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Worldwide innovations in the development of carbon capture technologies

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DOI: 10.1039/C2EE03403D

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Environmental Science
Cite this: Energy Environ. Sci., 2012, 5, 7281
www.rsc.org/ees REVIEW
Worldwide innovations in the development of carbon capture technologies and
the utilization of CO2
Peter Markewitz,a Wilhelm Kuckshinrichs,*a Walter Leitner,bc Jochen Linssen,a Petra Zapp,a
Richard Bongartz,a Andrea Schreibera and Thomas E. M€uller*d
Received 7th December 2011, Accepted 29th February 2012
DOI: 10.1039/c2ee03403d

While Carbon Capture and Storage (CCS) technologies are being developed with the focus of capturing
and storing CO2 in huge quantities, new methods for the chemical exploitation of carbon dioxide
(CCU) are being developed in parallel. The intensified chemical or physical utilization of CO2 is
targeted at generating value from a limited part of the CO2 stream and developing better and more
efficient chemical processes with reduced CO2 footprint. Here, we compare the status of the three main
lines of CCS technologies with respect to efficiency, energy consumption, and technical feasibility as
well as the implications of CCS on the efficiency and structure of the energy supply chain.

Introduction 24 Gt.1 However, a reduction of 50% of the global CO2 emissions

appears necessary to limit the long-term global average temper-
The CO2-footprint of the materials used in everyday life is a new ature rise to between 2
C and 2.4
C by the year 2050.2 The Blue
measure to evaluate the CO2 emissions linked with their Map Scenario of the International Energy Agency (IEA)
production and utilization. Reflecting the efficiency of the use of proposes a wide range of measures to achieve a CO2 emission cap
fossil resources, the CO2-footprint receives a lot of attention in of 14 Gt to meet the 2
C target. Carbon capture and storage
the light of the current climate discussion. By 2050, a business as (CCS) is seen as one of the most important single reduction
usual policy would lead to an increase of CO2 emissions by measures worldwide contributing with 8.2 Gt (Fig. 1). It is
a reduction option suitable for large stationary CO2 point
a sources, such as fossil power plants, cement industry, and
Institut f€ur Energie- und Klimaforschung – Systemforschung und
Technologische Entwicklung (IEK-STE), Forschungszentrum J€ ulich, refineries.
52425 J€ ulich, Germany. E-mail: w.kuckshinrichs@fz-juelich.de; Fax: +49 Parallel to the introduction of CCS technologies, Carbon
2461 61 2540; Tel: +49 2461 61 3590 Capture and Utilization (CCU) is aimed at using CO2 as
b
Institut f€
ur Technische und Makromolekulare Chemie, RWTH Aachen
a carbon source for chemical production and generating value
University, Worringerweg 1, 52074 Aachen, Germany. E-mail: leitner@
itmc.rwth-aachen.de; Fax: +49 241 80 22177; Tel: +49 241 80 26480 from a readily available feedstock.3,4 Exploiting a limited amount
c
Max-Planck-Institut f€ ur Kohlenforschung, Kaiser-Wilhelm-Platz 1, 45470 of the CO2 as raw material for chemical synthesis or for direct use
M€ ulheim an der Ruhr, Germany as gas or liquid can complement its storage in geological rock
d
CAT Catalytic Center, ITMC, RWTH Aachen University, Worringerweg formations.4 This includes the utilization of CO2 for producing
1, 52074 Aachen, Germany. E-mail: thomas.mueller@catalyticcenter.
rwth-aachen.de; Fax: +49 241 80 22593; Tel: +49 241 80 28594 platform and bulk chemicals, as well as increased utilization for

Broader context
The CO2 footprint of our everyday consumer products gives a measure of the intensity with which fossil energy carriers are employed
for their production and during their typical lifetime. Reducing the CO2 footprint seems mandatory, as the limited availability of
fossil energy carriers and the rising level of carbon dioxide in the atmosphere due to the CO2 emissions caused by combustion of
fossil energy carriers is a matter of growing public concern. However, until renewable energy sources become available to a greater
extent, the combustion of fossil energy carriers will continue and increased combustion of coal may even be necessary as a transition
technology. To counter this effect, CO2 capture technologies are being adjusted to the large scale of commercial power stations,
which are one of the major contributors to the global CO2 emissions. Once the CO2 is separated, the question arises of how to store
the captured CO2 for long periods of time or to make use of it as sustainable resource and feedstock. The latter means that, in
essence, we are entering into an anthropogenic carbon cycle. The present review discusses the status of CCS and CCU contributing
with scientific and technological information to the decision finding process that is needed in society and politics.

This journal is ª The Royal Society of Chemistry 2012 Energy Environ. Sci., 2012, 5, 7281–7305 | 7281
Fig. 1 CO2 reduction measures in the IEA Blue Map Scenario, data
from ref. 1.
Scheme 2 Criteria for making CO2 available by carbon capture (blue)
and evaluating the use of CO2 as raw material and gas (green).

concerning the necessary energy expenditure and storage

capacities. A high purity grade of the CO2-stream is generally
required in downstream processing in the chemical industry, as
catalysts, employed in chemical conversion, may be poisoned by
impurities, while impurities incorporated in the products may
impair certain applications (e.g., in the pharmaceutical
industry).4
The transport of carbon dioxide has been commercially real-
ized. Worldwide, currently over 4000 kilometres of CO2 pipelines
(mainly in the U.S. and Canada) are in operation. Many of these
pipelines have been built in the 1980’s. The CO2 is transported to
oil exploration sites and is used for enhanced oil recovery (EOR).
Scheme 1 Innovation phases of technologies for collecting, trans-
However, there are still other transport options, as e.g. truck,
porting, storing and exploiting CO2, adapted from ref. 6.
train and ship.7
The use of a limited part of the CO2 supply by means of
manufacturing polymers5 and fine chemicals.4 Moreover, the fixation and transformation can complement its storage in
physical use of CO2, e.g., in the petroleum and gas industry geological rock formations. This includes the utilization of CO2
(Enhanced Oil Recovery (EOR), Enhanced Gas Recovery for producing, e.g., platform and bulk chemicals,‡ polymers and
(EGR), and Enhanced Coal Bed Methane (ECBM)), may fine chemicals.4,5 There is an industrial policy perspective for the
become important applications in the energy supply field. utilization of CO2,8 but it may not be regarded a single solution
Carbon dioxide can be captured from CO2 containing gases by for the huge amounts of CO2 released by energy conversion
using technologies, which are commercially available (Scheme 1) processes, which characterizes the Teraton Challenge.9
and established in chemical processing. Because of other frame- For the utilization of CO2 as chemical feedstock, the low
work requirements, the application of CCS technologies in energy level of CO2 needs to be taken into account. For chemical
power plants needs a modification of existing technologies and transformation of CO2, energy is required, which can be supplied
the development of improved capture technologies. The main directly by using energy-rich reaction partners or indirectly as
challenges are the large flue gas flows, the chemical composition heat, light or electricity (Scheme 3).4,10 The energy supply may
of flue gases, a high degree of CO2 purity and the CO2 capture likewise coincide with emissions of carbon dioxide. To minimize
rate. Worldwide, activities are focusing at present on identifying the CO2-footprint, the utilization of energy from renewable
energy and cost efficient capture solutions. resources (e.g., electricity from wind power stations) is particu-
The purity of the CO2-stream† after separation is decisive for larly interesting. To evaluate the overall concept, a comprehen-
how much energy is needed for the capture of CO2 but also is sive assessment of the different options necessitates product-
a significant aspect for the transport, storage and exploitation of based complete CO2- and energy-balances that account for the
the carbon dioxide stream (Scheme 2). With increasing require- utilization of CO2 as well as the supply of energy, separation and
ments regarding the purity of the CO2, its capture is more transport.
expensive and requires more energy, whereas with regard to Whereas the storage of CO2 in geological rock formations is
compression, transport and storage, there may be advantages set for long periods, the period of CO2-fixation in products varies
greatly. Most attractive are uses, where large amounts of CO2 are
† The CO2-stream here is denoted as the gas obtained after separation of
the CO2. It consists mostly of CO2, but can also contain other ‡ Bulk chemicals are basic chemicals produced in quantities of more than
components. 10 000 t per annum.

7282 | Energy Environ. Sci., 2012, 5, 7281–7305 This journal is ª The Royal Society of Chemistry 2012
 also a cost analysis for different capture and transport options.
Also, the environmental impact of CCS technologies is analysed.
Last but not least, the worldwide state of development for CCS
and CO2-utilization is summarized (see also ref. 17–22). Even
though CO2-storage is not the priority of this paper, it is briefly
reviewed for the sake of completeness. For a detailed analysis
about storage options, the state of the art, monitoring tech-
niques, etc., the reader is referred to the literature.6,23–25

Carbon capture technologies

There are different commercial technologies to capture carbon
dioxide from gases. In chemical processing, there are many
examples, where the separation of CO2 from gas streams is
implemented on a large scale. The production of synthesis gas,
hydrogen and ammonia are just some examples.4 Technologies
like chemical absorption, physical absorption and membranes
are used today (Scheme 4).7,26,27 Detailed information about
these options can be found in the literature.7,28
Yet the large-scale implementation of CO2-capture in power
plants is linked to many technical challenges, in particular, in the
area of system integration (energy and stream management,
incorporation into the power plant process).29,30 Three tech-
nology routes15,16,28,30 are currently most intensively discussed
(Scheme 5):
Scheme 3 Energy balance for the reaction of CO2 with high-energy
reactants to low-energy products (top) and of CO2 with medium-energy
 CO2-capture from the flue gas stream after combustion
reactants to high-energy products (bottom). (Post-combustion);
 Use of nearly pure oxygen for fuel combustion instead of air,
which increases the CO2-concentration of the flue gas (Oxyfuel);
fixed in products, which are used for long periods and whereby and
added value is generated by the utilization of CO2 (Scheme 2).  CO2-capture from the reformed synthesis gas of an upstream
Feasible uses with a short CO2-fixation time are only relevant in gasification unit (Pre-combustion).
terms of net reduction of CO2 emissions, if the use is repeated All the process families need an additional energy input for gas
very often and substantial amounts of carbon dioxide are fixated separation, capture, conditioning and compression/liquefaction
in an anthropogenic carbon cycle. of the carbon dioxide.
The CCS and CCU technologies are found in very different
stages of innovation (Scheme 1).4,6,11,12 While certain technolo-
gies have been commercially implemented (EOR, production of
urea and methanol), others are found in the pilot stage or at the
threshold of demonstration (Oxyfuel, production of aliphatic
polycarbonates13,14). Yet others are found in a very early stage of
technical development or in the conceptualization stage (CO2-
membranes and artificial photosynthesis).
In this paper, we examine the status of research and develop-
ment of CO2-capture, transport and utilization as well as the
perspectives of the corresponding technologies. We will begin
with an overview on the worldwide status of CCS-technologies
and assess innovative industrially applicable approaches
regarding CCS, while we will only touch upon the physical and Scheme 4 Underlying principles for the capture of carbon dioxide.
chemical exploitation of CO2 including the organo-chemical
utilization of CO2 as the C1-building block.x Concerning
a detailed description and the fundamental aspects of the various
process concepts of CCS, we refer the reader to the literature (see,
e.g. ref. 7, 15 and 16). The focus lies on the discussion of tech-
nology aspects like energy efficiency, capture rates, degree of
impurities and environmental impacts. The analysis comprises

x CO2 as a C1-building block concerns chemical synthesis routes in which

CO2 is used as a carbon source. Scheme 5 Currently favoured CCS-process families.

This journal is ª The Royal Society of Chemistry 2012 Energy Environ. Sci., 2012, 5, 7281–7305 | 7283
 The energy penalty is reflected in a decrease in power plant The most important parameters for operating a post-
efficiency of typically 10 to 14% points. Post-combustion combustion CO2-capture unit are:
processes are assessed with an efficiency loss of 10–12% points,7,31  Flue gas volume stream (this is decisive for the size and thus
while an efficiency loss of ca. 10% points is currently stated for the investment costs of an absorber),
the Oxyfuel process.16 Yet considerable efficiency potentials are  CO2-content of the flue gas as well as the partial pressure of
seen for all technologies. In the mid- and long-term, losses in the CO2 (the partial pressure of the CO2 typically lies in the range
efficiency, ranging from 8–10% points, may be possible. Further of 3–15 kPa, at which the chemical absorption represents the
increases in efficiency may be possible by instituting CCS-tech- most suitable method),
nologies of the second generation, such as new gas separation  Degree of the CO2-separation (typical degrees of separation
processes based on the use of membranes and chemical looping are about 80–95%; higher degrees of separation require a larger
as alternative method for supplying oxygen (vide infra). dimensioning of the separator and cause a greater loss in
efficiency),
 Solvent volume stream (essentially determines the dimen-
CO2-capture after combustion: post-combustion processes sioning of the components found behind the actual absorption
When carbon dioxide is captured after the combustion process, unit),
including the subsequent flue gas cleaning (removal of dust,  Purity of the captured CO2.
sulfur and nitrogen compounds), the process line is described as
‘post-combustion’.32 From a current point of view, the most State-of-the-art. Within the framework of smaller pilot-scale
promising methods are the so-called ‘chemical absorption’ projects and initial commercial applications, several power
processes that are often denoted as chemical washes. The plants implementing CO2-capture from the flue gas have been
solvents favoured nowadays are those based on amines, or those built throughout the world. One of the worldwide largest CO2-
containing ammonia or alkali. Another technical variant is the washes in connection with a power plant process (320 MWel) is
use of amino acid salts. After the absorption, the CO2 is removed currently operated at Shady Point (Oklahoma, USA) for
from the solvent by a regeneration process induced by producing CO2 for the food industry. The amine-based chemical
a temperature increase and/or pressure decrease. The solvent is washes attain a separation capacity of 800 t CO2 per day, which
then recirculated and the separated CO2 processed for the corresponds to about 15% of the total CO2-quantity of the power
transport and subsequent storage. plant. Another example for the chemical absorption based on
amines is the Sleipner Project in Norway. On a natural gas
Development line. The absorption in liquid solvents is an offshore platform in the North Sea, each year about 1 million
industrially tested and widely applied CO2-separation technique, tonnes of CO2 are captured from the recovered natural gas via
with which high purities and degrees of separation can be a chemical wash and then pressed into a geological reservoir
attained. Currently, the most developed technique is the amine- (Utsira field).
based separation method. In particular, monoethanolamine
(MEA) and other amines have found widespread use. In Technical and scientific challenges. Chemical washing
connection with the particular requirements associated with the processes based on monoethanolamine (MEA) and other
power plant processes and flue gas compositions, the stability of solvents are associated with technical as well as fundamental
the solvents as well as the energy efficiency of the adsorption– constraints:
desorption cycle need to be further improved.18 Decomposition of the solvent in the presence of oxygen and other
A possible processing scheme of a plant for post-combustion foreign substances (dust): due to the less complex flue gas
capture of CO2 is shown in Scheme 6.33,34 After the flue gas is composition, the requirements of the chemical washes used today
cooled, the absorption takes place at a temperature of about in the chemical industry are less stringent compared to those of
40
C to 60
C. The CO2-loaded liquid is then directed to wash solutions intended for the cleaning of power plant flue
a regenerator (stripper). The low-pressure steam for the neces- gases. The relatively high oxygen content in power plant flue
sary temperature change for the regeneration of the washing gases causes degradation of the amines, which can be prevented
liquid is taken from the power plant process at a temperature of by adding so-called inhibitors. Residual dust may block the
about 100–140
C. Since the steam is no longer available for filling body and thus impair the operation of the corresponding
electricity generation, this leads to considerable decrease in the unit components.
efficiency of the power plant. Solvent degradation by reaction with sulfur dioxide or nitrogen
oxide from the flue gas: by reaction with SOx and NOx, amines
form salts that have to be precipitated at high temperatures in
special units (reclaimers). This can be avoided by lowering the
residual SO2-content of the flue gas. At about 10 ppm SO2, the
salt formation can be prevented.35 This value lies considerably
below the legally prescribed limit for flue gases released into the
atmosphere (70 ppm or 200 mg m3 SO2 for new plants in
Europe).
Higher energy demand for the solvent regeneration: the energy
Scheme 6 Processing scheme of a CO2-capture from the flue gas (post- input required for regenerating the solvent is decisive for the
combustion). overall efficiency of the post-combustion technique. The energy

7284 | Energy Environ. Sci., 2012, 5, 7281–7305 This journal is ª The Royal Society of Chemistry 2012
consumption (low-pressure steam) amounts to about 4 GJ per
tonne CO2 captured, whereby about 40–50% of the entire low-
pressure steam is needed for the regeneration step.36 Presumably,
the energy consumption can be cut by 50% by using more effi-
cient washing liquids. Further potential savings can be obtained
by optimal design and switching of the individual unit compo-
nents as well as optimisation of the entire system in order to
approach the thermodynamic limit.

