UNIVERSITÀ DEGLI STUDI DI GENOVA

DICAT
Dipartimento di Ingegneria delle Costruzioni, dell’Ambiente e del Territorio
16145 GENOVA - Via Montallegro, 1 - Tel. 39 - 010 3532491 - Fax 39 - 010 3532546

CORSO DI DOTTORATO IN

FLUIDODINAMICA E PROCESSI
DELL’INGEGNERIA AMBIENTALE
(XXIV CICLO)

CARBON CAPTURE,
SEQUESTRATION AND
TRANSPORTATION
(CCS&T)

Dottoranda: Michela Mazzoccoli

Genova, 23 Novembre 2009

PERT – Process Engineering Research Team

16145 GENOVA - Via Opera Pia, 15 - Tel. 39 - 010 3536504 - Fax 39 - 010 3532589
CONTENTS
1. Introduction
1.1. What is CCS&T
1.2. Why CCS&T

2. Carbon dioxide capture

2.1. Reference schemes
2.1.1. Consolidated reference schemes
2.1.1.1 Post combustion
2.1.1.2 Pre combustion
2.1.1.3 Oxyfuel combustion
2.1.2. Developing reference schemes
2.1.2.1 Advanced Zero Emission Power Plant (AZEP)
2.1.2.2 Chemical Looping Combustion (CLC)
2.1.2.3 High temperature fuel cells
2.2. CO2 separation technologies
2.2.1. Consolidated technologies
2.2.1.1 Chemical absorption
2.2.1.2 Physical absorption
2.2.1.3 Membranes
2.2.2. Innovative technologies
2.2.2.1. Adsorption onto solids
2.2.2.2. Carbonation-calcination
2.2.2.3. Molten carbonate fuel cells
2.2.2.4. Cryogenic separation
2.2.2.5. Hydrate-based separation
2.2.3. Risks

3. Carbon dioxide transport

3.1. Transport
3.2. Risks
3.3. Gas conditioning

4. Carbon dioxide storage

4.1. Geological formations
4.1.1. Depleted oil and gas reservoirs
4.1.2. Unminable coal seams
4.1.3. Deep saline aquifers
4.2. Deep ocean
4.3. Mineral carbonation
4.4. Forestation
4.5. Biofixation
4.6. Risks

5. Costs

6. Institutions and Research Centres

6.1. European Union
6.2. Carbon Dioxide Knowledge Sharing Network (CO2NET)
6.3. Geological Storage of CO2 – European Network (CO2GeoNet)
6.4. Intergovernmental Panel on Climate Change (IPCC)
6.5. National Energy Technology Laboratory (NETL)
6.6. Carbon Sequestration Leadership Forum (CLSF)
6.7. International Energy Agency (IEA)
6.8. Italian National Institute of Geophysics and Volcanology (INGV)
6.9. SINTEF
6.10.CanmetENERGY (Natural Resources Canada)

2
 6.11.Dutch research programmes
6.12.SOLVit

7. Projects
7.1. First projects
7.1.1. Sleipner
7.1.2. Snøhvit
7.1.3. In Salah
7.1.4. Weyburn
7.2. European Union projects
7.3. A USA project: FutureGen
7.4. Australian projects
7.5. Italian projects
7.5.1. Enel
7.5.1.1. Enel-ENI project
7.5.2. ENI
7.5.3. Techint
7.5.4. ECBM project in Sardinia
7.6. Other projects
7.6.1. CO2 Capture Project (CCP)
7.6.2. K-12 CO2 Injection Project
7.6.3. North Sea CO2 transport
7.6.4. Chilled Ammonia Process
7.6.4.1. Large bench scale pilot plant
7.6.4.2. Field pilot plants
7.6.4.3. Validation pilot plants
7.7. European company activities on CCS&T
7.7.1. Statoil
7.7.2. Vattenfall
7.7.3. Total
7.7.4. Siemens
7.7.5. RWE
7.7.6. Alstom

8. Research and Development (R&D)

8.1. R&D in carbon dioxide capture
8.2. R&D in carbon dioxide transport
8.3. R&D in carbon dioxide storage

9. Conclusion

3
1. INTRODUCTION

1.1 What is CCS&T

CCS&T, which is “Carbon Capture and Storage”, is a suite of technological processes
which involve capturing carbon dioxide (CO2) emitted by industry, compressing it and transporting
it to a suitable geological formation where it is injected, with the aim of isolating it from the
atmosphere for the long term.
The geological formation can be oil and gas reservoirs, unminable coal seams and deep
saline reservoirs.
CCS&T can be applied both to power generation from fossil fuels, principally coal and gas,
and to CO2-intensive industries such as cement, refineries, iron and steel, petrochemicals, oil and
gas processing and others [1].

Fig. 1.1/1 Schematic diagram of possible CCS systems [2]

4
1.2 Why CCS&T
Nowadays reducing the emissions of greenhouse gases (GHG) is one of the most
important challenges that we have to face up to.
According to the Intergovernmental Panel on Climate Change (IPCC) increasing emissions
of GHG will rise the average global temperature by 1.1 – 6.4 °C by the end of the 21 st century,
causing the serious consequences of climate change.
Climate models established by the IPCC indicate that these will occur if global warming
exceeds even 2°C above the pre-industrial average. In order to avoid such a high temperature
increase, it has stated categorically that global greenhouse gas emissions must be reduced by
50% - 80% by 2050 (compared to 1990 levels) [2].
The Third Assessment Report (TAR) of IPCC indicates that no single technology option will
provide to achieve this target mentioned above, but a portfolio of solutions is essential.

The European Council therefore set an energy policy called 20/20/20 by 2020 that foresees
[3]:

• a reduction of at least 20% in greenhouse gases by 2020;

• a 20% share of renewable energies in EU energy consumption by 2020;
• a reduction of 20% in energy demand by increasing energy efficiency by 2020.

