Carbon Capture and Storage Update - Energy and Environmental Sciences
Carbon Capture and Storage Update - Energy and Environmental Sciences
Carbon Capture and Storage Update - Energy and Environmental Sciences
Environmental
Science
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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)-fired 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,
available in the short and long term, and their technological maturity, before discussing CO2 transport
Received 12th July 2013
Accepted 13th September 2013
and storage. Current pilot plants and demonstrations are highlighted, as is the importance of optimising
the CCS system as a whole. Other topics briefly 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.
130 | Energy Environ. Sci., 2014, 7, 130–189 This journal is © The Royal Society of Chemistry 2014
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looping and calcium looping, together with low-temperature higher base-load efficiency – in the range of 48–52%.5 Super-
sorbents, as exemplars of CCS technologies which might be critical power plants operate with steam parameters in range
commercialised within 10–20 years, (solvent scrubbing and of 240 bar/600 C and ultra-super critical plants which operate
oxyfuel potentially being commercialised towards the begin- in the range of 350 bar/700 C/720 C or higher are under
ning of the period, with the other technologies towards the development.
end, though we have included ionic liquids as a natural However, owing to the relatively high-priced materials
adjunct to solvent scrubbing even though these solvents are required for their construction, the capital cost associated with
unlikely to be commercialised within 20 years). Of course, supercritical power plants is relatively high6,7 and this is an
there are other technologies (such as membranes) which active area of on-going research.
could also be considered, but are not covered here. We then For example, Yamamoto et al.8 reported the application of
move on to discuss a number of technologies that are either heat resistant material of high creep rupture strength and high
more niche or are further away from commercialisation (CO2 oxidation resistance up to 650 C, which have already been
utilisation through mineralisation or in direct production of developed for boilers and turbines of ultra-supercritical power
useful products). Transport of CO2 is then discussed, prior to plants. Viswanathan5 discussed the materials for ultra-
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storage. We then discuss the critical overarching themes: supercritical (USC) plants to withstand operating steam condi-
systems integration and policy design and implications for tions up to 760 C temperature and 35 MPa pressure, which are
investment. under development.
Throughout this paper, where efficiency penalties are
quoted, it should be noted that they are relative to a power 2. Developments in amine scrubbing
station which will have an underlying thermal efficiency of
between 40 and 60%. This means that an efficiency penalty of 2.1 Thermodynamic context
(say) 5% requires an increase in fuel-burn of 10% in order to CO2 capture by post-combustion chemisorption relies on the
produce the same amount of electricity. 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 interfa-
1.1 Current power generation cial phase equilibrium in addition to speciation in liquid phase
Despite recent global economic turmoil leading to appreciable and the enthalpy of absorption. Consequently, appropriate
reductions in global demand for oil and gas, demand for coal selection of a physical property model is of prime importance
has if anything signicantly increased in the period since 2005. for the correct modelling of CO2 capture processes.
In 2010, world coal demand was approximately 5000 million In the context of CO2 capture, aqueous alkanolamine solu-
tonnes of coal equivalent (Mtce). Under the IEA’s “Current tions are an extremely complex solution of molecular species,
Policies Scenario”, this is projected to grow to 7500 Mtce by electrolyte species and reaction products and, on certain time
2035. It is worth noting that the entirety of this growth (in all scales, reaction intermediates. The physical property model
scenarios) occurs in non-OECD countries. The share of global must be applicable to all phases and chemical equilibria for a
coal market arising from the non-OECD countries is expected to wide range of thermodynamic states. Several thermodynamic
rise from 66% to 82%.4 models have been used in the literature to represent the
Power generation is heavily dependent on coal-red plants absorption of acid gases in alkanolamine solution, and they can
throughout the world; in 2008, 41% of total global electricity be classied as one of three types: empirical models, equation
was obtained by coal combustion (corresponding to 8273 of state approaches and excess Gibbs energy approaches.
TWh). While this share is expected to drop to 32% by 2035 Empirical models are based on empirical mathematical
(corresponding to 11 200 TWh), coal remains the dominant relations, rather than theoretical considerations. Vapour-liquid
source of energy globally, with non-OECD demand doubling in equilibria (VLE) and chemical equilibria are represented in
the period to 2035. OECD demand for coal is expected to drop these models by tting numerical parameters on experimental
by as much as 33%—a result of a renewed “dash-for-gas” data. The resulting correlations, such as that of Gabrielsen
arising from the exploitation of reserves of shale gas (and other et al.9 for the partial pressure of CO2 as a function of the liquid
unconventional sources) and policies encouraging the reduc- phase CO2 loading, are oen easy to implement. However, as
tion of the carbon intensity of power generation.4 Conventional with all correlations, owing to their lack of theoretical under-
or so called “sub-critical” coal-red power generating plants pinning, they are typically unsuitable for predictive calculation
operate with low thermal efficiency (30–45%), which in turn or extrapolation.
incurs signicant fuel costs. This large fuel requirement will in Equations of state can be used to represent both liquid phase
turn increase exposure to fuel price volatility, thus increasing and gas phases (including electrolytes). Heterogeneous
the investment risk associated with this technology. For these approaches, using the excess Gibbs energy to obtain activity
reasons, sub-critical power plants are expected to displaced by coefficients in the liquid phase. These models typically need to
super-critical and ultra-supercritical power plants, reducing be coupled with a separate model to describe the gas phase; this
their market share from 73% in 2008 to 31% in 2035.4 Super- is oen a cubic equation of state. Homogeneous approaches are
critical power plants are considered to be a promising option based on the Helmholtz energy; such as the formulation of
for future coal-based power generation as they operate with Furst and Renon.10,11 Recently, the Statistical Associating Fluid
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Theory12,13 (SAFT) for potentials of variable range14 (SAFT-VR) Fig. 1 gives an example of a second generation, optimised
has been applied to aqueous mixtures of amines15 and alka- process for CO2 capture by amine scrubbing using 8 molal (m)
nolamines16,17 and CO2. This new approach provides an implicit piperazine (PZ).38,39 Compared to 30 wt% MEA it has twice the
treatment of the chemical reactions and ionic speciation in rate of CO2 absorption, 1.8 times the intrinsic working capacity,
these complex mixtures. Importantly, although the reaction 5 to 10% lower heat of absorption (a disadvantage), and a
products are also treated in an implicit fashion, it is possible to maximum stripper T/P of 150 C/8 bar.40
obtain an accurate description of the equilibrium carbamate/ In addition to the absorber, the process would probably
bicarbonate products.17 As a consequence, when these ther- include SO2 polishing with sodium alkali scrubbing and direct
modynamic models were incorporated in process models3,18 it contact cooling of the ue gas before the PZ absorber. It
was not necessary to describe the reaction products in the would also usually include a water wash and aerosol removal
process model, nor was an enhancement factor required to aer the absorber. Much of this additional ue gas contacting
describe the accelerating effect of the reactions on the mass could be incorporated into the same vessel as the CO2
transfer. This had the effect of signicantly reducing the size of absorption.
the process models and consequently it was possible to use
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these detailed dynamic, non-equilibrium models to perform 2.3 Overall energy performance
optimisation19 and control20 studies. It is noteworthy that the
2.3.1 Reboiler heat duty. The measured and projected
SAFT approach has been coupled with classical density func-
reboiler heat duty for CO2 capture from coal-red power plants by
tional theory approaches and has been used to predict vapour–
amine scrubbing has improved from as high as 5.5 MJ tCO21 in
liquid interfacial properties21 and the so-SAFT variant22 has
2001 to as little as 2.6 in 2012 (Fig. 2). Early estimates used 20 wt%
also been used to describe the thermophysical properties and
(MEA) with a simple stripper and absorber. Current systems assume
phase behaviour of ionic liquids in the context of CO2 capture.23
35 or 40 wt% MEA or other advanced amines with interheated
The third class of models uses the excess Gibbs energy to
strippers and intercooled absorbers or other comparable process
compute activity coefficients; they are oen based on already-
improvements. With a Carnot cycle analysis, the minimum heat
existing models for nonelectrolyte systems and extended with
duty to separate 12% CO2 in ue gas and produce pure CO2 at 1 bar
the Debye–Huckel theory to address electrolyte species. The
is 1 MJ t1. Therefore, the overall thermodynamic efficiency of the
model by Deshmukh and Mather24 is one of the simpler models,
separation process is approaching 40%.
and parameters have been regressed for some amines25 it
2.3.2 Equivalent work. Improvements in solvents and
assumes ideality for water and calculates the activity coefficient
processes have reduced the estimated equivalent work to
for diluted species with a virial term for interaction between
separate CO2 from coal-red ue gas from 450 kW h tCO21
species. The model by Pitzer26 is quite similar and has been used
removed in 2001 to as little as 200 kWh t1 in 2012 (Fig. 3).
to represent the solubility of CO2 in aqueous methyldiethanol-
These values include CO2 compression to 150 bar and usually
amine (MDEA) and piperazine (PZ).27 Among the more elaborated
include pump work and fan work. The work value of the reboiler
models using the local composition of the mixture, the
duty was estimated from a: Carnot efficiency based on the
electrolyte-NRTL (e-NRTL) and extended UNIQUAC (e-UNIQUAC)
reboiler temperature (Treb, C) and assuming a 75% turbine
models prevail. The e-NRTL model28,29 has been extensively used
efficiency, a reboiler approach T of 5 C, and a sink temperature
for CO2 absorption characterisation.30,31 The extended UNI-
of 40 C:41
QUAC32 provides the same theoretical basis as e-NRTL, with a
simpler formulation, and it has already proved its ability to Treb þ 5 40
Weq ¼ 0:75Qreb (1)
represent the alkanolamine system for CO2 absorption.33 Treb þ 5 þ 273
The development of amine scrubbing has been focused on its
The compression work was estimated by a regression of
application to coal-red power plants. Unless otherwise noted,
results from Aspen modelling of an multistage compressor with
the data and discussion on amine scrubbing that follows are
intercooling to 40 C:41
based on the application to coal-red power plants. However, 8
amine scrubbing should be useful for other applications. >
> 150
< > 4:572 ln 4:096 Pin # 4:56 bar
kJ Pin
Wcomp ¼
mol CO2 >
> 150
2.2 Process owsheet >
: 4:023 ln 2:181 Pin . 4:56 bar
Pin
The process technology using 30 wt% monoethanolamine (2)
(MEA) that has been evaluated by NETL34 to give a baseline for
the solvent scrubbing process can no longer be used as a The improvements include thermally stable solvents such as
representative baseline for post-combustion capture. A number piperazine, that can be stripped at 150 C to produce CO2 at 8
of vendors, including Fluor35 and MHI36 have developed bar. Rochelle et al.40 present estimates of thermodynamic effi-
processes and completed evaluations that give energy perfor- ciencies for other common separation processes: desalination
mances substantially better than that reported in the NETL by reverse osmosis – 21%, distillation – 14 to 35%, and air
analyses. In addition, a recent paper by Ahn et al. has illustrated separation – 25%. Since the minimum work for this separation
all the different types of owsheet congurations for the amine is about 110 kWh t1, it is improbable that further improvement
scrubbing process.37 from the current thermodynamic efficiency of about 50% will
132 | Energy Environ. Sci., 2014, 7, 130–189 This journal is © The Royal Society of Chemistry 2014
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Fig. 1 Intercooled Absorber/Interheated stripper with 8 m PZ. Stripper bottom at 150 C/7.9 bar. Weq ¼ 30.5 kJ mol1 CO2 ¼ 193 kW h per tonne CO2.
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2.4.3 Advanced stripper conguration. A number of This effect of thermal swing depends on the temperature of the
stripper congurations are available to minimise the loss of reboiler which is limited by the thermal degradation of
heat as water vapour. The interheated stripper is the best of the solvent. In previous work Tmax has been dened
these (Fig. 3).41 Other congurations that work almost as well as the temperature where the degradation rate constant is
include adiabatic ash with compression,41 cold rich bypass,41 2.9 108 s1, the same as that of 30% MEA at 120 C.45,46 A
matrix,42 two-stage heated ash,41 and multipressure.43 The quantitative measure of the effects of the heat of absorption and
interheated stripper uses 10 to 20% less energy than a simple Tmax is the estimated reboiler pressure with a representative
stripper.38 With an interheated stripper, less than 20% of the lean solvent, assumed to be saturated at 40 C to 0.5 kPa CO2
overhead vapour is water. Therefore, anhydrous solvents or given by the expression:
sorbents will not signicantly reduce the heat requirement by
avoiding the vaporisation of water. Pmax ¼ PH2O + PCO2 (3)
2.4.4 Reversible stripping. When the lean loading (or
where PH2O is the vapour pressure of water at Tmax and PCO2 is
solvent ow rate) is optimised to minimise energy consump-
tion, there is a tradeoff of sensible heat loss at high solvent rate given by:
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(high lean loading) and stripping steam use at low solvent rate
PCO2 ¼ 0.5 kPa exp((DHabs/R)(1/Tmax 1/313)) (4)
(low lean loading). With a close exchanger approach T (5 K), the
stripper typically only removes enough CO2 from the rich As reviewed by Freeman45 and Rochelle,46 the piperazine or
solvent to leave the maximum lean loading that allows for piperazine derivatives have been identied as solvents with the
adequate CO2 removal.40 An intercooled absorber using a greatest value of Tmax, resulting in greater values of Pmax. Many
solvent with a fast rate of CO2 absorption (such as 8 m PZ) amines have lower values of Tmax because they degrade by
should be able to achieve 90% CO2 removal with a lean loading formation of cyclic urea or by dimerisation through an
that gives an equilibrium CO2 partial pressure of 0.5 kPa at 40 oxazolidinone.46
C and a rich loading that gives an equilibrium CO2 partial Solvents with a low heat of absorption (<60 kJ mol-1) will not
pressure of 5 kPa at 40 C.44 Therefore, the difference between be competitive.42 These include systems relying on sodium or
the CO2 loading at these rich (5 kPa CO2 at 40 C) and lean (0.5 potassium carbonate and tertiary or hindered amines with
kPa at 40 C) conditions will give a useful estimate of the lower pKa values.
working capacity of the solution. Although vacuum stripping works with solvents that have a
low heat of absorption, it is not energetically competitive
2.5 Solvent selection for energy performance because of the additional compression work for the CO2.41,42
Three aggregated properties of solvents are related to energy A number of investigators are developing systems that
performance. These are summarised in Table 1 for a number of increase the effective heat of absorption by precipitating solids
potential solvents. out of the rich solution.47,48 One such system uses aqueous
2.5.1 Heat of absorption/Tmax/Pmax. Because amine scrub- potassium carbonate with precipitation of potassium bicar-
bing relies upon thermal swing regeneration, a greater heat of bonate. These processes will ultimately have to deal with the
CO2 absorption always provides reduced energy consumption.40 reliability issues posed by precipitating slurries.
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2.6 Normalised capacity – capacity/(m/10)0.25 device. The value of kg0 at an average loading is given for a
number of solvents in Table 1.
