Projektinfo 01/2014

Detailed information on energy research

CO2 capturing using lime

Existing power plants can reduce emissions by about
90 per cent using carbonate looping – and at acceptable costs

CO2 can be separated from the flue gases from power plants
with the aim of preventing climate-harming emissions.
However, the processes developed for this have been very
expansive until now. When capturing CO2 using quicklime,
on the other hand, the costs are much lower – around
15 euros per tonne of CO2. These plants for capturing CO2
from exhaust gases can be retrofitted in existing power plants.
The Technische Universität Darmstadt has demonstrated the
process using a one-megawatt pilot plant. The solid material
produced – quicklime – could be interesting for cement
plants, since this would reduce their energy consumption.

In order to reduce the emissions from coal-fired power plants, researchers and in-
dustry are developing processes to capture CO2 from flue gases. The disadvantage
of the processes, however, is that they considerably reduce the efficiency of the
power plants by 8 to 14 per cent. The loss of efficiency with carbonate looping, on
the other hand, is only about 5 per cent.
According to one forecast, this creates savings in relation to the electricity genera-
tion costs: with flue gas scrubbing using monoethanolamine (MEA scrubbing), the
electricity generation costs are about 55 euros per megawatt-hour. A good 40 euros
are forecast for carbonate looping. Although equally small electricity generation
costs amounting to roughly 42 euros are expected when combusting coal in a pure
oxygen atmosphere (oxyfuel), this technology cannot be retrofitted in existing power
plants but can only be installed in new ones. These figures relate to coal-fired
This research project power plants with a 1,050-megawatt electrical capacity, an efficiency of 45 per cent
is funded by the and a CO2 capture rate of 80 per cent.
Federal Ministry for Economic Affairs
and Energy (BMWi)
2 BINE-Projektinfo 01/2014

Two fluidised bed reactors limit energy losses

With carbonate looping, carbon dioxide (CO2) from the
flue gases of fossil-fuelled power plants can be made CO2-free flue gas CO2 for compression
available for geological storage or further use, whereby the
CO2 is first bound using limestone and then released.
As is usual, the flue gas from the power plant is first of
all desulphurised in the flue gas desulphurisation (FGD)
plant. It then comes into contact with lime (CaO) in a
carbonator (cover image). This part of the plant is a cir- Limestone (CaCO3) Fresh limestone (CaCO3)
culating fluidised bed reactor. This means that the flue Carbonisation Calcination
gas is fed through a porous plate into a vertical cylinder T = 650 °C T = 900 °C
or cuboid, which is filled with lime. The gas flows through Lime (CaO) Fuel
the lime, loosens it, and swirls it around. This increases
the reaction-capable surface of the lime.
The lime reacts with the CO2, releasing a large amount
of heat. This energy can be used via heat exchangers for
generating steam in power plants. In order to maintain Oxygen
the ideal reaction temperature of 650 °C, the carbonator
has to be cooled. The cleaned flue gas flows from the Ash
carbonator into a heat exchanger, where it is cooled. It Flue gas from the power plant spent lime (CaO, CaCO3)
is then freed of dust in a filter before being released to
the environment.
Following the carbonisation, the CO2 is bound in the Fig. 1 The carbonate looping process can be conducted
lime to form solid calcium carbonate (CaCO3). This is in two coupled fluidised bed reactors.
centrifugally separated from the flue gas in a cyclone
separator. The solid material is then fed into a second
fluidised bed reactor, which is called a calciner (Fig. 4).
The CO2 is separated from the calcium carbonate by
adding heat. This process is known as calcination and is
widely used in cement plants.
In the experimental plant, coal is combusted with pure
oxygen (oxyfuel atmosphere) in order to provide the re-
quired heat. Combustion in air would unnecessarily
strongly dilute the CO2 volume flow being captured as a
result of the contained nitrogen. Until now, relatively
large amounts of energy have been required to separate
pure oxygen from the air. This is where the largest effi-
ciency loss occurs with carbonate looping: in relation to
the overall power plant, this amounts to about 3 per cent.
The heat required for the calcination can, however, be Fig. 2 The pores increase after many cycles, which reduces the absorption
decoupled and reused for generating steam since it is of CO2 and increases the absorption of SO2.
released at a high temperature level. The optimum op-
erating temperature in the calciner ranges between 900
and 950 °C.