Energy efficiency and renewables will be the most sustainable solutions for security of
energy supply, in fact, the energy system will probably depend less and less on fossil fuels, but
such measures can lead to significant emission reductions in the long-term, CO2 emissions cannot
be reduced by 50% by 2050 if we do not also study sustainable fossil fuel technologies.
In fact world energy demand predicted to increase by 60% between 2002 and 2030, and
renewable energies to make up only a third of the energy mix by 2050.
Clearly, fossil fuels will remain the primary energy resource for a long time to come; in fact
fossil fuels represent an important element of the energy mix in the European Union as well as in
many other countries.
Above all, coal will continue to play a vital role
in the short-medium future, it represents the fossil
fuel with the largest and most widely distributed
global reserves – it is estimated to last for 130 years
(lignite) and 200 years (hard coal) – and many
countries have considerable amount within their
borders.
Coal is traditionally the key fossil fuel in power
production (used to generate some 30% of EU
electricity).
Moreover, most of the future growth in energy
consumption in a number of large emerging
economies is expected to be met from coal. Two-
thirds of the increase in global coal use will come
from China and India. Already today, one new coal-
fired power plant is put into operation every week
somewhere in the world.
However, all use of fossil fuels leads to CO2 Fig. 1.2/1 Siemens coal power plant
emissions, thus the issue arises how fossil fuel can be
used in the short-to-medium future in a more environment-friendly way [4].
CCS&T could be a good option in a portfolio of existing and emerging technologies with the
potential to bring the cuts of CO2 emissions needed to meet targets beyond 2020 and, at the same
time, to allow the continued use of fossil fuels.
European Technology Platform (ETP) experts claim that power plant with CCS&T
technology will be able to capture about 90% of generated CO2 during the early phases of
deployment of the technology.
5
 Furthermore CCS&T technologies can be applied for retrofitting/repowering applications as
well as for new plants.
The adoption of CCS&T technologies would enable the world to maintain reliable and
secure power generation, at the same time preparing for the eventual switch to a carbon neutral
energy system.

We also take into account that the basic elements of CCS&T technology (capture, transport
and storage of CO2) have already been developed and utilised by other sectors, such as the petro-
chemical industry, although in much smaller scales.
In fact CO2 capture is a well-known technology in different industrial processes, which
already separate CO2 from other gases both as by-product and as raw material highly purified, for
example in the beverage industry.
In regard to transport, there are already natural gas pipelines. Furthermore, since CO2 is
not explosive or inflammable like natural gas, the consequences in case of any leakage are
expected to be smaller than for the latter [5].
Moreover, most oil and gas fields have contained high-pressure CO2 for millions years, so
we can use the same natural trapping mechanisms which have already kept huge volumes of oil,
gas and CO2 underground for long time.
It has also been used in Enhanced Oil Recovery (EOR) process to increase oil production
by injecting it into wells.
Considering the CCS&T technologies importance, the EU Emissions Trading System will
recognise CO2 captured, transported and safely stored as not having been emitted.
Furthermore the European Council endorsed the Commission's intention to stimulate the
construction and operation by 2015 of up to 12 demonstration plants of sustainable fossil fuel
technologies in commercial power generation.
Also the EU Strategic Energy Technology Plan (SET-Plan) recognized the demonstration of
the use of CCS&T in fossil fuels-based power generation as one of the areas on which European
technology development should focus resources.
Besides on January 2007 the European Commission adopted Communication on
"Sustainable Power Generation from Fossil Fuels: aiming for near-zero emissions from coal after
2020" [1], which outlined the Commission's intention to bring forward an enabling legal and policy
framework for carbon capture and geological storage.
On May 2007 therefore the Working Group set up under the European Climate Change
Programme II consulted Member States and stakeholders (industry, NGOs, research and
academia) on the impact assessment, the options for managing risks, removing barriers and
promoting deployment, and the process for assessing the impacts of the options.
Moreover, the European Commission, European industry, NGOs, scientists and
environmentalists have united to form the European Technology Platform for Zero Emission Fossil
Fuel Power Plants (ETP-ZEP). It has been conceived to develop and deploy new competitive fossil
fuel power plant options with near zero CO2 emissions by 2020 [6].
A significant effort is currently underway in several areas of the technology that require
further research and development. To this end, the ETP-ZEP is developing a proposal for a large
demonstration programme, called the “ZEP Flagship Programme” that will comprise a set of
interrelated, large scale integrated CCS&T projects that will be operational across Europe by 2015;
the technology should be fully commercialised by 2020.

In conclusion the GHG emissions can be reduced by means of three types of mitigation
measures:

energy efficiency improvements and reduction in energy demand;

use of renewable energy sources (such as wind, solar energy and biomass);

capture and storage of CO2 currently emitted.

6
 Fig. 1.2/2 Wind power plant (Courtesy of Siemens)

Fig. 1.2/3 Biomass plant (Courtesy of Atel)

However, in order that CCS&T may be introduced on a commercial scale, there are still
some technical issues that must be overcome.
Thus extensive research is being undertaken in many countries around the world to study
new, promising concepts and improve existing technologies with the purpose of reducing costs and
energy consumed in capture. Simultaneously, tests are planned in power plants to validate these
newer technologies on a commercial scale.
Probably the future viability of CCS&T depends not only on fiscal incentives and a
regulatory framework, but on lower CO2 capture costs and improvement on plant efficiency.

References

[1] http://ec.europa.eu/environment/climat/ccs
[2] IPCC, 2005. IPCC special report on carbon dioxide capture and storage. Prepared by working group III
of the Intergovernmental Panel on Climate Change.
[3] http://ec.europa.eu/energy/strategies/2008/2008_01_climate_change_en.htm
[4] Peter Viebahn, Joachim Nitsch, Manfred Fischedick, Andrea Esken, Dietmar Schuwer, Nikolaus
Supersberger, Ulrich Zuberbuhler, Ottmar Edenhofer, Comparison of carbon capture and storage with
renewable energy technologies regarding structural, economic, and ecological aspects in Germany;
International journal of greenhouse gas control 1 (2007) 121-133.
[5] www.co2net.com
[6] http://www.zero-emissionplatform.eu/website/

7
2. CARBON DIOXIDE CAPTURE

2.1 Reference schemes

The aim of CO2 capture is to produce a concentrated stream of CO2 at high pressure that
can easily be transported to a storage site.
Nowadays reference schemes can be split in two categories:

- consolidated reference schemes that have been widely studied at least on small-scale and
include main equipments already used in industry;
- developing reference schemes that include technologies which are being studied.

2.1.1 Consolidated reference schemes

The three main schemes developed for CO2 capture are:

Post combustion systems that capture the CO2 from the flue gas produced by combustion of
the primary fuel in air;

Pre combustion systems that involve the removal of all or part of the carbon content from fuel
before burning it;

Oxyfuel combustion systems that use oxygen instead of air for combustion of the primary
fuel.