The capacity and viscosity of the solvent are reected in the
Piperazine or piperazine derivatives provide the greatest
sensible heat requirement of the stripper, given by:
values of kg0 . Secondary or primary amines are usually necessary
kJ Cp DT to provide an acceptable rate of CO2 absorption. Tertiary amines
Qsensible ¼ (5)
mol CO2 C and hindered amines are usually too slow to be used by
where Cp is the heat capacity of the solvent (kJ kg(H2O + themselves.
amine)1 K1), DT is the hot side approach T of the cross Several investigators are developing carbonic anhydrase
exchanger, and C is the capacity of the solvent (mol CO2 enzymes to catalyse the CO2 kinetics in otherwise slower
kg(H2O + amine)1). solvents.53,54 Unfortunately they have not yet developed
One quantitative measure of the intrinsic solvent capacity is enzymes that are effective at elevated T (>100 C). Furthermore,
the difference between the equilibrium CO2 concentration at the enzymes are most effective in tertiary amines and
40 C at 5 kPa CO2 and the equilibrium concentration at 40 C at carbonate solutions with low heats of CO2 absorption. These
0.5 kPa. These values allow for a reasonable driving force to systems will probably not be energetically competitive with
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provide 90% CO2 removal at conditions of coal-red power other second generation amine solvents that can be regen-
plants. These convenient units of capacity reect the general- erated at 120 to 150 C.
isation that the effective partial molar heat capacity of CO2
loading is typically near zero. 2.8 Solvent management
Greater solvent viscosity reduces the heat transfer coefficient
in the cross-exchanger. The optimum exchanger design will 2.8.1 Oxidative degradation. Monoethanolamine oxidises
result in a greater approach DT with a greater viscosity. There- at absorber conditions with catalysis by dissolved iron and
fore, it is appropriate to weight the intrinsic capacity by the manganese.55 This oxidation rate seems to have been econom-
viscosity to the 0.25 power, as reected in the normalised ically and environmentally acceptable in previous systems.35
capacity given in Table 1, capacity/(m/10)0.25.49 However, it is a nuisance and may be environmentally unac-
A number of amine systems provide greater normalised ceptable in larger systems. Inhibitors have been identied that
capacity than 7 M MEA. Hindered and tertiary amines usually are effective at absorber conditions.55 These additives appear to
provide greater capacity because their intrinsic stoichiometry degrade or are ineffective when used in cyclic systems with
requires only 1 mol amine mol CO21, as opposed to two for the elevated T representative of strippers.56
MEA system. As shown in Table 1, methyldiethanolamine, (a A number of amines are resistant to oxidation at absorber
tertiary amine) with piperazine and aminomethylpiperazine (a conditions, including piperazine, tertiary amines, and hindered
hindered amine) with piperazine are quite competitive. Greater amines. Tertiary amines appear to be oxidation inhibitors when
capacity is also provided by diamines such as piperazine used in blends with other amines. MDEA is effective in inhib-
because more equivalents of amine can be loaded into the iting the oxidation of MEA at absorber conditions.56,57
solvent before the viscosity becomes unacceptable. However, Closmann56 and Voice57 have shown in bench-
A number of researchers are investigating systems that scale experiments that even resistant amines are subject to
precipitate solids or separate a lean amine organic phase from reaction with dissolved and entrained oxygen that is carried
the rich solvent.50–52 These phase change systems will usually into the high temperature of the cross-exchanger. This oxida-
provide greater capacity, but they must deal with the reliability tion rate depends on the solubility of oxygen in the solvent
issues posed by precipitating slurries or two-phase systems. 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
2.7 Rate of CO2 absorption, kg0
CO2/H2O.
Because the optimisation of the absorber design will require 2.8.2 Other ue gas impurities. Coal-red ue gas contains
lower rich and lean loading to achieve 90% CO2 removal with a a number of impurities that impact processes for post-
reasonable amount of packing, the rate of CO2 absorption is an combustion capture. Existing plants that treat coal-red ue
important energy parameter of the solvent. A fast rate of CO2 gas include gas pretreating with sodium alkali scrubbing to
absorption facilitates reversible absorber performance at high remove practically all of the SO2, HCl, and coarser yash. This
rich and lean loading that will minimise energy use in an pretreating would not be expected to remove NOx, Hg, submi-
optimised system. CO2 typically absorbs by the process of cron y ash, and submicron H2SO4 aerosol.
diffusion with fast reaction in the boundary layer. The nor- 2.8.3 Nitrosamines. Secondary amines will combine with
malised absorption ux of CO2 (kg0 , mol m2 Pa1) is given NO2 in the inlet ue gas to produce nitrosamines that may
approximately by: create environmental risk in spills of disposal of spent solvent.
pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi It is probable that NO2 in the absorber inlet will be mostly
0 Flux kam ðamineÞDCO2
kg ¼ ¼ (6) absorbed by reaction with secondary and tertiary amines to
PCO2 ;i P*CO2 ;b HCO2
produce nitrite.58 At 100 to 150 C in the stripper, nitrite reacts
kg0 is a property of the amine, and not of the absorber contacting with secondary amines to quantitatively produce nitrosa-
device. It can be measured in a wetted wall column or similar mines.58 At 150 C, nitrosopiperazine thermally decomposes, so
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it will reach a steady-state concentration where the rate of Amine scrubbing for CO2 capture from natural gas is
decomposition is equal to the rate at which NO2 enters the commercially available. Since 1980, dozens of plants have
absorber. Pilot plant data with piperazine-based solvent suggest captured CO2 from combustion of methane or other clean fuels.
a steady-state concentration of about 1 mM nitrosopiperazine at Most are based on technology provided by Fluor (MEA, Econo-
typical power plant conditions using a stripper at 150 C.59 This mine) or MHI (KS-1). The Fluor applications include a 70 MWe
steady-state concentration will increase at lower stripper T and gas-red boiler and a gas-red turbine with a ue gas rate
with ue gas containing more NO2, so other solvents and equivalent to 80 MW of a coal-red boiler.
conditions may experience greater steady-state concentration. Two public databases demonstrate that amine scrubbing is
Amine solvents that do not include secondary amines may still near commercial on coal-red power plants.75,76 More than 25
be subject to this reaction with oxidative and thermal degra- pilot plants have tested amine absorption/stripping on coal-
dation product of the primary or tertiary amines that make up red ue gas at 0.1 to 5 MWe. Seven prototype systems have
the solvent.60 Nitrosodiethanolamine has been found in mon- been operated at 10 to 33 MW with coal-red ue gas and
oethanolamine solvent.61 UV treating is being tested as a compression of the CO2. There are no larger plants operating on
method to selectively decompose nitrosamine in amine coal-red gas, but one is under construction at 120 MW and
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solvents.62–64 The volatility of the nitrosamine is expected to be another eight plants at 140 to 765 MW in various states of
comparable to that of the parent amine.58 Any gaseous emis- planning, permitting, and FEED.
sions of nitrosamine should also be quickly decomposed by UV
exposure in the atmosphere. Therefore, air emission of nitro-
samine should pose negligible risk.65 2.10 Conclusions
2.8.4 Amine volatility Advanced amine systems will capture CO2 with heat duty less
Vapour losses. Because practical amines usually include at than 2.7 MJ tCO21 and equivalent work less than 250 kWh
least two or more hydrophilic groups such as amine, alcohol, or tCO21 (including compression to 150 bar).
ether, residual amine volatility at the top of the stripper can be The innovations contributing to reduced energy use include:
managed to less than 1 ppm by a water wash. Nguyen66 (1) Thermally stable amines such as 8 m piperazine that can
measured amine volatility in water and showed that two or more be regenerated at elevated pressure.
hydrophilic groups usually produce an amine volatility less than (2) Effective plate-and-frame cross exchangers and high
100 ppm at absorber lean conditions. In solutions loaded with capacity solvents such as PZ/MDEA and PZ/AMP.
CO2, diamines such as piperazine are substantially less volatile (3) Congurations such as the interheated stripper that
because of speciation to ions including protonated amine and effectively recover heat from the stripper overhead.
carbamate.67 Hindered amines and tertiary amines with methyl (4) Fast amines such as piperazine and absorber intercooling
groups tend to have greater volatility. Aliphatic monoamines that provide more reversible absorber operation with greater
without other polar groups have unacceptable volatility. rich and lean loading.
Several investigators68 have been developing systems with (5) Amines with high heat of CO2 absorption that maximise
amino acids (partially neutralised by K+) which should be the energy performance of thermal swing regeneration.
nonvolatile ions. Other vendors may be using amines such as
hydroethylpiperazine with three or more hydrophilic groups Remaining issues of secondary environmental impact with
that have practically no volatility and may not require a water advanced amines have acceptable solutions:
wash. (1) Amine oxidation can be minimised by using amines such
Amine aerosols. Vapour amine may condense in the absorber as piperazine and MDEA that are resistant to oxidation and by
on submicron hydrophilic aerosol or particulate to produce stripping dissolved oxygen at <100 C.
small aerosol drops that are not removed by typical contacting (2) Nitrosamines can be managed by avoiding secondary
internals in the absorber or water wash.69 Several pilot plants amines or by thermal or UV decomposition.
have reported amine emissions as high as 200 ppm from pilot (3) Vapour losses of amine can be avoided by water wash with
plants with 1 to 3 ppm SO3 in the inlet ue gas.70–73 The resulting volatile amines or by using non-volatile amines.
aerosol can be effectively removed by a bre lter mist elimi- (4) Amine aerosol losses can be eliminated by a bre lter.
nator 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 3. Ionic liquids as alternative solvents
acid with low or no volatility. for CCS
It has been suggested that the use of ionic liquids (ILs) as
2.9 Development status alternative solvents would have many advantages over conven-
Since 1930, hundreds of plants have used amine scrubbing to tional amine-based CO2 extraction. The general area of IL use
remove CO2 from hydrogen, natural gas, and other gases that for CCS has been reviewed recently.77–84 In addition to a
contain little oxygen. The plants use monoethanolamine, potentially lower demand for energy in the solvent regeneration
diethanolamine, MDEA/PZ, and a number of second and third step, ILs have lower volatility, lower vapour pressure, are non-
generation solvents. ammable, are more thermally stable, and are easier to recycle.
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The comparison of ILs with molecular organic solvents has Table 2 Henry’s Law constants for CO2 in selected ILs. Data is taken
been discussed in a recent review3 and also discussed the general from Muldoon et al.85 [eFAP] ¼ tris(pentafluoroethyl)tri-
fluorophosphate; [pFAP] ¼ tris(heptafluoropropyl)trifluorophosphate;
implications of changing the cation and anion (see Fig. 4) or
[bFAP] ¼ tris(nonafluorobutyl)trifluorophosphate; [ace] ¼ acesulfa-
employing mixtures. The recent developments in this eld will mate; [sac] ¼ saccharinate
be reviewed here, and the implications of IL physical properties
and functionalisation on CO2 solubility will also be explored. H (bar)
Cation Anion 25 C 60 C
3.1 Relationship between IL physical properties and CO2 [C4C1im] [PF6] 53.4 0.3 81.3 0.8
solubility [C4C1im] [NTf2] 33.0 0.3 48.6 0.9
Henry’s constant is a quick and useful measure of CO2 solubility [C6C1im] [NTf2] 31.6 0.2 45.6 0.3
[C6(3C1)py] [NTf2] 32.8 0.2 46.2 0.3
in ILs. Henry’s law constants for CO2 in a range of different ILs [(C6H4F9)C1im] [NTf2] 28.4 0.1 48.5 0.4
are shown in Table 2. The highest solubility of CO2 recently [(C8H4F13)C1im] [NTf2] 27.3 0.2 44.7 0.5
reported was in [C5C1im][bFAP], which contains a highly uori- [C6C1im] [eFAP] 25.2 0.1 42.0 0.1
21.6 36.0 0.3
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3.3 Conventional ILs tributylphosphonium ILs (coupled with amino acid anions)
exhibiting the best physicochemical properties, such as a low
Unfortunately, there is currently no comprehensive model for
glass transition temperatures (in the range from 69.7 to
gas solubility in ILs.97 However, some general trends can be
29.6 C) and thermal stability to above 200 C.105 The salt (2-
observed. Increasing the cation alkyl side chain length increases
hydroxyethyl)-trimethyl-ammonium(S)-2-pyrrolidine-carboxylic
CO2 solubility, likely by increasing the available volume for CO2
acid salt or [Choline][Pro] has been demonstrated to be able to
due to a decrease in cation–anion interactions.98,99 It is clear that
capture and release CO2, where CO2 is released by bubbling N2 in
there are mainly physical phenomena (such as dispersion
forces) dominating CO2–IL interactions when unfunctionalised the solution106 (of course, further measurements are necessary
ILs are employed, with only weak chemical complexes form- under a CO2 atmosphere). There is, however, some concern over
melting point changes when amino acid anions absorb CO2.82
ing.100 The enthalpy of CO2 physical absorption by these ILs is
A variety of imidazolium or tetraalkylphosphonium cations
generally about 20 kJ mol1. This results in a lower energy
have been combined with amino acid anions to make
requirement than for amine solutions in the regeneration step,
AAILs.107–109 Potential advantages of using amino acids include
but not overall: as discussed above, a lower heat of absorption
their low cost, biodegradability and low toxicity. Also, AAILs can
can lead to a higher overall energy requirement. The structural
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3.4.4 Reversible ILs. Reversible ILs, based on amidinium facilitates CO2 transport through the membrane.128 AAILs sup-
(i.e. DBU) or guanidinium alkylcarbonate salts, also show good ported on porous silica displays higher efficiency then when used
CO2 reactivity and high absorption capacity.114–119 The “molec- as a bulk liquid phase. These supported TSILs achieve 2 : 1
ular” state of the system consists of a 1 : 1 mixture of a proton IL : CO2 capture capacity through carbamate formation.