State-of-the-art and pilot plants. Currently there are an

increasing number of post-combustion pilot plants, whereby the
captured CO2 is in a range of 0.125 to 500 tons per day.37 Even
though amine-based CO2-washes have been implemented on an Scheme 8 Process diagram of the post-combustion pilot plant in
Niederaußem.41,42
industrial scale, these units have not reached the necessary size
for a power plant. Consequently, an essential challenge is their
optimal thermodynamic design and incorporation into the power with a water content of less than 500 ppm. The primary aim is to
plant process, namely, the ‘‘scaling up’’ of such pilot plants develop a post-combustion method with an efficiency loss
(Scheme 7). The volume streams of the flue gas treated in today’s (including CO2-processing) of less than 10% points. In a next
pilot plants and their corresponding power of below 1 MWel37 are step, the construction of a larger amine wash-based demonstra-
minimal compared to that of an entire power plant. The next step tion plant is planned at the site Eemshaven (The Netherlands),
is the construction of demonstration plants with a power rating where 200 000 tonnes CO2 per year will be captured.41,42
of >10 MWel up to 250 MWel30 before the data can be transferred One German electricity supplier (E.ON AG) has internally set
to today’s conventional power plants with a capacity of 500– its aim to equip all power plants built after 2020 with CO2-
1000 MWel. capture technology. The post-combustion technology is favoured
A pilot plant, which cleans a partial stream of the flue gas, is due to the possibility of a retrofitting of existing power plants, the
currently being operated on the basis of an amine wash (MEA proven technical feasibility as well as the relatively few changes
30 wt%) at the coal power plant in Esbjerg (Denmark).38,39 The required to the actual power plant process. Moreover, there are
CO2-capture capacity is ca. 1 t h1 at a MEA-volume stream of still considerable efficiency potentials and cost-cutting possibili-
about 40 m3 h1. This unit comprises all the required components ties. The target is to reach efficiency losses of less than 10% points
including a reclaimer and has been in operation since 2006.38 as well as CO2-avoidance costs of ca. 30 V per t CO2. In the long
After about 1000 h of operation (500 h thereof in permanent term, even an efficiency loss of only about 8% points is consid-
operation), experience on the interplay of the unit components as ered feasible. At the same time, it is aimed to raise the efficiency
well as the influence of SO2 has been gained. During the first of conventional hard coal-fired power plants to 50% (Project
runs, the energy consumption of the pilot plant was 4.4 GJ t1 50plus, power plant Wilhelmshaven). In a first step, altogether 7
CO2, and the required solvent quantity was 2.4 kg t1 CO2.38,39 In smaller post-combustion pilot plants will be built onto existing
a second project phase, the energy consumption has been power plants with a power rating of <10 MWel (Table 1).43,44
reduced to 3.7 GJ t1 CO2.37 It is one of the main objectives to
further reduce the energy consumption40 aiming at a heat Future developments. More efficient solvents for absorption of
consumption of 2 GJ t1 CO2-captured (at a capture rate of 90% CO2 will enable to significantly reduce the energy input for the
and capture costs of 20–30 V per t CO2). regeneration and to decrease the solvent degeneration. The
In 2010, a post-combustion pilot plant started operation at the current amine-based washes require a high-energy expense, which
power-plant site Niederaußem, Germany (Scheme 8).41,42 An is incurred for desorption of the CO2-loaded solvent. The use of
amine-based wash is being tested there, whereby steam is with- sterically hindered or tertiary amines (aMDEA, MDEA, and KS-
drawn for regenerating the CO2-loaded liquid from the prelimi- 1), frequently in combination with activators for accelerating the
nary heat stretch. A carbon capture of 90% is aimed for; the CO2 reaction, seems to be promising, as they need less energy for
stream is 7.2 t per day. The first test runs showed a purity of ca. desorption as well as for operating the pumps and compressors.
94 vol% CO2. The objective is to obtain purities of over 99 vol% Moreover, the risk of corrosion can be reduced. Another option
is utilizing amino acid salt solutions that are characterized by
a low absorption enthalpy and a low vapour pressure. Moreover,
they exhibit high selectivity, low degradation and high capacities.
Furthermore, they allow high purities of the CO2-stream to be
attained.45 A key factor for the applicability of an absorption
solvent is an extended lifetime and it is anticipated that significant
advances will come from increased understanding of the degra-
dation mechanisms (oxidative and thermal degradation, reaction
with acidic gases, and side reactions with CO2).
The application of aqueous carbonate solutions (e.g., K2CO3)
represents another interesting option, since they are especially
Scheme 7 Scale-up phases for CCS technology development. distinguished by a high thermal stability, resistance to oxygen as

This journal is ª The Royal Society of Chemistry 2012 Energy Environ. Sci., 2012, 5, 7281–7305 | 7285
Table 1 Planned CCS-pilot plants of a German electricity supplier (E.ON AG)a

Place Technology Plant size Amount of CO2 Commissioning

Maasvlakte (NL) Amine (‘‘CORAL’’) 0.3 MWel 2 kt per annum 2008

Karlshamn (SWE) Chilled ammonia 3 MWel 15 kt per annum 2008
Datteln (D) Chilled ammonia n.a. n.a. 2009
Heyden (D) Amine 7.5 MWel 45 kt per annum 2010
Staudinger (D) Amine 0.4 MWel n.a. 2009
Wilhelmshaven (D) Amine 5 MWel n.a. 2010
n.a. (D) Amine (K1-S Solution) 7.5 MWel n.a. 2010
a
n.a. not available.

well as by relatively low absorption and desorption heat values. A base process with an efficiency of about 46%, the loss in efficiency
disadvantage is the low reaction rate, which can be raised by is estimated to be #7.2% points (including CO2-compression and
using additives. An alternative is the so-called ‘‘chilled ammonia’’ CO2-processing).52–55 This method is also principally feasible as
method, in which the CO2 is bound via ammonia and water. This a retrofitting option for existing power plants.
method is marked by a low intrinsic energy demand for absorp-
tion and desorption. In addition, ammonia represents an absor- Reduced efficiency. Efficiency losses are in a range of 10 to 14%
bent that can be produced inexpensively on a large scale.40,46–50 points including capturing and compression of the CO2,7,28,56
whereby the efficiency losses due to compression and liquefaction
Carbonate looping. The ‘carbonate looping’ (often denoted as of CO2 amount to 2–3% points.57 Options to reduce the energy
‘dry sorption’) represents one further post-combustion tech- losses include the development of new solvents, optimization of
nique. Here, calcium oxide (CaO) is carbonized in a reversible the scrubber process (absorption/desorption) and improved heat
and exothermic reaction at 600–700
C and the formed calcium integration of the scrubber and compression process into the
carbonate (CaCO3) calcination in an endothermic reaction at ca. overall power plant process. In the most optimistic scenario,
900
C. The core element of the carbonate looping process is which considers the use of highly developed solvents, all possi-
a dual fluidized-bed reactor (Scheme 9), in which the absorber bilities to reduce the heat demand for regeneration and the
material is cyclically transported between the carbonator (CO2- implementation of all economically feasible heat integration
absorption) and the regenerator (CO2-desorption).51 The regen- methods, energy losses of 9.1% points were calculated (including
eration of the calcium oxide can be enhanced under reduced compression and liquefaction and assuming a capture rate of
pressure.8,52 The released carbon dioxide stream can attain a high 90%).28
degree of purity.
Carbonate looping using CaO/CaCO3 as the absorbing Comparative evaluation of post-combustion technology. There
material is distinguished by the inexpensive and high availability are various advantages, which might promote the application of
of the starting materials. The absorbing material deactivates post-combustion technology:
relatively fast, and permanent and considerable amounts are  Chemical absorption processes are well known;
needed to replace the deactivated material. Although fresh  High optimization potential to reduce energy losses;
CaCO3 has to be continuously added to the process, CaCO3 is  Retrofitting of existing power plants is possible;
sufficiently available and the deactivated CaCO3 is recycled  No fundamental changes of the original power plant process
readily, e.g., by reusing it as a construction material.8 are necessary;
The energy input and the process costs are linked mainly to the  Highest purity of the CO2 (>99.99%) of all carbon capture
reactivation step. Unlike the classical washing techniques, the technology routes.
heat of absorption can be integrated in the power plant process Disadvantages of the post-combustion technology are:
resulting in lower losses in efficiency. Starting from a coal-fired  High costs;
 Comparably large environmental impact; and
 Flexible operation mode has yet to be demonstrated.

Combustion in pure oxygen: Oxyfuel process

The term ‘‘Oxyfuel process’’ denotes the combustion of carbon-
containing fuels with pure oxygen (Scheme 10). After the flue gas
cleaning and washing, the flue gas essentially consists of
a mixture of carbon dioxide and steam. Unlike conventional
power plants, for which the CO2-content in the flue gas ranges
from 12–15 vol%, the carbon dioxide content in Oxyfuel plants
lies at about 89 vol%. By condensing the steam, one obtains
a pure CO2 flue gas, which, after being first demoisturized, dried
Scheme 9 Carbonate looping process. and compressed, can be transported to the storage site.

7286 | Energy Environ. Sci., 2012, 5, 7281–7305 This journal is ª The Royal Society of Chemistry 2012
 separation. Otherwise, a lower degree of purity would lead to
higher residual gas concentrations, which, in turn, would mean
a higher energy consumption of the subsequent components
(e.g., CO2-liquefaction). Thus, an optimum has to be found for
the entire process.28,59
Steam generator: in general, the excess of oxygen during the
combustion process has to be minimized. Today’s power plants
run with an air excess of about 15% or more in order to ensure
complete combustion and to minimise corrosion.63,64 Excessive
Scheme 10 Processing scheme of CO2-capture (Oxyfuel). residual oxygen after the combustion adversely affects the energy
consumption of the flue gas processing, like purification and
compression. Some components related to air and flue gas are
Development line. Nowadays, the oxygen for the combustion operated below atmospheric pressure to prevent the slip of hot
process is supplied by means of cryogenic air separation units, in flue gas to the atmosphere. Unregulated air ingress can amount
which oxygen is separated from the air by condensation at low to several percent (2–4%) of the entire flue gas volume. In an
temperatures (<182
C). This method is being applied world- Oxyfuel plant, such an infiltration would cause the required CO2-
wide on a large scale in the steel industry and in ‘gas-to-liquid’ purity not being reached and would lead to additional energy
plants (fuel from natural gas). The oxygen quantities of the costs.59,64
currently largest planned units are in the range of 800 000 m3 Denitrification and desulfurization: the nitrogen contained in
h1.58 By comparison, a hard coal-fired power plant unit with an the fuel is responsible for the formation of nitrogen oxides.
electrical power capacity of 500 MW and an efficiency of 43% Through the lower flue gas volume streams (no atmospheric
requires, with stoichiometric combustion, an oxygen quantity of nitrogen), the nitrogen oxide concentrations are higher than in
approx. 270 000 m3 h1. Combustion with excess oxygen (today’s a conventional power plant. Whereas typical lignite-fired power
excess air coefficients of large plants lie at about 1.15) raises the plants maintain the NOx-limit values (200 mg m3) with the help
necessary O2-quantity accordingly. of primary measures (e.g., sub-stoichiometric combustion),
When fuel is burned with pure oxygen, the combustion secondary measures may be necessary (selective catalytic reduc-
temperature is higher than that in conventional combustion and tion in DENOX-units) in lignite-fired power plants with CCS-
requires—due to the different heat- and flow-specific limiting technology. To prevent the degradation of the MEA-solvents,
conditions—a modification of the steam generator as well as the residual SO2-concentrations have to be reduced significantly
measures for limiting the combustion temperature, as the heat compared to today’s coal power plants (vide supra).
stability of the applied materials is limited. Thus, a large fraction
of the CO2-rich combustion gas (about two-thirds of the volume State-of-the-art and pilot plants. In 2008, a pilot plant began
stream of the flue gas) is directed back into the combustion operation at the lignite power plant site Schwarze Pumpe, Ger-
chamber (Scheme 10). Furthermore, unreacted oxygen is recy- many, for testing the Oxyfuel method. Having a thermal power
cled back into the oxidation process, thereby decreasing the rating of 30 MWth (coal input: 5.2 t h1, O2: 10 t h1), it is
residual oxygen content in the flue gas. The combustion with currently the worldwide largest Oxyfuel pilot plant.65,66 Since the
pure oxygen leads to largely reduced amounts of flue gas and to combustion process runs at very high combustion temperatures,
a changed radiation heat transfer of the flue gases (due to the nitrogen oxides are formed in significant amounts. Whereas
altered CO2- and H2O-concentration), thereby necessitating conventional lignite-fired power plants forego the taking of NOx-
a new design of heat-exchanger surfaces, a modification of secondary measures, the use of denitrification units (selective
burners, combustion chamber geometries as well as the imple- catalytic reduction) is necessary to maintain the required emis-
mentation of an optimized flue-gas canal system.28,59 sion limits. Until June 2009, 1200 operating hours have been run
in the Oxyfuel mode and about 1000 t CO2 were captured with
Technical and scientific challenges. The recycling of a consid- a purity of 99.7%, and a degree of carbon capture of 90%.
erable fraction of the flue gas stream back into the combustion Moreover, one goal is to realize the advanced ultra-supercritical
chamber as well as the changed amount of excess air presents 700
C-power plant technology (live steam temperature 700
C,
numerous challenges. For example, the reduced amount of excess efficiency without CCS: 50%) with the Oxyfuel method. Current
oxygen causes burning out problems and corrosion on the estimates assume an efficiency loss of 8–10% points, whereby
combustion chamber walls. Another important point is the about 6% points of the efficiency losses result from the air
optimal thermodynamic integration of the CO2-processing into separation unit.
the actual power plant process to reduce efficiency losses. This Further important projects on Oxyfuel are being conducted in
means, e.g., to improve the heat balance by integration of multi- Canada (CANMET Project, 0.3 MWth), Japan (1.2 MWth) and
staged CO2-condensors. Further challenges are:16,28,59–62 the USA (1.5 MWth). Moreover, the Australian Callide research
Air-separation methods: the air separation requires a high- project has been running since 2006, whereby the work on the
energy input, which decisively influences the losses in efficiency of pilot plant (2 MWth) has been finished. Currently, construction
the Oxyfuel power plant. Hence, increasing the efficiency is an of an Oxyfuel unit with a power rating of about 30 MWel is being
important target parameter. The required purity of the necessary prepared in the Callide coal power plant (Unit A) and should
oxygen is about 99.5 vol% (remainder: N2, Ar). This standard is start up this year. In Europe, further Oxyfuel pilot plants are
to be maintained upon further increasing the efficiency of the air currently being operated in the Netherlands (2.5 MWth) as well