All the three schemes contain components developed and widely used in industry, but for
other main processes and for other purposes. Thus they are usually at a smaller scale and need
huge efforts to integrate, to scale-up and to optimise the process components.
Furthermore capture and compression need roughly 10-40% more energy than the
equivalent plant without capture [1].
For this reason the reduction of energy penalty is one of the primary goals on CO2 capture
technologies.

Fig. 2.1.1/1 (a) CO2 post-combustion capture at a plant in Malaysia (Mitsubishi Heavy Industries).
(b) CO2 precombustion capture at a coal gasification plant in North Dakota, USA.

8
2.1.1.1 Post combustion

CO2-lean gas

PC / CFB / CO2 CO2 CO2

NGCC Capture Purification Compression

Fig. 2.1.1.1/1 Schematic diagram for post-combustion CO2 capture

N2,O2,H2O
to Atmosphere

Natural gas

CO2 to
Compression

CO2
capture

Air Gas turbine

Steam
Generator

Steam
turbine

Fig. 2.1.1.1/2 An example of post-combustion CO2 capture process

Post combustion technology is based on capture of the carbon dioxide from flue gas stream
(currently emitted to the atmosphere) produced by the combustion of fuel.
The overall post-combustion capture system includes two main components:

a power plant island almost identical to the well established power generation systems;

a new device to separate the CO2 from the exhaust gases.

There are different separation processes: chemical absorption, solid sorbents, membranes
and cryogenics, but chemical absorption is considered to be the most suitable method for post
combustion capture because of the low CO2 partial pressure.
In a modern Pulverized Coal (PC) power plant or a Natural Gas Combined Cycle (NGCC)
power plant an organic solvent such as monoethanolamine (MEA) is typically employed to CO2
capture.

9
 This reference scheme is already tested and commercially available in the oil and gas
industry, in fact the separation of CO2 from raw natural gas (which typically contains significant
amounts of CO2) is practised on a large scale, using technologies similar to those used for post
combustion capture.
Moreover this system is the closest to large-scale commercial development especially as it
can also be retrofitted to existing fossil fuelled power plants.
However the main problem with post-combustion capture is the low concentration of CO2 in
the flue gas (normally 3-15% by volume), in fact the CO2 is diluted by the nitrogen that entered with
the introduced combustion air, therefore high volume of flue gas has to be treated.
Furthermore for the power plant with post combustion CO2 capture, there is a high increase
of the energy penalty because of the necessary thermal energy for the regeneration of the
chemical solvent and the post-combustion approach also leads to an increase of emissions in
many categories of impacts as eutrophication, summer smog and health impacts.
In addition for a new pulverized-coal power plant the efficiency is estimated decrease by
around 10 percentage points from 41-45% to 30-35% [1].

In order to improve the plant efficiency it is possible to separate CO2 under pressurised
conditions by means of chemical absorption after boiler but before expansion.
For example the study of Bryngelsson M. et al. [2] investigated the possibility of applying
CO2 capture technology to a Hybrid Combined Cycle (HCC) with Pressurized Fluidized Bed
Combustion (PFBD) that permits the use of a smaller and more efficient CO2 capture plant as CO2
partial pressure increase. Moreover it is possible to use a cheaper and less reactive solvent than
the most common MEA as potassium carbonate K2CO3.
The hybrid combined cycle that uses two fuels instead of one (e.g. natural gas and coal) is
more complex, but also more efficient than single fuel cycle, in fact the HCC overall efficiency is
5.2 % higher than the NGCC/PC efficiency.
The main penalties of this solution are:

volume penalty: due to the CO2 separation upstream of the expander, the power output in the
expander decreases linearly with the lower mass flow. For the same reason less steam is
produced in the steam cycle, therefore the power output decreases in the steam turbine as
well;

thermal penalty: as the temperature prior to expansion is lower than in case without CO2
capture, again the power output decreases both in the expander and in the steam turbine.

To partly compensate for these penalties, the CO2-lean flue gas can be humidified.

10
2.1.1.2 Pre combustion

Fuel CO2 CO2 CO2

Capture Purification Compression

IGCC/IRCC

Fig. 2.1.1.2/1 Schematic diagram for pre-combustion CO2 capture

Syngas CO2
Production Capture

CO2 to
Compression

Fuel

Comburent

Shift N2,O2,H2O
Slag Conversion H2 rich to Atmosphere
Fuel Gas

Steam
Generator

Gas turbine
Air Steam
turbine

Fig. 2.1.1.2/2 An example of pre-combustion CO2 capture process

Pre combustion carbon capture involves the removal of the carbon from natural gas, oil or
coal prior to combustion, leaving hydrogen. The latter can be used as fuel in power plants or fuel
cells and as feedstock for chemical production.
This reference scheme involves:

synthesis gas production;

water gas shift reaction;

CO2 separation.

Synthesis gas production

Synthesis gas (composed of hydrogen (H2), carbon monoxide (CO), and minor amounts of
other gaseous constituents) is mainly produced from natural gas by means of steam reforming and
autothermal reforming and from coal through gasification.

11
 Steam reforming of natural gas, sometimes referred as steam methane reforming (SMR), is
the most common method of producing hydrogen.
At high temperatures (700 – 1100 °C) and in the pre sence of a metal-based catalyst
(nickel) steam reacts with methane to produce carbon monoxide and hydrogen:

CH4 + H2O → CO + 3 H2

Autothermal reforming (ATR) uses oxygen and carbon dioxide or steam in a reaction with methane
to form synthesis gas. The reaction takes place in a single chamber where the methane is partially
oxidized. The reactions can be described in the following equations:

2CH4 + O2 + CO2 3H2 + 3CO + H2O (using CO2)

2CH4 + ½ O 2 + H2O 5H2 + 2CO (using steam)

In the gasification plants coal, or any other solid or liquid fuel, is partially combusted with
sub-stoichiometric amount of oxygen (and usually some steam) at elevated pressure (typically 30-
70 atmospheres) to form a synthesis gas.
In the power plants an emerging technology as Integrated Gasification Combined Cycle
(IGCC) can be use to gasify coal which, as mentioned previously, represents the fossil fuel with the
largest and most widely distributed global reserves.
However the gasification of solid fuels has been a well-known and industrially available
technology for many years, but not widely used yet for power purposes.

