when
considering that H2 production via electrolysis of water is a very
energy intensive process. Furthermore, both methods of
producing methanol consume a great deal of thermal energy,
and the lifecycle eciency, particularly considering that the
original source of energy for the production of H2 is electricity,
is exceptionally low. It has been argued503 that pumped storage
of the electricity, combined with the use of electric vehicles is
around ve times more ecient in terms of miles driven than
using the electricity to produce hydrogen, then methanol, then
using this to run an internal combustion engine.
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14.4
Future outlook
At present, utilisation of CO2, particularly CO2 from anthropogenic sources, is low. The use of anthropogenic CO2 in place of
CO2 derived from natural deposits will oer small emissions
reductions, although in the context of climate change mitigation, the impact will be insignicant. In the short term,
increased deployment of EOR has the potential to oer the
largest economic stimulus for large point sources to capture
and subsequently store their CO2. However, a clear framework
for regulating and incentivising wide-scale deployment of CCS
and EOR that also addresses potential liability issues associated
with EOR coupled with permanent storage needs to be established. Further work is also required to assess the feasibility and
any potential deployment issues associated with EOR and
permanent storage particularly at o-shore locations.
CO2-to-fuels technology is far from commercial status and
will have to compete with other unconventional methods of
producing liquid fuels, such as GTL and CTL in addition to
other means of storing and utilising energy such as high eciency batteries and ultracapacitors. The future of CO2-to-fuels
technology, therefore, remains highly uncertain because of
the inherent thermodynamic eciency penalties.
15. Policy design and implications for

investment
15.1
Introduction
The preceding sections of this paper have discussed the range of

CCS technologies under development. Whilst it is perhaps too
early to say which set of technologies will come to dominate the
eld, it is certainly the case that any CCS technology will require
policy support to ensure deployment at the scale and volume
required to deliver on climate change goals.525 This section
reviews the recent history of policy support for CCS, focusing on
the power generation sector in the UK and EU, and discusses
the continuing policy challenges which are faced, together with
the implications for potential investment in CCS projects. The
focus reects the key role that decarbonisation of the electricity
generation sector is expected to have in meeting CO2 emissions
reduction goals, the leading role that the UK is taking with a
package of measures intended to support CCS projects both in,
and beyond, the demonstration phase, together with the EUwide policies to support demonstration projects.526
It is not the purpose of this section to review estimated
costings for dierent technologies, since this subject is highly
contestable and frequently quite subjective. A recent review of
costs in industrial settings deals with this subject527 and an
excellent summary of recent pilot and large-scale costing data is
available from the Global Carbon Capture and Storage Institute
on a yearly basis.528
16. A recent history of UK and EU CCS

policy
In 2007, the UK Government launched a competition for
demonstrating post-combustion capture on a coal-red power
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station, to be operational by 2014, aiming to make the UK a

world leader in this globally important technology.529,530 Two of
the applicants for the competition were awarded funding for
Front End Engineering and Design (FEED) work. The 2010
Spending Review conrmed that Government would provide up
to 1 billion for the successful project, but on the same day as
this announcement was made, one of the remaining applicants
withdrew from the competition on the grounds that the
economic conditions were not right, leaving only one remaining
applicanta post-combustion retrot to part of ScottishPowers
Longannet coal-red plant. During the same year, the UK
Government rearmed its commitment to a further three CCS
demonstration projects, and completed a market sounding
exercise to help the department to explore workable options for
the CCS demonstration project selection and funding
processes, and learn about projects being considered by
industry.531 A key development was the decision to make gas
red generation eligible for the competition, following recommendations by the Committee on Climate Change.532
It was originally intended that funding for the further three
projects would be nanced by a levy on consumer bills, but this
levy was later shelved. Longer term, the CCS funding mechanism
is bound up in the Electricity Market Reform (EMR) process.533 At
the EU level, it was anticipated that the New Entrant Reserve
funding (commonly referred to as the NER 300) would be available from the auctioning of 300 million EU ETS allowances, at the
time expected to raise between V4.5 and V9.0 billion in total with
a substantial fraction of this to be available for CCS projects
across the EU. To be eligible, all prospective NER 300 projects are
required to secure 50% co-funding from other sources.534
In December 2010, the UK Government launched a consultation on the EMR which set out a proposed package of policies
to ensure that low-carbon technologies become a more attractive choice for investors, and adequately reward back up
capacity to ensure the lights stay on. These reforms were driven
by Governments belief that the current market will not deliver
on the Governments objectives for decarbonisation, security of
supply or aordability for consumers.535 The four key EMR
mechanisms are:
(1) A Feed-in Tari (FiT) to stabilise and top-up the revenues
of low-carbon generators including CCS, transferring electricity
price risk from generators to consumers, through a Contract for
Dierence (CfD).
(2) A carbon price oor to reduce uncertainty for investors
and incentivise low-carbon generation by topping up the EU
ETS carbon price.
(3) An Emissions Performance Standard (EPS) to put an
annual limit on the amount of CO2 that a plant can emit,
equivalent to 450 gCO2 kW h1 for plant operating at baseload,
thereby eectively prohibiting new unabated coal-red plant
but new allowing new unabated CCGT plant.
(4) A capacity mechanism to ensure that there is sucient
generating capacity to meet peak demand.
The EMR consultation process was followed by a White
Paper during 2011536 and in 2012 by a dra Energy Bill537 which
set out the legislative framework for the proposals. In the
meantime, however, ScottishPower pulled out of the rst
demonstration plant competition in October 2011, with the UK