donor (i.e. alcohol) and organic base, and shows excellent CO2 However, in the presence of small amounts of water (1% by mass),
capacity and good CO2 : N2 selectivities (Scheme 1).101,120–122 the capture capacity can reach an equimolar ratio as shown in
These new ILs are interesting CO2 capture options, though the Scheme 2.129 A combination of SILMs and TSILs may be a better
higher volatility of the alcohol component may hinder deploy- choice for CO2 capture at elevated temperatures and pressures.130
ment. To avoid this, the alcohol group can be incorporated into However, there remain drawbacks, including leaching of the IL
an IL cation side chain.123 CO2 absorbances of 1.04 : 1 (relative through membrane pores when the pressure drop is higher than
to base) have been reported for this strategy, which is 20 times the liquid stabilising forces within the matrix. In order to over-
higher than the solubility in the neat IL, and can be achieved in come this limitation, polymerisable ILs as membranes could be a
under 10 min.123 CO2 release can be achieved by mild heating possible option for CO2 separation.100
(90–120 C) and the IL re-used. It should be noted that for very 3.4.7 Poly(IL)s. Poly(ionic liquid)s are a new technology for
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strong bases (e.g. MTBD, tetramethylguanidine), CO2 may CO2 capture. The absorption and desorption of CO2 by poly(IL)s
actually react with the IL cation,124 which would imply sensi- is faster than bulk ILs.131–134 Moreover, desorption by vacuuming
tivity of CO2 absorbance to H2O presence. Functionalisation of is completely reversible, though would not be energetically
the guanidines or amidines, including tethering of the alcohol viable in a power generation context. It may be that they are a
group to the base,125 may avert these difficulties. potential choice for sorbent and membrane material for CO2
3.4.5 Protic ILs. One way to overcome the high cost of separation. Fig. 6 shows CO2 absorption data for three type of
dialkylimidazolium cation synthesis is to use protic ILs, which poly(IL)s: poly[1-(4-vinylbenzyl)-3-butylimidazolium tetra-
are acid–base complexes.120 If a weak acid is employed, then a uoroborate] (PVBIT), poly[1-(4-vinylbenzyl)-3-butylimida-
strong CO2 complex can be formed, though these ILs will be very zolium hexauorophosphate] (PVBIH), and poly[2-(1-
hydrophilic. Functionalised protic ILs can dissolve large quan- butylimidazolium-3-yl)ethyl methacrylate tetrauoroborate]
tities of CO2 under anhydrous conditions; those based on (PBIMT), which are roughly analogous to polymerised versions
uorinated alcohols have been shown to capture 2.04 molar of [CnCmim][BF4]. PVBIT and PVBIH have been reported to take
equivalents of CO2, and the viscosities of these salts is relatively only 4 min and PBIMT only 3 min to reach 90% capacity, and
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 volatil-
ities and increased contact area between the gas and ILs, over-
coming 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
Scheme 2 Proposed mechanisms of CO2 capture by AAILs: (a) and (b)
contain functional groups capable of chemically complexing with
without water; (c) with water.129
CO2. They show higher selectivity in CO2 separation than [C4C1im]
[NTf2] for CO2–CH4 gas mixtures because the amine group
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around 30 min to reach their full capacities. By comparison, fuel being burned in a mixture of oxygen and recycled ue gas
monomeric BIMT and [C4C1im][BF4] required more than 400 (RFG). Unlike conventional fossil fuel-red power stations that
min to reach their equilibrium capacity. Higher capacities were use air as the oxidant, an oxy-red plant employs an Air Sepa-
also reported for the poly(IL)s, up to 2.1 times higher than ration Unit (ASU) to produce an oxygen stream. The oxygen
[C4C1im][BF4].131 However, these gures should be taken in stream is combined with RFG to produce an oxygen enriched
context with the extremely rapid reactions of solvents such as gas for the oxidant. The recycle is necessary to moderate the
MEA and PZ, described above. Studies of any new solvent, such otherwise excessively high ame temperature that would result
as ILs should compare their rates of uptake to those of standard from burning in pure oxygen. Aer the removal of water and
solvents, if the aim is to develop a replacement industrial-scale other impurities from the ue gas exhaust stream, high-purity
technology, as opposed to simply investigating interesting CO2 is produced. The combustion of fuel in an oxygen and
chemistry. They must also regenerate the CO2 under an atmo- RFG mixture was proposed in the early 1980s for the purpose of
sphere of CO2 to demonstrate reaction reversibility. Surpris- producing a high-purity CO2 stream for use in Enhanced Oil
ingly, the VBIT and VBIH monomers did not absorb CO2 Recovery (EOR)139 and for simultaneously reducing greenhouse
because of their crystalline structure, and the liquid BIMT gas emissions from fossil fuel energy generation.140 Pilot scale
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monomer had the same absorption capacity as [C4C1im][BF4],131 studies were subsequently carried out141–143 in the following
indicating that the polymeric structure itself conferred greater decades. During the last decade, the global research activity has
CO2 capacity, perhaps by lowering ion–ion interactions. Poly(IL) increased to the point where several demonstration phase
s with [PF6] anions displayed higher efficiency than [BF4] or projects have begun and the commercial concept is expected
[NTf2] based polymers and higher absorption and desorption before 2020. Oxyfuel combustion can be applied to several fuels,
rates. Interestingly, while increasing the alkyl chain length of including coal (oxy-coal combustion), natural gas or blends of
ILs signicantly increases gas permeability and diffusivity, the biomass and coal. Most interest has focused on oxy-coal
reverse trend is observed for poly(IL)s, possibly due to steric combustion due to the abundance, reliability and high carbon
hindrance.134 The efficiency of polymeric structures can also be content of the fuel. The following sections refer to oxy-coal
enhanced by modifying the monomers, such as using oligo- combustion unless otherwise stated.
(ethylene glycol) or nitrile-containing alkyl groups, though this
will complicate synthesis.87 Lower cost options, such as tri- 4.1 Process considerations
ethylene tetramine lactate, can absorb nearly 1 : 1 CO2.135
In comparison to air-red plants, the implementation of oxyfuel
Biopolymers (chitin and chitosan) also have been used in the
operation will lead to a number of plant conguration changes
process of CO2 capture. These biopolymers are environmentally
and additional unit operations, i.e. recycle loop, ASU, CO2
friendly, renewable, biodegradable and almost non-toxic. There
purication and compression. The optimum recycle ratio is
are two hydroxyl groups in chitin while there is an additional
generally 0.7; this yields oxygen levels in the oxidant environ-
amine group in chitosan. The IL [C4C1im]Cl has been used as a
ment that typically range from 25 to 30% because at these
solvent to break the strong inter- and intramolecular hydrogen
conditions, the ame and heat transfer characteristics reason-
bonds, but it cannot disrupt the crystalline domains of chito-
ably approximate those of air-red pulverised fuel (PF) boilers.
san.136 The result is that chitin–IL and chitosan–IL mixtures
Oxygen excess levels are 15–20% for air-ring conditions but are
have increased CO2 sorption capacity (8.1% higher than the IL)
kept lower for oxyfuel conditions to no more than 10% in order
under mild conditions (30 C, 1 atm CO2 pressure in CO2 xa-
to minimise ASU operational costs. Flue gas oxygen content is
tion and release processes). There are many potential environ-
typically 3%. The ue gas stream should be cooled, scrubbed
mental and performance benets from using such recyclable,
and dried before being diverted for the primary recycle. Partic-
non-corrosive and non-volatile CO2 absorption media.93,136
ulates are removed in order to avoid accumulation of solids in
the boiler and prevent the ue gas recirculation fan and gas
3.5 Molecular simulations of CO2 with ILs passages from unnecessary wear due to erosion. Several options
There have been a number of molecular simulation studies for conguration of a secondary recycle stream exist.144
focused on the dissolution of CO2 in ILs. A recent review83
highlights the most relevant advances. In conventional ILs, CO2 4.2 Energy performance
dissolves in free volume spaces within the IL matrix without Oxyfuel combustion induces an energy penalty to the process
greatly affecting the structure, accounting for the rather caused by the requirements of producing O2 and compressing
unusual solubility proles.137 This is also likely responsible for CO2. Using current technology, the overall plant efficiency is
the lower regeneration energy, as the CO2–IL interactions are reduced by 8–12%.145 However, oxyfuel combustion does allow
relatively weak. By contrast, amine–TSILs form strong chemical for process exibility and improved combustion efficiency. One
complexes with CO2, which has been studied by simulation.138 strategy to reduce the energy penalty is the use of pressurised
oxyfuel combustion cycles. An advantage of pressurised
4. Oxyfuel combustion technology systems is that the combustion power cycle utilises the higher
heating value of the fuel and produces more gross power
Oxyfuel combustion is one of the most developed technologies compared to conventional atmospheric oxyfuel combustion
for carbon capture and storage. Oxyfuel combustion refers to power systems. Elevated dew point and higher available latent
140 | Energy Environ. Sci., 2014, 7, 130–189 This journal is © The Royal Society of Chemistry 2014
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enthalpy in the ue gases lead to higher thermal energy 4.3 Pollutant emission and removal
recovery from the water in the ue gases. Pilot scale experi-
An operational benet of oxyfuel combustion is the reduction of
mental trials by ENEL have shown that pressurised
NOx and SOx emissions. Oxyfuel combustion offers highly
systems146,147 have increased heat transfer rates in the Heat
reduced NOx emissions, because NOx in the recycled gas can be
Recovery Steam Generator (HRSG), allowing the possibility of
reburned by contact with ame-generated hydrocarbons, which
burning cheaper coals and reducing the size of components,
act as a reducing agent to produce N-volatiles, consisting of
which will lead to a reduction in capital costs. The pressurised
ammonia and cyanide species that may subsequently produce
oxyfuel system is achieved by pre-compressing oxygen in the NOx or N2 depending on the conditions. Moreover, as nitrogen
ASU which leads to high pressure combustion ue gases and a from the air is largely eliminated from the process by substi-
reduction in the work duty of the CO2 compression unit.
tution with RFG, thermal and prompt-NOx formation rates are
Overall, the amount of compression work between the ASU and
highly reduced. The amount of NOx emitted per unit of energy
compression unit is reduced in comparison to conventional
generated can be reduced to around a third that of air-
atmospheric oxyfuel operation. Sensitivity studies by Massa-
ring.157–159 Recent experimental investigations of NOx forma-
chusetts Institute of Technology have determined that
tion during oxyfuel combustion of pulverised coal160,161 have
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in oxy-coal combustion.172 While the increase in Hg concen- Accurate turbulence models are required since turbulence
tration is due to the removal of diluent nitrogen, the increase in has important effects on mixing, kinetics and heat transfer with
Hg oxidation may be explained by increased chlorine concen- greater signicance under oxyfuel conditions. At present, Rey-
tration in oxyfuel combustion. Strategies to control Hg emis- nolds Averaged Navier Stokes (RANS) models are considered an
sions include injection of activated carbon sorbents or forcing acceptable compromise between accuracy and computational
oxidation to water soluble Hg2+ forms to then be removed by cost. Large Eddy Simulations (LES) are more computationally
conventional FGD scrubbing. intensive and have recently been applied to oxyfuel combus-
Air Products have developed the possibility of co-removal of tion.178 LES was found to be capable of capturing the intermit-
SOx, NOx and mercury during compression using their “Sour Gas tency effects of the coal ame and the importance of gas
Compression” technology.173 The process relies on the oxidation radiative properties was also demonstrated in the calculations.
of NO to NO2 to convert SO2 to H2SO4174 in the presence of water. As computational resources increase, more sophisticated
Mercury will dissolve and react in the nitric acid formed as a methods such as LES should replace classical turbulence
condensate. The technology is based on the “lead chamber models for CFD.
process”. Further investigations are required to determine the
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are also being investigated. In this technology, RGF is not used, expressed in terms of mg MJ1 or some similar unit, to avoid
so water or steam will act as a temperature moderator. Similarly, misleading comparisons with gas emissions from air-red units
the technology will lead to reduction in equipment size and will where pollutants are diluted with N2 from the air.
utilise novel turbomachinery that can generate power from the
expansion of steam–gas mixtures.186
5.1 Pilot plant studies
As oxyfuel combustion approaches the commercial demon-
stration stage of development, some technical uncertainties Although functioning pilot plant units are still limited in
remain, such as those related to ue gas cleaning; however, no number (as indicated in Table 3), studies are being undertaken
fundamental technical barriers have been encountered with the in numerous countries, and oxyfuel CFBC is being considered
operation of pilot and demonstration scale test facilities. The in many other industrially important countries such as Rus-
successes of demonstration projects will provide practical sia191 and Australia.192 Also, there is now an international
information and experience needed to push forward oxyfuel workshop on oxyfuel FBC, which is held annually.193 To date,
technology to commercial realisation. 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
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5. Oxyfuel CFBC necessary gas velocity and solid circulation rate in terms of heat
Until recently, the obvious route for oxyfuel combustion was via transfer requirement. CanmetENERGY in Canada currently has
conventional pulverised coal-red (PC) boiler technology as one of the most detailed and well-reported programs, based on
discussed above, and there is already one large European oxy- results from two pilot plants which are capable of being oper-
fuel PC demonstration plant, with more planned in the future ated in oxyfuel mode, with full ue gas recycle: a nominal
(see Section 4.5). However, recently oxy-red uidised bed 75 kWth unit and a larger 0.8 MWth unit. Successful runs on the
combustion (FBC) has also become increasingly important as a 75 kWth unit were achieved and reported in 2007194 and much of
potential technology offering both fuel exibility and the the emissions data195 discussed below come from this unit.
possibility of ring or co-ring biomass with CO2 capture. For
utility applications, a high velocity version of FBC, in which gas 5.2 Gas and other emissions from oxyfuel CFBC
velocities are of the order of 4 to 8 m s1, called circulating
Air-red CFBC technology normally produces low emissions of
uidised bed combustion (CFBC) is employed, and this tech-
SO2 on addition of limestone, low NOx due to its low operating
nology is available in the supercritical mode at sizes of up to 460
temperatures, low emissions of organic species in the form of
MWe,187 with larger (550 MWe units) currently being built.188
unburned hydrocarbons, and also low emissions of heavy
CFBC is now a widely used technology for the power industry
metals.196,197 At the moment it is far from clear how pure ue
for difficult fuels (e.g. low volatiles content or high sulphur, ash
gases should be to allow the least-cost production of CO2 for
or moisture content or for almost any waste material). In this
piping and sequestration. However, it is reasonable to assume
technology, the fuels are burned in a turbulent bed of an inert
that if a technology such as oxyfuel CFBC has inherently low
material, thus ensuring high heat transfer rates, and good solid
emissions then this must represent an advantage.
mixing. Furthermore if sulphur capture is required, limestone
A series of trials194,195 indicated that fuel nitrogen conver-
can be added to the bed, ensuring SO2 is removed in solid form
sions were oen about half that seen from air-red trials, with
(CaSO4, anhydrite), which can be landlled. While this tech-
fuel nitrogen conversions down to 1.5 to 3.5%. More recently,
nology was explored 35 years ago189 in its bubbling bed mode
Duan et al.198 investigated the effect of operating parameters on
(uidising velocities 1 to 2.5 m s1), it was not until the last
NO formation using a 50 kWth oxy-red CFB, without ue gas
decade that the oxyfuel FBC technology received serious atten-
recycle, and also found that NO production with 21% O2/79%
tion, when two large boiler companies, Alstom190 and Foster
CO2 was lower than for the air-red case.
Wheeler, began to carry out pilot-scale test work and other
CFBC can be regarded as a low SO2 emissions technology,
studies to see if it could be developed as commercial CFBC
due to its ability to use limestone to trap SO2 in situ. A key
boiler technology with CO2 capture.
difference between air- and oxy-ring is that unless the CFBC is
As discussed above, in oxyring, ue gases must be recycled
operated above about 870 C, the CaO/CaCO3 equilibrium
in order to keep combustion temperatures to manageable levels
indicates that capture will be with CaCO3 directly (so-called
(in the case of CFBC, less than 1000 C). However, unlike oxy-
direct sulphation), rather than with CaO produced from the
red PC units, the hot solids which are an integral part of
rapid calcination of limestone at temperatures above 790 C,
CFBC technology can also be used for extra heat transfer and
due to the much higher partial pressures of CO2 in an oxyfuel
steam production, either in the primary reaction loop and/or in
CFBC. The global reactions which describe sulphur capture in a
external uid bed heat exchangers. This means that unlike PC
CFBC are given below:
systems, where perhaps 70–80% of the ue gas must be recy-
cled, lower levels of ue gas recirculation are possible, which CaCO3 + SO2 + 1/2O2 ¼ CaSO4 + CO2 (7)
would allow oxyfuel CFBCs of any given thermal output to be
built; these can potentially be 30 or 40% smaller than the CaCO3 ¼ CaO + CO2 (8)
equivalent air-red units, and thus improve plant cost savings.