Quicklime is suitable for desulphurisation

With carbonate looping, the lime is generally re-circulated
(Fig. 1). However, quicklime has to be continually removed
and replaced with new calcium carbonate (make-up).
This is because the quicklime becomes less able to
bind CO2 as the number of carbonisation and calcina- In the calciner, the limestone is calcined to form quicklime (CaO). The need
tion cycles increases. for fresh lime is increased by the reaction of the material with sulphur dioxide
The reaction speed in the carbonator is determined by (SO2). This produces gypsum (CaSO4). This reaction is irreversible with the
the interactions between the lime particles and the CO2. prevailing temperatures.
By means of a rapid, purely chemical reaction, the CO2is SO2 and CO2 do not react with the lime independently from each other but
initially bound to the particle surface by forming a cal- mutually influence each other’s ability to be bound in: sulphur dioxide reduc-
cium carbonate (CaCO3) layer. The reaction then contin- es the binding of carbon dioxide whereas the alternating calcination and
ues more slowly, since the CO2 has to first diffuse under carbonisation increases the absorption of SO2. This means that the quick-
this layer in order to come into contact with the lime. lime can also be used for desulphurisation after the carbonate looping. The
The pores of the lime particles gradually sinter. After flue gas desulphurisation (FGD) plants installed in power plants are nor-
many cycles, the reactivity reduces to about 15 to 20 per mally operated with lime.
cent (Fig. 2). In order to enable good CO2 capture rates, In principle, it is also possible to regenerate the quicklime that is deacti-
the process is continually fed with fresh limestone vated after many cycles in order to re-add it to the carbonate looping. For
(CaCO3), which is cheaply available as a natural raw ma- this purpose the quicklime must be treated with water vapour. The forma-
terial. tion of calcium hydroxide increases the pore surface so that the reactivity is
 BINE-Projektinfo 01/2014 3

Chimney Chimney

CO2-free flue gas CO2 + H2O

Gas analysis
CO, CO2, NO, SO2, O2

Cyclone

Cyclone
Coal

Fluidised bed carbonator

Fluidised bed calciner

Make-up
(CaCO3) Coal

Propane
T = 650 °C

T = 900 °C
Propane
Air
CaCO3
Combustion chamber

Air Air
CaO
Propane Propane

Air Air Air

Preheater Preheater

Flue gas
with O2 enriched air

Fig. 3 Simplified schematic showing the structure of the 1-megawatt experimental plant at TU Darmstadt.

Aspen plus simulation model

has been further developed
In addition to the pilot plant, the project consortium has
also further developed a process model using the Aspen
Kamin Plus software. The programmersKamin have supplemented
the missing components in the circulating fluidised bed
CO3 freies Rauchgas using a fluidised bed reactor code. They CO2 +have
H2O adapted
the program to the design of the built plant and validated
Gasanalyse
it withCO,
theCOexperimental
,NO, SO2, O2 results, whereby the calculated
2
CO2 absorption rates closely match the experimental re-
Zykoln sults. It is intended to validate and optimise the process
Zykoln
Kohle model more comprehensively during the next project
Karbonator T = 650 °C

phase.
MakeupIt is also planned to develop 3D models for the
Kalzinator T = 900 °C

fluidised
(CaCO3) bed [Link] In order to validate these models,
it is also planned to incorporate profile measurements
Wirbelschicht

Wirbelschicht

Propan in the reactors. Propan

Luft
Fig. 4 The CO2 and lime are separated again in the calciner. CaCO3
Luft Testing the carbonate looping
in flexibleCaO
operation
Propan Propan
Brennkammer

Based on the previous findings, the 1-megawatt system

Luft at TU Darmstadt has been undergoing optimisation since
Luft Luft Vorwärmer
increased again. After capturing in the calciner, a pure CO2 gas flow is pro-
Vorwärmer the beginning of 2014.
duced. As with all known capturing processes, this must be compressed for
Rauchgas During the next few years, the engineers will be con-
the transport. Besides the use of pure oxygen for the combustion in the ducting experimental series to test the behaviour mit Owith
2
angereicherte Lu
calciner, this is the second aspect that significantly reduces the efficiency many load changes. This is in order to gain knowledge to
of the overall power plant process. optimally design the technology for flexible power plant
When compressing to a pressure of 100 bars at a temperature of 30 °C, a loss operation. This is because in future coal-fired power
of efficiency of 2.5 to 4 per cent can be expected in accordance with the process. plants will be carrying out increasingly frequent and
Installing carbonate looping in a power plant therefore lowers the overall quicker load changes in order to balance out the fluctu-
efficiency by about 5 to 7 per cent. This is a good value when compared with ating injection of renewable energies. This also varies
other capturing processes. the flue gas flow and the requirements for the two fluid-
Engineers have been researching the process in recent years with a 1-mega- ised bed reactors in carbonate looping systems.
watt pilot plant at TU Darmstadt, whereby they have achieved CO2 binding Furthermore, not just black coal but also lignite is being
rates of more than 80 per cent in the carbonator. Because the CO2 released deployed as a fuel. The next step will then be the con-
during the combustion with coal in the calciner is completely captured, this struction and operation of a pilot plant with a 20-mega-
means that more than 90 per cent is captured overall. watt thermal capacity.
4 BINE Projektinfo 01/2010
BINE-Projektinfo 01/2014