Government citing increased costs and the inability to reach a
commercial agreement as the reasons. At the same time, it was
conrmed that the 1 billion of public funds set aside for the
rst demonstration would be available for a new process.538
This new process was launched as a Commercialisation
Programme and involves a competition through which
successful applicants will receive direct funding from the 1
billion budget and also the possibility of further revenue-based
support under the CfD FiT mechanism proposed in the EMR.
Applicants for funding from the new process must be able to
demonstrate at commercial scale and be operational by 2016
2020.539 The separate process by which the EC selected projects
for funding under the NER 300 scheme continues in parallel to
the UK Governments Commercialisation Programme.
However, under the rst round of the NER 300, no CCS projects
were granted funding, though funding is still potentially available in the second round. The level of funding available through
the NER 300 process will be considerably less than was originally hoped because the market price of EU ETS allowances is
well below the level envisaged when the process was set up. The
EC currently anticipate that the total level of funding from the
process will be between V1.3 billion and V1.5 billion, with
funding for any individual project capped at 15% of the total,
meaning a maximum of V292337 million for any one project.
At the time of writing (May 2013), the UK Government has
announced the two preferred bidders for the Commercialisation Programme competition. These are the White Rose project,
an oxyfuel-based project based at Drax, North Yorkshire and
proposed by a consortium of companies including Alstom, Drax
and BOC, working closely with National Grid and who together
form Capture Power;540 and the Peterhead project in Aberdeenshire, Scotland, involving Shell and SSE. Both projects are
currently performing front-end engineering design studies.
Table 9 details projects which were shortlisted for funding by
both the EU and UK CCS competitions.
16.1
Implications for investment in CCS
The generic investment challenges faced by renewable energy

and nuclear power plants operating in liberalised energy
markets are well understood. The combination of high capital
costs and very low operating costs means that such plant are
typically price takers because once constructed, it typically
makes most sense to run them whenever they are physically
able to do so, almost regardless of electricity prices. It is
conventional gas and coal-red plant that have the price maker
role and have the dominant inuence over electricity prices as
they are generally able to remain protable over a wider set of
operating regimes and pass variations in fuel costs through to
consumers.541 In practice this means that potential investors
will tend to prefer low capital cost conventional gas-red power
station projects with operating costs linked closely to electrical
output, even if the lifetime levelised costs of electricity from
higher capital cost projects are similar.541
CCS introduces another set of challenges because it also
carries relatively high fuel and operation and maintenance
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Table 9
Review
EC and UK CCS project shortlists
EC NER 300 CCS projects (ranked order)
UK CCS projects (alphabetical order)
Project
Type, fuel
Country
Project
Type, fuel
Don Valley Power Project

Belchatow CCS Project
Green Hydrogen
The Teeside CCS Project
UK Oxy CCS Demo
(White Rose Project)
C.GEN North Killingholme
Power Station
Zero Emission Porto Tolle
ULCOS-BF
Pre-combustion, coal
Post-combustion, coal
Industrial application, gas
Oxyfuel, coal
UK
Poland
Netherlands
UK
UK
Captain Clean Energy Project

Peterhead Gas CCS Project
The Teeside CCS Project
White Rose Project
Post-combustion, gas
Oxyfuel, coal
Pre-combustion, coal,
petcoke, biomass
Post-combustion, coal, biomass
Industrial application, gas
UK
Italy
France
EC NER 300 Reserve list