This lower volume of ue gas means that emissions are best CaO + SO2 + 1/2O2 ¼ CaSO4 (9)
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Table 3 List of pilot plant oxyfuel FBC facilities (modified from Wall et al.192)
Alstom, Windsor, CT, USA 3 MWth Feasibly studies on O2 fuel FBC Unit did not employ ue gas recycle,
technology but R&D on the unit, which began in
2001, represents the beginning of
the company’s development of oxy-
fuel 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 company’s program
in oxyfuel FBC)
Foster Wheeler, VTT and 0.1 MWth Provided design and operational Foster Wheeler used VTT, Finland
Lappeenranta University of data for oxyfuel CFB, with ue gas along with CanmetENERGY
Technology, Finland recycle facilities to test numerous fuels and
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CanmetENERGY, Canada 0.1 and 0.8 MWth Support of national Canadian limestones573 as a prelude to their
program on oxy-fuel CFB demonstration plant at
CIUDEN199,207
CIRCE, University of Zaragoza, 100 kWth Bubbling FBC used to generate
Spain fundamental data
University of Utah, Utah, USA 0.33 MWth Generation of fundamental
knowledge
Metso Power, Finland 4 MWth Developing commercial technology A co-operation between Metso and
Fortum, with fundamental studies
performed by Chalmers University,
Sweden574
Czestochowa University of 0.1 MWth Generation of fundamental data Unit has also been used to support
Technology, Poland Foster Wheeler’s program
ICB-CSIC Spain 3 kWth Bubbling bed facility used for
generation of fundamental data
Southeast University, China 100 kWth Generation of fundamental data
Zhejiang University, China 30 kWth Bubbling bed used to generate
fundamental knowledge
North China Electric Power NA Batch pressurised bubbling bed
University facility (using 10 g of fuel) capable of
operating up to 4.5 MPa
Typically, limestone conversion in a CFBC is relatively low have also recently examined SO3 concentrations for a 1.5 MW
with the 30–45% utilisation being regarded as acceptable. The pilot-scale PC combustor and a 330 kW pilot-scale CFB test
work of Jia et al.194,195 has suggested that limestone utilisations facility (using a PRB coal with 0.2% S, a Utah coal with 0.5% S
are comparable or lower for oxyfuel CFBC combustion. and an Illinois coal with 4% S). Unfortunately, they appear only
However, to date, insufficient studies have been carried out to to have examined SO3 levels for the Utah coal, for which they
determine this issue unequivocally, although recent tests from conclude that SO3 levels are similar for both air and oxy-ring
the 30 MWth CIUDEN demonstration unit have also suggested under their conditions. They also point out that the presence
somewhat lower limestone utilisation.199 CanmetENERGY of particles may provide more opportunities for SO3 formation
work200 has suggested that high-temperature steam, at the levels via catalytic processes, but note again that SO3 concentrations
present when burning any hydrocarbon fuel, enhances the do not appear to be noticeably affected by the amount of
sulphation in both the air ring and oxyfuel case, but more so limestone addition.
for air ring, so that sulphation is better or comparable in air Recently, CanmetENERGY has also examined co-ring of up
ring to oxyfuel combustion (Fig. 7). to 80% wood with a bituminous coal and found that trace
The issue of SO3 emissions, given its potential to cause elements in the ue gas are negligible.201 On the question of Hg
corrosion, is something which is also of interest for oxyfuel emissions, there are still rather limited data. Font et al.203 have
systems, for two reasons: the use of recycled ue gases will likely investigated the fate of Hg and other trace elements employing
increase SO3 levels; and potentially high oxygen concentrations, a 90 kWth oxy-red bubbling FBC. Here the pH of the leachate
particularly at the base of the bed, might also enhance its for the bed ash was in the range of 10.7–11.1, and for the cyclone
formation. There is currently a dearth of information on this y ash even lower (pH ¼ 8). As expected, most trace elements
subject for oxy-FBC systems; however, from preliminary tended to report to the overhead streams (i.e. cyclone and y
research done by CanmetENERGY on its 0.8 MWth CFBC, levels ash). Interestingly, in this work the bulk of the Hg was found in
do not seem excessive at 2 ppmv or less,201 albeit that the the elemental form. By contrast, in some recent work done at
bituminous coal used contains only 0.56% sulphur. Ahn et al.202 CanmetENERGY on a bituminous coal, Hg emissions were
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unused O2, and thus no energy is expended for the gas sepa-
ration and no gas separation equipment is needed. However,
the efficiency 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 effi-
ciency of the underlying thermodynamic cycle to that of a steam
cycle, rather than a more efficient 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 prom-
ising 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
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according to:
Fig. 7 Sulphation conversion profiles under oxy-fired conditions for
varied concentrations of H2O (with air-fired profiles overlaid). (2n + m)MexOy + CnH2m / (2n + m)MexOy1
+ mH2O + nCO2 (10)
0.8 mg m3 or less with about 80% of the Hg present in an The exit gas stream from the fuel reactor contains CO2 and
oxidised form.204 H2O, and a stream of CO2 is obtained when H2O is condensed.
The reduced metal oxide, MexOy1, is transferred to the air
5.3 Larger-scale tests and industrial plans reactor where it is oxidised, reaction (11):
Foster Wheeler commissioned 8 months of trials at CanmetE-
MexOy1 + 1/2O2 / MexOy (11)
NERGY and these trials demonstrated excellent control on CO2
levels and combustion conditions.205 Overall performance was The air, which oxidises the metal oxide, produces a ue gas
excellent, which is a very positive sign for the development of containing only N2 and some unused O2. Depending on the
the technology. Foster Wheeler was also the rst to commer- metal oxide and fuel used, reaction (10) is oen endothermic,
cialise supercritical CFBC technology (Lagisza power plant, while reaction (11) is exothermic. The total amount of heat
Poland) and with this technology as the basis, Foster Wheeler is evolved from reaction (10) and (11) is the same as for normal
now working with the power company ENDESA on the devel- combustion, where the oxygen is in direct contact with the fuel.
opment of a 300 MWe supercritical Flexi-Burn® CFBC. The The metal oxides used for the oxygen transfer are called
predicted CO2 capture for this technology is 90% of emissions oxygen carriers. The reactor system is normally made up by two
and it is anticipated that it could be available by 2020.206 Foster interconnected uidised beds, with the oxygen carrier in the
Wheeler also believes that it could offer such technology at the form of particles being circulated between the two beds, Fig. 9.
600–800 MWe size with 600 C steam temperature. CLC was rst introduced by Lewis et al. as way to produce
Demonstration tests are currently underway at the 30 MWth pure CO2 from fossil fuels, using two interconnected uidised
CIUDEN pilot CFB demonstration unit, which will provide a full beds.209,210 Much later, Ishida et al. proposed the use of
experimental CCS platform for the demonstration and valida- chemical-looping combustion for climate mitigation and also
tion of exible air/oxyfuel CFB combustion.199,207 An interesting started laboratory research on oxygen-carrier materials.211
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 demonstra-
tion; 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.
6. Chemical-looping combustion
6.1 Introduction
Chemical-looping combustion has emerged as an attractive
option for carbon dioxide capture because CO2 is inherently Fig. 8 Chemical-looping combustion. MexOy/MexOy1 denotes
separated from the other ue gas components, i.e. N2 and recirculating oxygen carrier material.
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means that CLC with solid fuels will require a different design
of the fuel reactor, as well as oxygen carriers with other prop-
erties. The following key issues have been identied in relation
to fuel reactor performance: solid fuel conversion, gas conver-
sion and CO2 capture.
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There is also work with chemical-looping of solid fuels 6.5 Chemical-looping with oxygen uncoupling (CLOU)
directed towards hydrogen production, rather than complete
Chemical-Looping with Oxygen Uncoupling (CLOU) is closely
combustion, which is similar to the chemical-looping reform-
related to chemical-looping combustion but differs from CLC
ing and water-splitting processes proposed for gaseous fuels. A
through the spontaneous release of oxygen in the fuel reactor.
chemical-looping process for the production of syngas using
For instance, the CuO/Cu2O system has an equilibrium oxygen
solid fuels and two interconnected uidised beds was patented
partial pressure of 0.02 bar at a temperature of 913 C. This
more than 60 years ago.225 Some more recent processes involve
means that, at this temperature, the O2 concentration could be
using lime to enhance fuel conversion to H2 by in situ CO2 reduced down to a minimum of 2% in the air reactor, while
removal, e.g. the Alstom Hybrid Combustion–Gasication oxygen could be released up to maximum 2% in the fuel reactor.
Process and the GE Fuel-Flexible Process.231 With respect to
As the presence of fuel in the fuel reactor will consume oxygen
water-splitting, it should be mentioned that going back 80–90
released, a very rapid release of oxygen is possible. CLOU using
years, the main process for hydrogen production was the so-
CuO has been shown to work not only in laboratory batch
called steam-iron process. In this process, iron oxide was
uidised-bed tests with CuO and solid fuel,263,264 but also in
reduced by coal to iron, and the iron was then reacted with
continuous operation with solid fuel.265 Also, combined
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The presently studied technology, i.e. systems that operate for the fuel reactor system, and costs downstream of the fuel
under atmospheric conditions and temperatures of 800–950 C, reactor to accommodate for incomplete conversion, e.g. oxygen
would have signicantly lower efficiency in power production as polishing. Consequently, a good understanding of these costs is
compared to natural gas combined cycle (NGCC) plants. CLC for needed to nd the optimal solution and realise the great
higher pressures and temperatures need signicant develop- potential of this technology.
ment efforts. However, there are a number of applications
where gaseous fuel CLC could be used for steam/heat
production. 7. Calcium looping, CaL
The following conclusion can be made for CLC with solid Calcium looping is a family of CO2 capture technologies that
fuels: use CaO as a regenerable sorbent of CO2:
The technology is similar to established combustion of coal
in circulating uidised beds. CaO(s) + CO2(g) $ CaCO3(s), DH298K ¼ 178.8 kJ mol1 (12)
There is a unique potential for dramatic reduction in cost
and energy penalty for CO2 capture. Both the carbonation and calcination reactions are carried
CLC operation with low-cost mineral ilmenite works well, out at high temperatures (650–700 C and 900 C, respectively),
but to reach high performance, additional development is allowing for efficient heat recovery in the process or steam cycle
needed, either with regards to reactor system or the oxygen of a power generation system. The technology has attracted, in
carrier material used. the last 10 years, a great deal of attention, and several
Oxygen carrier materials other than ilmenite could provide comprehensive reviews have been recently published.283–287 Only
signicant improvement of performance, but it is not clear if the main aspects and newest developments are discussed in
are they available at reasonable costs. this section.
The following options to have a complete conversion of the The use of this chemical loop was rst attempted in the 19th
gas to CO2/H2O in the fuel reactor are available: (i) oxygen century as it was noted that gasication gases would have a
polishing, (ii) separation/recycling of unconverted gas (iii) using higher heating power when coal was gasied in the presence of
two fuel reactors in series and (iv) CLOU oxygen carriers. CaO. This idea was exploited in the acceptor gasication
For scale-up, a more detailed understanding of the process, which tested the principle in a continuous pilot rig
processes in the fuel reactor is needed to design and optimise using an interconnected uidised bed coal gasier and a
the fuel reactor system, in order to assess how the performance combustor operated at high pressure.288 Other hydrogen
will be affected by the properties of the oxygen carrier and the generation processes have been investigated from the 90s,
reactor design. focusing on the sorption enhanced reforming principle.289 The
The optimisation of the fuel reactor system will primarily rst application of Ca-looping as a post-combustion CO2
need to consider three costs, i.e. costs for oxygen carrier, costs capture process was patented by Hirama et al.290 They also
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proposed a practical solution for the calcination problem: the sufficient bed inventory (400 kg m2) and solids circulation rate
oxy-combustion of an additional ow of fuel in a uidised-bed (0.5–2.2 kg m2 s1), even with highly deactivated calcium
calciner to provide the “Heat” arrow of Fig. 10, that can be oxide.302,303 This test facility was also used to test the principle of
effectively recovered in a steam cycle to generate more power.291 low-temperature combustion of biomass (700 C) for in situ CO2
This section briey reviews the status of these two main groups capture.304,305 Capture rates were limited in this rig to 4 mol CO2
of CO2 capture processes. A third subsection reviews recent m2 s1 because of the need to limit gas velocities to ensure
developments on sorbent performance issues that are common sufficient holdup of solids in the 6 m riser. This limitation was
for both process routes. removed at IFK, University of Stuttgart that designed and oper-
ated a 10 kWth pilot plant, consisting of a CFB carbonator (12.4 m
7.1 Post-combustion CO2 capture by CaL height) and a bubbling uidised-bed calciner. Experimental
results showed capture rates close to those expected in large scale
For large scale novel energy processes such as the CaL system, it
commercial systems (up to 10 mol m2 s1).306 A 200 kWth pilot
is essential to carry out detailed process simulation and thermal
plant was also recently completed at IFK, with three inter-
integration exercises to assess the viability of the full system
connected circulating uidised-bed reactors, which were
under expected operating conditions, evaluate power genera-
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attrition of the sorbent and the subsequent elutriation of nes, conditions).361 A different method for reactivation has also been
and by ash fouling. It is noteworthy that even when fully proposed recently:362 a small regeneration reactor (recarbona-
degraded in reactivity, CaO from natural limestone still takes up tor) is added between the carbonator and calciner vessels to re-
0.16 g CO2 per gram, a high value compared to many other carbonate the particles leaving the carbonator (calcination–
potential sorbents. The thickness of the carbonate layer formed carbonation–recarbonation cycles) using a small ow of pure
on the free internal surfaces of CaO is a critical parameter to CO2 from the calciner’s off-gas. The slight increase in the
explain the end of the fast reaction period. However, some carbonate conversion in each cycle sustains the residual activity
important phenomena are not well explained by this simple at around 0.15 to 0.2, which is close to the optimum design
theory, such as the temperature dependency of the CO2 carrying target for post-combustion systems.
capacity and steam effects,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 8. Low temperature adsorbents
using a mechanism well established for other gas–solid reac- A large number of adsorbents have been recently proposed and
tions: they model the CaCO3 growth as islands on the CaO investigated as possible candidates for carbon capture at low
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surface. The fast carbonation stage is completed when these temperature. The selection of the best samples cannot be based
islands merge. With the increase of reaction temperature, the only on their adsorption properties (i.e. capacity, heat of
sizes and heights of the CaCO3 product island increases while adsorption, kinetics) because other factors may play a crucial
the island density decreases. Only a few parameters are needed role in the overall process. For this reason, economic criteria
to t the observed carbonation rate curves in a wide range of have to always be taken into account, not only with regards to
temperatures. The calcination reaction of highly cycled particles the costs of synthesis but also to the size of the equipment (i.e.