Water gas shift reaction

The synthesis gas (syngas) is then processed in a water-gas-shift reactor, which converts
the CO to CO2 and increases the CO2 and H2 molecular concentrations in the syngas stream.
Shift conversion is typically carried out in two stages:
- a high temperature for rapid initial conversion of CO;
- a low temperature stage for high degree of conversion.
As the conversion is highly exothermic, a cooler is necessary after the first stage. The
cooler produce intermediate pressure steam, which can be added to the intermediate pressure
steam produced by the combined cycle heat recovery system [3].
There are two generic types of shift conversion catalysts commercially available:
- “sweet” shift process: a sulphur-sensitive catalyst is used, therefore sulphur compounds,
principally H2S, must be removed before the gas is exposed to the shift conversion catalyst;
- “sour” shift process: the shift conversion stage is used before the removal of sulphur.
The latter process is more expensive, however it has the advantage that removal of sulphur
(in the form of H2S) and CO2 can be combined in the same unit and it also gives better process
efficiency [4].

CO2 separation

As CO2 is present at high concentration and at high pressure in the syngas, it can be
captured by means of physical absorption processes which use physical solvent as methanol or
polyethylene glycol (with commercial brands called Rectisol and Selexol).
Membrane separation units that can selectively permeate H2 and retain CO and CO2 are
also promising for IGCC power plants.

Because in the pre-combustion scheme, unlike post combustion capture, it is possible to

use physical solvents which do not need to be heated, but simply require the pressure reduction to
release the CO2, the energy requirements for CO2 capture and compression may be of the order of
half that required by post combustion capture.
Therefore for IGCC plants the efficiency is estimated decrease only by around 7 percentage
points from 38-47% to 31-40% [1].

12
 In addition, with pre-combustion capture, a reduction in all environmental impact categories
is achieved compared to the conventional power plants [5].
However pre-combustion capture scheme have to pay an efficiency penalty for the shift
reaction. Also in a plant with CO2 capture there is a lost mass of CO2 that does not pass through
the turbine and generate power. In addition, a highly efficient hydrogen turbine is not yet available,
optimised and developed for CCS&T. Moreover pre-combustion capture can not be retrofitted to
existing plants.
Furthermore, although IGCC power stations emit lower levels of conventional pollutants
than existing coal plants, they can be considered complex and capital costs are higher than for
conventional pulverized coal plants.

For current and near future IGCC processes, the gasification technologies the most
matured for high-rank coals which needs temperatures of about 1500 °C are Shell, GE and
Conoco Phillips. The first one uses dry feeding systems, while GE and Conoco Phillips are slurry
fed processes.
Chen and Rubin [6] analyzed the effects of adding CCS&T to an IGCC system employing a
GE quench gasifier.
Also Huang et al. [4] chose the Shell and GE gasifiers to study CO2 capture in coal fired
oxygen fed entrained flow IGCC power plants.
The GE IGCC showed lower efficiency than the Shell system. This was primarily due to the
thermodynamic disadvantages of the slurry feed system. This technology option, however,
provides more net power than the Shell plant and it is slightly less expensive per MW generated
than other one.

Fig. 2.1.1.2/3 Shell IGCC

Fig. 2.1.1.2/4 GE IGCC

13
2.1.1.3 Oxyfuel combustion

O2 separation Oxy-firing CO2 CO2

plant Purification Compression

Nitrogen Water

Fig. 2.1.1.3/1 Schematic diagram for oxyfuel combustion CO2 capture

CO2 to
Compression

Condenser

Water

Nitrogen

Recycled
flue gas Steam
Generator
ASU
Fuel

Air Steam
turbine
Oxygen

Fig. 2.1.1.3/2 An example of oxyfuel combustion CO2 capture process

In the oxyfuel or oxyfiring combustion the fuel is combusted in an enriched oxygen

environment using pure oxygen (95-99%) diluted with recycled CO2 or H2O to control the
combustion temperature. Therefore the flue gas consists mainly of CO2 and water vapour, the CO2
concentration is greater than 80% by volume. The water vapour is then removed by cooling and
compressing the gas stream.
Further treatment of the CO2-rich gas may be needed to remove noncondensed gases
(such as nitrogen) from the flue gas before the CO2 is sent to storage; these gases can be
removed during the compression/liquefaction process.

When the coal is combusted with oxygen, it is critical to be able to control temperature in
the combustor region. Several tests indicate that a concentration of 27% will lead to very similar
combustion characteristics as in an air supported flame [7], it is thus necessary to control the
oxygen concentration. For this reason the flue gas is recycled.

14
 In the oxygen fired Circulating Fluidised Bed (CFB) the recirculated solids, returning to the
combustor from the external solid loop, constitute an additional control variable. Combustor
temperature can be maintained by simply cooling a greater portion of the solids recirculation by
use of internal heat transfer surfaces. This makes possible to operate at high oxygen
concentrations with lower flue gas recycle rates, thus avoiding any potential agglomeration [7].

In the oxyfuel combustion compared with air combustion the volume of gases flowing
through the furnace is reduced somewhat, and the volume of flue gas (after recycling) is reduced
by about 80%.
Croiset and Thambimuthu [8] observed that during oxy-fuel combustion, the amount of NOx
exhausted from the system can be reduced as regards that produced in air combustion.
However Croiset and Thambimuthu also observed that the conversion of coal sulphur to
SO2 decreased from 91% for the air case to about 64% during oxy-fuel combustion. They
suggested that part of the sulphur is retained in the ash or that a fraction of SO2 is further oxidises
to SO3. They also held that there is a high SO3 concentrations in the flue gas recycled. Potential
corrosion of the furnace and CO2 transportation systems due to high sulphur compounds
concentrations in the flue gas could result in the need for desulphurization of the recycled flue gas
for oxy-fuel combustion.

The carbon capture with oxyfuel combustion does not have real disadvantages like the
volatility or rapid degradation of solvents and no energy is required for chemical or physical solvent
regeneration as it occurs in post or pre combustion. On the other hand for oxygen production in the
air separation unit a relatively large amount of energy, 7–10% of the total system input, is needed.

Fig. 2.1.1.3/3 Oxyfuel combustion capture (Vattenfall)

Today oxygen combustion is well understood on a small scale and all the major
components applied to boilers exist on an industrial scale.
Various oxyfuel cycles with air separation unit (ASU) and CO2/H2O recycling in fact have
been proposed and studied among which the Graz, Water and Matiant (combined) cycle.