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as in Great Britain (3 MWth). Within the European CCS Reduced efficiency. It seems to be possible to achieve a CO2
demonstration programme a 250 MWel demonstration plant is purity of 99.5 vol% using a downstream rectification process,
planned sited in Compostilla (Spain).30 which enables to reduce the fractions of Ar, NOx and O2.
According to calculations of Kather and Klostermann59 energy
Future developments. The production of pure oxygen with losses amount to 10% points (net, LHV) if state-of-the-art
conventional cryogenic techniques reduces the power plant effi- cryogenic technologies for air separation and gas processing are
ciency by ca. 7% points. The capture as well as the processing of used. An optimized heat balance (e.g. integration of compres-
the CO2 intended for transport cost additional 3% points. sors) can reduce the efficiency losses to 9% points. Using opti-
Besides optimizing the whole system, the potential to raise the mized cryogenic air separation processes (e.g. multi-column
efficiency mainly lies in oxygen production. From today’s process) reduces the energy losses to approximately 8% points.
perspective, possible ways to increase efficiency are: However, the additional energy demand of the Oxyfuel process
 technically improving the cryogenic process (e.g., by imple- depends strongly on parameters like O2 purity, capture rate and
menting the three-column process), thereby cutting the energy air ingress. For obtaining higher oxygen purity, higher capture
demand for the air separation by about 20%,28,67 and rate and lower air ingress, increased technical effort is required,
 separating oxygen from the air with other methods, such as which will lead to higher costs.
by using ceramic membranes or chemical looping. Mixed ion electron conducting membranes technology
(MIEC) seems to be a promising candidate for the air separation,
Membranes. Advances in the process for producing pure which could reduce the energy losses further. Energy losses in
oxygen by means of new high-temperature membranes can a range of 6 to 10% points seem to be possible.64,72–74 Chemical
improve the efficiency and cost-effectiveness of the whole plant looping research is actually focusing on investigating suitable
due to improved integration in the thermodynamic process of the materials. Efficiency losses are estimated to be approximately 8%
power plant.68 A key component is the high-temperature air points.54 Membrane and chemical looping technology are in very
separation membrane, which is permeable to oxygen ions above early stages of research and development. They are far away
a material-dependent temperature (mostly >700
C). The mass from commercial application. They have to be regarded as
stream of the separated oxygen hereby depends on the partial capture technologies of 2nd CCS generation.
pressure difference over the membrane, the membrane thickness
and the temperature. Since only oxygen penetrates the membrane, Comparative evaluation of Oxyfuel technology. There are
a high purity can be obtained provided that leaks within the several advantages, which might promote the application of
membrane module are avoided.8,69,70 Basic prerequisites for Oxyfuel technology. These are:
a large-scale utilization of membrane techniques in power plants  Environmental impacts are low;
are adequate membrane materials, an optimal process design and  Cryogenic air separation technology is well known;
a sufficient mechanical strength of the membranes.  High potential to reduce energy losses.
Disadvantages are:
Chemical looping. Chemical looping offers another possibility  Modification of burners and boiler design are necessary;
to supply the oxygen by using metal oxides as O2-carrier  Probably no retrofitting option; as well as
(Scheme 11). Here, in the reactor the fuel is oxidized not by  High costs.
molecular oxygen but rather by the oxygen carrier. The metal
oxide is then regenerated in another reactor by using air as the
Decarbonisation of the combustion gas: pre-combustion
oxidation agent. With the help of the metal oxide, the nitrogen
processes
contained in the air is not directed to the combustion process.
Accordingly, a CO2-rich flue gas can be produced after The method for capturing CO2 from the fuel gas exploits the
condensing the water. Concerning the oxygen carriers, very high combination of converting the fuel to a hydrogen-rich synthesis
requirements are placed on the reactivity and the regeneration gas and capturing the resulting CO2 from the fuel gas. The
capability in repeated oxidation–reduction cycles.8,71 Labora- decarbonized fuel gas is then directed to a combined gas and
tory-scale and pilot-scale tests are running worldwide to identify steam turbine cycle process for generating electricity. The CO2-
suitable materials with the necessary long-term stability. capture takes place after the fuel gas production and the
conversion of the carbon monoxide to CO2 and H2.

Development line. The conversion of fossil fuels to synthesis

gas occurs by partial oxidation in a gasification process. The use
of coal or heavy oil requires cleaning of the synthesis gas in order
to remove ash particles, alkali and sulfur compounds as well as
other impurities. By a subsequent catalytic conversion, the CO is
reacted with steam as oxidant to form carbon dioxide and
hydrogen (CO-shift reaction). Since the fuel gas is available after
the CO-shift at high pressure and consists of high H2-fractions,
the CO2-capture is advantageous by using physical solvents. This
type of gas separation is marked by moderate reductions in
Scheme 11 Illustration of chemical looping combustion. efficiency and costs. It is being commercially used in some

7288 | Energy Environ. Sci., 2012, 5, 7281–7305 This journal is ª The Royal Society of Chemistry 2012
branches of the chemical industry and is, thus, state-of-the art favoured, as H2S and COS can also be removed from the fuel
technology.75 An air separation unit is placed before the gasifi- gas. A methanol-based absorbent serves as the solvent, which
cation process in order to increase the yield in the gasification can be regenerated with the help of nitrogen and a temperature
step, to keep atmospheric nitrogen out of the synthesis gas change. The advantage of these washes is the possibility to
process, as well as to minimize the volume streams and, hence, combine the fuel gas desulfurization with the CO2-capture. After
the unit components. After the conversion of the CO, the fuel gas the washes, the H2S and COS fractions in the fuel gas are less
produced in this way consists almost exclusively of carbon than 1 ppm.80
dioxide and hydrogen (Scheme 12).76 Another technology to separate H2 and CO2 is the pressure
swing adsorption (PSA), where CO2 is selectively absorbed in
State-of-the-art and pilot plants. Since the 1980s, ‘Integrated a set of switching beds containing layers of solid adsorbents such
Gasification Combined Cycle’ (IGCC) power plants without as activated carbon, alumina and zeolites.81 The process is built
CO2-capture have been built, which operate with coal, residual around adsorptive separations of cyclic character, with two basic
oil and petroleum coke. However, only five coal fired IGCC steps: adsorption, in which the more absorbable species are
power plants have been built worldwide since the mid-1990s selectively removed from the feed gas, and regeneration
(Buggenum 253 MW, Wabash River 262 MW, Tampa 250 MW, (desorption), when these species are removed from the adsorbent
Puertollano 300 MW and Nakoso 250 MW).77 So far, IGCC so that it can be ready for the next cycle.
power plants are less reliable compared to conventional coal fired Operating gas turbines with synthesis gas is state-of-the-art.
power plants. Long start-up periods and low availability are The operation with hydrogen-rich fuel gas, however, demands
related to high operational and maintenance costs.28 The tech- changes of the operation mode, adaptations of the combustion
nical shortfalls of the plant in Puertollano, e.g., were caused chambers as well as other burner concepts. The fuel gas is diluted
mainly by the gasification unit.78 with nitrogen from the air-separation unit or with process steam
For gasifying coal on a large scale, gasifier types based on for increasing the power and limiting the work temperatures.
a solid-bed process are being applied worldwide. The solid-bed Thus the formation of nitrogen oxides is countered.82
gasification process according to the Sasol–Lurgi method
currently has a market share of over 75%.79 Fluidized-bed Technical and scientific challenges. The efficiencies of IGCC-
gasifiers and entrained-bed gasifiers are particularly suited for power plants are comparable to those of conventional steam
the operation of an IGCC-power plant. Entrained-bed gasifiers power plants.7,28,56 Nonetheless, the required availabilities could
allow higher coal throughputs, which allow the construction of not be attained with some of the existing IGCC-plants. More-
units with a higher capacity. Moreover, a wide spectrum of coal over, such power plants are more complex and the investment
types can be exploited (e.g., lignite coal and hard coal). For costs are clearly higher than those of conventional power
converting the carbon monoxide in synthesis gas to CO2 and H2, plants.83 Consequently in the past, only few coal-fired IGCC-
the acid–gas shift method and the desulfurized synthesis gas shift power plants have been built. Thus, the essential challenges are
are utilized currently. The former method necessitates the use of improving the availability as well as reducing the costs.
sulfur-resistant catalysts in the CO-shift reactor, as the desul- Compared to conventional power plants, those with CCS-tech-
furization takes place only after the CO-shift reaction. nology might be advantageous because of the high product
Physical washes can be used for the CO2-capture process due flexibility. Thus, the synthesis gas might also be used for
to the favourable partial pressure of CO2 and the higher overall producing chemicals or fuels (e.g., methanol) or the produced
pressure. Nowadays, the use of physical solvents (e.g., rectisol) is hydrogen can be used for other applications (e.g. fuel cells). This
possibility to manufacture other products besides electricity and
heat (poly-generation) might also lead to a higher plant utiliza-
tion and greater flexibility.

State-of-the art and pilot plants. Coal fired IGCC plants with
CCS-technology are generating great interest, although many
plans to invest in IGCC power plants have been cancelled. One
planned project is the IGCC plant in Hatfield (Great Britain),
with a power rating of 900 MWel and a capture rate of more than
90%, which has been approved for funding within the European
CCS demonstration programme.30 The construction of
a demonstration plant with a capacity of 270 MWel is also
planned in Canada, where the start-up of this unit is expected in
2015. Since 2006, construction of a coal-fired IGCC plant with
CCS-technology has planned at the power plant site H€ urth. The
heart of this power plant is an entrained-bed gasifier (40 bar,
complete quench), which is suitable for the use of lignite and
hard coal. A target efficiency of ca. 44% is stated for the opti-
mized power plant with CCS-technology. The degree of carbon
Scheme 12 Schematic representation of an IGCC-plant with CO2- capture is about 92%, and the specific emissions value is 107 g
capture.76 CO2 per kW h.

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 Future developments. The use of fuel gas in a gas turbine places is being discussed nowadays for those plants that will be built in
great demands on the fuel gas cleaning, in particular the removal the near future. This concept infers that for a later retrofitting
of dust. Hydrogen-rich fuel gases (hydrogen fraction of over with CCS technology, certain unit components should be
50%) are currently used in gas turbines of a smaller power rating designed accordingly already in the planning stage (refer to
in refineries.84 The utilization of hydrogen-rich gases in heavy- ref. 94).
duty gas turbines (F-class) is the current focus. The feasibility of From experience, the efficiency of a retrofitted power plant is
the combustion of hydrogen-rich gases in gas turbines has been lower than that of an optimally designed new power plant.
shown in a large-scale demonstrator of a combustion chamber. Considering the substantial losses in efficiency of power plants
However, the design of the compressors, turbines and burners with combined CCS, the decision for a CCS-retrofitting is
has to be further developed and optimized.75 Plans for pilot determined by the remaining economic lifetime and may be
projects are currently concentrating on the thermodynamic worthwhile for relatively new plants. Another important crite-
optimal integration of CO2-capture into the overall process. The rion is the additional need for space for installation of CCS-units.
first step involves proving the principal technical feasibility of Thus, it is estimated that, e.g., for a MEA-wash, including the
IGCC-power plants with CO2-capture. Since oxygen is required components for the subsequent CO2-processing (liquefaction
for the gasification process, the costs for such IGCC-power and compression), an additional 50% of the original total area is
plants are higher and the plants individually consume more needed.76 How far a CCS-retrofitting changes the power
energy. A more energy-efficient supply of oxygen for the pre- dynamics and thus deviates from the optimal running mode of
combustion power plants can contribute considerably towards a power plant is an important question from the viewpoint of the
improving the respective efficiency and reducing operation costs. power plant operator and cannot yet be answered. The high
efficiency losses upon retrofitting cause a reduction in the orig-
Efficiency losses. Efficiency losses in commercially operated inal power supply. Consequently, the energy supplier has to
coal fired IGCC plants caused by carbon capture with physical decide whether to compensate for these energy shortfalls by
scrubbing processes are in the range of 9 to 12% points.28,57,85–88 A either building more power capacity or buying this additional
combined CO2 separation and water gas shift reaction could lead power on the market.
to further reduction of energy losses.89 Substituting physical Among the most favourable CCS-technology lines, only those
scrubbing processes by application of polymeric membranes applying the post-combustion process (e.g., amine scrubbers) are
could reduce the energy losses to 8% points.28,85 The capture rate considered suitable for a retrofitting. For the other technology
of today’s IGCC power plants with physical washes might be lines, practically no operation experience exists or fundamental
lower compared to that of other power plant concepts with CCS technical problems have to be solved first. A suitability of the
because some CO2 is needed for stable gas turbine operation and Oxyfuel method for a retrofitting of existing power plants has not
meeting NOx requirements.28 yet been clarified. First model-supported simulations (see ref. 95)
show that a power plant operation with oxygen and air might be
Comparative evaluation of the IGCC technology. There are feasible. Nonetheless, it is unknown how far high-temperature
some advantages, which might favour implementation of the corrosion or carbonization effects of the boiler material may
IGCC technology: impair the function or life span of the boiler. A complete
 High efficiency potential; replacement of a steam generator, which represents one of the
 Poly-generation of electricity and hydrogen gives flexibility. most expensive construction components, would equal the costs
Disadvantages of the IGCC technology are: of building a completely new power plant. Since the pre-
 High investment costs; combustion variant represents an entirely different technology
 Lower availability and reliability so far; line compared to a conventional steam power plant, it is not
 Less technology experience compared with conventional suitable for retrofitting. Even though the retrofitting of existing
power plant technologies. IGCC-plants with CCS-units is being discussed internationally,
it does not play a role due to the low number of such power
plants existing throughout the world. Hence, only the retrofitting
Classification of CO2-capture approaches for retrofitting of
with the post-combustion method is discussed in the following.
power plants
As mentioned above, high residual concentrations of SO2 in
It is anticipated that the CCS-technology will be commercially the flue gas degrade the amine-based solvents used today.
available at the earliest as of 2020. Even though the power plants Moreover, it is still unclear, which degree of purity is required for
built until this date should exhibit the highest efficiencies, they the transport and storage of CO2. Hence, the SO2-concentrations
will not have CCS-technology. Since 2005, approximately must be clearly reduced below current levels, making it necessary
350 GW new coal fired power plants have been built worldwide. to enlarge the SO2-stripping units. For an existing power plant,
Additionally, old coal fired power plants have been substituted this means that the existing flue gas stripper would have to be
by new coal fired power plants.90–93 According to the actual modified. An alternative is to exchange the degraded solvent
energy projections of the International Energy Agency (IEA), the more often.
capacity demand of coal-fired power plants will increase until Large quantities of low-pressure steam are needed to desorb
2020 in a range of 350 to 675 GW. Consequently, retrofitting of the CO2-rich amine liquid. As this steam is no longer available
existing power plants with CCS technology is an important for the electricity generation, its removal is decisively responsible
option. To minimize the losses of efficiency as well as to keep for the substantial losses in efficiency. Thermodynamic calcula-
costs low, a prospective ‘capture-ready’ concept for power plants tions96 show that about 65% of the complete low-pressure steam