in a CaL is assumed to be very fast, but this has only recently the volume of the adsorbent needed); the regeneration energy
been conrmed experimentally.346 Sulphation rates of CaO in demand (i.e. the heat of adsorption); the cycle time (i.e. equi-
CaL reactors (carbonator or calciner) are also a recent subject of librium and kinetic properties and process selected, pressure or
investigation. The large make-up ow of fresh limestone char- vacuum swing adsorption (PSA or VSA) vs. temperature swing
acteristic of most CaL systems allows for lower CaSO4 content in adsorption (TSA)); the hydrothermal stability; the loss of
the system than in equivalent desulphurisation units using performances due to the presence of impurities in the feed
CaO. Open pore structures of the sorbent in a CaL can also alter stream.
the rate and the extent of sulphation. Arias et al.347 reported Based on these observations the best adsorbent should have
sulphation kinetics of CaO particles at low levels of conversion high CO2 capacity at low pressure, high selectivity for CO2, fast
to CaSO4, whilst Anthony and co-workers348 focused their adsorption/desorption kinetics, good mechanical properties,
investigations on the performance of synthetic Ca-based high hydrothermal and chemical stability, as well as low costs of
sorbents. Attrition is another important issue in CaL because synthesis.
it affects capture efficiency, sorbent cost and operational cost. Zeolites, as well as carbon-based materials, are the most
Particles have been shown to break up mainly during the rst widely investigated classes of adsorbents. In recent years a
calcination. In addition, attrition has been found to be highly considerable research effort has been put in the development of
sensitive to limestone choice.349,350 a new class of adsorbent, MOFs (metal–organic frameworks), as
Several approaches have been investigated to improve initial promising candidates for CO2 separation. In addition, a large
sorbent properties and/or reactivate spent sorbents, but many variety of functionalised (mostly amine-based) adsorbents has
still require detailed studies at the process level to ensure their been recently produced. The very encouraging results obtained
viability for large-scale commercial applications. Lisbona are opening a new eld for the investigation of new possible
et al.351 studied the integration of the sorbent cost and its adsorbents for carbon capture applications.
carrying capacity and mechanical performance for different
options applied to an existing coal-red power plant. They
demonstrated that the optimum CO2 carrying capacity that 8.1 Zeolites
involves minimal heat requirements in the calciner is relatively Zeolites are crystalline aluminosilicates characterised by a highly
modest (at around 20% of Ca conversion). However, for pre- ordered open structure. They can differ greatly for the framework
combustion applications higher activities may be desirable. In type, the size and shape of the channels and cages as well as the
general, R&D activity continues on the main techniques Si/Al ratio. With regard to carbon capture applications, type X
explored for sorbent improvement: hydration,352–354 and A zeolites have been widely investigated.363 They are gener-
283,284,287,355 283,286
doping, thermal pre-activation, and synthetic ally characterised by a relatively high CO2 capacity at low pres-
sorbents.286,287 Low cost methods based on co-precipitation can sure, which makes them very promising candidates for CO2
yield synthetic sorbents with high melting points and a separation from ue gases.364–371 Generally 13X is indicated as the
carbonation conversion above 75% aer 50 cycles.356,357 The use best candidate for post combustion PSA applications with values
of supports like alumina358 or cements containing CaO and of the CO2 uptake between 2 and 3 mol kg1 at 0.1 bar, at
Al2O3359, 360 have recently been shown to improve the durability temperatures between 15 and 35 C. Despite the relative high
of CaO sorbent (some of them above 0.50 g g1 sorbent aer 30 heat of adsorption (36–37 kJ mol1),364,368 the high working
carbonation–calcination cycles under severe calcination capacity and selectivity make zeolite 13X one of the best choice
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for CO2 capture from ue gas streams.364,365,368,369 For this reason CO2 uptake follows the sequence, Mg > Ni Co > Zn, with
13X is generally used as a benchmark material for low- values of the CO2 capacity for Mg-MOF-74 being almost double
temperature adsorbents for carbon capture applications. than that for 13X.389,392–394 Mg-MOF-74 is characterised by a high
Despite the good adsorption properties for CO2, zeolites are selectivity for CO2395 and the heat of adsorption is generally
generally highly hydrophilic; the presence of water induces an higher than the one of zeolites with values of about 47 and 41 kJ
alteration of the electric eld reducing the strength of interac- mol1 for the Mg and Ni form respectively.389,393,396,397 The higher
tion between the quadrupole of CO2 and the cations, resulting ionic character of the Mg–O bond improves the affinity with
in a lower uptake.372,373 Detailed studies on the effect of the CO2, but on the other hand, it makes the Mg form more
presence of small amounts of water on the CO2 uptake of hydrophilic than the analogous Ni form. Studies to compare the
zeolites were presented by Brandani and Ruthven372,373 and, effect of water on CO2 adsorption for Ni-MOF-74 and commer-
more recently by Li et al.374 and Lee et al.,375 concluding that the cial zeolites were performed by LeVan et al.;391 although the CO2
presence of even very small amount of water greatly reduces the capacity was found to reduce in presence of water for all the
adsorption performance of zeolites. materials, the effect was less pronounced for Ni-MOF-74. Liu
The nature and the distribution of the cations inside the et al.398 reported that the H2O molecules interact specically
zeolite framework play a crucial role in the nal CO2 adsorption
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low-pressure carbon capture. Multi-walled CNT functionalised purity of about 71% and a recovery of about 60% were achieved
with APTES have shown a signicant improvement of the CO2 aer continuous running of the process using a simple 6-step
uptake compared to the pristine sample.407–409 cycle (without purge) for a week.
The Science and Engineering Research Council (SERC) of
8.4 Mesoporous silicas Singapore in 2009 launched a research programme on Carbon
Capture and Utilisation (CCU), which includes a collaborative
Mesoporous silicas are generally characterised by low CO2
project418 between the adsorption and process systems research
uptake due to the weak surface interaction with CO2 molecules.
groups at National University of Singapore (NUS), Nanyang
What makes them attractive for carbon capture is the possibility
Technological University (NTU) and Institute of Chemical and
to introduce functional groups (usually amine-based groups) to
Engineering Sciences (ICES). A pilot plant that was designed
increase the affinity with CO2. The advantage of having large
based on the results from a detailed simulation study, has been
and uniform pores is that it is possible to introduce surface
constructed. 1 m long columns with 0.3 m internal diameter
modication, reducing possible steric hindrance of the
were used and the plant is expected to capture around 3 tCO2
adsorption sites. As a result of the introduction of functional
madsorbent3 per day using a simple 4-step Vacuum Swing
groups, a signicant increase of CO2 uptake at low pressure has
Adsorption (VSA) with Zeochem 13X and synthetic dry ue gas.
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9. Direct air capture technology submarines426 and spaceships427 though it is important to note
that the concentration of CO2 is in these locations is signi-
9.1 Introduction cantly higher than that within the atmosphere. CO2 must also
Direct air capture is the process of removing CO2 from the air be removed from air prior to air liquefaction to avoid opera-
and generating a concentrated stream of CO2 for sequestration tional issues associated with dry ice formation.428 However, the
or re-use. It belongs to a group of technologies referred to as volume of air that must be handled to capture comparable
negative emissions, or carbon dioxide removal (CDR) technol- amounts of CO2 to traditional CCS technologies is far greater.
ogies. Other negative emissions technologies include bioenergy This has signicant implications on energy consumption and
enhanced carbon capture and storage (BECCS); augmented the required plant size. As a consequence, capture technologies
ocean disposal (or ocean liming); biochar production and uti- that require pre-processing of air, such as drying, heating,
lisation; the dispersion of naturally occurring bases such as cooling or pressurising will not be economical.429 This rules out
serpentine and olivine across the land; and the enhancement of technologies typically used for small-scale air capture such as
biological CO2 sinks such as reforestation, afforestation and membrane separation (large pressure gradients and multiple
aquatic biomass via ocean fertilisation. These technologies are passes required to achieve a high-purity CO2 stream);430 cryo-
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beyond the scope of this paper, though the interested reader genic separation (cooling and compression required); and
may refer to a recent techno-economic analysis of negative zeolite, activated carbon and alumina-based molecular sieves
emissions technologies by McGlashan et al. for more informa- (adversely affected by moisture and low adsorption capacities at
tion.424 In fact, we will only very briey review recent develop- ambient conditions). Two main approaches have been
ments in air capture technologies here. proposed for direct air capture (i) wet air capture systems and
Compared with traditional CO2 capture from concentrated (ii) dry air capture systems. Whilst both capture processes
point sources; direct air capture offers a number of purported require energy to regenerate the sorbent, the energy demand
advantages. Firstly, air capture provides a means of adjusting scales proportionally to the mass of CO2 captured as opposed to
the atmospheric CO2 concentration in the increasingly more the volume of air processed. For those seeking more informa-
likely event that mitigation efforts fall short of targets and the tion than this brief overview, the reader is encouraged to read a
atmospheric greenhouse gas inventory reaches dangerous levels recent review by Goeppert et al.431
or takes a trajectory towards stabilisation at dangerous levels.
Air capture could also offer an option for addressing CO2
emissions from mobile and distributed sources, such as vehi- 9.2 Wet air capture systems-the soda/lime process
cles, fuel use in buildings and geographically isolated industry, The most developed approach for wet air capture is the soda/
where direct capture and integration into a centralised CCS lime process.431 This uses aqueous sodium hydroxide (NaOH)-
network would be either impractical and/or uneconomical. based solutions to extract CO2 from ambient air in a packed-
Furthermore, direct air capture technology could be installed by column,432 convection tower433 or spray-tower contactor
storage site operators to manage fugitive emissions from the system.434 Aer the contactor, the NaOH solution is regenerated
CCS network and leakage from geological formations. In addi- via caustic recovery (or causticisation), where slaked lime (an
tion, it has been suggested that direct air capture technology aqueous solution of Ca(OH)2) is reacted with the dissolved
could potentially be situated anywhere, such as deserts, waste- sodium carbonate (Na2CO3) product to form a calcium
land and the ocean, provided there is access to an available carbonate (CaCO3) precipitate mud. The CaCO3 mud is ltered,
energy source and sequestration sites. However, there are also dried and transferred to a rotary kiln where it is calcined at
signicant disadvantages to the technology. Removing and temperatures in excess of 900 C to produce a concentrated
concentrating CO2 from air at 390 ppm to a pure stream stream of CO2 and a calcium oxide (CaO) powder. The CaO
(>90%) implies a greater energy input, and treatment of a vastly powder is then dissolved in water to regenerate the slaked lime
greater volume of gas than CO2 capture from concentrated solution.
point sources. For example, the thermodynamic minimum The requirement of substantial thermal energy for lime
energy required to extract CO2 from ambient air is 20 kJ mol1 regeneration represents a signicant drawback of this process.
compared with 8.4 kJ mol1 and 5.3 kJ mol1 to capture and Baciocchi et al. estimated that process energy demands are
concentrate CO2 from the ue gases of natural gas-, and coal- likely to range between 7.6 and 11.6 GJ tCO21 (334–510 kJ mol
red power stations containing 5% and 15% CO2 respectively CO21) with drying, pre-heating and calcining of the CaCO3
at 65 C. Furthermore, the actual energy consumed by air accounting for the majority of the total energy demand.435 Other
capture technology will be signicantly larger than the ther- energy intensive processes considered in the Baciocchi et al.
modynamic minimum, as is the case for CCS systems. Zeman estimates were CO2 compression and air separation to produce
et al. estimated that the energy demand of a large-scale MEA- O2 for an oxyfuel kiln. As a consequence, CO2 abatement costs
based process for CO2 capture from concentrated sources for this process are high, typically quoted as 240–500 US$ tC1
would be 181 kJ mol1, which is far greater than the thermo- (65–136 US$ tCO21);436 much higher than some estimated cost
dynamic minimum energy requirement.425 of CCS at 30–50 US$ tCO21 437 (some authors of this paper
Direct air capture has been practiced on a small scale for might suggest a more conservative range of costs, from $50–
decades for the purpose of maintaining safe levels of CO2 in $120 tCO21 depending upon source and capture technology).
Recent papers by the American Physical Society438 and House
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et al.439 have stated costs may be even higher, in the region of conventional climate change mitigation technologies. Cost
US$600 and US$1000 per ton of CO2 respectively, though it estimates vary substantially ranging from as low as 20 US$
should be noted that these costings are disputed by researchers tCO21 to as high as 1000 US$ tCO21 and it is highly likely that
within the air capture community.429,440 air capture will offer one of the most expensive options for
mitigating climate change. For this reason, other, cheaper
9.3 Alternative wet air capture systems options for addressing climate change such as reducing the
In attempts to eliminate the energy intensive lime regeneration carbon intensity of electricity generation through efficiency
step, the paper and pulping industry have been developing and savings in existing power plants, increased deployment of
piloting an alternative approach that involves direct caustici- renewable energy technologies, nuclear power and CCS should
sation with titanates.441 The energy required to regenerate tita- be aggressively pursued before air capture is considered. Ulti-
nanates is much lower than for CaO; 90 kJ mol1 compared to mately, commercial deployment of air capture technology will
179 kJ mol1. 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
9.4 Dry air capture systems be realised, the future carbon price must also be high, i.e. more
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essentially pegged to fuel prices (gas in the UK), the main 10.2.4 Future coal-red power stations. It is interesting to
sources of risk associated with investing in a power plant, with note that, despite their improved efficiency, super-critical power
or without CCS, are the load factor, dispatch frequency, fuel and plants are less exible in their operation than their sub-critical
carbon costs. It is, therefore, evident that the least risky option counter parts. The reason for this is the lack of steam drum in
will be to invest in a power station that is fuel exible, has low the power plant, meaning that the rate at which they can ramp
greenhouse gas (GHG) emission per unit of output and can up (or down) their power output is relatively low. In this context,
operate in a exible (i.e. load following) manner. The authors the addition of a post-combustion CO2 capture process could
would emphasise that this rationale (fuel and operational ex- actually be an advantage. One can envision a scenario in which
ibility) should hold for investment into any fungible energy the degree of steam extraction for the solvent regeneration can
network, i.e. the arguments presented herein are held to be be manipulated to instantly provide more steam for power
equally applicable to any energy system comprising diverse generation when circumstances dictate. This concept is
generation sources. explored further below.