Getica CCS Demo Project
Peterhead Gas CCS Project
Post-combustion, coal
Post-combustion, gas
costs, a carbon cost for the residual CO2 emissions which

cannot be captured, and a potential long-term liability associated with the stored CO2. Whilst the support oered through
the FiT mechanism proposed in the EMR suits the characteristics of low operating cost plant such as nuclear and wind
power, the fuel costs associated with CCS plants suggest that it
may require a premium payment that is linked to those fuel
costs.
The relatively high variable costs of CCS (when compared to
nuclear or wind power for example) mean that CCS plants can
generally be expected to have a lower position in the electricity
market merit order, which may lead to lower load factors for
some CCS plant. This load following role in the UK electricity
market has typically been lled by a combination of relatively
new, low-capital-cost CCGT plants, and coal plants whose build
costs were sunk several decades ago. A CCS plant in the current
market may therefore be squeezed between low variable cost
price takers (nuclear and wind) and low capital cost price
makers (CCGT). Of course, conventional CCGT, whilst lower
carbon than conventional coal, is still not low-carbon, which
presents an opportunity for low-carbon, potentially loadfollowing plant such as CCS. Depending on the contribution
of nuclear and wind power to the generation mix, a proportion
of any CCS eet may be able to run at, or near, baseload, but the
characteristics of CCS described above still present a signicant
challenge, particularly if, as some suggest, levelised costs for
CCS are likely to show only small reductions over the next few
decades as potential reductions in capital cost are oset by
carbon price increases.542
In the relatively small literature on CCS as an investment
proposition, there appears to be something of a consensus
emerging that the policy support mechanisms under consideration, both internationally and in the UK, are unlikely to deliver
the level of CCS deployment that many suggest will be
required.543 In their 2009 paper, Abadie and Chamorro544
concluded that in the face of the risks associated with uncertain
returns, investment in CCS on coal plants will be delayed. They
Romania
UK
also concluded from a real-options based assessment that the

CO2 price required to overcome these risks and incentivise CCS
investment was more than four times that which is suggested by
a typical Net Present Value (NPV) assessment, and still more
than three times even if the additional capital cost is covered by
full subsidy.545 From their analysis of CCS investments in the US
policy context, Hamilton and colleagues546 suggest that given
nth of a kind cost estimates available and the projected value of
avoided carbon emissions under the then proposed US carbon
cap and trade bills, Super Critical Pulverised Coal (SCPC) plant
with CCS would not present a breakeven proposition until aer
2030. Osmundsen and Emhjellen547 argue in their 2010 paper
that CCS does not oer a protable proposition and delivers
CO2 abatement at very high cost. Others contend that the EU
ETS on its own wont lead to large scale CCS deployment,548 a
view that has some support from within the industry.549 Flannery550 contends that CCS today lacks both an economically
viable policy framework and a business model. With a dierent
analytical approach, Evar assessed stakeholder perceptions of
the uncertainties over CCS technology development and
whether support levels will be sucient: he concluded that
experts express certitude in the prospects for deploying largescale CCS technology in the UK, all the while questioning
several underlying technical and policy premises that are
necessary to ensure this goal.551
Further issues which concern analysts are pipeline network
sizing and the potential long-term liability that CO2 storage
represents. It is argued by some stakeholders that with current
policy there is a danger of a piece-meal build-up of pipelines,
when a more coordinated approach might be more cost eective in the long run,531 a view which has some support.552 The
eect of a sub-optimal pipeline network is to make overall costs
per unit of output (MWh of electricity or tonne of CO2 stored)
higher than they could otherwise be. Concerns over the long
term liabilities associated with CO2 storage are oen raised in
the context of the investment proposition of CCS,550,553 whilst
others question the degree to which the long term CO2 storage
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liability is a commercially insurable risk.554 On the other hand,

the EU directive on CO2 storage, which seems likely to mandate
a long term liability fund, may go some to way to addressing
these concerns.555
16.2 Continuing challenges facing CCS policy support