7290 | Energy Environ. Sci., 2012, 5, 7281–7305 This journal is ª The Royal Society of Chemistry 2012
of a coal-fired steam power plant is needed for the desorption
process. A retrofitting requires modifications of the low-pressure
turbine part, of the preheaters (heat exchangers before the steam
generator), of the condenser as well as of the cooling water
pumps. Since the low-pressure part of the turbine can only be
supplied with one-third of the steam, two stages of a three-stage
designed low-pressure steam turbine cannot be used. From pilot
plant experiments, it is known that a pressure of about 3.2 bar is
necessary for regenerating the CO2-rich amine solvent. As this
pressure would fall below this level during a partial-capacity
operating mode, the required steam would have to be taken from
the mid-pressure part of the turbine at a very much higher
pressure level, which, in turn, would lead to additional losses in
efficiency.96
Fig. 2 Schematic phase diagram of pure CO2.
A retrofitting with a MEA-unit leads to a 30% higher cooling
water demand than that of a conventional power plant with pipelines are generally not actively cooled, the ambient temper-
CCS.96 The higher water consumption is essentially attributed to ature is (besides the pressure) decisive for the aggregate state of
the components amine wash, flue gas cooling as well as CO2- the carbon dioxide during the transport. Above the critical
compression. In particular, the flue gas cooling before the temperature of 304.2 K (31.2
C), the CO2 is in supercritical state
absorber causes a clear increase in the total heat load to be and resembles a liquid with respect to its density and flow
removed. Which ‘capture-ready’ measures should be taken behaviour. Because of its high dissolution capability for many
depends on the cooling water system. Thus, in a closed cooling hydrophobic substances, supercritical CO2 is used as a solvent
circuit, additional space has to be planned for cooling towers. (e.g., in the food industry and petrochemical industry).100–102
With freshwater cooling, it has to be guaranteed that an addi- Another important property is that CO2 readily dissolves in
tional take-up of fresh water is possible.36 water. Under standard conditions, about 0.9 l gaseous CO2
About 25% of the total losses in efficiency are attributed to the dissolves itself in one litre water in the form of carbonic acid.
processing of the carbon dioxide, before it is transported to the Note that the pH value of the aqueous carbonic acid can be tuned
storage site.96 Incorporating the heat resulting from the by adjusting the CO2 pressure.103,104
compression of the CO2 intended for transport is highly signifi- For choosing the appropriate transport option, the required
cant for improving the energy balance by decreasing these effi- capacities, the geographical location, security issues and the
ciency losses. technical facilities need to be considered. For discontinuous
One advantage of amine-based units is that, in the case of transport, as by truck, train or ship an intermediate storage
a malfunction of the washes, the power plant can continue to be option has to be planned for matching the continuous capture of
operated. Moreover, there is the possibility to enter step-wise CO2 from the power plant. Currently, CO2 is transported by
into the CO2-capture process by determining the CO2-partial truck, ship or pipeline. The transport by truck and train in
streams or to hereby set constant flue gas streams as a function of pressure vessels is feasible for small amounts (up to a few thou-
time.76 Furthermore the possibility of a better flexibility of power sand tons CO2 per year) to be transported over short distances.
plants with wash liquid-based CCS is notable. In the context of The preferred option for the transport of large CO2-quantities
a liberalized electricity market with corresponding electricity (e.g., for EOR) is currently via pipelines. Worldwide, there are
price deviations, the regeneration of wash liquids could be done over 4000 kilometres of CO2-pipelines (mainly in the USA and
in time periods, in which the electricity prices are relatively low.97 Canada), although the covered areas and the lengths of the
Limiting conditions and testing criteria have been formulated networks are not comparable with natural gas or petroleum
about whether a power plant is suited for a CCS-retrofitting.97,98 networks. Existing CO2-pipelines (mostly built in the 1980s)
Besides the aforementioned need for space, additional cooling transport primarily CO2 used for enhanced oil recovery. The
water, and the availability of CO2 storage, the concept comprises existing pipelines have been operated reliably and safely for more
the turbine design, heat-exchanger designs, incorporation of than two decades and can be regarded as state-of-the-art tech-
compression heat into the heat balance as well as the absorber/ nology.24,105,106 A statistical analysis of incidents in the USA
desorber unit design.97 The efficiency of retrofitting a ‘capture- points out that there have been no serious accidents.107 Few CO2-
ready’ power plant may be by about 1.5% points higher as pipeline damages were caused by problems with overpressure
opposed to that of an unprepared power plant.36 The additional valves and seals, poor welding seams as well as corrosion
specific construction costs of a plant retrofitted with a MEA-unit damages. Typical costs for the transport of CO2 in pipelines are
are more than 20% higher than the costs for a new, optimized onshore 1–7 Euro per tonne CO2 and 100 km, whereas
power plant equipped with MEA.62,99 the offshore transport costs 1–11 Euro per tonne CO2 and
100 km.24,105,106
CO2-transport
CO2-storage
For logistic and economic reasons, CO2 must be transported at
high densities. The phase diagram with the melting and vapour Worldwide, the options to store CO2 in geological storage
pressure curves of pure CO2 is given in Fig. 2. Since CO2- formations are being discussed intensively. The storage of CO2 in

This journal is ª The Royal Society of Chemistry 2012 Energy Environ. Sci., 2012, 5, 7281–7305 | 7291
the ocean is connected with negative impacts on the oceanic flora storage projects worldwide is shown in Table 3.24,105 The annually
and fauna and prohibited according to international agreements stored CO2-quantities vary from a few thousand tonnes up to
(OSPAR, London Convention). In geological storage options, a million tonnes CO2 (for comparison: a new generation 500 MW
the carbon dioxide is trapped in gas-tight rock formations, hard coal unit emits ca. 2.4 million tonnes CO2 per year). An
whereby the following options are discussed: analysis of the storage capacities in Germany shows that the
 Deep-lying, unused brine-containing porous rock layers so- onshore potential is sufficient for only a few power-plant
called ‘saline aquifers’ onshore, as well as below the ocean generations.
bottom,
 Depleted natural gas- and petroleum reservoirs including
Aspects of CO2-purity with respect to CCS-technologies
almost depleted reservoirs, whereby the amounts of oil and gas
extracted can be increased by CO2-injection (Enhanced Oil After the carbon dioxide is captured, the gas stream still contains
Recovery, EOR; Enhanced Gas Recovery, EGR), as well as impurities. Different requirements may be placed on the purity of
 Coal seams possibly combined with the recovery of coal the carbon dioxide regarding its transport, storage or utilization.
seam gas (Enhanced Coal Bed Methane, ECBM). In general, the stricter the purity requirements are, the greater the
The CO2 is stored by structurally trapping it below a gas-tight technical complexity and energy expenditure and, hence, the
barrier rock formation (e.g., clay stone or salt) with a convex costs for CO2-capture and its processing. Therefore, it is
shape or without structural encapsulation in extensive storage important to find a technically and economically feasible
reservoirs. At typical pressures and temperatures in saline aqui- optimum over the entire chain (power plant as well as the
fers, the density of the CO2 is lower than that of the ambient rock capture, treatment, transport, storage and/or utilization of CO2).
formation water. Because of its power to rise up, the CO2-phase As no consensus has been reached yet about the necessary CO2
is encapsulated below the convex, gas-tight rock layer. In the purity, they cannot be stipulated at present. This uncertainty is
medium term, a considerable amount of carbon dioxide is dis- reflected in the current CCS-directive of the European Union,
solved in the rock formation water, and becomes mineralized in which states that the gas mixture to be stored should ‘over-
the long term.108 Typically, only storage reservoirs located at whelmingly’ contain CO2. Possible dangers are considered
depths of more than 800 m are suitable for storage of CO2. insofar as the respective concentrations of the substances in the
Worldwide, the largest CO2-storage potential is ascribed to CO2-stream are required to be below a level that would harm the
saline aquifers (see Table 2).6,24,109 Because of their high salt integrity of the transport infrastructure or the storage reservoir
concentrations, the water content of these rock layers is other- and that would pose a significant environmental and health risk.
wise not economically exploitable. Exhausted natural gas and In consequence, the composition of the impurities, which ulti-
petroleum fields also represent a considerable potential. Injected mately cause the undesired side effects (e.g., corrosion), needs to
into nearly depleted reservoirs, the supercritical CO2 mobilizes be evaluated. Since the materials applied to construct CO2-
the remaining hydrocarbons and simultaneously increases the pipelines are known and many years of experience have been
pressure there. Both processes lead to an increased petroleum acquired, the technical requirements for the material in combi-
and natural gas yield. Such hydrocarbon reserves have inherently nation with the impurities can be specified clearly. The effects
proven their gas-tightness, because otherwise they could not have concerning CO2-storage are still the focus of research. Here, one
stored oil or gas there over geological eras. For EOR, EGR and has to differentiate between the possible interactions with the
ECBM, there are big uncertainties of the safety and duration of geological storage surroundings as well as the requirements
underground CO2 storage. The adsorption processes in coal resulting from the storage periphery (e.g., pipe materials, cement)
seams can be used to store CO2, too. In this case, the released at the conditions of the injection.
methane has to be captured in order not to imperil the climate
protecting effect. Purity grade and flue gas processing. How the impurities affect
The as yet largest, currently operated CO2-storage reservoir in the energy costs of the subsequent flue gas treatment (compres-
an aquifer is located below the North Sea. Above the Sleipner sion) depends on the respective contaminants. This will be
natural gas field in the Norwegian Sector, ca. 1 million t CO2 per illustrated using the following simplified comparison of pure
year are being separated as byproduct from the recovered natural carbon dioxide and a CO2-stream with impurities. The assumed
gas and injected into the Utsira sandstone formation located at CO2-purities were selected exemplarily in order to analyse the
a depth of about 1000 metres. Besides the technical demonstra- principal effects of individual contaminants on the compression
tion and economic feasibility, methods for monitoring the work. It is assumed that the carbon dioxide to be stored is
injected CO2 are explored. A selection of currently running CO2- compressed to a pressure of 120 bar by using a two-step

Table 2 Estimations of CO2-storage capacities (109 t CO2)a

CO2 storage Global24 Europe6 Germany109

Deep saline aquifer 1000–10 000 30–500 12–28

Oil/natural gas field 600–1200 10–15 3
Non-exploitable coal seams/ECBM 3–200 n.a. 0.4–1.7
a
n.a.: no information available.

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Table 3 Classification of realized and planned storage projects

Project (location) CO2-source Type of storage Amount of CO2

In Salah (Algeria) CO2-separation from natural gas Natural gas field/saline aquifer 1200 kt per annum (since 2004)
Sleipner (Norway) CO2-separation from natural gas Saline aquifer in maritime area 1000 kt per annum (since 1996)
Weyburn (Canada/USA) Coal Natural oil field (EOR) 1000 kt per annum since 2000
K12b (Netherlands) CO2-separation from natural gas Natural gas field (EGR) 100 kt per annum (since 2004)
Otway (Australia) Natural gas separation Depleted gas field 50 kt per annum (2007–2009)
Snohvit (Norway-offshore) CO2-separation from natural gas Natural gas field/saline aquifer 0.75 kt per annum (since 2007)
Permian Basin (USA) Natural deposits, industry Several oil fields (EOR) 500 000 kt (since 1972)
Gorgon (Australia -offshore) CO2-separation from natural gas Saline aquifer 129 000 kt (2008–2010)
Lacq (France) Oxyfuel power station Depleted gas field 150 kt (2010–2012)
Ketzin (Germany) External delivery Saline aquifer 60 kt planed (start in 2008)
Nagaoka (Japan) Industrial production Saline aquifer 10 kt (2004–2005)
Frio Brine (USA) Industrial production Saline aquifer 3 kt (2005–2006)
Quinshu (China) Industrial production ECBM (pilot project) 200 t

compressor with intermediate cooling, which compresses the a given storage volume than that possible for storing pure carbon
carbon dioxide in several stages to 58 bar. The completely dioxide.
condensed carbon dioxide is then raised to a pressure level of 120 The following gives an estimate of the effect of carbon dioxide
bar by using pumps (see Scheme 13 and Fig. 3). mixtures consisting of several impurities. Two mixtures are listed
The respective physical-state points (1, 2, 3, 4) are found in exemplarily in Table 5 to illustrate the influence of impurities on
both images. The necessary compression work to raise the the compression work.110 Note that they are not to be equated to
pressure of the pure carbon dioxide is 0.089 kW h kg1. The mixtures that actually occur for CCS demonstration plants.
density of the compressed CO2 is calculated at 564 kg m3. In The energy demand for the compression is essentially deter-
the case of impure carbon dioxide, a higher amount of mined by the compressor work. Although the purity of mixture
compression and pump work is necessary due to the different A1 (89.3 vol%) is lower than that of A2 (92.3 vol%), the specific
properties (critical pressure and critical temperature) and compression work is less for A1 than for A2 (Fig. 6).110 This is
because a two-phase area has to be passed through during the attributed to the specific physical properties of the components
compression. From a process-engineering point of view, it has to and their respective concentrations in the gas mixture. For both
be ensured that the mixture has first been completely condensed mixtures, the densities are depicted in Fig. 7,110 which both lie
before the pressure is raised by the pumps. Since the individual clearly below that of pure carbon dioxide, which infers that
components have other properties than carbon dioxide, the a higher storage capacity is needed.
amount of work for the compression depends on the composition In practice, it is attempted to separate the components of the
of the impurities. The following shows how single components contamination as far as possible before the liquid pump. Typical
influence this process, whereby impurities of 5% and 10% are purities of the carbon dioxide to be stored are in the range 93–
assumed exemplarily in order to better illustrate the relationships 98% CO2. However, with respect to energy consumption, the
(Table 4).110 separation is disadvantageous. With this in mind, one has to find
To be able to recognize the effects of the individual substances, an optimum regarding purity, degree of carbon dioxide captured
the extra compression work for each respective impurity was and energy expense, which meets economic criteria, ensures
compared with the aforementioned case of a pure CO2-stream safety and the purity requirements prescribed for storage.110
(Fig. 4).110 If the contamination, e.g., consists only of nitrogen,
the compression work is 9% and 15% greater due to the higher Purity grade and CO2-transport. The composition of the
boiling point of the particular gas mixture (with 5% and 10% cleaned flue gas depends on the actual power plant process as
impurities, respectively). Most impurity components cause an
increase on the compression work. An exception is sulfur
dioxide, as it has a lower boiling point than that of carbon
dioxide and, thus, requires less compression work.
Moreover, the presence of impurities affects the density of the
gas mixture. All impurity components cause a reduction of the
density and, hence, of the storage capacity (Fig. 5).110 For
example, in the case of a 5% or 10% N2-contamination, approx.
30% or 40% less carbon dioxide, respectively, can be stored at

Fig. 3 Compression of a pure (left) and contaminated CO2-stream

Scheme 13 Simplified CO2-compression system. (right).

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Table 4 Boiling pressures and molar masses of binary CO2-mixtures (90% and 95% purity)

Contaminant

H2 CH4 N2 CO O2 Ar CO2 SO2

1
Molecular mass kg kmol 2 16 28 28 32 40 44 64
95% CO2–5% Contaminants
Molecular mass—mixture kg kmol1 41.9 42.6 43.2 43.2 43.4 43.8 44.0 45.0
Boiling pressure Bar 127 67 79 77 72 72 58 53
90% CO2–10% Contaminants
Molecular mass—mixture kg kmol1 39.8 41.2 42.4 42.4 42.8 43.6 44.0 46.0
Boiling pressure Bar 143 75 94 91 84 83 58 50

Fig. 6 Effects of impurities of flue gases (CO2-mixtures) on the

Fig. 4 Effect of impurities on the compression work (1 to 120 bar) in compression work.
comparison to pure CO2.