The remainder of this section is laid out as follows; we rst
provide a high level description of post-combustion CO2 capture
10.3 Integration strategy
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viable option in decarbonising power plants. Subsequently, generate power in a exible way. Furthermore, we suggest that
direct extraction of steam from the steam cycle of the main the position of fossil fuel-based power plants in the power
power plant has become the preferred option. Owing to the generation merit order is changing. With the increasing inter-
desired conditions within the reboiler (T ¼ 120 C, P ¼ 0.2 MPa), mittency associated with the diverse energy network envisioned
this energy is best obtained via condensation of saturated steam for the UK in the 2030’s and beyond, this capacity for exible
at P z 0.25 MPa. In the case of a sub-critical coal-red power operation will command a special premium.
station, it has been shown that the optimal location for the The concept of storing CO2-rich solvent on-site was originally
extraction of this steam from the steam cycle is between the IP proposed by Chalmers and Gibbins.455 This concept has recently
and LP turbines.453 As before, one can partition the contribu- been quantitatively proven456 to provide an important reduction
tions to QRegen into that obtained by the condensation of steam, in operating cost456 and as a buffer between the dynamic behav-
QCond, and that obtained by sensible heat transfer by sub- iour of the power plant and the required steady state operation of
cooling the condensate, QSub-cool. Once this steam has been a CO2 transport network. In particular, Arce et al. have shown that
condensed, the resulting condensate is then returned to the adjusting the degree of solvent regeneration in sympathy with
steam cycle. It has been shown19 that the fraction of QRegen prevailing market prices for energy, fuel and carbon (i.e.
obtained from QSub-cool is negligible. Thus, the condensate increased solvent regeneration or a lower lean solvent loading at
should, therefore, be returned with the minimum degree of sub- times of low energy prices, and reduced levels of solvent regen-
cooling in order to avoid an additional penalty on the power eration at times of high energy prices) can lead to an appreciable
plant associated with returning large quantities of sub-cooled reduction in operating cost. Furthermore, allowing CO2 to accu-
liquid to steam cycle. Specically, the condensate should be mulate in an on-site solvent inventory can enhance this effect. As
returned to the condensate heating train, as opposed to the alluded to above, this idea can be used in conjunction with super-
power cycle condenser.453 More sophisticated approaches to critical power plants to enhance their exibility, and, therefore,
heat integration between power and capture plants and the CO2 their protability in a diverse energy generation system.
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
11. CO2 transport
decarbonisation of the power plant. In particular, the recovery 11.1 Introduction
of heat from the inter-coolers of the compression train was CO2 can be transported by pipeline, ship, rail or road. The
found to be especially important. The vast majority of integra- choice of transport will depend on the quantity of CO2 that
tion studies concentrate on the modication of the solvent needs to be transported, the distance and terrain to be travelled,
phase, either by designing new solvents or by carrying out heat and the specications of the CO2 stream produced at the
integration and recovery studies. However, a recent paper capture facility.457 In most cases, transporting CO2 via pipeline
illustrates how the humidity of the inlet exhaust gas stream at will be the most cost effective mode of transport. The instances
the base of the absorber will play an important role in the where transport by ship may prove more economical would be if
process operation. It would appear that a dry exhaust gas will CO2 needs to be moved over very large distances (>1000 km) or
require a shorter column than a wet gas, leading to an appre- over large bodies of water. Transport via rail or road is only
ciable reduction in capital cost.18 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 Basic operation
As discussed in the introduction, in any power generation Prior to pipeline transport, CO2 is compressed to a supercritical
network, there are clear benets associated with being able to uid (sc-CO2) or liquid state (i.e. a dense-phase uid). CO2 exists
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as a supercritical uid above its critical point, 31.1 C and 74 rst purpose-built CO2 tanker, which can ship up to 1825
bar. This is the most efficient phase for transporting CO2 by tonnes of CO2 at 40 C and 18 barg. Yara International char-
pipeline as it has both the high density of a liquid and the ters the other three ships which have capacities between 900
favourable ow characteristics of a gas. However, it is not and 1200 tCO21.191,460 Work is on-going to develop ships with
possible to maintain pipeline temperatures above the critical the capacities required for large-scale CCS deployment. Maersk
temperature in all situations. It is, therefore, important to are currently working on pressurised, semi-refrigerated CO2
ensure pressures drops are managed and pipeline pressures are tankers with capacities up to 45 000 tonnes.461
kept above vapour–liquid equilibrium conditions to maintain a
single-dense-phase ow and avoid liquid slugs and other
operational problems that may eventuate if conditions fall 11.4 Pipeline design and operation considerations
within the region where a two-phase (gas–liquid) ow may CO2 pipelines must be designed and constructed at an optimal
occur. Operating pressures of existing CO2 pipelines are in the cost in such a way that they are reliable and safe to operate,
range of 85 to 210 bar where CO2 is a dense-phase uid over a posing minimal risk to local populations and the environ-
wide range of temperatures. To maintain sufficiently high ment.462 Pipeline design is primarily inuenced by the required
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pressures over long distances, intermediate pumping (or throughput and hydrodynamic properties of the CO2, such as
booster) stations are required at certain intervals along the density, phase behaviour, viscosity and compressibility. There-
pipeline. For shorter distances, booster stations may be avoided fore, factors affecting the hydrodynamic properties of CO2,
by increasing the pipeline inlet pressure; however, more energy including temperature, pressure, ow rate and composition,
would be consumed for compression and thicker walled pipe- need to be modelled and characterised as part of the design
line would be required. process. The presence of impurities, particularly water, may also
In terms of CO2 transport by ship, it is most efficient to lead to operational problems concerning corrosion, gas hydrate
transport CO2 as a cryogenic liquid. Aspelund et al. has calcu- and ice formation. As a consequence, pipeline entry specica-
lated optimum conditions for CO2 transport by ship of 6.5 bar tions are set in order to minimise or even avoid these problems.
and 51.2 C.458 Large scale liquefaction would primarily 11.4.1 CO2 specications. CO2 from natural sources is
involve cooling via compression and expansion of the feed gas. saturated with water and typically composed of 98.372–98.350%
Some loss of CO2 is expected as a consequence of boil off and CO2; 1.521–0.136% N2; 0.107–1.514% CH4 and trace amounts of
the ship’s emissions would be in the region of 3 to 4% per 1000 H2S.462 Therefore apart from dehydration, minimal gas treat-
km.457 Losses can be minimised by utilising a refrigerated ment is required. Anthropogenic CO2 on the other hand, tends
container ship or by re-capturing and liquefying the boil-off gas. to be much less pure, containing other impurities such as CO,
Ship-based transport systems require intermediate storage O2, H2S, SOx, NOx and H2. Amines, NH3, methanol and glycols
facilities, and the equipment and infrastructure for loading and may also be present as a consequence of CO2 capture, dehy-
unloading CO2 at the loading docks, and storage sites to link dration and corrosion control. The exact levels will vary
continuous production of CO2 at capture facilities with discrete depending on the source, capture process and gas treatment
transport of CO2 by ship. steps.
Ships are more exible than pipelines as they are able to The level of impurities that can be tolerated will depend on
transport CO2 in volumes far below the design capacity. Ships the storage method (or end use) and the transportation method.
therefore offer the potential to collect CO2 from multiple sites EOR specications tend to be strict (Table 7) as certain impu-
on the way to the storage site and can better adapt to uctua- rities will have detrimental effects on the process. In the case of
tions in the CO2 production rate of the emitter. EOR, there is an economic incentive to remove certain impu-
rities down to very low levels and design CO2 specications for
optimum oil recovery efficiency. However, transporting CO2 for
11.3 Existing experience storage purposes does not share this relationship and removing
Globally, there is approximately 6000 km of pipeline infra- impurities in anthropogenic CO2 down to very low levels
structure in operation for CO2 transportation purposes, most of imposes a signicant energy and cost penalty on the process.
which is based in the US and Canada for transporting CO2 to Therefore, CO2 specications for storage purposes will most
sites for enhanced oil recovery (EOR).459 At present, most of the likely be determined on the basis of cost-benet analyses,
CO2 used for EOR is sourced from natural deposits, though regulatory and legislative requirements, and health and safety
there are a few projects utilising CO2 from anthropogenic considerations.
sources. Table 6 provides a summary of the major long-distance A few studies have attempted to dene CO2 specications for
CO2 pipelines currently operating. There is also limited opera- transport and storage purposes. The Dynamis project463 upda-
tional experience of onshore and offshore pipelines trans- ted specications that were initially proposed for pre-
porting CO2, derived from natural gas production, for combustion CO2 capture technologies as part of the ENCAP
sequestration in saline aquifers at the Snøhvit LNG facility, project464 to take into account safety and toxicity limits. As a
Sleipner, and In Salah. consequence, allowable levels of H2S, CO, SOx and NOx gases
Ship-based CO2 transport experience is far more limited. At have been lowered in accordance with their short term exposure
present, there are only four small ships, transporting food-grade limits (STELs). To meet these specications, additional gas
CO2 in northern Europe.457 Anthony Veder Group operates the treatment measures such as regenerative absorption columns
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Canyon Reef Kinder Morgan USA 4.4 352 140 Gasication Plant EOR 1972
(SACROC)
Bati Raman Turkish Petroleum Turkey 1.1 90 170 Dodan Field EOR 1983
Sheep Mountain BP AMOCO USA 9.2 772 132 Sheep Mountain EOR 1983
North
Cortez Kinder Morgan USA 19.3 803 186 McElmo Dome EOR 1984
Bravo Kinder Morgan USA 7.3 350 165 Bravo Dome EOR 1984
Central Basin Kinder Morgan USA 20 278 170 Denver City Hub EOR 1985
Bairoil — USA 8.3 180 — Gas manufacturing plant EOR 1986
Snøhvit Statoil Norway 1 160 — Separation from natural gas Storage 1996
Weyburn North Dakota USA & Canada 5 328 186 & 204 Gasication Plant EOR 2000
Gasication Co.
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In Salah BP Algeria 1.0 17 185 Separation from natural gas Storage 2004
Sleipner Statoil Norway 0.7 153 100 Separation from natural gas Storage 2006
Table 7 Typical entry specification for CO2 pipelines serving EOR The presence of impurities also reduces the density of dense-
operations635 phase CO2, particularly at conditions close to the vapour–liquid
equilibrium boundary.465,466 As a consequence, pipelines trans-
Constituent Specication Reason
porting CO2 containing large amounts of impurities must be
CO2 >95% MMP operated at higher inlet pressures to achieve the desired
N2 4% MMP throughput. A thicker walled pipeline or tougher pipeline
Hydrocarbons 5% MMP material may also be required at a higher infrastructure cost.
H2O 480 mg m3 Corrosion Pressure and temperature drops within pipelines are also
O2 10 ppm Corrosion
affected by the CO2 composition. The presence of impurities
H2S 10–200 ppm Safety
Glycol 0.4 ml m3 Operations with lower critical temperatures and pressures than CO2
Temperature 65 C Material integrity 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
may be required in addition to the standard SOx and NOx set length of pipeline.467 To account for increased pressure
removal (FGD, low NOx burners and SCR), increasing gas drops, more booster stations would be required at shorter
treatment energy and infrastructure costs. intervals to keep the pressure sufficiently high to maintain a
Ecofys have also produced CO2 transport/storage specica- dense-phase ow. However, adding more booster station
tions based on impurities that are likely to be present in CO2 substantially increases pipeline infrastructure costs, and in any
from a coal-red power plant.465 The Ecofys specications are case, this option is not feasible for subsea pipelines. Alterna-
similar to those dened by the Dynamis project, although they tively, the pipeline would have to be operated at a higher inlet
did not dene tolerance limits for SOx and NOx based on their pressure.
assumption that these impurities will not cause operational Yan et al. carried out a cost-benet analysis to determine the
problems in the absence of a separate water phase. Both the effect of removing typical non-condensable impurities found in
Dynamis and Ecofys specications recommend a maximum anthropogenic CO2 (N2, H2, O2 and CH4) to different levels (1%,
water level of 500 ppm to avoid precipitation of a separate water 4% and 10%).468 They found that limiting the amount of non-
phase, which has been identied as the main factor inuencing condensable compounds to <4% was optimal in terms of
corrosion, gas hydrate and ice formation. balancing gas treatment and compression costs, although a
11.4.2 Impact of impurities on pipeline capacity and higher limit of <10% may be acceptable for short distances.
operating pressure. Impurities affects the physical and trans- 11.4.3 The role of impurities in pipeline corrosion. Internal
port properties of dense-phase CO2 in a number of ways. Firstly, pipeline corrosion issues are primarily caused by the presence
the presence of impurities opens out the range of pressures of an aqueous phase. CO2 dissolves in “free water” leading to
where vapour and liquid CO2 exist in equilibrium. Impurities the formation of carbonic acid, which is highly corrosive to
with lower critical temperatures and pressures than CO2, such carbon steel (the material typically used for natural gas and
as H2, N2, CH4, O2, CO and Ar, are the most problematic as these existing CO2 pipelines). This type of corrosion is termed “sweet
impurities open out the range of pressures above the vapour corrosion”. An aqueous phase may form if the water vapour
liquid equilibrium boundary of pure CO2.465 This impacts the content exceeds the saturation vapour level at any point within
minimum operating pressure of a CO2 pipeline, which must be the pipeline. Alternatively, accidental ingress of water may
increased with increasing impurity content to avoid two-phase occur due to a malfunction at the gas conditioning facility or
ows. during a maintenance shutdown.
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A reasonable amount of work has been published on the amines such as MEA will have the opposite effect on the pH of
corrosive properties of CO2–H2O systems at conditions relevant an aqueous phase and thus hinder corrosion. In fact, glycols are
to natural gas pipelines; however, there is far less published commonly used corrosion inhibitors in natural gas pipelines.
research at conditions relevant to CO2 pipeline transport. Experience from the petrochemical industry has found that
Corrosion rates are dependent on the operating conditions, H2S will also cause corrosion. At partial pressures <0.0035 bar,
including pressure, temperature, water vapour content, ow H2S interacts with carbon steel in the presence of an aqueous
rate, steel composition and exposure time. The presence of phase to form iron sulphide.465 As is the case with FeCO3, FeS
other impurities will also inuence corrosion rates. Corrosion can precipitate onto the surface of the carbon steel, forming a
rates as high as 20 mm per year have been reported for carbon protective layer that inhibits further corrosion. However, H2S at
steel exposed to water-saturated CO2 at relatively high temper- partial pressures >0.0035 bar can cause “sour corrosion” (or
atures and pressures, although the literature is not in general sour cracking), primarily via sulphide stress induced cracking
agreement, with different authors reporting signicantly (SSIC) and hydrogen induced cracking (HIC). It has also been
different corrosion rates at quite similar conditions.469,470 The reported that the presence of CO in CO2–H2O mixtures can
primary cause of these discrepancies is most likely due to the cause transgranular stress cracking corrosion. Cracking corro-
differences in the ow rates, exposure time, material-to-water
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Kinder Morgan, the largest CO2 pipeline operator, species a injected at high pressures deep underground; the principal
maximum water level of 640 ppm.465 Considering water can be storage sites are saline aquifers, depleted oil and gas elds, and
removed down to 400–500 ppm in vapour–liquid separator deep coal seams. Most assessments of storage capacity consider
drums, a 400–600 ppm water level limit seems appropriate. that saline aquifers have the largest storage potential, while oil
Furthermore, this is well below the 60% relative humidity and gas elds offer the economic incentive of additional
threshold at typical pipeline operating conditions (0–50 C and hydrocarbon recovery when the CO2 is injected. CO2 injection is
85–200 bar), where the minimum water solubility of dense- routine in the oil industry for improved recovery with many
phase CO2 is 1500 ppm.478 However, it is likely that more projects around the world, while CO2 storage itself has been
conservative water level requirements may have to be specied successfully implemented at several sites. The best publicised
when transporting CO2 containing high concentrations of NOx, example is at Sleipner, offshore in the Norwegian North Sea,
H2S and CH4. Furthermore, water level specications for ship where around 1 Mt per year of CO2 separated from produced
transport will be less exible owing to the lower operating condensate hydrocarbon has been injected each year since
temperature. Water level specications will most likely remain 1996, to avoid the payment of a carbon tax.