15
Graz cycle

The Graz cycle consists of a high temperature Brayton cycle (CO2 compressor, combustion
chamber and High Pressure Turbine HPT) and a low temperature Rankine cycle (Low Pressure
Turbine LPT, condenser, Heat Recovery Steam Generator HRSG and High Pressure Turbine
HPT) [9].
Fuel and oxygen are fed to the combustion chamber; steam as well as CO2 is supplied to
control the combustion temperature.
Then the fluid is expanded in the HPT and the hot exhaust gas is used in the following
HRSG to vaporize and superheat H2O for another HPT. Then it is further expanded in the LPT.
In the condenser the separation of CO2 and H2O takes place by water condensation. The
water is preheated, vaporized and superheated in the HRSG; whereas CO2 is compressed and it is
partly separated for further use or storage, partly it is recycled to the combustion chamber.

CO2 CO2
compressor compressor

CO2

CO2 to
Feed compression
O2 pump
HRSG Condenser
pump

H2O

Fuel Combustor

HPT Steam LPT

turbine
CO2
Steam compressor
Condenser

Fig. 2.1.1.3/4 Graz cycle scheme

16
Water cycle

The Water cycle is a cycle with combustion products as working fluid and with two
combustors.
It is produce a high-pressure, superheated mixture of mainly H2O and CO2 which is
expanded in a series of turbines.
In the condenser H2O and CO2 are separated, the water is heated and steam is recycled to
the combustion chamber [10].

O2 Fuel O2

Condenser CO2
compressor

Combustor Reheat
Combustor

Condenser
pump
Fuel HPT LPT
CO2 to
Recuperator compression

H2O
Feed
pump

Fig. 2.1.1.3/5 Water cycle scheme

17
Matiant cycle

MATIANT (contraction of the names of the two designers MAThieu and lANTovski) cycle is
basically a gas cycle and consists of a supercritical CO2 Rankine-like cycle combined with a
regenerative CO2 Brayton cycle [11].
The working fluid is a mixture of mainly CO2 and H2O, it is expanded in a MPT, and then it
is reheated in a second combustion chamber. It is further expanded in a LPT.
This fluid is then cooled in a recuperator giving up its heat to CO2 flow which is expanded in
HPT and recycled to combustion chamber.
After the recuperator, the water is condensed. The remaining gas is manly CO2 and it is
compressed, it is partly sent to storage and partly it is sent to recuperator.

CO2
HPT compressor

Fuel

Combustor
H2O
O2

Condenser
MPT LPT

CO2
pump

Recuperator
Fuel
Combustor

O2 CO2

Fig. 2.1.1.3/6 Matiant cycle scheme

However the oxyfuel combustion scheme is currently only demonstrated on laboratory-

sized equipment; for coal and larger-scale power processes it is not well-established yet [12].
In addition this scheme requires gas turbines that use CO2/H2O as working fluid, which has
different expansion characteristics than nitrogen used in conventional turbines. The optimal
pressure ratio for CO2 turbines is higher than for conventional turbines, which implies that the
efficiency of a CO2 turbine for typical pressure ratios nowadays is lower than the efficiency of
traditional turbines. Existing gas turbines cannot simply be adapted for CO2 as working fluid; hence
complete new gas turbines (combustor and compressor) need to be developed [13].
Nevertheless, apart from that, experience shows that there is no significant difference from
air combustion; the boiler can utilize modern standards with supercritical data and a completely
conventional steam turbine process; the desulphurisation is also conventional, but with CO2
instead of nitrogen as the main gas component [12].

18
Oxygen separation

As regards oxygen separation from air, today the most common process is a cryogenic air
separation unit (ASU). Currently this technology is used in industrial applications, but for large
power plants it will be much larger than any existing today; in fact, it is calculated that air
separation units approximately four times larger will be required.
Other technologies are polymeric membranes and vacuum swing adsorption (VSA).
However the first one could be used to generate very low purity oxygen in limited quantities
for specific air-enrichment purpose and VSA is well suited for small-scale oxygen production.
Notwithstanding this, in order to improve the economics and thermal efficiency of oxy-fuel
power production, new technologies are being developed to separate oxygen from air using less
energy.
In the future more efficient processes such as Ion Transport Membranes (ITMs) could be
used.
The ITMs are ceramic membranes which are permeable to oxygen and no to other
substances and require less energy than current methods of oxygen production.
During operation, oxygen molecules are adsorbed onto the surface of the ceramic
membrane, where they are dissociated and ionised by electron transfer from the membrane. Under
a gradient of oxygen partial pressure on the opposite side of the membrane, oxygen ions are
transferred within the lattice of the material, then release the electrons and form oxygen molecules
again [7].
The ITM oxygen process achieves a high-purity, high flux separation of oxygen from air.
These membrane materials in fact allow the rapid transfer of oxygen ions, achieving a flux higher
than polymeric membranes, with theoretically infinite selectivity.
However most ion transport membrane materials are only permeable to oxygen at
temperatures above 700°C (975 K), the membrane ther efore needs to be heated.
There are three main types of ceramics membrane: perovskite, fluorite and mixed.
Perovskite ion transport ceramics have the chemical structure ABO3. There may be a
mixture of 2 or more elements in the A-site and/or the B-site (e.g. Ba0.5Sr0.5Co0.8Fe0.2O3-δ).
Fluorite ion transport ceramics have the structure AO2 (e.g. ZrO2).
Both types can conduct both electrons and oxygen ions through the ceramic lattice. Most
materials are better at conducting either electrons or oxygen ions. Also, some membranes may
have very high ionic conductivity but low stability in a particular environment.
Mixed membranes are made of a mixture of two materials, in order to take advantage of the
best traits of each.
Perovskite membranes have higher fluxes in the 700°C – 1000°C range than fluorite
membranes [14].
Much research has been conduced on ITMs, above all with perovskite structure, also
because of their applications in pressure-driven oxygen generators, partial oxidation reactors, and
as electrodes for fuel cells.
For some years Air Products and Chemical (AIPC) in cooperation with U.S. Department of
Energy (DOE) is studying ITM oxygen technology to significantly reduce the capital and costs
associated to oxygen production [15].

Fig. 2.1.1.3/7 Ion Transport Membrane (Air Products)

19
2.1.2 Developing reference schemes

Nowadays to improve the CO2 capture process, new technologies are developing. The
most important are:

Advanced Zero Emission Power Plant (AZEP): a novel oxyfuel power cycle that consist of a
Mixed Conducting Membrane (MCM) reactor instead of the conventional chamber in a gas
turbine;

Chemical Looping Combustion (CLC): a process which uses a metal oxide as an oxygen
carrier instead of air for the oxidation of the fuel;

High temperature fuel cells: Solid Oxide Fuel Cells (SOFCs) and Molten Carbonate Fuel Cells
(MCFCs) could be used for their potential application to CO2 separation because of production
of CO2-rich anode exhaust flow.