mechanisms
The UK and EU clearly do have substantial policy support
oerings for CCS but the key question is whether they will be
sucient to deliver both the early-stage investment in demonstration plants and the large-scale CCS deployment that will be
required if the technology is to make a meaningful contribution
to meeting climate policy goals. Research undertaken by the UK
Energy Research Centre556558 suggests that signicant concerns
remain and these can summarised as follows:
Technology and construction risk is a particularly important
factor deterring investment at present. The multiplicity of CCS
technologies, each of which has diering technological characteristics, makes this factor especially dicult to tackle. The
high up-front capital costs of CCS projects (and the uncertainty
around those costs), together with delays in the UK demonstration programme, and the EMRs emphasis on premium
payments for electricity generated rather than up-front capital
grants, are exacerbating this risk.
The infrastructural barriers to CCS investment include the
rst-of-a-kind costs associated with developing a CO2 transportation network, and the lack of a systematic policy approach
to coordinating and optimising the network through, for
example, pipeline oversizing. There are also more general
uncertainties about the legal liabilities of CO2 storage.
CCS has signicant and variable fuel-related operating costs,
which creates a fuel price risk. Although fossil fuel plants are
typically price makers, with the ability to pass fuel price
increases on to consumers, there are concerns that the FiT CfD
support mechanism for UK projects may remove this natural
hedge unless the mechanism is also linked to fuel prices.
CCS has relatively high operating and fuel costs, which may
mean that load factor risk could become important by the late
2020s. In particular, CCS plant might be required to operate
exibly (and therefore at lower load factors) when there is
increased penetration of very-low-marginal-cost nuclear and
wind power plants. This has the potential to increase the unit
costs (/MWh) of CCS generation, thus undermining the
attractiveness of CCS investments unless investors can be sure
of receiving high prices when plants do run, or can be
compensated in some other way, for example through the
proposed capacity payment mechanism. This risk is potentially
greater for coal CCS than gas CCS, due to the higher capital
intensity of coal plant.
Whilst other low carbon power generation technologies such
as nuclear, wind and solar photovoltaics also generally require
support, the unique characteristics of CCS present both
signicant opportunities and policy challenges. The opportunities include the potential for dispatchable, exible, low
carbon generationwhich will have particular value in electricity systems with large contributions from technically or
economically inexible generation such as wind and nuclear

power. Combining these attributes with the potential for
geographically diversied fuels sources explains why CCS
technologies feature so strongly in many countries CO2 emissions reduction strategies. However, policy design does need to
recognise the specic techno-economic characteristics of CCS
and the need for substantial capital grants for early projects,
address the inherent fuel price risk, and ensure that the CO2
transportation networks are built up in the most ecient longterm manner. The Global CCS Institute have called for
substantial, timely and stable policy support,526 reinforcing the
IEAs call for a stable but exible policy framework.525 What is
also clear is that time is of the essence if CCS technologies are to
be developed and deployed at the scale implied by global policy
aspirations.
17. UK and EU legislative responses to

CCS
This section explores the main features of the EU and UK
legislative frameworks for CCS. This analysis is cast against a
not inconsiderable concern over the nancial and regulatory
risk management dimensions of the technology. What is
revealed in particular is the need for greater regulatory certainty
and legal and nancial assurances for would be CCS investors
and operators of CCS storage sites.
17.1
The CCS directive
The Directive559 provides the legislative basis for safe geological

storage of carbon dioxide. It makes passing references to
capture and transport activities. There are comprehensive
requirements for storage addressing the life cycle of prospective
storage sites. In particular, there is coverage of: storage site
selection (Article 4); permits for exploration (Article 5), storage
permits (Article 6); and operation, closure and post-closure
obligations (Chapter 4). Finally, there are rules prescribed for
transfer of site-based responsibilities (Article 18).
In summary, the CCS Directive provides a signicant
number of risk management opportunities for UK regulators
while placing signicant costs on storage operators. For
example, not to approve storage sites with risky geological
proles, to seek strict permit conditions such that human error
will be reduced in respect of technical compliance, etc. Additionally, among the regulatory risk management opportunities
available to governments are the rights of authorities to require
the following:
That no storage site which may leak or create undue
environmental or health risks shall be permitted;
That no storage site shall be permitted without requisite
levels of nancial security and technical excellence;
That a storage site shall not operate without a permit and
observance of all permit conditions;
That a storage site must feature eective monitoring and
reporting requirements to the regulatory authority;
That the regulator must be notied immediately of leakages or irregularities at the site;
View Article Online
That a storage site will be closed for breach of permit