at <50 ppm to avoid gas hydrate and ice formation during There are four principal mechanisms by which the CO2
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human health impacts at the surface, and chemical interactions As an example, Fig. 16 shows the estimated storage capacity
with reservoir and caprock. Three geographical regions are in large regional aquifers in the continental US.480 A total
providing most of the additional information; these are the capacity of over 100 Gt is calculated, sufficient to make a major
Colorado Plateau of USA, onshore southern Italy and Tyrrhenian contribution to mitigating CO2 emissions in North America.
sea adjacent to Sicily, and the North Sea. Some brief highlights of The methodology combines an assessment of both the storage
this expanding literature include that CO2 uids do react with capacity and how fast the CO2 can be injected. However, the
sandstone reservoirs, albeit slowly via oxidation–reduction actual capacity in CO2 storage reservoirs at present remains
pathways.484,485 However, these can oen remain out of equilib- essentially unvalidated, as we discuss next.
rium for several million years.486 CO2 uids in oil elds do not 12.2.1 Dening the storage reservoirs and storage complex.
react strongly with mud caprocks, and so form secure retention The rst step towards CO2 storage for many nations has been
for tens of millions years.487 An important stabilisation mecha- the evaluation of potential storage volumes beneath their
nism is for CO2 to come into contact with large volumes of national territory. Prominent leaders in such assessments have
formation water, greatly enhancing dissolution for long-term been Australia, followed by USA and Canada, and subsequently
stability.488 In a worst-case scenario, CO2 can leak slowly to the an overall appraisal for all European-27 states. These initial
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surface for many millennia489 without monitoring or safety estimates demonstrated much more than adequate storage
precautions. Around such natural leakage sites, the excess capacity for the next 100 years of emissions, and are now being
human death rate is extremely low, at less than one in 30 million rened through second and third generation compilations.
per year.490 The current information thus shows that geochem- There is no standardisation of these methods. It is likely that
ical factors in reservoirs and caprocks for CO2 storage need not global nance will require improved standardisation of deni-
be adverse, if factored into site choice. tion for reserves, to enable valuation of assets. Consequently
different states currently approach storage differently. USA
assessments typically assume that all available storage volume
12.2 Regional assessments of storage capacity can be utilised within a reservoir, and can tend to optimism. By
To make a signicant contribution to reducing atmospheric contrast, some European states consider only discrete closed
emissions, it will be necessary to store several Gt of CO2 each structures and ignore the intervening connections of saline
year worldwide, and many Mt in large regional aquifers in areas formations. Several European states have calculated their entire
with signicant industry and fossil-fuel power generation. storage volume, but have reduced its upper limit by assuming
Assessment of the storage capacity takes into account the generic efficiencies of CO2 emplacement within the reservoir,
factors mentioned above: the likely increase in pressure, CO2 and by calculating maximum permitted injection pressures,
movement and trapping processes. These are normally incor- which avoid fracturing caprocks. Some states, notably Norway,
porated into analytical or numerical models to estimate how have now started to undertake dynamic reservoir simulations,
much CO2 can be safely stored and the likely extent of CO2 which also tend to reduce proposed storage capacities. None of
migration in the subsurface. 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.
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increase storage tonnages, for example, by systematic extraction that leads to pessimistic outcomes. Existing test injections of
of groundwater, even though engineering optimisation will be CO2494 show that 19 of 20 pilots have not experienced adverse
an essential part of any commercial project. As the CCS pressure buildup with the exception of terminating injection at
endeavour starts to enter into development of the rst pilot Snøhvit. In a related piece of modelling prediction Cavanagh495
projects, it is likely that much more intense scrutiny of candi- states that the boundary conditions of permeability of the
date site information on storage will occur, around each enclosing seal are important and should lie between 1018 m2
commercial injection location. That will start to provide infor- for pressure bleed-off and 1020 m2, or less to retain pressure.
mation to test the predictions made during generic assessments This range coincides with “good quality” hydrocarbon caprocks.
of regional storage formations, which although are expected to Zoback and Gorelick496 inferred an increased risk that seis-
be accurate, they are—as we have commented already—still micity will be induced, especially onshore, by injection of large
unvalidated. volumes of CO2. These earthquakes, it is claimed would cause
Additional complexities can arise when licensing and regu- multiple storage sites to rupture and leak CO2. However, this
lation activities collide with natural subsurface geometries of has been widely critiqued on the basis that (i) licensing of a
reservoir and seal.491 Regulators and lawyers are concerned to storage site before injection and monitoring aer injection will
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avoid damage or trespass into adjacent subsurface property, eliminate known tectonic sites and (ii) will detect anomalous
whilst also attempting to ensure maximum certainty in identi- small tremors before buildup to larger events, (iii) that a pres-
fying injected CO2. In many states of the USA, this may be sure anomaly can be managed by water production, (iv) that
resolved by the acquisition of rights to pore space utilisation physical leakage of CO2 as a consequence of seismicity would
across surrounding properties, although it remains unclear if only occur if the tremor site coincided in space and depth with
this will be to protect against a simple case of physical CO2 the physical CO2—which is very unlikely, (v) the pressure pulse
movement, or will the much greater geographical area of pres- anomaly will decay within 50 years from the time of peak CO2
sure increase be regarded as adversely affected? Different injection rate.
European states have different historical approaches. For From a practical point of view, it still remains very unclear
example, in Germany, different regions are bound by ancient how large-scale CCS storage reservoirs may be evaluated and
mining rights, such that even the federal state cannot interfere. tested. Initial experimental projects, even on industrial scale,
By contrast, the UK has taken a centralised approach where the inevitably choose high-quality reservoirs; assessing the regional
rights to all pore space are managed for the Crown Estate. impact of injection, and assessing the interaction of multiple
However, federal European law has not helped, in that the injections into the same reservoir remains a problem with no
European Emissions Allowance Directive denes a very local clear solution. This causes some analysts to propose that large-
storage site, consisting of the dened reservoir and caprock. By scale, high-quality investigations of saline aquifer regional
contrast, the European CCS Directive allows denition of a geology will be required before any licensing can occur.497
much greater subsurface volume, which can contain multiple Clearly this can take 5 or even 10 years, and may cost many tens,
layers of reservoirs and multiple seals. Unplanned CO2 migra- probably hundreds, of millions of dollars. If undertaken in a
tion from a European Emissions Allowance reservoir need not failsafe and stage-gated process, such investigations could act
be a leakage from a CCS Directive complex. These legal as a terminal slowing of the rollout for commercial CCS. This
approaches will need to be harmonised during the progress of remains a real problem, as there are numerous unpublished
early CCS injection demonstrations. examples of commercial investigations worldwide for CO2
12.2.2 Challenges to the concept of large volume storage. storage which have failed to meet the required performance
Although the practise of injecting dense-phase liquid CO2 is targets and have resulted in the cancellation of project devel-
well established and although the assumed progress is towards opments. Determination of adequate storage, suitable for the
multi-million-tonne-per-year injection sites—some objectors CO2 tonnages envisaged during the entire power-plant lifetime,
still raise potential uncertainty in fundamental processes. is likely to be the rate determining step for CCS worldwide.
These are on subsurface pressure, induced seismicity, aquifer Innovation is badly needed in the technical evaluation of
contamination, and reservoir evaluation. Firstly, we discuss the storage, linked to suitable business models and regulatory
pressure management of subsurface injection. Adding large permissions.
tonnages of CO2 into the subsurface usually implies adding 12.2.3 CO2-enhanced oil recovery. CO2 has been injected
additional uid volume, and in a conned reservoir or aquifer, into the subsurface for many decades for the purpose of
that will inevitably tend towards an increase of uid pressure. improving oil recovery, as mentioned in the beginning of this
Economides & Economides492 suggest that nite poor volumes section. This is overwhelmingly in the USA in southern states of
below ground will limit CO2 injection to 1% of pore space whilst west Texas, Mississippi and Louisiana; although the longest
also reducing rates of injection. Countering this, Cavanagh, duration project is at Rangely and the best-known project for
Blunt and Haszeldine493 point out that, although pressure CCS is Weyburn in Saskatchewan. Most of these 70 or so
buildup needs to be specically managed, perfect containment projects have been and are supplied with CO2 from natural
of pressure by reservoirs below ground is exceptional, and that accumulations of volcanic derivation, so provide some infor-
the rate of pressure dissipation over a large area is the impor- mation on subsurface behaviour but less as an analogue for the
tant factor. If pessimistic assumptions are made of compart- CCS techno-economic system. Four CO2 injection projects are
mentalised storage reservoirs, with impermeable boundaries, currently in operation, with a further nine planned to be
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operating by 2016. Of these, about 75% intend to undertake leakage, are potential difficulties which can be managed with
CO2-EOR where, using conventional injection and production known techniques. CO2 storage is not a passive process but one
plans, 3 tonnes of CO2 produce one additional barrel of oil. The that with responsive monitoring and engineering can be ach-
primary purpose of those projects is to produce oil rather than ieved at scale, efficiently and securely. More work is needed on
to dispose of CO2. This can have a benet in that such projects how to provide sufficient condence in storage site evaluation,
encourage and enable the development of efficient and low-cost to positively inform the process of starting a CCS power-plant
CO2 capture technology, and such projects may fund the development. Additionally, there is a need to produce greater
building of pipeline transportation networks for CO2. However, certainty in the fail-safe retention of CO2, which is shown both
viewed from the objective of CCS, such projects have two by trapping processes measured at laboratory scale and by
signicant disadvantages: the rst problem is that CO2-EOR calculations from natural analogues.
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
13. CO2 sequestration via ex situ
secure long-term retention. Second, the carbon budget overall mineral carbonation
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CO2 released from the combustion of 1 ton of coal in a coal-red wollastonite) and generate valuable by-products may help to
power plant.502,503 progress technologies to the pilot and demonstration phases.
A feasibility study carried out by O’Connor et al.504 estimated Furthermore, it is likely that CO2 mineralisation of waste
that an industrial-scale mineral carbonation operation based streams will nd niche applications for hazardous waste
on the NETL process would impose a 30–50% energy penalty on remediation and as a means for some industries to produce
the power generation process; 75% of this penalty was attrib- valuable by-products from their waste whilst reducing their CO2
uted to grinding the feedstock to <37 mm. On the basis of these emissions. However, if CO2 mineralisation technologies are to
calculations, sequestration costs alone were estimated at 50– offer the kind of CO2 storage capacities required for climate
100 US$ tCO21, an order of magnitude higher than the current change mitigation applications, economically feasible
cost of geological storage at 5–10 US$ tCO21.437 O’Connor’s processes utilising naturally occurring Mg- and Ca-silicates
costings are still used as the official best-case scenario esti- must be developed; and the energy required to grind mate-
mated costs for mineral carbonation by many of the important rials to the required size distribution, together with the low
organisations and agencies advising on climate change and value of the produced material will make this an exceptionally
mitigation strategies, such as the IEA and IPCC.437,457 challenging proposition.
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another signicant fraction used for urea production.511 At by drilling additional targeted and deviated bore-holes. EOR
present, the market for CO2 is several orders of magnitude also competes with other methods of enhanced resource
smaller than the amount of CO2 released into the atmosphere production, such as unconventional gas and tight oil, coal-to-
each year from anthropogenic sources and approximately 60 liquids (CTL) and gas-to-liquid (GTL) technologies.
times smaller than the amount of CO2 emitted from large CO2 to chemicals. There are a vast amount of different
point sources (14 000 Mt per year).512 The following sections chemicals that in theory could be produced using CO2 as a C1
provide a brief overview of the current status of CDR feedstock; however, many would either prove impractical to
technology. produce from CO2 on an industrial scale or have limited
14.2.1 CO2 as a technological uid. CO2 has a number of market potential. Scheme 3 outlines a number of promising
commercial applications as a technological uid, including CO2-derived synthetic targets and their current global market.
enhanced oil recovery (EOR), enhanced gas recovery (EGR), Of particular interest are alkylene carbonates and poly-
enhanced coal bed methane (ECBM) and numerous food and carbonates, which have current global markets of several
beverage applications. CO2 is also used as a coolant in air hundred kt per year515–517 and 4 Mt per year3 respectively,
conditioning units, as a fumigant, for controlling the pH of inorganic carbonates (60 Mt per year),518,519 urea (160 Mt per
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process water in water treatment applications, and as a green year);520 polyurethane (18 Mt per year),521 and acrylic acid and
solvent (including its use in dry cleaning).513 At present, most of acrylates (10 Mt per year).522
the CO2 used for EOR (50 Mt per year) and by the food and 14.2.2 Urea. Urea has been produced from CO2 on an
beverage industry (8 Mt per year) is sourced from natural CO2 industrial scale for many years and currently represents the
reservoirs;512 therefore minor emissions reductions could be largest market for CO2 outside of EOR.3 Urea is manufactured
achieved by utilising captured CO2 instead. via a two-step process that involves the exothermic reaction of
EOR offers one of the largest potential markets for CO2. In a liquid ammonia and dry ice (solid CO2) to form ammonium
recent report, Advanced Resources International estimated carbonate, followed by the endothermic decomposition and
that at least 8 billion tons of CO2 could be sequestered using dehydration of ammonium carbonate to yield urea. The overall
EOR in the US alone.511 This, in turn, would produce between 4 process is exothermic and no catalyst is required.
and 47 billion barrels of additional domestic resources. Given According to the International Fertiliser Association, current
that the US has only 1.6% of the World’s proven oil reserves, global production of urea is 159.4 Mt per year.520 Given that
there is potential for signicant growth in CO2 use and between 0.735 and 0.75 tonnes of CO2 are consumed per tonne
subsequent sequestration via EOR, particularly as oil produc- of urea, CO2 consumption as a consequence of urea production
tion declines in existing wells in the Gulf States. Despite this, is around 119.6 Mt per year. The overwhelming market for urea
the future of EOR is uncertain. High CAPEX and OPEX costs is that of the fertiliser industry, which consumes over 80% of
and uncertainty over long-term oil prices, unclear and ill- total global urea production.3
dened regulations governing EOR activities, and wavering
public support have all impeded deployment of EOR.514
Furthermore, offshore 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 offshore platform
retrot costs, cash ow issues, and alternative, cheaper options
for maintaining oil production in depleting reservoirs, such as
Industrial Global
volume CO2 usage Lifetime of
Process Mt per year Mt per year storage
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The climate change mitigation potential of ramping up urea 14.4 Future outlook
production is poor. As discussed by Fennell,503 the storage of
At present, utilisation of CO2, particularly CO2 from anthropo-
CO2 within urea is short, since the chemical breaks down upon
genic sources, is low. The use of anthropogenic CO2 in place of
application as fertiliser, releasing the CO2 into the atmo-
CO2 derived from natural deposits will offer small emissions
sphere.523 In addition, N2O emissions, of which fertiliser use is
reductions, although in the context of climate change mitiga-
the main source, correspond to around a third of anthropogenic
tion, the impact will be insignicant. In the short term,
N2O emissions, further reducing the case for increasing urea
increased deployment of EOR has the potential to offer the
production as a means for stimulating the development and largest economic stimulus for large point sources to capture
deployment of CCS/CCU technology. and subsequently store their CO2. However, a clear framework
for regulating and incentivising wide-scale deployment of CCS
14.3 CO2-to-fuels and EOR that also addresses potential liability issues associated
with EOR coupled with permanent storage needs to be estab-
The production of fuels from CO2 is ostensibly an attractive lished. Further work is also required to assess the feasibility and
goal, given that the global fuels market is roughly two orders of
any potential deployment issues associated with EOR and
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station, to be operational by 2014, aiming to ‘make the UK a demonstration plant competition in October 2011, with the UK
world leader in this globally important technology’.529,530 Two of Government citing increased costs and the inability to reach a
the applicants for the competition were awarded funding for commercial agreement as the reasons. At the same time, it was
Front End Engineering and Design (FEED) work. The 2010 conrmed that the £1 billion of public funds set aside for the
Spending Review conrmed that Government would provide up rst demonstration would be ‘available for a new process’.538
to £1 billion for the successful project, but on the same day as This new process was launched as a ‘Commercialisation
this announcement was made, one of the remaining applicants Programme’ and involves a competition through which
withdrew from the competition on the grounds that the successful applicants will receive direct funding from the £1
economic conditions were not right, leaving only one remaining billion budget and also the possibility of further revenue-based
applicant—a post-combustion retrot to part of ScottishPower’s support under the CfD FiT mechanism proposed in the EMR.