All the three schemes can be considered an oxyfuel concept as they separate oxygen from
nitrogen by means of different technologies.

2.1.2.1 Advanced Zero Emission Power Plant (AZEP)

Steam
turbine
Recycled
gas

Q CO2 to
Fuel Compression

O2 Condenser
MCM reactor

Water

Gas turbine
Air
Steam Oxygen-
Generator depleted air

Fig. 2.1.2.1/1 Schematic process for AZEP

AZEP is a novel oxyfuel combustion scheme where the conventional combustion chamber
in a gas turbine is substituted by a Mixed Conducting Membrane (MCM) reactor, which combines
oxygen production, fuel combustion and heat transfer.
Compressed air enters the MCM reactor, where oxygen passes through the high-
temperature membrane and is transported to the combustion chamber. The heat of combustion is
transferred to oxygen-depleted air, which is expanded in a conventional turbine. Steam is
generated from the turbine exhaust and the CO2/H2O stream generated in the combustion
chamber, which is then expanded in a steam turbine.
The combustion products are recycled to the membrane reactor inlet to control the
combustion temperature.
The use of a conventional turbine is essentially the advantage of AZEP in comparison with
classical oxyfuel combustion which uses gas turbine with CO2/H2O as working fluid. Therefore the
AZEP concept combines well with current technology requiring minor adaptations in gas turbine
(working fluid has lower oxygen content). Obviously, MCM technology is not well-known yet [13].

20
2.1.2.2 Chemical Looping Combustion (CLC)

Gas turbine
CO2 to
CO2 Compression
turbine
Condenser

Air MeO Water

Oxygen-
depleted air
Me

OX RED
reactor reactor
Steam
Generator
Fuel

Steam
turbine

Fig. 2.1.2.2/1 Schematic process for CLC

CLC was proposed by Richter and Knoche [16] in 1983 for the first time. It is a promising
technology which uses a solid-state oxygen carrier, i.e. a simple metal oxide, to oxidiser the fuel;
therefore combustion takes place without any direct contact between air and fuel.
The process is very similar to a conventional fluidized-bed boiler, although with two reactors
instead of one. The metal is in fact oxidized in an air blown reactor and the metal oxide is then
reduced in the fuel reactor.
The oxidation reaction (1) and the reduction reaction (2) are given by following equations
respectively [17]:

MeyOx-1 + ½ O 2  MeyOx (1)

(2n+m) MeyOx + CnH2m  (2n+m)MeyOx-1 + mH2O + nCO2 (2)

In equations (1) and (2) MeyOx is metal oxide, MeyOx-1 is a reduced metal, CnH2m is an
alkane fuel molecule.
As the oxidation of the metal is exothermic, the oxygen-depleted air is available at high
temperature and pressure (in case of a pressurised reactor) and can be used for power production.
The flue gas mainly consists of CO2 and H2O and the dilution with nitrogen is avoided. Thus
the water vapour is easily separated by condensation.
In addition the flue stream can be utilised for power generation, either by expansion or
steam generation.

In this process the energy penalty for CO2 separation is lower than pre and post
combustion capture schemes where CO2 is diluted with other combustion products, furthermore it
does not require energy to separate oxygen from air.

21
 In the CLC the metal oxide performance is essential. The metal oxide should be mixed with
an inert stabiliser to provide adequate mechanical stability and improve chemical reactivity.
Investigations have been made for iron oxide and various other metal oxides (Ni, Cu, Mn, Co). Out
of all, nickel oxide (NiO) exhibits the most promising properties [16].
In case of hard coal and lignite is used in the process, it is necessary to consider the
possible detrimental effects of impurities, the oxygen carrier in fact becomes mixed with unburned
char which may be transferred to the air reactor and release CO2, and it may also be degraded by
trace elements and difficult to separate from the ash.
The solution can be either to use a cheap carrier such as iron, which is disposable after
short use, or to find another way of gasifying the coal that does not produce gas stream impurities.
Another thing very important is to maintain the same pressure of the gases in the duct that
connects the CLC-reactors for solids transport. This duct is that through which the solids separated
from the oxygen-depleted air in the cyclone fall down to the fuel reactor.
If pressure difference occurs the oxygen-depleted air could enter into the fuel reactor.
The occurrence of this pressure gradient is the consequence of the presence of two
turbines, the air turbine and the CO2-turbine, both resulting in different inlet pressures at part-load.
The plant then needs to be controlled in such a way that the pressure at the air turbine inlet
becomes equal to that at the CO2-turbine inlet [16].

This scheme has recently been demonstrated as working well in a laboratory scale, burning
natural gas, syngas and coal. There is significant operational experience in prototypes in the size
range 300 W to 50 kW, with operational times of typically 30 to 100 h [7].
However it has not been used yet in a full-scale plant and it can not be easily retrofitted to
an existing plant.

22
2.1.2.3 High temperature fuel cells

High temperatures fuel cells as Solid Oxide Fuel Cells (SOFCs) and Molten Carbonate Fuel
Cells (MCFCs) can be fuelled with hydrogen, syngas or natural gas.
They allow the oxidisation of fuels involving the transportation of ions through the electrolyte
from cathode flow (air flow) to anode flow (fuel flow), avoiding the mixture of the two flows and the
dilution with nitrogen. For this reason CO2 capture at fuel cells can be considered an oxyfuel
concept.
Both SOFCs and MCFCs lead to a high CO2 concentration in the anode exhaust flow.
Moreover fuel cells directly convert the chemical energy of fuel into electrical energy, thus
they can generate electricity at higher efficiency and produce lower amount of CO2 than
conventional power plants.
However the present development of high temperature fuel cells suggests that their
application to large scale power plants will occur in a medium-term.