Fig. 7 Effects of flue gas impurities on the storage density (120 bar,
40
C).

well as on the respective CO2-capture method. Typical impurities

Fig. 5 Effect of impurities on the storage density in comparison to pure for the respective CCS technology lines differentiated according
CO2 (120 bar).
to the energy sources are listed in Table 6.111,112 Whereas the
fractions of argon and nitrogen dominate in the Oxyfuel tech-
Table 5 Composition of flue gases (dry) after the capture assumed in the niques due to air penetration, the contaminants CH4 and H2
analysis of the storage capacity occurring in the pre-combustion process result from the actual
gasification process. Also SO2, NOx, CO and O2 are found in the
Constituents [vol%] Pure CO2 Mixture A1 Mixture A2
power-plant flue gases.
CO2 100.0 89.3 92.3 The composition of the transported gases in a selection of U.S.
Ar — 5.7 0.1 CO2-pipelines is depicted in Table 7.112 The anthropogenic
N2 — 0.3 2.9 sources deal with the synthesis gas production, which explains
H2 — — 4.1
CH4 — — 0.5 the H2S-content as well as the fraction of hydrocarbons with
CO — — 0.1 a lower molecular mass. Upon comparing the compositions from
SO2 — 1.6 — Tables 6 and 7, the differences in the respective compositions of
O2 — 3.1 —
Molar mass [kg kmol1] 44.0 43.7 41.7
the impurities are obvious.
SP pressure [bar] 58 82 100 In general, it applies that the impurities cause a higher loss in
transport pressure compared to the transport of pure CO2.112

7294 | Energy Environ. Sci., 2012, 5, 7281–7305 This journal is ª The Royal Society of Chemistry 2012
Table 6 Typical impurities of flue gases7,111,112 CCS as an option for climate protection
Coal Natural gas Stringent targets to minimize greenhouse gases demand a wide
CCS technology line Component (vol%) (vol%) spectrum of corresponding measures, which comprise all energy
Post-combustion SO2 <0.01 <0.01 sectors as well as industry, commerce, transport as well as
NOx <0.01 <0.01 households. Over 40% of the worldwide CO2-emissions are
N2/Ar/O2 0.01 0.01 caused by electricity generation in fossil fuel power plants. Thus,
Pre-combustion H2S 0.01–0.6 <0.01
this becomes especially relevant in the context of reducing
H2 0.8–2.0 1
CO 0.03–0.4 0.04 greenhouse gas emissions. Measures to be taken regarding fossil
CH4 0.01 2 fuel power plants constitute substituting carbon-rich with
Oxyfuel SO2 0.5 <0.01 carbon-poor energy sources, raising the efficiency of power
NOx 0.01 <0.01
N2/Ar/O2 3.7 4.1 plants as well as capturing carbon dioxide and subsequently
storing it, which is accompanied by an overhaul of the power
plant parks.
As current energy scenarios of the International Energy
Due to the differing properties of the components, the pressure Agency (IEA) show, CCS technologies are particularly signifi-
loss varies greatly. In practice, this means that the pressure at the cant within the scope of worldwide strategies to reduce green-
beginning of the transport has to be much higher than that house gases.116 The IEA projects an increase in today’s CO2
necessary for the actual CO2-storage. An alternative option is to emissions of around 29 billion t per annum to about 62 billion t
integrate additional CO2-pumps or CO2-compressors along the per annum until the year 2050.105 This goes hand in hand with an
course of the pipeline. increase in atmospheric CO2 concentrations to ca. 550 ppm and
a mean temperature increase of 3–4
C. In two scenarios,
Quality criteria for the pipeline transport. The U.S. company a period until 2050 was evaluated. In the first scenario (ACT
Kinder Morgan, which builds and operates CO2-pipelines, has Map scenario), a clear CO2 reduction is attained, so that by 2050,
set standards for the CO2-mixtures to be transported (Table 8).113 about 35 billion tonnes less CO2 will be emitted annually
There are different reasons for setting such criteria. Thus, compared to today’s emissions. This would correspond to a CO2
a minimum purity of 95% CO2 is required in order to guarantee concentration of about 485 ppm in 2050 (Fig. 8).105 The second
the mixability with petroleum. Substances such as sulfur, IEA reduction scenario (BLUE Map scenario) predicts
nitrogen and nitrogen oxides adversely affect the mixability, a decrease in carbon dioxide emissions to about 48 billion t CO2
whereas H2S and hydrocarbons of low molecular weight posi- per annum. Compared to the typical emissions scenario, this
tively affect it. This also explains the relatively high threshold for would correspond to a reduction of about 77% and, accordingly,
hydrocarbons. Further reasons for limiting the respective to a CO2 concentration of about 445 ppm in 2050.
impurities concern material, corrosion and safety aspects. For both scenarios, the particular contributions of the indi-
These standards can be applied only partially to the transport vidual sectors in reducing carbon dioxide emissions are shown in
of CO2-mixtures originating from power plant processes. The Fig. 8.105 In both cases, the energy generation sector contributes
recommended limits { for CO2-pipelines operating with power the greatest towards minimizing CO2 emissions. In both
plant CO2 mixtures (from pre-combustion- or post-combustion scenarios, CCS represents the single measure that contributes
units) are given in Table 9.113,114 most towards reducing CO2 emissions. The CCS-fraction of the
Some of the reasons for limiting the individual substances are total reduction in carbon dioxide due to energy generation is ca.
likewise found in Table 9.107,113,115 For instance, excessive water 21% and ca. 26% for the ACT and BLUE map scenarios,
content in the CO2-mixture is disadvantageous to the pipeline respectively. These results illustrate the importance of CCS-
transport, as this would promote corrosion and the formation of technology in a global context and show that CCS is becoming
hydrates. If solid hydrates accumulate, there is a risk of block- an increasingly attractive option for reducing carbon dioxide
ages and damage to the pipeline periphery (e.g., valves). A emissions.
danger of corrosion results from the formation of carbonic acid,
in particular in combination with other components (such as
SO2 and H2S). The formation of free water, which would boost Economic perspective
the corrosion risk, is also problematic. An excessive water
fraction is generally undesired, since it reduces the energy effi- As mentioned above, there are tendencies to make CCS tech-
ciency of the entire process. Moreover, there is the danger that nologies commercially available from the year 2020 onwards.
the properties of the pipeline material (carbon steel) would be CCS-technologies may be an important option upon stipulating
adversely affected, e.g., by becoming brittle. Likewise undesired stringent reduction targets on the CO2 emissions.117 As there are
is oxygen as an impurity, since together with water, it can many power plants being planned or in construction,118 it may be
accelerate oxidation reactions, which may lead to corrosive necessary to retrofit plants built before 2020 without CCS-tech-
damage. nology. The European CCS-directive envisions a CCS-retrofit-
ting of power plants with a power rating of greater than 300 MW,
whose construction has been begun since 2009. The new
construction of CCS-power plants depends on the energy cost-
{ Limits set within the framework of the EU project ‘‘DYNAMIS’’, effectiveness as well as political framework conditions that
www.dynamis-hypogen.com decisively influence the investment decisions of the energy supply

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Table 7 Gas compositions in existing pipelines112

CO2 CH4 N2 H2S C2Hn CO O2 Source

Canyon Reef 95% 5% <0.5% 100 ppm — — — Anthropogenic

Central Basin 98.5% 0.2% 1.3% — — — — Natural
Sheep Mountain 96.8% 1.7% 0.9% — 0.6% Natural
Bravo Dome 99.7% — 0.3% — — — — Natural
Weyburn 96% 0.7% <300 ppm 0.9% 2.3% 0.1% <50 ppm Anthropogenic

Table 8 Quality requirements for CO2-pipelines in the USA113

Component Concentration Criterion

CO2 >95% Mixability

N2 <4% Mixability
CmHn <5% Mixability
H2O <480 mg m3 Corrosion
O2 <10 ppm Corrosion
H2S <10–200 ppm Safety
Glycol <0.04 ppmv Operation
Temperature <50
C Material

companies. Such framework conditions include the further Fig. 8 Global CO2-reduction in the scenarios of IEA for 2050.
development of the emissions trade, policies on renewable ener-
gies, as well as the future development of primary energy-carrier Cost-effectiveness of CCS: costs for generating power and
prices. avoiding CO2. To project the cost-effectiveness of CCS technol-
ogies, it is relevant to view the costs to generate power (LCOE)
Additional fuel demand upon implementation of CCS-technol- and, concerning the reduction in CO2-emissions, the costs to
ogies. Due to the necessity of gas separation, the efficiency of avoid CO2 (CAC). The electricity generation costs with CCS
a power plant with CCS is always lower than that without CCS. specify the costs of the power production chain comprising the
Decisive for the greater fuel demand of such a power plant is the power plant with CO2-capture, transport and storage of CO2 and
ratio of the efficiency without and with CCS. The additional thus allow a comparison with other technologies for electricity
power needed to compensate for this stems from the ratio of the generation. The parameter here is one unit of electricity, which
efficiency without (hold) and that with CCS (hnew). The addi- flows into the grid, e.g., one MWh. In contrast, the CO2-avoid-
tionally required power amounts to [(hold/hnew)  1]  100 (in ance costs denote those expenses that result for the CO2-quan-
%). In the case of an exemplary hard coal power plant with an tities, which are not released into the atmosphere and, hence are
efficiency of hold ¼ 46% and a post-combustion plant with effi- ‘avoided’. Here, the parameter is one unit of CO2, e.g., one tonne
ciency losses of 12% points, approximately 35% more fuel is CO2. The avoidance costs are figured by comparing the reference
needed. If one succeeds in reducing the efficiency losses to 8% technology without CCS with the corresponding technology
points, the amount of additionally needed fuel is diminished to using CCS. One has to differentiate between the CO2-avoidance
ca. 21%. costs and the CO2-capture costs. The former are always higher

Table 9 Recommended limits for CO2-streams for pipeline transport113,114

Component Concentration Criterion

H2O 500 ppm Technical: below solubility limit of H2O in CO2.

No significant cross-effect of H2O and H2S, cross-
effect of H2O and CH4 is significant but within
limits for water solubility
H2S 200 ppm Health and safety considerations
CO 2000 ppm Health and safety considerations
O2 Aquifer < 4 vol%, EOR 100–1000 ppm Technical: range for EOR, because lack of
practical experience on effects of O2 underground
CH4 Aquifer < 4 vol%, EOR < 2 vol% As proposed in ENCAP project
N2 <4 vol% (all condensable gases) As proposed in ENCAP project
Ar <4 vol% (all condensable gases) As proposed in ENCAP project
H2 <4 vol% (all condensable gases) Further reduction of H2 is recommended because
of its energy content
SOx 100 ppm Health and safety considerations
NOx 100 ppm Health and safety considerations
CO2 >95.5% Balanced with other compounds in CO2

7296 | Energy Environ. Sci., 2012, 5, 7281–7305 This journal is ª The Royal Society of Chemistry 2012
than the CO2-capture costs because of the reduction in efficiency was assumed. A moderate price escalation was assumed for the
and the necessary compensation by a higher power and a higher energy carrier development.
fuel input. At first, the electricity generation costs were calculated without
The costs to generate electricity or respectively to avoid CO2 figuring in the costs of certificates. This would correspond to
result from several factors, which are essentially delineated by the a (theoretical) situation without certificate trade, whereby CCS,
technology, the energy carrier prices and other factors affected e.g., would be legally stipulated. The direct comparison of power
by the environmental and climate-political framework (e.g., the plant variants allows conclusions to be drawn about the change
price for CO2-certificates) as well as by the time-line. Due to the in the origination costs without the cost-effectiveness of plants
long lifetimes of power plants and the corresponding long-term being already answered upon consideration of a certificate
binding of capital, these framework conditions are particularly market. A clear increase in the electricity generation costs
significant for investment decisions. through CCS can be determined for the different variants
The certificate costs result from the remaining CO2-emissions (Fig. 9). As a whole, the electricity generation costs are the lowest
(without or with CCS), for which a certificate has to be made for lignite-fuelled power plants and are the highest for natural
available, and the certificate price, which reflects the market price gas-fuelled power plants. Upon introducing CCS, the electricity
for CO2. Independent of the mechanism of the first allocation of generation costs rise by 37% (natural gas), 58–65% (hard coal)
certificates (so-called ‘grandfathering’ vs. auctioning) it is and 71–81% (lignite). Here it is obvious that the power plants
sensible and necessary to consider the certificate costs for the with high capital costs show the strongest increase of the elec-
electricity supply to completely represent the economic situation. tricity generation costs. This again underscores the importance of
If a power plant does not own certificates, the certificates actually the additional investment costs for CCS. Even though slight
have to be bought. If a power plant does own certificates, advantages may arise for Oxyfuel power plants with carbon
opportunity costs are incurred, since certificates that are needed capture that are fuelled with lignite or hard coal, the results show
are not available for sale. Thus, the allocation mechanism affects that, for the individual fuels, no clear preference for a CCS-
the profit situation and liquidity. technology line can be derived.
Breakdown of the generation costs according to the individual
Electricity generation costs and CO2-avoidance costs. In recent types of expenses underscores the argumentation (Fig. 9). Of
years, a number of studies focusing on costs of CCS were pub- central importance is the increase in capital costs upon intro-
lished.6,7,119–122 Here, CCS and reference plants without CCS are ducing CCS for coal-fired power plants. Compared to power
considered. Post-combustion, pre-combustion and Oxyfuel plants without CCS-technology, the additional investment costs
concepts are assumed for the fuels lignite and hard coal, whereas for those with CCS-technology are essentially attributed to
a post-combustion plant is assumed for natural gas. The elec- investments for carbon capture. Additionally, the importance of
tricity generation costs are based on assumptions of efficiencies, fuel costs becomes clear: the higher the energy penalty (due to the
investment costs, and levels of CO2-capture, among others, efficiency loss), the higher the increase in fuel costs.
compiled within the scope of the current public literature Regarding natural gas, the electricity generation cost depends
(Table 10). The cost calculations are based on an economic life more strongly on the higher natural gas supply prices and the
span of 40 years (coal), 25 years (natural gas), and an interest rate lower investments compared to those for coal-fired power plants.
of 5%. The number of full load hours is gaining importance, as in For all power plant variants with CO2-capture, however, the
the case of increased integration of renewable energies the expenses for the transport and storage of CO2 are low compared
number of full load hours is expected to decrease. The depicted to the CO2-capture costs as well as to the entire electricity
electricity generation costs also contain the expenses for the
compression/liquefaction of carbon dioxide for a pipeline
transport of 350 km and for the storage in a saline aquifer at
a depth of 1000 metres, including the monitoring costs. For
transport and storage of CO2, average cost of 5 V2011 per t CO2

Table 10 Basic data for calculation of LCOE and CAC

Fuel price V2011 per GJ Ref.

Lignite 1.52
Hard coal 2.63 123
Natural gas 6.39 123

Transport and storage costs V2011 per t CO2

Fig. 9 Electricity generation costs (LCOE) of fossil fuel power plants for
5.00 2020 and cost structure (T + S: transport and storage; fuel; O + M:
operation and variable and fixed cost for maintenance; Capex: capital
Escalation % per annum Ref. expenditure) for a reference power plant without carbon capture (REF)
and with carbon capture (other variants) for 7500 h full load hours.
Fuel price 1.20 123
Operation and maintenance 1.50 Certificate costs were not considered (basic data adapted from ref. 119).
Transport and storage costs 1.50 PF: pulverized fuel; IGCC: integrated gasification combined cycle;
CCGT: combined cycle gas turbine.