conditions;
That the storage site operator will comply with strict
closure and aercare requirements;
That all environmental and related nancial liabilities may
be placed on the storage site operator;
That there shall be proportionate penalties for regulatory
infractions;
That emission allowances be purchased to cover leakage
events.
The sheer weight and nature of risk management opportunities available to the regulator and the commensurate risk
management standards, procedures and nancial and related
liability requirements placed upon the storage site operators
suggests that a cooperation or partnership approach
between industry and regulators to risk management and
related long-term and nancial liability for leakage is
necessary.
In respect of commercial scale storage sites, it is worth
recalling that geological storage will extend over long periods of
time. As such the CCS Directive spells out framework requirements to ensure the long-term stewardship of storage sites. The
Directive thus provides for sites to be transferred to Member
State control in the long term, however, that can only occur once
the Competent Authority has been assured that no leakage is
likely to occur. (The operator retains responsibility for a site
whilst it presents a signicant risk of leakage.) Under the CCS
Directive, a storage site shall be transferred (legal liabilities
included) to the state when:
All available evidence indicates that the CO2 will be
completely contained for the indenite future;
A minimum period before transfer to be determined by the
competent authority has elapsed;
A nancial contribution for the post-transfer period
covering at least the costs for monitoring for 30 years has been
made and;
The site has been sealed and the injection facilities have
been removed. As this is the second key decision in the lifecycle
of a storage site (the rst being the decision to permit the site
for use), a Commission review is foreseen at this stage too.
There is a perception (CCS Directive, Article 18) that potential storage site operator liabilities and nancial obligations end
within approximately 20 years (given as a minimum period).
However, the nature of Directive Article 18.1-2 language is such
that the conditions 1(a) complete and permanent storage may
not be proven by that time, (b) the 20 year period is a minimum,
and 2(c) site evolution towards a situation of long-term
stability may not be proven by that time. As such, this loose
Directive language oers regulators an open door to deny the
transfer of responsibility from the storage site operator to the
competent authority at the 20 year threshold. In such circumstances, it has previously been demonstrated that regulators do
not accept such a transfer of responsibility in analogous environmental law elds (in Canada and the United States) pertaining to waste management facilities and contaminated land
sites. Transfers can be innitely stalled by competent authorities, through requests for more monitoring data for example.
Review
This issue ought to be considered by rms operating in

particularly risk adverse government jurisdictions.
17.2
The Environmental Liability Directive560
The CCS Directive itself does not address the specic mechanics
of liability. Hence, we must look to the Environmental Liability
Directive and the Emissions Trading Scheme Directive given
that the CCS Directive delegates this matter to them.
Further to Article 34 of the CCS Directive, the Environmental
Liability Directive brings storage site operations within the
liability framework of the European Union. As such, operators
of CCS sites have obligations in respect of the prevention and
remediation of environmental damage associated with such
sites. This applies to all relevant environmental damage and
corresponding duties of prevention (Article 5) and remediation/
mitigation (Article 6) under the Environmental Liability Directive. Financial security measures are also to be undertaken by
storage site operators further to Article 14 of the Environmental
Liability Directive. A exible interpretation of Article 14 allows
for the use of ceilings on nancial instruments. It also allows for
the exclusion of liability on behalf of operators, where they are
not at fault or are otherwise not negligent.
17.3.
The Emissions Trading Directive561
If we move on to the Emissions Trading Directive, by virtue of

the inclusion of geological storage sites under Annex I of the
Emissions Trading Directive, installations will be required to
surrender allowances for any emissions from the site, including
leakage, as calculated pursuant to the Monitoring and Reporting Guidelines for CCS. The amount of the Financial Security
(FS) for this obligation can be based on the potential total tons
of emissions, including those due to leakage(s), multiplied by
the market cost of purchasing an equivalent amount of allowances. This calculation will require (i) estimates for the total
tons of emissions that may be released, including those due to
leakage(s), (ii) the timing of emissions, and (iii) costs of allowances when releases occur.
Guidance Document 4 observations aside, there is unavoidable uncertainty about the future price of EU Allowances (EUA)
at the time of any potential leakage. There is no cap on the EUA
price; the penalty for excess emission (100 V t1) does not
relieve the operator of the need to provide allowances to cover
the emissions, and is not, therefore, a cap on EUA prices.
The need to hedge against such risk becomes important
when it is likely that liability for allowances would entail greater
costs over time as carbon prices rise. Furthermore, the
assumption of long-term emissions credits liability would mean
that allowances which are bought in the future, as a compensatory measure for loss of CO2 stored, would be with a signicantly higher price tag than those bought today, which would
further defer investments.
As such, a liability of this kind is not insurable and presents
an incalculable risk to potential storage site operators.
In terms of nancial risk derived from liability, it is worth
noting that the purchase of emissions credits serves as a climate
change mitigation and prevention strategy in itself. Arguably,
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damage in terms of failed climate change mitigation is already

covered in respect of the types of damage listed in the EU Environmental Liability Directive (2004/35/EC) (including, but not
limited to species loss, marine ecosystem damage, fundamental
changes in land use, damage to land, damage to water, etc.).
These types of damage occur as a result of anthropogenic climate
change as well, which is why CO2 as a pollutant has already been
determined to be remediated under climate change mitigation
measures. Thereby, if CCS operators are legally required to buy
emissions credits and CCS operators also bound to cover liability
of the same leakage event, there is a clear double-payment by the
private sector. This problem of double-counting liability has to
be addressed by counterbalanced regulatory solutions that push
forward CCS technology investment.
17.4
EU state aids/competition law
There may be those that point to state aids/competition law