The market for lime Imprint

Project organisation
The idea of utilising lime in power plants and then selling it on to the cement industry Federal Ministry for Economic Affairs
dates back to the 1980s. At that time, German power plant operators began using lime and Energy (BMWi)
to filter sulphur dioxide (SO2) from the flue gases. Amongst other things, sulphur 11019 Berlin
dioxide is deemed to be responsible for acid rain, which damages for example the Germany
forests. The comprehensive use of flue gas desulphurisation (FGD) plants has reduced Project Management Jülich
the SO2 emissions from power plants by about 95 per cent. Forschungszentrum Jülich GmbH
A limestone-based process has become widely used in power plants for capturing SO2 Dr Wolfgang Körner
from flue gases. In FGD plants, sulphur dioxide reacts with lime and oxygen to form FGD 52425 Jülich
gypsum. This calcium sulphite is chemically identical to natural gypsum. In particular, it Germany
is further processed by the cement and gypsum industry for producing gypsum panels.
Project number
According to the German gypsum federation, the Bundesverband der Gipsindustrie, 03ET7018
FGD gypsum meets around half of Germany’s gypsum requirements.
ISSN
With carbonate looping, quicklime is produced as a waste product. This is required in 0937 - 8367
cement plants. Until now the factories have produced it themselves. This process stage Publisher
is one reason for the high energy requirement and the high CO2 emissions in the cement FIZ Karlsruhe · Leibniz Institute
industry. Quicklime is produced by calcining the CO2 contained in naturally occurring for Information Infrastructure
limestone using considerable energy. This means that there will presumably be a market Hermann-von-Helmholtz-Platz 1
for the quicklime once carbonate looping has become commercially implemented. This 76344 Eggenstein-Leopoldshafen
would lower the emissions and energy consumption at cement plants. Germany

The sale of quicklime enables power plant operators to reduce the specific costs for Author
capturing CO2 from flue gases. That would reduce the previously forecast costs of 15 Christina Geimer
euros per tonne of captured CO2. That is an important argument in terms of carbonate Copyright
looping’s marketing prospects. Until now the price per tonne of CO2, which within the Cover image, Fig. 1, 3: EST, TU Darmstadt
European Union is determined by a carbon permit market, has been less than 5 euros. Fig. 2: Grasa, G. S. et al.: Reactivity of
Since fewer carbon permits will be issued in future, the price is expected to rise. highly cycled particles of CaO in a car-
bonation/calcination loop. In: Chemical
Engineering Journal. Vol. 137 (2008),
Issue 3, p. 561–567, [Link]
org/10.1016/[Link].2007.05.017
Fig. 4 BINE Information Service
Project participants Text and illustrations from this publication
can only be used if permission has

Concept and design: iserundschmidt GmbH, Bonn – Berlin, Germany · Layout: KERSTIN CONRADI · Mediengestaltung, Berlin, Germany
>> Project coordination: Department of Energy Systems and Technology (EST) at the Technische Universität
Darmstadt, Prof. Dr.-Ing. Bernd Epple, [Link]@[Link], [Link] been granted by the BINE editorial team.
>> Support with the plant design and operation: Fisia Babcock Environment GmbH, Gummersbach, We would be delighted to hear from you.
Germany
>> Support with the plant design and operation: Alstom Carbon Capture GmbH, Wiesbaden, Germany
>> Provision and analysis of the limestone: Rheinkalk GmbH, Wülfrath, Germany
>> Provision of the technical gases: Linde AG, Pullach, Germany
>> Provision of coal: Grosskraftwerk Mannheim AG, Germany Contact · Info
>> Advice with the incorporation in coal-fired power plants: [Link] New Build & Technology GmbH,
Questions regarding this Projektinfo brochure?
Gelsenkirchen, Germany
We will be pleased to help you:
>> Advice with the incorporation in lignite-fired power plants, provision of lignite:
RWE Power AG, Essen, Germany +49 228 92379-44
kontakt@[Link]
Links and literature BINE Information Service
> > [Link]/en/co2-scrubbing-post-combustion-capture/ Energy research for application
> > Ströhle J. u. a.: Carbonate looping experiments in a 1 MWth pilot plant and model validation. A service from FIZ Karlsruhe
In: Fuel. (2014) In Press, Corrected Proof, [Link]
> > Ströhle, J. u. a.: CO2-Abscheidung aus Kraftwerksabgasen mittels Kalkstein. Teilprojekt: Untersuchungen Kaiserstraße 185-197
im Technikumsmaßstab. Schlussbericht. FKZ 0327771C. TU Darmstadt. EST (Hrsg.). Juli 2013, 104 S. 53113 Bonn, Germany
> > Rodríguez, N. u. a.: Comparison of experimental results from three dual fluidized bed [Link]
test facilities capturing CO2 with CaO. In: Energy Procedia. Vol. 4 (2011), p. 393 – 401,
[Link]

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