Solid Oxide Fuel Cell (SOFC)

-
e
To CO2 capture - +

Oxygen-depleted air
CO2 + H2O +
CO + H2

Fuel Air

Anode Electrolyte Cathode

Fig. 2.1.2.3/1 SOFC conceptual scheme

SOFCs have ceramic electrolytes which require temperatures around 1000 °C to achieve
sufficient ionic conductivity.
Anode and cathode reactions are the following:

H2 + O2-  H2O + 2e- (anode)

½ O 2 + 2e-  O2- (cathode)

Hydrogen is generated from the fuel by steam

reforming and CO-shift reactions.
The cathode exhaust flow is oxygen-depleted
air; the anode stream contains a variable proportion
mixture of CO, CO2, H2 and H2O.
Thus the SOFC concentrates all the CO2
production in the anode exhaust, in case of CO2
capture is required, the anode and cathode stream
need to be maintained separated in order to avoid CO2
rich anode stream to be diluted with nitrogen.
Fig. 2.1.2.3/2 SOFC (Siemens)

23
 In this way the CO2 separation is easy and with low energy penalty
In order to further increase CO2 concentration it is possible to oxidise the anode exhaust
flow with pure oxygen in an afterburner. The afterburner can be a burner fuelled with pure oxygen,
an oxygen conducting membrane reactor, a second SOFC or a water gas shift membrane reactor
afterburner [18].

Molten Carbonate Fuel Cell (MCFC)

-
CO2 e
- +
CO2 + H2O +
CO + H2
Oxygen-
CO2 capture depleted air

Fuel Air + CO2 Air

Anode Electrolyte Cathode

Fig. 2.1.2.3/3 MCFC conceptual scheme

MCFCs have an alkali carbonates electrolyte, which is fluid at around 650 °C.
Anode and cathode reactions are the following:

H2 + CO32-  H2O + CO2 + 2e- (anode)

½ O 2 + CO2 + 2e-  CO32- (cathode)

As above seen, the MCFC

requires the presence of CO2 both in
the anode and in the cathode flow.
However the majority of CO2 is
concentrated in the anode exhaust.
A possible configuration to
capture CO2 is to burn the anode
stream with air, recirculate the
combustion flue gas rich in CO2 to
cathode and use the heat of cathode
exhaust to generate steam
producing energy for CO2
separation. The drawback of this
scheme is that CO2 rich anode flow
is diluted with nitrogen [13].

Fig. 2.1.2.3/4 MCFC

24
 Alternatively, to increase CO2 concentration, it is possible not recirculate the combustion
flue gas, but only CO2 after the CO2 separation (see Fig. 2.1.2.3/3).
Furthermore MCFC can be placed downstream to conventional power plants to concentrate
and separate CO2 feeding the cathode with exhaust gases generated by these power plants (see §
2.2.2.6).

25
2.2 CO2 separation technologies

There is a wide range of technologies to capture CO2. Some are already commercially
available, especially to separate CO2 from raw natural gas or to supply it to the food industry,
whereas others are developing technologies.
The choice of a specific capture technology is determined largely by the process conditions
under which it must operate and by the type of reference scheme used.

2.2.1 Consolidated technologies

Among consolidated technologies are included the following methods:

• Chemical absorption;
• Physical absorption;
• Membrane.

2.2.1.1 Chemical absorption

There are two types of absorption: chemical absorption and physical absorption.
In the first case the gas reacts with the liquid forming a chemical compound; whereas in the
physical absorption the gas is dissolved in the liquid forming a solution.
In the chemical absorption therefore the bond between absorbed and solvent is stronger
and its dissolution requires more energy.
Chemical absorption, in particular using amine solutions such as Monoethanolamine
(MEA), is a commercialized technology used in natural gas industry for several years and it is
regarded as the most mature process.
This process is commonly used for treating gas streams with low- and moderate-CO2 partial
pressure [19].

A typical absorption process consists of two major sections (see Fig. 2.2.1.1/1):

an absorption section where CO2 in the flue gas is absorbed into the liquid solvent;

a regeneration section where the absorbed CO2 is stripped out by means of heat.

Figure 2.2.1.1/1 Typical absorption process

26
 In the absorption section the flue gases from the power plant flow through an absorber
column counter currently with the absorbent (packed bed columns are preferred over plate
columns because of their higher contact area).
The CO2-lean gas can enter a water wash scrubber in which water, absorbent vapour and
droplets are recovered and recycled back into the absorber to decrease the solvent loss. The
treated gas then is vented to the atmosphere.
The rich solvent containing chemically bound CO2 is pumped to the top of a stripper after
being heated by means of the hot stream of ‘CO2-lean’ regenerated solvent.
The chemical solvent is regenerated in the stripper at elevated temperatures and a
pressure not much higher than atmospheric. Heat is supplied to the reboiler located at the bottom
of the stripper using low-pressure steam which acts as stripping gas.
Steam is recovered in the condenser and fed back to the stripper, after which the produced
CO2 gas leaves the condenser and is sent to compression.
Finally, the lean solvent is pumped back to the absorber after being cooled heating the
CO2-rich solvent through a heat exchanger. [20]
.
At present, there are several absorption solvents for CO2 capture:

• Amines:
○ Monethanolamine (MEA);
○ Diethanolamine (DEA);
○ 2-(butylamino)ethanol (BEA);
○ N-ethylethanolamine (EEA)
○ N-methyldiethanolamine (MDEA);
○ N,N-diethylethanolamine (DEEA);
○ 2-(methylamino)ethanol (MMEA);
○ 2-(ethylamino)ethanol (EMEA);
○ 2-(2-aminoethyl-amino)ethanol (AEEA);
○ Diglycolamine (DGA);
○ Diisopropanolamine (DIPA);
○ Piperazine (PZ);

• Sterically hindered amines:

○ 2-amino-2-methyl-1propanol (AMP);
○ 2-amino- 2-hydroxymethyl-1,3-propanediol (AHPD);

• Carbonate:
○ Sodium carbonate (Na2CO3);
○ Potassium carbonate (K2CO3);

• Ammonium

• Amino acids

Alkanolamines

Aqueous solutions of alkanolamines are the most commonly used chemical absorbents for
the removal of acidic gases (CO2 and H2S) from natural, refinery and synthesis gas streams.
The reaction of carbon dioxide with primary and secondary amines can be expressed by
zwitterions mechanism [21]. The first step is the production of an intermediate zwitterion (a
chemical compound that carries a total net charge of 0, thus electrically neutral but carries formal
positive and negative):

CO2 + RR’NH ←→ RR’NH+COO−

27
 Theoretically, the zwitterion can be deprotonated by any base present in the solution,
producing a carbamate ion and a protonated base:

RR’NH+COO− + RR’NH ←→ RR’NCOO− + RR’NH2+

The overall chemical reaction of amines with CO2 is given by:

CO2 + 2RR’NH ←→ RR’NCOO− + RR’NH2+

After CO2 has been absorbed by an amine, a secondary reaction leads to the hydrolysis of
parts of the carbamate to bicarbonate and the regeneration of parts of amine:

RR’NCOO− + H2O ←→RR’NH + HCO3 −

As can be seen, there is a requirement of 2 mol of amine/mol of CO2 for the formation of
stable bicarbonate compounds resulting in the capture of CO2.