restrictions on regulatory solutions for nancial instrument and
long-term liability regulation further to the CCS Directive. It is
noted to date that the UK and German Governments have taken a
favourable position in this regard by adopting a exible approach
to state aids and it would appear that the European Commission
is similarly disposed. There is also a strong argument to suggest
that in its essence, carbon dioxide storage represents a public
good or service that fulls a government function of mitigating
climate change. By storing carbon that would otherwise have
been inevitably produced in order to satisfy energy demand,
storage serves to mitigate climate change and to meet binding
emissions reduction targets that are placed upon Governments
within an EU and international legal context. Given the additional
point that carbon storage may well turn out to be a cost vs. revenue
neutral activity some easing of state aids rules/competition law
should apply. This argumentation is supported by the EC Treaty
obligation of competition law not to obstruct the performance, in
law or in fact, of the particular tasks assigned to services of
general economic interest (i.e. the provision of carbon storage for
climate change prevention and mitigation).
Thus far, leading Member State Governments have taken a
sensible approach to state aid regulation and CCS. For this
reason, it is not suggested that a formal procedure be
commenced to review the EU General Block Exemption Regulation or Guidelines for State Aid for Environmental Protection562 with the aim of codifying new principles and rules in
respect of CCS. This would constitute a drawn-out and
cumbersome process. Given the history of CCS Directive negotiation, there would be further uncertainty about the result and
Member States and non-State interests that are without direct
and active interests and projects in the eld of CCS would still
be in a position to inuence the outcome in a manner that may
not best serve Member States and private sector actors that wish
to advance CCS technology. There is also the observation that
the revision of EU state aids regulation and guidance for CCS
should have taken place at a time that was commensurate with
the creation of the CCS Directive. Re-opening the debate would
only lead to further market uncertainty at a time when the CCS
Directive is just now being enforced.
17.5
The UK regulatory response
Legislative developments at European level have created a

regulatory framework for oshore CCS within the European
Community, whilst amendments to the London Protocol on the
Prevention of Marine Pollution by the Dumping of Waste and
Other Matter (1972) and the Convention for the Protection of
the marine Environment of the North-East Atlantic (OSPAR
Convention) to allow for sub-seabed geological storage, provide
an international regulatory dimension. Whilst supporting the
amendments to the London Protocol and OSPAR Convention in
2007, UK announced a competition for funding a full-scale
demonstration project.
The Energy Bill was unveiled in 2008 which detailed a
framework for the licensing, enforcement and registration of
CCS. The Department for Business, Enterprise & Regulatory
Reform (BERR) expected that the Bill would provide a sound
system, which would enable private sector investment in CCS
projects and along with the Planning and Climate Change Bills,
ensure legislation that underpins the long term delivery of our
energy and climate change strategy. Creative legislative solutions in addition to the provision of nance will need to operate
in tandem if rst-mover gains in the emerging CCS industry in
the UK are to be won in the CCS eld.
17.6
The Energy Act 2008563
In summary, the Energy Review of 2006 concluded that should

it be proved that CCS is cost eective, the next stage would
need to be commercial demonstration. In Budget 2007, the
Government announced a competition to design and build
full-scale demonstration of CCS projects and it was launched
in November 2007. The Energy Act 2008 established the
enabling provisions for regulating oshore CO2 storage in the
UK in November 2008. Furthermore, consultation on the
proposed oshore CO2 licensing regime, including dra
regulations to implement that regime was done in September
2009.
The Energy Act introduces a regulatory framework for the
licensing of the oshore storage aspect of CCS. Furthermore,
the Act states that there is a right of the Crown to have sole
jurisdiction from the UK coast line for up to 200 miles out to sea
(the so-called Exclusive Economic ZoneEEZ) in relation to the
storing of gas. The Government may also designate Gas
Importation and Storage Zones within the EEZ. For operators
seeking to undertake CCS activities within the newly designated
EEZ, a lease and presumably a rental payment will be required
from the Crown Estate. According to this Act, all natural
resources belong to the coastal state (i.e. the UK) including
storage space under the sea bed.
The Act also provides a regulatory regime for CO2 storage for
certain relevant existing oshore oil and gas legislation. For
example, the oil and gas installation decommissioning regime
found in the Petroleum Act (1998) will be applied to facilities
used for CO2 storage. The licensing regime also regulates
storage in depleted and partially depleted hydrocarbon elds
under the sea bed and in non-hydrocarbon geological features,
such as deep saline formations.
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A regime based upon licensing is introduced and requires a

licence from the relevant authority for activities relating to the
storage of CO2 (with a view to its permanent disposal).
According to the Act, the Secretary of State or the Scottish
Ministers grant a licence that may also attach a set of particular
requirements for a specic applicant. The licence may include
provisions relating to nancial security in respect of future
obligations, as well as obligations between the closure of an
installation and the termination of a licence.
The Act also introduces a detailed section about the
enforcement of licences and criminal oences and sanctions
when activities are undertaken without a licence or where a
licence holder fails to abide by its prescribed conditions. The
1998 Act also prescribes detailed plans and approvals that
require persons seeking to abandon an installation oshore to
provide an abandonment programme which sets out the
measures proposed to be taken in connection with the abandonment of an oshore installation or submarine pipeline.
17.7
Energy Act 2010564
This legislation implements elements of: The UK Low Carbon