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generation costs. Altogether, the analyses clearly show that ref. 129–137). Most studies consider the post-combustion
potential cost-saving measures have to focus on the power plant capture route with coal as fuel and MEA scrubbing. More recent
base process and the CO2-capture. studies include the Oxyfuel route, while pre-combustion is
Comparison of the CO2-avoidance costs shows that these costs underrepresented. New, second generation capture technologies,
are lowest for lignite-fired power plants and highest for natural such as chilled ammonia or membranes, have not yet been
gas-fired power plants (Fig. 10).124 Regarding natural gas, this is subject of a LCA analysis.
essentially attributed to the fact that even without CCS, the Underlying assumptions have a considerable impact on the
natural gas-fired power plants clearly show lower specific CO2- outcome of the LCA analyses.128 A significant aspect concerns
emissions. Hence, successful savings have then to be ‘bought’ by the efficiencies of today’s and future power plants. For hard coal,
high expenditures. The CO2-avoidance costs run at 35–40 V per t the assumed efficiencies for a power plant without CCS vary
(lignite) und 42–44 V per t (hard coal) and thus slightly favour from 37% up to 54%, representing diverse stages of technology,
the lignite-fired variants. Also in this case, this slight advantage is but also different technology concepts. Assumptions concerning
related to the high specific CO2-emissions of the lignite-fired the efficiency losses due to the capture system vary between 6 and
power plants without CCS. 18% points. Other parameters with considerable impact on the
The MIT study ‘‘The Future of Coal’’122 quotes individually results are capture efficiency and quality of CO2 captured.
calculated CO2-avoidance costs for coal-fired power plants, Variation in CO2 removal efficiency by 5% points results in
which are much lower than those cited in ref. 125. For hard coal- changed values for the GWP by 20%.130 Independent of the
IGCC plants, these cost estimates of 20 $ per t CO2 may be due to capture technology, the type of fuel has the highest impact on the
optimistic expectations regarding the investment costs. The results.
McKinsey study ‘‘Carbon Capture and Storage: Assessing the In the first step, an inventory of all inputs and outputs of the
Economics’’ states CO2-avoidance costs of 33–50 V per t for entire system was evaluated. These values were then categorised
power plants at the beginning of the commercial use of CCS.6 and assigned to a specific environmental impact, whereby each
Upon considering the cited CO2-avoidance costs of 35–40 V per t impact is characterised by a specific impact equivalent. The
(lignite) and of 42–44 V per t (hard coal), this applies largely for absolute impact equivalents per kWh of electricity produced for
coal-fired CCS power plants. Note that technical and economic each impact category are presented in Fig. 11. As it is sometimes
base parameters (such as power plant efficiency, power, fuel difficult to interpret these absolute values, each effect is bench-
prices, and fixed costs) were estimated differently and different marked in a normalisation step against the known overall effect
calculation methods and limiting criteria were applied. for this class, whereby the world average is chosen as reference
system. All data are related to the total global emissions for the
year 2000, where the global hard coal electricity generation was
Environmental relevance
5136 TWh.138
While the application of CCS in power generation leads to For the pulverised hard coal combustion technology without
a reduction in CO2-emissions and thereby to a reduction in the capture (Fig. 11), the Global Warming Potential (GWP,
global warming potential (GWP),126 a more comprehensive expressed in kg CO2-equivalent) varies from 765 g CO2-eq. per
investigation is necessary to account for other environmental kWh (future plant of 2025)129 to 1092 g CO2-eq. per kWh (old PC
effects.19,127,128 Beside direct emissions at the power plant itself, plant of 2000).130 The values for the Acidification Potential (AP,
other major contributors are upstream processes for coal supply in kg SO2-equivalent) scatter between 0.39 g SO2-eq. per kWh140
or solvent production (post-/pre-combustion), oxygen supply and 2.76 g SO2-eq. per kWh.130 Most important here is the
(Oxyfuel), and downstream processes such as waste treatment assumed flue gas treatment, but also the coal composition. The
but also transport and storage. The holistic approach of Life Eutrophication Potential (EP, in kg PO43-equivalent) and
Cycle Assessment (LCA) opens up the field of vision to addi- Photochemical Oxidation Potential (POCP, in kg C2H4-equiva-
tional fuel supply, changed waste composition and amounts as lent) vary with the efficiency.
well as the environmental impact of chemicals (see, e.g.

Fig. 10 CO2 avoidance costs (CAC) for CCS-power plants for 2020 for Fig. 11 Environmental impacts of hard coal combustion without
7500 h full load hours. Certificate costs were not considered. Basic data capture, normalised to total global emissions in 2000 (adapted from
adapted from ref. 119. ref. 139).

7298 | Energy Environ. Sci., 2012, 5, 7281–7305 This journal is ª The Royal Society of Chemistry 2012
 To estimate the relative importance of the environmental energy penalty, improvement of flue gas treatment, and the
effects, the data were normalised. Hard coal power generation distribution of SO2 and NOx in the compressed CO2 stream vs.
has a considerable share of the global GWP with 10.6%, while the flue gas emissions.142 The environmental effects of IGCC power
share of global AP is small (2.6%). The effects on the EP and plants have been little investigated. Values for GWP between
POCP are even smaller. 692 g CO2-eq. per kWh and 862 g CO2-eq. per kWh and for AP
Upon introduction of a MEA-based post-combustion capture between 0.5 g SO2-eq. per kWh and 0.9 g SO2-eq. per kWh have
technology, the GWP is substantially reduced (Fig. 12). Note been quoted. GWP decreases from 11.5% to 2.9%, while the
that the reduction is less than the proportion of CO2 captured (in share of AP on the global impact increases from 1.5% to 1.8%.
most studies 90%), which is explained readily by the higher EP and POCP remain rather low compared to the global values.
amount of CO2 to be captured for CCS systems due to efficiency
losses and, consequently, increased coal consumption. Addi- Status of development of CCS, CO2-exploitation and
tionally, this higher coal demand results in an increase of -recycling
methane emissions during mining and transport of the hard coal.
All LCA analyses show an increase in all other impact cate- Currently running and planned large-scale CCS projects
gories. The AP and EP of a MEA post-combustion system
Currently, there are a considerable number of pilot-scale plants
increase even though further reductions of SO2 and NOx emis-
worldwide, with which the various CCS-technologies are being
sions by improved flue gas desulfurization (FGD) and selective
evaluated, whereby post-combustion plants clearly predomi-
catalytic reduction (SCR), respectively, are assumed. The
nate.143,144 Planned large-scale projects as well as larger pilot-
underlying reason is the emission of ammonia during MEA
scale power plants that are differentiated according to their
production and degradation130,141 as well as ammonia slip from
respective input energy sources, power ratings as well as the
the SCR. Furthermore, more SO2 and NOx are emitted during
technology routes are listed in Scheme 14.145
coal transport by ship, typically by heavy-oil-fuelled freighters;
For the CO2-capture in gas power plants, the Mongstad
the latter also causing an increase in POCP.
project is aimed at CO2-capture in combination with a gas power
One impact category, which is significantly affected by post-
plant (Karsto, 280 MWel, maximum heat decoupling 350 MWth)
combustion technology, is the Human Toxicity Potential (HTP),
and a refinery. For the first stage, the capture of 100 000 t CO2
which may increase up to 200% for post-combustion systems.
per year is planned; afterwards the plant shall be developed to
This follows from heavy metal and organic emissions into air and
reach an annual capture capacity of 1 million tonnes CO2. The
water, mainly ethylene oxide emissions from the MEA
currently largest Oxyfuel pilot-scale power plant in the world is
supply,130,135 and heavy metal and phosphate emissions into
found at the German lignite-fired power plant site ‘‘Schwarze
water from landfilling coal ash.
Pumpe’’ with a power rating of 30 MWth. Within the scope of the
Normalisation shows that by CCS power generation the GWP
Australian CCS research initiative, an Oxyfuel plant is being
goes down to 2.6%. The contribution to the share in the global
built at the coal power plant site Callide (Queensland). Within
AP increases from 2.6% to 3.2%, while the contribution to EP,
the framework of the Spanish Ciuden project, the construction of
POCP and HTP is small. It has to be pointed out, that AP is
a coal-fired Oxyfuel plant (20 MWth) is currently being pushed.
a regional impact and CCS shifts the acidification potential from
Also to be mentioned are the activities at the power plant site
the region of power production to regions of coal mining and
‘Mountaineer’ (U.S.), where a post-combustion plant (chilled
transport.
ammonia) with a power rating of 54 MWth is currently being
The environmental effects of the Oxyfuel process (Fig. 13) are
built.
similar. While the GWP decreases, the values for AP lie between
Whereas power plants of a lower power rating (<50 MW) are
38% and 40%, for EP between 43% and 58% and for POCP
being built or already being operated, large-scale power plants
between 23% and 123%. The reason for the large scatter might be
are in planning. In Europe, numerous large-scale projects are
in the differences concerning the assumptions on efficiency and
being planned that are targeted at the actual capture, transport as
well as storage of carbon dioxide. These include the coal power-
plant projects Kingsnorth (2  400 MW), Ferrybridge (480 MW)

Fig. 12 Relative environmental impacts of hard coal combustion with Fig. 13 Relative environmental impacts of hard coal Oxyfuel tech-
MEA capture, normalised to the total global emissions in 2000 (adapted nology, normalised to the total global emissions in 2000 (adapted from
from ref. 139). ref. 139).

This journal is ª The Royal Society of Chemistry 2012 Energy Environ. Sci., 2012, 5, 7281–7305 | 7299
 Presently in the world, there are four large projects in which
the capture, transport and storage of carbon dioxide are being
simultaneously demonstrated. They are the projects Sleipner
(Norway), Weyburn (USA–Canada), In Salah (Algeria) and
Snøhvit (Norway). The amount of stored carbon dioxide of the
four projects totals to about 7 million t per annum. Also to be
mentioned here are the EOR-activities in Rangeley (USA), where
CO2 has been utilized for petroleum exploration for 20 years.
Furthermore, numerous other large storage projects are being
planned, in particular, in the U.S. and Canada. It is estimated
that the amount of CO2 stored will rise to 24 million tonnes CO2
until the year 2012.
Within the scope of the GHG-program of the IEA, a survey
was begun with the aim of compiling and summarizing the
Scheme 14 Overview on CCS-projects (Status 2010) with amine (red experiences gained from so-called CCS ‘grand’ projects. Such
circles) and ammonia (purple circles) based post-combustion, pre- projects infer large pilot plants, demonstration plants as well as
combustion (yellow circles) and Oxyfuel process (blue circles). The flag commercial chemical plants and storage projects. In all,
marks projects supported by the EU. 28 projects or plants (Table 11) were identified.143 The largest
CCS-plants are commercial chemical plants, which are imple-
mented, e.g., in the context of producing ammonia and
and Tilbury (1600 MW) in Great Britain, for which feasibility
hydrogen as well as for processing Liquefied Natural Gas
studies are presently being developed. Moreover, construction of
(LNG).
a coal-fired power plant (411 MWel, heat decoupling 411 MJ s1)
equipped with a post-combustion unit is planned at the Danish
coal power plant site Nordjylland. At the Canadian power plant
site ‘Boundary Dam’, the retrofitting of a coal power plant
CO2-capture methods of the second generation
(100 MWel) with a post-combustion washing unit is being plan- Besides the previously described methods to capture CO2 and
ned. The carbon dioxide captured there is to be used in petroleum separate air in power plants, there are many other innovative
exploration. Furthermore, the German activities comprise the technical possibilities to achieve this. Membrane-based methods
construction of post-combustion plants (Wilhelmshaven and as well as the dry sorption of CO2 (carbonate looping) are
J€
anschwalde), a pre-combustion plant at the site H€ urth and the currently the most promising techniques (Scheme 15) for reali-
building of an Oxyfuel plant at the power-plant site J€anschwalde. zation on the large-scale.146,147 Moreover, the ‘chemical looping’

Table 11 Worldwide largest realized CCS-projects

Project/Plant Criterion

Bellingham Cogeneration Facility Separation > 100 kt per annum

CASTOR Project Separation (from exhaust gas) > 10 kt per annum
Great Plains Synfuel Plant Separation > 100 kt per annum
In Salah Injection > 10 kt per annum, separation > 100 kt per annum
K12-B Injection > 10 kt per annum
Ketzin Injection > 10 kt per annum
MRCSP Michigan Basin Injection > 10 kt per annum
Nagaoka Injection > 10 kt per annum
Otway Basin Project Injection > 10 kt per annum
Pembina Cardium Project EOR Monitoring > 10 kt per annum
Petrona Fertilizer Plant Separation (from exhaust gas) > 10 kt per annum
IFFCO CO2 Recovery Plant Phulpur Separation > 100 kt per annum, separation (from exhaust gas) > 10 kt per annum
Chemical Co. ‘‘A’’ CO2 Recovery Plant Separation > 100 kt per annum, separation (from exhaust gas) > 10 kt per annum
IFFCO CO2 Recovery Plant Aonla Separation > 100 kt per annum, separation (from exhaust gas) > 10 kt per annum
Prosint Methanol Plant Separation (from exhaust gas) > 10 kt per annum
Rangely CO2 Project EOR monitoring > 10 kt per annum
SECARB-Cranfield II EOR monitoring > 10 kt per annum
Shady Point Power Plant Separation (from exhaust gas) > 10 kt per annum
Sleipner Separation > 100 kt per annum, injection > 10 kt per annum
Snøhvit LNG Project Separation > 100 kt per annum, injection > 10 kt per annum
Schwarze Pumpe Separation (from exhaust gas) > 10 kt per annum
IMC Global Soda Plant Separation > 100 kt per annum, separation (from exhaust gas) > 10 kt per annum
SRCSP Aneth EOR Pradox Basin EOR monitoring > 10 kt per annum
SRCSP San Juan Basin Storage in coal seam > 10 kt CO2
Sumitomo Chemicals Plant Separation (from exhaust gas) > 10 kt per annum
Warrior Run Power Plant Separation (from exhaust gas) > 10 kt per annum
Weyburn EOR monitoring > 10 kt per annum
ZAMA EOR Project EOR monitoring > 10 kt per annum

7300 | Energy Environ. Sci., 2012, 5, 7281–7305 This journal is ª The Royal Society of Chemistry 2012
 Physical and chemical utilization of CO2
The physical utilization of carbon dioxide ranges from its
application as a coolant and refrigerant to uses in fire extin-
guishers and cleaning processes to its use in the petroleum and
natural gas industry for Enhanced Oil Recovery (EOR) and
Enhanced Gas Recovery (EGR). In recent years, numerous
application areas have been developed and intensively studied.
These include the extraction of natural materials, the processing
and recycling of polymer and rubber products as well as the
impregnation of wood.
The chemical utilization of CO2 as a C1-building block in
synthesis offers the possibility of incorporating it into products
and materials either permanently or at least for a longer period.
Scheme 15 Overview of gas separation processes. This option reflects an emerging anthropogenic carbon cycle
similar to that of photosynthesis. The thermodynamic stability of
CO2 (end production of combustion) and its kinetic inertia (low
method represents an alternative variant for supplying oxygen. reactivity) can be overcome by using energy-rich starting mate-
As all these methods are still found in the early stage of devel- rials as reaction partners and the use of suitable catalysts,
opment, these methods are often characterized as CCS-methods respectively, as has been proven by existing industrial processes
of the ‘‘second generation’’. and manifold research results. Alternative to energy-rich starting
Membranes are materials that selectively allow gases to materials, an endergonic process may be driven by incorporation
permeate through them (Scheme 16). The membrane-based of heat, electricity or light. The highest reduction in CO2 foot-
capture of gases is employed on a large scale for separating CO2 print is achieved, when the energy for chemical processing is
from natural gas.7 Currently, worldwide efforts concentrate on supplied from renewable resources, such as wind power, solar
developing dense, porous, or ion-/electron-conducting collectors or panels.
membranes for capturing CO2 in power plant processes. The The options for chemically exploiting CO2 vary with respect to
selectivity of the membranes for the permeability of various gases the maturity of the technologies. With existing technologies,
essentially depends on the membrane material and transport carbon dioxide is used as a raw material in numerous important
mechanisms. The stream of the gas through the membrane is chemical processes. Currently, the most important applications
decisively determined by the partial pressure difference of the are for the production of urea (107 million t per annum), meth-
gases between the permeated side and the retention side. Hence, anol (2 million t per annum), cyclic carbonates (0.04 million t per
the use of membranes is a technique particularly suitable for annum) and salicylic acid (0.025 million t per annum).
separation at high gas pressures. Several innovative technologies are on the cusp of industrial
The membrane-based separation has the potential to enable realization. The synthesis of carbonates and polycarbonates
improved efficiency and the cost-effectiveness of the whole plant. from CO25,13,149,150 allows immediate accessibility to many
The use of membranes is particularly interesting for H2/CO2- markets in the chemistry and polymer sector.14 The hydrogena-
separation148 because of the large difference in the physico- tion of CO2 to important chemical products such as methanol
chemical properties of the two gases. Here, one can choose and formic acid151 and their derivatives is being intensively
between separating hydrogen or carbon dioxide. Also for the studied. Also the Reverse Water Gas Shift (RWGS) reaction
production of pure oxygen for the Oxyfuel method membranes (eqn (1)) is a feasible option for access into the chemical value
are an interesting option as the conventional cryogenic tech- chain via CO. Since hydrogen is nowadays produced practically
niques are essentially responsible for the losses in efficiency and only from fossil resources, a reduction in the CO2-emission could
the efficiency potential mainly concerns the oxygen production be realized by using H2 from other sources (e.g., wind power or
(vide supra). biomass). The utilization of H2, for example, for producing
methanol (via the reactions given in eqn (2) and (3)) would then
have to be weighed accordingly:

CO2 + H2 # CO + H2O DH298K ¼ +41 kJ mol1 (1)

CO + 2H2 # CH3OH DH298K ¼ 90.8 kJ mol1 (2)

CO2 + 3H2 # CH3OH + H2O DH298K ¼ 49.8 kJ mol1 (3)

Especially attractive in chemical utilization of CO2 is the

aspect that CO2 has unlimited availability. There are various
sources of carbon dioxide for its chemical utilization. In the
chemical industry, carbon dioxide is produced in relatively pure
form. Thus, about 120 million metric tons of CO2 are formed
Scheme 16 Illustration of gas separation with membranes. yearly as a byproduct during the synthesis of ammonia.