Longannet coal-red plant. During the same year, the UK Applicants for funding from the new process must be able to
Government reaffirmed its commitment to a further three CCS demonstrate at commercial scale and be operational by 2016–
demonstration projects, and completed a market sounding 2020.539 The separate process by which the EC selected projects
exercise to ‘help the department to explore workable options for for funding under the NER 300 scheme continues in parallel to
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the CCS demonstration project selection and funding the UK Government’s Commercialisation Programme.
processes, and learn about projects being considered by However, under the rst round of the NER 300, no CCS projects
industry’.531 A key development was the decision to make gas were granted funding, though funding is still potentially avail-
red generation eligible for the competition, following recom- able in the second round. The level of funding available through
mendations by the Committee on Climate Change.532 the NER 300 process will be considerably less than was origi-
It was originally intended that funding for the further three nally hoped because the market price of EU ETS allowances is
projects would be nanced by a levy on consumer bills, but this well below the level envisaged when the process was set up. The
levy was later shelved. Longer term, the CCS funding mechanism EC currently anticipate that the total level of funding from the
is bound up in the Electricity Market Reform (EMR) process.533 At process will be between V1.3 billion and V1.5 billion, with
the EU level, it was anticipated that the New Entrant Reserve funding for any individual project capped at 15% of the total,
funding (commonly referred to as the NER 300) would be avail- meaning a maximum of V292–337 million for any one project.
able from the auctioning of 300 million EU ETS allowances, at the At the time of writing (May 2013), the UK Government has
time expected to raise between V4.5 and V9.0 billion in total with announced the two preferred bidders for the Commercialisa-
a substantial fraction of this to be available for CCS projects tion Programme competition. These are the White Rose project,
across the EU. To be eligible, all prospective NER 300 projects are an oxyfuel-based project based at Drax, North Yorkshire and
required to secure 50% co-funding from other sources.534 proposed by a consortium of companies including Alstom, Drax
In December 2010, the UK Government launched a consul- and BOC, working closely with National Grid and who together
tation on the EMR which set out a proposed package of policies form “Capture Power”;540 and the Peterhead project in Aber-
to ‘ensure that low-carbon technologies become a more attrac- deenshire, Scotland, involving Shell and SSE. Both projects are
tive choice for investors, and adequately reward back up currently performing front-end engineering design studies.
capacity to ensure the lights stay on’. These reforms were driven Table 9 details projects which were shortlisted for funding by
by Government’s belief that ‘the current market will not deliver both the EU and UK CCS competitions.
on the Government’s objectives for decarbonisation, security of
supply or affordability for consumers’.535 The four key EMR
mechanisms are: 16.1 Implications for investment in CCS
(1) A Feed-in Tariff (FiT) to stabilise and top-up the revenues The generic investment challenges faced by renewable energy
of low-carbon generators including CCS, transferring electricity and nuclear power plants operating in liberalised energy
price risk from generators to consumers, through a Contract for markets are well understood. The combination of high capital
Difference (CfD). costs and very low operating costs means that such plant are
(2) A carbon price oor to reduce uncertainty for investors typically ‘price takers’ because once constructed, it typically
and incentivise low-carbon generation by topping up the EU makes most sense to run them whenever they are physically
ETS carbon price. able to do so, almost regardless of electricity prices. It is
(3) An Emissions Performance Standard (EPS) to put an conventional gas and coal-red plant that have the ‘price maker’
annual limit on the amount of CO2 that a plant can emit, role and have the dominant inuence over electricity prices as
equivalent to 450 gCO2 kW h1 for plant operating at baseload, they are generally able to remain protable over a wider set of
thereby effectively prohibiting new unabated coal-red plant operating regimes and pass variations in fuel costs through to
but new allowing new unabated CCGT plant. consumers.541 In practice this means that potential investors
(4) A capacity mechanism to ensure that there is sufficient will tend to prefer low capital cost conventional gas-red power
generating capacity to meet peak demand. station projects with operating costs linked closely to electrical
The EMR consultation process was followed by a White output, even if the lifetime levelised costs of electricity from
Paper during 2011536 and in 2012 by a dra Energy Bill537 which higher capital cost projects are similar.541
set out the legislative framework for the proposals. In the CCS introduces another set of challenges because it also
meantime, however, ScottishPower pulled out of the rst carries relatively high fuel and operation and maintenance
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EC NER 300 CCS projects (ranked order) UK CCS projects (alphabetical order)
Don Valley Power Project Pre-combustion, coal UK Captain Clean Energy Project Pre-combustion, coal
Belchatow CCS Project Post-combustion, coal Poland Peterhead Gas CCS Project Post-combustion, gas
Green Hydrogen Industrial application, gas Netherlands The Teeside CCS Project Pre-combustion, coal
The Teeside CCS Project Pre-combustion, coal UK White Rose Project Oxyfuel, coal
UK Oxy CCS Demo Oxyfuel, coal UK
(White Rose Project)
C.GEN North Killingholme Pre-combustion, coal, UK
Power Station petcoke, biomass
Zero Emission Porto Tolle Post-combustion, coal, biomass Italy
ULCOS-BF Industrial application, gas France
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costs, a carbon cost for the residual CO2 emissions which also concluded from a real-options based assessment that the
cannot be captured, and a potential long-term liability associ- CO2 price required to overcome these risks and incentivise CCS
ated with the stored CO2. Whilst the support offered through investment was more than four times that which is suggested by
the FiT mechanism proposed in the EMR suits the character- a typical Net Present Value (NPV) assessment, and still more
istics of low operating cost plant such as nuclear and wind than three times even if the additional capital cost is covered by
power, the fuel costs associated with CCS plants suggest that it full subsidy.545 From their analysis of CCS investments in the US
may require a premium payment that is linked to those fuel policy context, Hamilton and colleagues546 suggest that given
costs. ‘nth of a kind’ cost estimates available and the projected value of
The relatively high variable costs of CCS (when compared to avoided carbon emissions under the then proposed US carbon
nuclear or wind power for example) mean that CCS plants can cap and trade bills, Super Critical Pulverised Coal (SCPC) plant
generally be expected to have a lower position in the electricity with CCS would not present a breakeven proposition until aer
market merit order, which may lead to lower load factors for 2030. Osmundsen and Emhjellen547 argue in their 2010 paper
some CCS plant. This ‘load following’ role in the UK electricity that CCS does not offer a protable proposition and delivers
market has typically been lled by a combination of relatively CO2 abatement at ‘very high cost’. Others contend that the EU
new, low-capital-cost CCGT plants, and coal plants whose build ETS on its own won’t lead to large scale CCS deployment,548 a
costs were sunk several decades ago. A CCS plant in the current view that has some support from within the industry.549 Flan-
market may therefore be squeezed between low variable cost nery550 contends that ‘CCS today lacks both an economically
‘price takers’ (nuclear and wind) and low capital cost ‘price viable policy framework and a business model’. With a different
makers’ (CCGT). Of course, conventional CCGT, whilst lower analytical approach, Evar assessed stakeholder perceptions of
carbon than conventional coal, is still not low-carbon, which the uncertainties over CCS technology development and
presents an opportunity for low-carbon, potentially load- whether support levels will be sufficient: he concluded that
following plant such as CCS. Depending on the contribution ‘experts express certitude in the prospects for deploying large-
of nuclear and wind power to the generation mix, a proportion scale CCS technology in the UK, all the while questioning
of any CCS eet may be able to run at, or near, baseload, but the several underlying technical and policy premises that are
characteristics of CCS described above still present a signicant necessary to ensure this goal’.551
challenge, particularly if, as some suggest, levelised costs for Further issues which concern analysts are pipeline network
CCS are likely to show only small reductions over the next few sizing and the potential long-term liability that CO2 storage
decades as potential reductions in capital cost are offset by represents. It is argued by some stakeholders that with current
carbon price increases.542 policy there is a danger of a piece-meal build-up of pipelines,
In the relatively small literature on CCS as an investment when a more coordinated approach might be more cost effec-
proposition, there appears to be something of a consensus tive in the long run,531 a view which has some support.552 The
emerging that the policy support mechanisms under consider- effect of a sub-optimal pipeline network is to make overall costs
ation, both internationally and in the UK, are unlikely to deliver per unit of output (MWh of electricity or tonne of CO2 stored)
the level of CCS deployment that many suggest will be higher than they could otherwise be. Concerns over the long
required.543 In their 2009 paper, Abadie and Chamorro544 term liabilities associated with CO2 storage are oen raised in
concluded that in the face of the risks associated with uncertain the context of the investment proposition of CCS,550,553 whilst
returns, investment in CCS on coal plants will be delayed. They others question the degree to which the long term CO2 storage
170 | Energy Environ. Sci., 2014, 7, 130–189 This journal is © The Royal Society of Chemistry 2014
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liability is a commercially insurable risk.554 On the other hand, economically inexible generation such as wind and nuclear
the EU directive on CO2 storage, which seems likely to mandate power. Combining these attributes with the potential for
a long term liability fund, may go some to way to addressing geographically diversied fuels sources explains why CCS
these concerns.555 technologies feature so strongly in many countries’ CO2 emis-
sions reduction strategies. However, policy design does need to
recognise the specic techno-economic characteristics of CCS
16.2 Continuing challenges facing CCS policy support and the need for substantial capital grants for early projects,
mechanisms address the inherent fuel price risk, and ensure that the CO2
The UK and EU clearly do have substantial policy support transportation networks are built up in the most efficient long-
offerings for CCS but the key question is whether they will be term manner. The Global CCS Institute have called for
sufficient to deliver both the early-stage investment in demon- ‘substantial, timely and stable’ policy support,526 reinforcing the
stration plants and the large-scale CCS deployment that will be IEA’s call for a ‘stable but exible’ policy framework.525 What is
required if the technology is to make a meaningful contribution also clear is that time is of the essence if CCS technologies are to
to meeting climate policy goals. Research undertaken by the UK be developed and deployed at the scale implied by global policy
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That a storage site will be closed for breach of permit This issue ought to be considered by rms operating in
conditions; particularly risk adverse government jurisdictions.
That the storage site operator will comply with strict
closure and aercare requirements; 17.2 The Environmental Liability Directive560
That all environmental and related nancial liabilities may
The CCS Directive itself does not address the specic mechanics
be placed on the storage site operator;
of liability. Hence, we must look to the Environmental Liability
That there shall be proportionate penalties for regulatory
Directive and the Emissions Trading Scheme Directive given
infractions;
that the CCS Directive delegates this matter to them.
That emission allowances be purchased to cover leakage
Further to Article 34 of the CCS Directive, the Environmental
events.
Liability Directive brings storage site operations within the
The sheer weight and nature of risk management oppor-
liability framework of the European Union. As such, operators
tunities available to the regulator and the commensurate risk
of CCS sites have obligations in respect of the prevention and
management standards, procedures and nancial and related
remediation of environmental damage associated with such
liability requirements placed upon the storage site operators
sites. This applies to all relevant “environmental damage” and
suggests that a “cooperation” or “partnership” approach
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damage in terms of failed climate change mitigation is already 17.5 The UK regulatory response
covered in respect of the types of damage listed in the EU Envi-
Legislative developments at European level have created a
ronmental Liability Directive (2004/35/EC) (including, but not
regulatory framework for offshore CCS within the European
limited to species loss, marine ecosystem damage, fundamental
Community, whilst amendments to the London Protocol on the
changes in land use, damage to land, damage to water, etc.).
Prevention of Marine Pollution by the Dumping of Waste and
These types of damage occur as a result of anthropogenic climate
Other Matter (1972) and the Convention for the Protection of
change as well, which is why CO2 as a pollutant has already been
the marine Environment of the North-East Atlantic (OSPAR
determined to be remediated under climate change mitigation Convention) to allow for sub-seabed geological storage, provide
measures. Thereby, if CCS operators are legally required to buy an international regulatory dimension. Whilst supporting the
emissions credits and CCS operators also bound to cover liability
amendments to the London Protocol and OSPAR Convention in
of the same leakage event, there is a clear double-payment by the
2007, UK announced a competition for funding a full-scale
private sector. This problem of double-counting liability has to
demonstration project.
be addressed by counterbalanced regulatory solutions that push
The Energy Bill was unveiled in 2008 which detailed a
forward CCS technology investment.
framework for the licensing, enforcement and registration of
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A regime based upon licensing is introduced and requires a let their consumers know about any potential changes to their
licence from the relevant authority for activities relating to the contract in terms of pricing or any other changes as such within
storage of CO2 (with a view to its permanent disposal). a certain period of time.
According to the Act, the Secretary of State or the Scottish
Ministers grant a licence that may also attach a set of particular 17.8 The storage of carbon dioxide (licensing etc.)
requirements for a specic applicant. The licence may include regulations 2010565
provisions relating to nancial security in respect of future
obligations, as well as obligations between the closure of an These Regulations introduce a permitting regime for offshore
installation and the termination of a licence. CCS activities under the authority of Energy Act 2008. Further-
The Act also introduces a detailed section about the more, they set out a range of requirements that operators need
enforcement of licences and criminal offences and sanctions to full in order to obtain a storage site permit from the
when activities are undertaken without a licence or where a Secretary of State. The Regulations cover the conditions for
licence holder fails to abide by its prescribed conditions. The granting licences and exploration permits, obligations of the
1998 Act also prescribes detailed plans and approvals that storage operator, closure of the storage site, post-closure period,
and nancial security.
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