Transition Plan a national strategy for climate and energy.
This Plan will deliver emission cuts of 18% on 2008 levels by
2020 (and over a one third reduction on 1990 levels) on the way
to achieving a reduction of at least 80% by 2050. The Plan makes
it clear that we need to cut emissions in a way that helps the
sustainable development of our economy, society and environment. This means keeping energy supplies safe and secure,
maximising economic opportunities and protecting the most
vulnerable consumers.
17.7.1 Carbon capture and storage and decarbonisation.
The Energy Act 2008 forms a nancial incentive to support four
CCS demonstration projects on power stations which are being
powered by coal through a levy mechanism on electricity
suppliers. In addition, according to the Act, the Government is
required to prepare regular reports on the progress that has
been made on the decarbonisation of electricity generation in
UK and the development and use of CCS.
17.7.2 Schemes for reducing fuel poverty. The energy
suppliers have been forced by this Act to reduce the price of fuel
for vulnerable consumers in order to reduce fuel poverty when the
Voluntary Agreement with the energy suppliers ended in 2011. A
fundamental part of these schemes is social price support, which
comes in the form of an electricity bill refund to certain groups of
people that are more vulnerable in comparison with others.
17.7.3 Regulation of gas and electricity markets. This part
of the Act claries the responsibilities of Ofgem with respect to
climate change, protecting consumers and increasing energy
security. The Energy Act 2010 gives more authority to the
Secretary of State to introduce a Market Power Licence Condition for electricity generators that will make it easier for Ofgem
to address certain issues arising from the exploitation of market
power where there are constraints on the amount of electricity
that can be transmitted.
For instance, the Secretary of State has the power to modify
supply licences so that it can be made certain that suppliers will
Review
let their consumers know about any potential changes to their

contract in terms of pricing or any other changes as such within
a certain period of time.
17.8 The storage of carbon dioxide (licensing etc.)
regulations 2010565
These Regulations introduce a permitting regime for oshore
CCS activities under the authority of Energy Act 2008. Furthermore, they set out a range of requirements that operators need
to full in order to obtain a storage site permit from the
Secretary of State. The Regulations cover the conditions for
granting licences and exploration permits, obligations of the
storage operator, closure of the storage site, post-closure period,
and nancial security.
17.9
Environmental Permitting (EP)566
The EP Regulations 2010 comprise a common set of denitions,

processes and controls for the permitting of specied activities
to prevent pollution. In doing so, it has rationalised various
permitting regimes into a common framework that is easier to
understand and use. For example, it only requires businesses to
have one permit instead of several permits for activities falling
under the regulations on one site and by doing so, it allows the
regulators to focus recourses on higher risk activities.
Four amendments were made to the EP Regulations 2010
and took eect in 2011. The rst two amendments arise from
the need to transpose certain parts and provisions of the CCS
directive. The third amendment is in respect to oshore CCS
activities, and the nal amendment is regarding the gas
produced by anaerobic digestion plants.
17.10
Liability implications and developments in the USA
The proposed license is very similar to the licences granted to

the petroleum production industry. The licence wouldsubject
to specic consent for drilling of any wellpermit the
conduction of intrusive exploration. Furthermore, it expresses
time limited rights to apply for storage permits which would
allow site operators to construct storage facilitiesincluding
oshore facilitiesin order to store the liqueed CO2. Moreover, the licence provides the necessary framework to demonstrate the legal obligations that site operators have with respect
to ensuring the safe/secure containment of CO2 under geological formations, decommissioning the site aer use and the
monitoring of the stored materials behaviour during and aer
the completion of storage operations.
Interestingly, the US Environmental Protection Agency has
adopted a more exible regulatory approach. It has nalised
requirements for CCS through the development of permitting
for a new class of storage wells (Class VI) to be used specically
for geological storage of CO2. The EPA has proposed a default
50-year time-frame for CCS liability with the provision that the
acting EPA Director may shorten or lengthen that period based
on risk data gathered during the permitting process. Additionally, this new permitting system will allow for nancial guarantees for CCS to be chosen from a variety of dierent options
View Article Online
Review
which would allow for greater market competition and rapid