This journal is ª The Royal Society of Chemistry 2012 Energy Environ. Sci., 2012, 5, 7281–7305 | 7301
Furthermore, CO2 is formed during ethylene oxide production, like gas separation by membranes, methods for producing
in refineries and during the cleaning of natural gas. Moreover, oxygen, chemical looping as well as dry sorption (carbonate
carbon dioxide results as a byproduct during the production of looping) are regarded as the most promising candidates for
synthesis gas as well as during fermentation processes. The grade a long-term implementation of carbon capture. As all these
of purity of carbon dioxide from ammonia production and from technologies are still in the early research and development stage,
fermentation suffices for practically all synthesis purposes. a large-scale application in power plants is expected only later on
Carbon dioxide captured from power plants can likewise be in the future. They are thus often called CCS-processes of the
used as a raw material. Nonetheless, due to possible impurities in ‘‘second generation’’.
the CO2-stream in the power plant, scrubbing might first be A clear increase of the electricity generation costs through
necessary before the CO2 can be materially used. The various CCS can be expected. The increase is highest for lignite-based
impurities in the flue gases include O2, N2, H2O, H2S, CO, CO2, power plants (71–81%) and lowest for natural gas-based power
SO2, NOx, heavy metals as well as other hydrocarbons. Certain plants (37%). The costs are linked closely to the capital expen-
criteria have to be met upon cleaning the CO2-streams. From diture. Additionally, the importance of fuel costs becomes clear:
a chemical point of view, the stability of the applied catalysts the higher the energy penalty (efficiency loss), the more fuel is
towards catalyst poisons plays a particularly important role and consumed and the more the cost increase. Although optimistic
has to be controlled. Also impurities incorporated into the costs parameters are expected for the IGCC concept, there is no
products may restrict the use in certain fields of application (e.g., clear preference for a single CCS technology line. The CO2
as pharmaceuticals). In contrast to classical chemical syntheses, avoidance costs range between 34 and 38 V (lignite) and more
where other cleaning steps typically follow the incorporation of than 60 V per ton CO2 (natural gas). In a regime with increasing
CO2, the purity of CO2 is essential for its direct physical utili- share of renewable energies, where the level of full load hours is
zation. Since CO2 is often used without further processing steps, expected to decrease, the power generation costs and the CO2
e.g., in the food and beverage industries, CO2-impurities can play avoidance costs are expected to increase considerably. The
a decisive role here. Since further cleaning of the carbon dioxide increase is higher for those power plants with a high share of
accrues costs, one likewise has to consider the economic balance. investment costs.
Moreover, from an ecological viewpoint, the additional energy The introduction of CO2 reduction technologies goes along
expenditure for the CO2-cleaning is likewise significant. with an increase of environmental impact (except the global
There are numerous reactions, where CO2 can be employed for warming potential (GWP)) regardless of the process routes or
chemical synthesis (see, e.g. ref. 4,152–159). Active catalysts are fuel used. This is related to the loss in efficiency and the corre-
available for coupling carbon dioxide with energy-rich unsatu- sponding additional demand for fuel, operating materials (e.g.
rated substrates such as epoxides,13 butadiene or acetylene. solvents) and increasing waste. Therefore, an extensive further
Direct carboxylation of hydrocarbons by inserting CO2 into the optimisation at the power plant alone will not have a recognis-
C–H bond of alkanes, aromatics or olefins is regarded as a door able effect. Reduced environmental impacts can be achieved by
for ‘‘dream reactions’’ of modern catalyst research;160 this would improving upstream processes. When solvents are used in the
open up an elegant route for producing fine chemicals. This process, the toxicological impact on humans and the environ-
pathway would allow the conversion of methane and CO2 to ment increases. Beside that the acidification potential (AP)
acetic acid, benzene and CO2 to benzoic acid, and ethylene and increases noticeably, shifting the impact from the power plant to
CO2 to acrylic acid. Other options are further along the devel- the extraction and transportation of fuel. In comparison to other
opment path. The electro-catalytic and, in particular, the photo- industries the central impact for power production is the GWP,
catalytic reduction of CO2161 would be the most elegant way to which will be decreased.
exploit carbon dioxide, since it mimics the synthesis performance Parallel to the implementation of CCS, the technical and, in
of nature in photosynthesis. However, current heterogeneous particular, chemical exploitation of carbon dioxide (CCU) can
and homogeneous catalysts as well as the technical systems still offer an interesting though limited contribution to the reduction
need to be improved before they can attain technically viable of CO2 emissions. Here, the captured CO2 is a raw material,
efficiencies. which can be made use of in the value creation chain of the
chemical industry. Increased utilization of CO2 may lead to
a reduced carbon footprint of the products. The fixation period
Conclusions
and fixation quantity are decisive for climate protection.
As current energy scenarios show, CCS-technologies are Nevertheless, the utilization of carbon dioxide is an important
becoming a highly important option within the scope of world- option in the total strategy of ‘carbon management’. In partic-
wide strategies to reduce greenhouse gas emissions. Whereas ular, it offers an attractive alternative to the geological storage of
carbon capture is already being commercially applied in certain carbon dioxide, enabling us to exploit CO2 as a valuable resource
branches of industry, e.g. in natural gas processing and chemical in many different applications.
production, the use of these technologies in power plants has not
yet reached such a level of maturity. In particular, with regard to
the capture process as well as CO2-processing, it is important
Acknowledgements
to reduce efficiency losses and investment costs further in order
to satisfy economic and environmental demands. Here, it is This contribution is based on a study commissioned by the
especially important to build demonstration units to reach German Federal Ministry for Economy and Technology (Bun-
market maturity in 10 to 15 years. Additional future technologies desministerium f€
ur Wirtschaft und Technologie, BMWi), Berlin,

7302 | Energy Environ. Sci., 2012, 5, 7281–7305 This journal is ª The Royal Society of Chemistry 2012
Project number 25/08 AZ I D4 – 02 08 15. We acknowledge Dr 29 Iea Ghg, CO2 Capture and Storage – R, D&D Projects Database,
M. J. Bl€
umich for the translation. London, 2009.
30 Zep, EU Demonstration Programme for CO2 Capture and Storage
(CCS)—ZEP’s Proposal, Brussels, 2008.
Notes and references 31 S. Weil, in COORETEC-Workshop, www.cooretec.de, 2009.
32 M. Wang, A. Lawal, P. Stephenson, J. Sidders and C. Ramshaw,
1 IEA, Energy Technology Perspectives – Scenarios & Strategies to Chem. Eng. Res. Des., 2011, 89, 1609–1624.
2050 978-92-64-08597-8, OECD/IEA, Paris, 2010. 33 D. Hein and T. Fischer, Technologiepotenziale und -ziele aus Sicht der
2 United Nations Intergovernmental Panel on Climate Change Forschung, Berlin, 2002.
(IPCC). €
34 O. Korkmaz, G. Oeljeklaus and K. G€orner, 40
3 W. Kuckshinrichs, J. Linssen, P. Markewitz, P. Zapp, M. Peters, Kraftwerkstechnisches Kolloquium K€ unftiges Brennstoff- und
B. K€ ohler, T. E. M€ uller and W. Leitner, STE Research Report, Technollogieportfolio in der Kraftwerkstechnik, Dresden, 2008.
2009, 07/2009. 35 A. B. Rao and D. S. Rubin, Environ. Sci. Technol., 2002, 36, 4467–
4 M. Peters, B. K€ ohler, W. Kuckshinrichs, W. Leitner, P. Markewitz 4475.
and T. E. M€ uller, ChemSusChem, 2011, 4, 1216–1240. 36 R. Irons, J. Davison, G. Sekkapaan and J. Gibbins, 3rd Int. Conf. on
5 T. E. M€ uller, Preprints of Symposia, American Chemical Society, Clean Coal Technologies for our Future, Cagliari, Sardinia, 2007.
Division of Fuel Chemistry, 2008, vol. 53, p. 317. 37 H. Fahlenkamp, B. Epp, S. Telge, C. Stankewitz and M. Dittmar, in
6 McKinsey, Carbon Capture and Storage: Assessing the Economics, Efficient Carbon Capture for Coal Power Plants, ed. D. Stolten and
www.mckinsey.com, 2008. V. Scheerer, Wiley-VCH Verlag GmbH, Weinheim, 2011, pp. 201–
7 IPCC, Carbon Dioxide Capture and Storage—Special Report of the 238.
Intergovernmental Panel on Climate Change, Cambridge University 38 P. e. a. Feron, in 3rd Int. Conf. on Clean Coal Technologies for our
Press, Cambridge, England, 2005. Future, Cagliari, Sardinia, 2007.
8 F. Ausfelder and A. Bazzanella, Verwertung und Speicherung von 39 J. Knudsen, P.-J. Vilhelmsen, O. Biede and J. Jensen, in GHG 8,
CO2, DECHEMA, Frankfurt am Main, 2008. Trondheim, 2006.
9 M. Mikkelsen, M. Jorgensen and F. C. Krebs, Energy Environ. Sci., 40 P. Feron and G. Puxty, in Efficient Carbon Capture for Coal Power
2010, 3, 43–81. Plants, ed. D. Stolten and V. Scheerer, Wiley-VCH, Weinheim, 2011,
10 F. Jin, Z. Huo, X. Zeng and H. Enomoto, in Advances in CO2 pp. 113–149.
Conversion and Utilization, ed. A. Hu, ACS Washington, DC, 41 P. Moser, in NRW Kompetenznetzwerk Kraftwerkstechnik,
2010, pp. 31–53. Gelsenkirchen, 2008.
11 M. Peters, T. E. M€ uller and W. Leitner, TCE, 2009, 813, 46–47. 42 P. Moser, S. Schmidt, G. Sieder, H. Garcia, I. Ciattaglia and
12 W. Kuckshinrichs, P. Markewitz, J. Linssen, P. Zapp, M. Peters, H. Klein, Energy Proc., 2009, 1, 807–814.
B. K€ ohler, T. E. M€ uller and W. Leitner, in Schriften des 43 B. Fischer, in IZT Kongress 2009, Berlin, 2009.
Forschungszentrums J€ ulich, Forschungszentrum J€ ulich, J€
ulich, 44 H. Rode, in COORETEC-Workshop, www.cooretec.de, 2008.
2010, vol. 60, pp. 1–139. 45 T. Jockenh€ ovel, R. V. Schneider and H. Rode, VGB PowerTech,
13 W. K. Offermans, Y. Dienes, W. Leitner, T. Reier, A. Reinholdt, 2009, 4/2009, 89–94.
M. G. J. M€ uller, T. E. Weirich and T. E. M€ uller, Green Chem., 46 K. G€ orner, Post-Combustion Carbon Capture (PCC),
2012, 14, 1168–1177. Gelsenkirchen, 2008.
14 W. Leitner, T. E. M€ uller and C. G€
urtler, in Annual Report 2010, ed. 47 F. Kozak, A. Petig, E. Morris, R. Rhudy and D. Thimsen, GHG9,
J. Sch€ afer, Bayer AG, Leverkusen, 2011, pp. 32–37. Washington, 2008.
15 BMWi, Forschungs- und Entwicklungskonzept f€ ur emissionsarme 48 A. Schimkat, Energiespektrum, 2008, 3/2008, 28–29.
fossil befeuerte Kraftwerke. Bericht der COORETEC- 49 K. Thomsen, in Efficient Carbon Capture for Coal Power Plants, ed.
Arbeitsgruppen BMWi-Dokumentation 527, Berlin, 2003. D. Stolten and V. Scheerer, Wiley-VCH Verlag, Weinheim, 2011, pp.
16 BMWi, Leuchtturm COORETEC – Der Weg zum zukunftsf€ ahigen 155–169.
Kraftwerk mit fossilen Brennstoffen, Berlin, 2007. 50 F. Yi, H.-K. Zou, G.-W. Chu, L. Shao and J.-F. Chen, Chem. Eng.
17 F. Johnsson, Greenhouse Gases: Sci. Technol., 2011, 1, 119–133. J., 2009, 145, 377–384.
18 N. MacDowell, N. Florin, A. Buchard, J. Hallett, A. Galindo, 51 C. Hawthorne, M. Trossmann, C. Galindo Cifre, A. Schuster and
G. Jackson, C. S. Adjiman, C. K. Williams, N. Shah and G. Scheffknecht, Energy Proc., 2008, 1, 1387–1394.
P. Fennell, Energy Environ. Sci., 2010, 3, 1645–1669. 52 J. Str€
ohle, A. Galloy and P. Epple, Energy Proc., 2008, 1, 1313–1320.
19 J. Wilday, N. Paltrinieri, R. Farret, J. Hebrard and L. Breedveld, 53 J. C. Abanades, J. C. Anthony, D. Alvarez, D. Y. Lu and
Symp. Ser., 2011, 156, 339–346. C. Salvador, AIChE J., 2004, 50, 1614–1622.
20 J. C. M. Pires, F. G. Martins, M. C. M. Alvim-Ferraz and 54 B. Epple and J. Str€ ohle, in Efficient Carbon Capture for Coal Power
M. Simoes, Chem. Eng. Res. Des., 2011, 89, 1446–1460. Plants, ed. D. Stolten and V. Scheerer, Wiley-VCH Verlag,
21 H. D. Coninck, M. D. Best-Waldhober and H. Groenenberg, in Weinheim, 2011, pp. 505–522.
Developments and Innovation in Carbon Dioxide (CO2) Capture 55 J. Str€ohle, A. Lasheras, A. Galloy and B. Epple, Chem. Eng.
and Storage Technology, ed. M. M. Maroto-Valer, Woodland Technol., 2009, 32, 435–442.
Publishing Ltd, Oxford, 2010, pp. 64–92. 56 M. Finkenrath, Cost and Performance of Carbon Dioxide Capture
22 S. Bouzalakos and M. M. Maroto-Valer, in Developments and from Power Generation, International Energy Agency, Paris, 2010.
Innovation in Carbon Dioxide (CO2) Capture and Storage 57 G. G€ ottlicher, Energetik der Kohlendioxidr€ uckhaltung in
Technology, ed. M. M. Maroto-Valer, Woodhead Publishing Series Kraftwerken, VDI Verlag, D€ usseldorf, 1999.
in Energy, Oxford, 2010, vol. 1, pp. 1–24. 58 G. Beysel, in Kraftwerkstechnisches Kolloquium, Dresden, 2004.
23 F. D. Agron and J. P. Osborne, Terrestrial Sequestration of Carbon 59 A. Kather and M. Klostermann, in Efficient Carbon Capture for Coal
Dioxide, Nova Science Publ., New York, 2011. Power Plants, ed. D. Stolten and V. Scheerer, Wiley-VCH Verlag,
24 IEA, CO2 Capture and Storage, IEA/OECD, Paris, 2008. Weinheim, 2011, pp. 271–292.
25 K. S. Lackner, in Efficient Carbon Capture for Coal Power Plants, ed. 60 G. Sekkapan, P. Melling, M. Anheden, G. Lindgren, F. Kluger,
D. Stolten and V. Scherer, Wiley-VCH Verlag, Weinheim, 2011, pp. I. Molinero, C. Maggauer and A. Doukelis, in 8th International
573–598. Conference on Greenhouse Gas Control Technologies, Trondheim,
26 D. M. D’Alessandro, B. Smit and J. R. Long, Angew. Chem., 2010, 2006.
49, 6058–6082. 61 L. Str€ omberg, G. Lindgren, M. Anheden, N. Simonsson and
27 J.-R. Li, Y. Ma, M. C. McCarthy, J. Sculley, J. Yu, H.-K. Jeong, M. K€ opcke, in 8th International Conference on Greenhouse Gas
P. B. Balbuena and J.-C. Zhou, Coord. Chem. Rev., 2011, 255, Control Technologies, Trondheim, 2006.
1791–1823. 62 R. Vagani, F. Chatel-Pelage, F. Gautier and P. Pranda, in 8th
28 A. Kather, S. Rafailidis, C. Hermsdorf, M. Klostermann, International Conference on Greenhouse Gas Control Technologies,
A. Maschman, K. Mieske, J. Oexmann, I. Pfaff and J. Rohloff, Trondheim, 2006.
Research and Development Needs for Clean Coal Deployment 978- 63 J. Nazarko, A. Schreiber, W. Kuckshinrichs and P. Zapp, in Ris€ o
92-9029-449-3, IEA Clean Coal Centre, London, 2008. International Energy Conference, Ris€ o, Denmark, 2007.