deployment of lower-cost solutions in the CCS industry.
Complementing this approach, as of 27 March 2012, New
Source Performance Standards567 (NSPS) addressing carbon
emissions are to be applied to new and, rather confusingly,
existing power plants. No new standards have yet been set for
existing power plants. Although it is anticipated that the
majority of new power plants that will become operational are
natural gas combined cycle plants, new coal-red power plants
could meet the NSPS by capturing and permanently sequestering their GHG emissions using CCS technologies. Under the
regulations, plants would have the exibility to phase in CCS
using a 30-year emissions average. This would allow for both
improvements to CCS technology equipment to be introduced
at the plant or to delay implementation until aer plant
construction when CCS technologies become more ubiquitous
and technology investment costs are at the right level.
18.
Conclusions
Carbon capture and storage is a key climate change mitigation

technology and is currently in the process of being demonstrated worldwide. There exist a large number of dierent
technologies for CO2 capture, ranging from currently available
technologies such as amine-scrubbing through to 2nd or 3rd
generation technologies with potentially superior thermodynamics, such as chemical or carbonate looping. Safe and secure
CO2 storage has been demonstrated, and is still being demonstrated, at a number of sites across the world, with multi-year
injections of around 1 Mt per year at a number of sites. Total
CO2 storage capacity is also being proven, but will be sucient
for many years of CO2 emissions. In addition, CO2 is regularly
transported safely in pipelines across large parts of the USA and
Canada.
A number of technologies have been proposed which would
potentially allow CO2 to be captured directly from the air, or to
utilise captured CO2 to produce useful products. Extreme care
should be exercised when evaluating the climate benets and
scalability of such processes.
The nancial case for CCS requires that it operates in a
exible manner, load-following ability is extremely important to
the long-term economics.
Acknowledgements
PSF thanks the RCUK Energy Programme and Engineering and
Physical Sciences Research Council for support under EP/
K000446 and Matt Boot-Handford for a PhD studentship
under EP/I010912/1. Joseph Yao thanks the Grantham Institute
at Imperial College for their support.
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Carbon capture and storage update

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Cite this: Energy Environ. Sci., 2014, 7,

M. E. Boot-Handford,a J. C. Abanades,b E. J. Anthony,c M. J. Blunt,d S. Brandani,e

Received 12th July 2013

economic and legal aspects of CCS.

Department of Chemical Engineering, Imperial College London, South Kensington,

Instituto Nacional del Carb

Energy and Resource Technology Centre, Craneld University, Craneld, Bedford,

Department of Earth Science and Engineering, Imperial College London, South

Chalmers University of Technology, 412 96 Goteborg, Sweden

McKetta Department of Chemical Engineering, The University of Texas at Austin,

130 | Energy Environ. Sci., 2014, 7, 130189

able to vary their output in response to changes in demand (or

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looping and calcium looping, together with low-temperature

Current power generation

Despite recent global economic turmoil leading to appreciable

This journal is The Royal Society of Chemistry 2014

Energy & Environmental Science

Developments in amine scrubbing

CO2 capture by post-combustion chemisorption relies on the

Energy Environ. Sci., 2014, 7, 130189 | 131

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Energy & Environmental Science

Theory12,13 (SAFT) for potentials of variable range14 (SAFT-VR)

The process technology using 30 wt% monoethanolamine

132 | Energy Environ. Sci., 2014, 7, 130189

Fig. 1 gives an example of a second generation, optimised

Overall energy performance

2.3.1 Reboiler heat duty. The measured and projected

The compression work was estimated by a regression of

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Energy & Environmental Science

Fig. 2 Reboiler heat duty for amine scrubbing on coal-red power

Fig. 3 The total energy requirement for amine scrubbing to separate

come easily. A typical coal-red power plant produces about

This journal is The Royal Society of Chemistry 2014

Features of second-generation processes

2.4.1 Absorber operating T and intercooling. In processes

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Energy & Environmental Science

2.4.3 Advanced stripper conguration. A number of

Solvent selection for energy performance

Three aggregated properties of solvents are related to energy

This eect of thermal swing depends on the temperature of the

where PH2O is the vapour pressure of water at Tmax and PCO2 is

As reviewed by Freeman45 and Rochelle,46 the piperazine or

Energy properties of amine alternatives49

134 | Energy Environ. Sci., 2014, 7, 130189

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Normalised capacity capacity/(m/10)0.25

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The capacity and viscosity of the solvent are reected in the