This journal is ª The Royal Society of Chemistry 2012 Energy Environ. Sci., 2012, 5, 7281–7305 | 7303
 64 R. Castillo, Appl. Energy, 2011, 88, 1480–1493. 100 W. Leitner, Acc. Chem. Res., 2002, 35, 746–756.
65 D. Kosel and M. Biele, in 10. J€ ulicher Werkstoffsymposium, J€
ulich, 101 W. Leitner and P. G. Jessop, in Supercritical Solvents, ed. P. Anastas,
2009. Wiley-VCH, Weinheim, 2010, vol. 4.
66 U. Burchardt, M. Biele, S. Lysk, D. Radunsky and J. Jacoby, 40. 102 U. Hintermair, W. Leitner and P. Jessop, in Handbook of Green
Kraftwerkstechnisches Kolloquium K€ unftiges Brennstoff- und Chemistry, ed. W. Leitner and P. G. Jessop, Wiley-VCH,
Technologieportfolio in der Kraftwerkstechnik, Dresden, 2008. Weinheim, 2010, vol. 4, Supercritical Solvents, pp. 101–187.
67 P. Leifeld, Diploma thesis, RWTH, Aachen, 2008. 103 S. K. Kumar, L. Greiner, A. Kraynov, T. E. M€ uller, B. Niemeijer
68 H. Stadler, F. Beggel, M. Habermehl, B. Persigehl, R. Kneer, and W. Leitner, Chem. Commun., 2010, 46, 6705–6707.
M. Modigell and P. Jeschke, Int. J. Greenhouse Gas Control, 2011, 104 S. K. Karmee, C. Roosen, C. Kohlmann, S. Luetz, L. Greiner and
5, 7–15. W. Leitner, Green Chem., 2009, 11, 1052–1055.
69 I. Pfaff and A. Kather, Energy Proc., 2009, 1, 495–502. 105 IEA, Energy Technology Perspectives – Scenarios & Strategies to
70 R. Kneer, M. F€ orster, D. Abel, H. R. Maier, M. Modigell, 2050, Paris, 2008.
R. Niehuis and R. Peters, VGB PowerTech, 2006, 10, 74–81. 106 M. Odenberger and R. Svensson, Transportation Systems for CO2
71 A. Lyngfelt and T. Mattisson, in Efficient Carbon Capture for Coal Application to Carbon Sequestration, Chalmers University,
Power Plants, ed. D. Stolten and V. Scheerer, Wiley-VCH Verlag, Gothenburg, 2003.
Weinheim, 2011, pp. 475–496. 107 J. Gale and J. Davison, Energy, 2004, 29, 1319–1328.
72 H. Stadler, F. Beggel, M. Habermehl, B. Persigehl and R. Kneer, Int. 108 R. Zevenhoven and J. Fagerlund, in Developments and Innovation in
J. Greenhouse Gas Control, 2011, 5, 7–15. Carbon Dioxide (CO2) Capture and Storage Technology, Woodhead
73 R. Kneer, D. Toporov, M. Forster, D. Christ, C. Broeckmann, Publishing Series in Energy, 2010, vol. 2, pp. 433–462.
E. Pfaff, M. Zwick, S. Engels and M. Modigell, Energy Environ. 109 F. May, VGB PowerTech, 2005, 85, 32–37.
Sci., 2010, 3, 198–207. 110 R. Castillo, in 4th Int. Conf. on Clean Coal Technologies, Dresden,
74 S. Engels, F. Beggel, M. Modigell and H. Stadler, J. Membr. Sci., 2009.
2010, 359, 93–101. 111 IEA, Impurities on CO2 capture, transport and storage, London,
75 IEA, Energy Technology Perspectives – Scenarios & Strategies to 2004.
2050, Paris, 2006. 112 P. Seevam, J. M. Race and M. J. Downie, in CCS Summer School,
76 M. Fischedick, W. G€ unster, H. Fahlenkamp, H.-J. Meier, Vancouver Island, 2008.
F. Neumann, G. Oeljeklaus, H. Rode, A. Schimkat, J. Beigel and 113 E. Visser, C. Hendricks, M. Barrio, M. M€ olnvik, G. Koeijer,
D. Sch€ uwer, VGB PowerTech, 2006, 86, 108–117. S. Liljemark, A. Austegard and A. Brown, DYNAMIS CO2
77 M. Wietschel, M. Arens, C. D€ otsch, S. Herkel, W. Krewitt, Quality Recommendations, www.dynamis-hypogen.com, 2007.
P. Markewitz, D. M€ ost and M. Scheufen, Energietechnologie 2050: 114 E. Visser, C. Hendricks, M. Barrio, M. M€ olnvik, G. Koeijer,
Schwerpunkte f€ ur Forschung und Entwicklung, Fraunhofer Verlag, S. Liljemark, A. Austegard and Y. Gallo, Int. J. Greenhouse Gas
Stuttgart, Germany, 2010. Control, 2008, 2, 478–484.
nd
78 P. Casero, in 2 International Freiberg Conference on IGCC & XTL 115 F. D. Doctor, in 5th International Conference on Greenhouse Gas
Technologies, Freiberg, Germany, 2007. Control Technologies, Cairns, Australia, 2000.
79 O. Turna, in 2nd International Freiberg Conference on IGCC & XTL 116 H.-J. Wagner, W. Kuckshinrichs and C. Groß, STE Preprint, 2009,
Technologies, Freiberg, Germany, 2007. vol. 2009.
80 A. Prelipceanu, H.-P. Kaballo and U. Kerstecioglu, in 2nd 117 J. Linssen, P. Markewitz, D. Martinsen and M. Walbeck, Brennstoff-
International Freiberg Conference on IGCC & XTL Technologies, W€ arme-Kraft, 2006, 58, 59–62.
Freiberg, Germany, 2007. 118 P. Markewitz, A. Schreiber, P. Zapp and S. V€ ogele, Zeitschrift f€
ur
81 K. Ariga, S. Ishihara, H. Abe, M. Li and P. Hill, J. Mater. Chem., Energiewirtschaft, 2009, 31–41.
2012, 22, 2369–2377. 119 European Technology Platform for Zero Emission Fossil Fuel
82 K. Payrhuber, in 2nd Int. Freiberg Conf. on IGCC & XTL Power Plants (ZEP), European Technology Platform for Zero
Technologies, Freiberg, 2007. Emission Fossil Fuel Power Plants (ZEP), 2011.
83 W. Renzenbrink, J. Evers, D. Keller, K. J. Wolf and W. Apel, Energy 120 Gobal CCS Institute, Economic Assessment of Carbon Capture and
Proc., 2008, 1, 615–622. Storage Technologies, 2011 update, Global CCS Institute, 2011.
84 M. Scholz and K. Payrhuber, SAFE Conference – Sustainable Fossil 121 IEA NEA OECD, Projected Costs of Generating Electricity, OECD,
Fuel for Future Energy, Rome, 2009. Paris, 2010.
85 V. Scheerer and J. Franz, in Efficient Carbon Capture for Coal Power 122 Mit, The Future of Coal, Cambridge, 2007.
Plants, ed. D. Stolten and V. Scheerer, Wiley-VCH Verlag, 123 D. Lindenberger, C. Lutz and M. Schlesinger, Energieszenarien f€ ur
Weinheim, 2011, pp. 431–468. ein Energiekonzept der Bundesregierung EWI/GWS/PROGNOS,
86 C. Kunze and H. Spliethoff, Fuel Process. Technol., 2010, 91, 934– K€ oln/Osnabr€ uck/Basel, 2010.
941. 124 P. Markewitz and S. V€ ogele, Energiewirtschaftliche Tagesfragen,
87 M. Grabner, O. von Morstein, D. Rappold, W. Gunster, G. Beysel 2004, 54, 601–605.
and B. Meyer, Energy Convers. Manage., 2010, 51, 2179–2187. 125 A. L€ oschel, Die Zukunft der Kohle in der Stromerzeugung in
88 E. S. Rubin, C. Chen and A. B. Rao, Energy Policy, 2007, 35, 4444– Deutschland 1/2009, Berlin, 2009.
4454. 126 P. Zapp, A. Schreiber and W. Kuckshinrichs, VGB PowerTech,
89 S. Walsburger, E. van Dijk and R. van den Brink, in Efficient Carbon 2009, 89, 95–102.
Capture for Coal Fired Power Plants, ed. D. Stolten and V. Scheerer, 127 J. Koornneef, A. Ramirez, W. Turkenburg and A. Faaij, Energy
Wiley-VCH Verlag, Weinheim, 2011, pp. 241–264. Proc., 2011, 4, 2293–2300.
90 IEA, World Energy Outlook 2006, International Energy Agency 128 J. Marx, A. Schreiber, P. Zapp, M. Haines, J. Fr. Hake, J. Gale,
OECD/IEA, 2006. Environmental Evaluation of CCS Using Life Cycle Assessment
91 IEA, World Energy Outlook 2009, International Energy Agency (LCA), IEA Greenhouse Gas R&D Programme, 2010.
OECD/IEA, 2009. 129 C. Bauer, T. Heck, R. Dones, O. Mayer-Spohn and M. Blesl, Final
92 IEA, World Energy Outlook 2008, International Energy Agency Report on Technical Data, Costs, and Life Cycle Inventories of
OECD/IEA, 2008. Advanced Fossil Power Generation Systems, Paul Scherrer Institut
93 IEA, World Energy Outlook 2011, International Energy Agency (PSI) and Institut f€ ur Energiewirtschaft und Rationelle
OECD/IEA, 2011. Energieanwendung, Univ. Stuttgart (IER), 2009.
94 IEA, CO2 Capture Ready Plants. Technical Study, London, 2007. 130 J. Koornneef, T. van Keulen, A. Faaij and W. Turkenburg, Int. J.
95 K.-D. e. a. Tigges, in GHG 9, Energy procedia, Washington, 2008, Greenhouse Gas Control, 2008, 2, 448–467.
vol. 1. 131 A. Korre, Z. Nie and S. Durucan, Energy Procedia, 2009, 1, 3771–
96 P. Ploumen, in GHG 8, Trondheim, 2006. 3778.
97 J. e. a. Gibbins, in GHG 4, Vancouver, 2004. 132 I. S. Modahl, C. A. Nyland, H. L. Raadal, O. Karstad, T. A. Torp
€
98 TUV-Nord, Climate Change Standard TN-CC006. and R. Hagemann, Joint Actions on Climate Change, Aalborg,
99 M. Fischedick, W. G€ unster, H. Fahlenkamp, H.-J. Meier and Denmark, 2009.
F. Neumann, VGB PowerTech, 2006, 86, 108–117. 133 N. A. Odeh and T. T. Cockerill, Energy Policy, 2008, 36, 367–380.

7304 | Energy Environ. Sci., 2012, 5, 7281–7305 This journal is ª The Royal Society of Chemistry 2012
134 M. Pehnt and J. Henkel, Int. J. Greenhouse Gas Control, 2009, 3, 147 D. St€over and W. A. Meulenberg, in Symposium Innovation durch
49–66. Energieforschung, ed. ef. Ruhr, Gelsenkirchen, 2005.
135 A. Schreiber, P. Zapp and W. Kuckshinrichs, Int. J. Life Cycle 148 M. Czyperek, P. Zapp, H. J. M. Bouwmester, M. Modigell,
Assess., 2009, 14, 547–559. K.-V. Peinemann, I. Voigt, W. A. Meulenberg, L. Singheiser and
136 B. Singh, A. H. Strømman and E. G. Hertwich, Int. J. Greenhouse D. St€over, Energy Proc., 2008, 1, 303–310.
Gas Control, 2011, 5, 911–921. 149 M. R. Kember, A. Buchard and C. K. Williams, Chem. Commun.,
137 P. Viebahn, J. Nitsch, M. Fischedick, A. Esken, A. Pastowski and 2011, 47, 141–163.
D. Schuwer et al., RECCS Strukturell-€ okonomisch-€ okologischer 150 D. J. Darensbourg, J. R. Andreatta and A. I. Moncada, in Carbon
Vergleich regenerativer Energietechnologien (RE) mit Carbon Dioxide as Chemical Feedstock, ed. M. Aresta, Wiley-VCH,
Capture and Storage (CCS), Wuppertal Institut, 2007. Weinheim, 2010.
138 A. W. Sleeswijk, L. F. C. M. van Oers, J. B. Guinee, J. Struijs and 151 G. Laurenczy, Chimia, 2011, 65, 663–666.
M. A. J. Huijbregts, Sci. Total Environ., 2008, 390, 227–240. 152 G. Centi, G. Iaquaniello and S. Perathoner, ChemSusChem, 2011, 4,
139 P. Zapp, A. Schreiber, J. Marx, M. Haines, J.-F. Hake and J. Gale, 1265–1273.
Int. J. Greenhouse Gas Control, 2012, 8, 12–21. 153 A. Ion, C. V. Doorslaer, P. Jacobs, V. Parvulesco and D. D. Vos,
140 Z. Nie, A. Korre and S. Durucan, Energy Proc., 2011, 4, 2510– Prepr. Pap.—Am. Chem. Soc., Div. Fuel Chem., 2010, 55, 47–48.
2517. 154 R. W. Dorner, D. R. Hardy, F. W. Williams and H. D. Willauer,
141 S. Knudsen and S. M. K. Randall, Summary Report: Amine Energy Environ. Sci., 2010, 3, 884–890.
Emissions to Air During Carbon Capture. Phase I: CO2 and Amines 155 P. Braunstein, D. Matt and D. Nobel, Chem. Rev., 1988, 88, 747–
Screening Study for Effects to the Environment, Norwegian 764.
Institute for Air Research (NILU), 2009. 156 L.-N. He, Z.-Z. Yang, A.-H. Liu and J. Gao, in Advances in CO2
142 A. Schreiber, P. Zapp and J. Marx, J. Ind. Ecol., 2012, DOI: 10.1111/ Conversion and Utilization, ed. Y. Hu, ACS, Washington, DC,
j.1530-9290.2011.00435.x. 2010, pp. 77–101.
143 J. Gale, T. Dixon, B. Beck and M. Haines, in Climate Change 157 M. Cokaja, C. Bruckmeier, B. Rieger, W. A. Herrmann and
Congress 2009, Copenhagen, 2009. F. E. K€uhn, Angew. Chem., Int. Ed., 2011, 50, 8510–8537.
144 J. Lambertz and J. Heithoff, Energiewirtschaftliche Tagesfragen, 158 W. Leitner, Coord. Chem. Rev., 1996, 153, 257–284.
2008, 58, 16–19. 159 W. Leitner, Angew. Chem., Int. Ed. Engl., 1995, 34, 2207–2221.
145 K. Thambimutu, in GHG 9, Washington, 2008. 160 A. Uhe, M. H€ olscher and W. Leitner, Chem.–Eur. J., 2012, 18, 170–
146 CO2-Abscheidung und -Speicherung – eine Zukunftsoption f€ ur die 177.
deutsche Klimaschutzstrategie?, ed. U. Koss and W. Kuckshinrichs, 161 A. J. Morris, G. J. Meyer and E. Fujita, Acc. Chem. Res., 2009, 42,
et al., J€
ulich, 2005. 1983–1994.

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