Among aqueous amines, monoethanolamine (MEA) (primary amine) has been extensively
used.
It has in fact several advantages as a solvent such as high reactivity, low cost, high
absorbing capacity on a mass basis, reasonable thermal stability and thermal degradation rate
[22].
However there are some disadvantages: the energy requirement of the process is high
because of the high enthalpy of reaction with CO2 and the formation of a stable carbamate (using
MEA as solvent power generation can be reduced by 20%), the high vapour pressure cause
vaporization losses, the solvent reacts with other chemical constituents in the process solution
forming degradation products. SO2 and NO2 in fact can be react with MEA to form non-regenerable
degradation products as heat-stable salts.
The presence of heat-stable salts causes a number of adverse effects, including a
reduction in acid gas absorption capacity of amine, an increase in solution viscosity, an increase in
foaming tendency of the solution and an increase in corrosion.
It is thus necessary to make up solvent concentration due to the degradation and chemical
losses [19].
Moreover MEA is more corrosive than many other alkanolamines. In particular increasing
O2 partial pressure or solution velocity, raising solution temperature, increasing CO2 loading or
amine concentration cause corrosion rate increase [23].
Therefore some chemical additives such as corrosion inhibitors, antifoam agents, oxygen
scavengers, and salt neutralizers have been developed.
MEA is also toxic, so as it is expected that a part of the MEA solvent (through evaporation
or entrained as droplets) can leave the stripper together with the CO2-lean flue gas flow, it is
necessary to take into account these emissions [24].

Especially to optimize the MEA process and thus to reduce steam consumption and cost of
CO2 capture other solutions have been analyzed.
For example A. Aroonwilas and A. Veawab [25] have studied a modified configuration of the
MEA conventional scheme: split flow configuration (see Fig. 2.2.1.1/2). In this new configuration
rich-solution coming from the absorber is divided into two streams.
The first stream enters the top of the regenerator, flows downward, leaves the regenerator
from the midpoint, and enters the absorber at the midpoint. The second stream enters the
regenerator at the midpoint, flows downward, leaves the regenerator from the bottom, and
eventually enters the absorber at the top.
The researchers have found that the split flow configuration reduces the energy penalty. In
fact conventional MEA process requires approximately 4.8 MJ/kg CO2 to strip CO2 during solvent
regeneration while the split flow configuration requires approximately 3.2 MJ/kg CO2.

28
Figure 2.2.1.1/2 Process flow diagrams of: (a) conventional amine process and (b) split flow process

Another disadvantage of the CO2 capture process is that it involves monitoring and
manipulation of many components and over a hundred parameters, including temperatures, flow
rates, pressures, and levels of reaction instruments and moreover the handling of critical
parameter value directly impacts performance of the plant and CO2 capture efficiency.
Thus C.W. Chan et al. [26] have conducted a research work for building a decision support
system that can monitor, control and diagnose the CO2 capture process.
The decision support system is called Carbon Dioxide Capture Monitoring and Diagnostic
(CDCMD) System.
The knowledge base consists of knowledge about the plant and its components, the
parameters, and their normal and abnormal operating ranges. Plant components that have
abnormal parameter values indicate that abnormal operating conditions have occurred.
The knowledge base also consists of the remedial actions that would address these
abnormal situations.
Thus the CDCMD system can help the operator to monitor the operating conditions of the
CO2 capture pilot plant by continuously comparing the measured values from sensors with normal
or desired values. Deviations from the normal ranges would set off an alarm to advise the operator
that a problem has occurred.

However in order to avoid MEA process problems, much search have been devoted to find
new solvents that are superior to MEA.

29
 New solvents should have:

higher capacity for CO2 capture;

lower energy for regeneration;

higher absorption/desorption rates and regeneration at lower temperatures;

lower volatility and better stability;

less degradation;

lower corrosivity;

no toxicity.

Blended amines

Some research has been done on the use of mixtures of single alkanolamines, known as
blended amines due to their process advantages over the single amine.
The overall reaction rate that determine the overall mass transfer rate is high for primary
amines (as MEA), somewhat lower for secondary amines (as DEA) and very low for tertiary amines
(MDEA). In fact only primary and secondary amines directly react with carbon dioxide to form
carbamates which contributes to increasing the overall rate of absorption cause tertiary amines
lack the extra hydrogen atom to form this compound.
On the other hand, for the regenerability the opposite tendency is observed: tertiary amines
are most favourable [27].
Therefore the blended amines (mixtures typically of primary or secondary amines with
tertiary amines) combine low energy requirement and high CO2 absorption capacity (tertiary
amine) together with a fast CO2 absorption rate (primary or secondary amine).
Typical mixture of amines is MEA-MDEA solution or MDEA blended with piperazine (PZ), a
cyclic secondary amine.
The drawback is that although the blended solvent typically requires less energy for solvent
regeneration compared to MEA, reflecting a lower steam cost, it requires a larger capital
investment as their CO2 capture performance is lower.
For instance MEA–MDEA solutions can require absorber height of more than three times
the height for MEA solution in order to achieve an identical CO2 removal target from flue gas.
The favourable saving is thus achieved when the MEA–MDEA process is operated under
appropriate mixing ratio and operating conditions [25].

P. D. Vaidya and E. Y. Kenig [28] have investigated the characteristics of N-

ethylethanolamine (EEA) and N,N-diethylethanolamine (DEEA) as chemical solvents.
EEA is obtained from the reactions between ethylamine (obtained from ethanol) and
ethylene oxide (obtained from the oxidation of ethylene which, in turn, can be prepared by
dehydration of ethanol). Ethanol can be prepared from agricultural products and/or residues. Thus,
EEA represents an especially promising absorbent, as it can be prepared from renewable
resources.
DEEA can also be obtained from renewable resources.
Due to its tertiary amine characteristics DEEA has low reactivity with respect to CO2, but
the addition of EEA as an activator would possibly lead to increase CO2 absorption rates. This
absorbent blend would combine the high CO2 loading capacity of DEEA with the high reactivity of
EEA.

Due its configuration DEEA promotes the CO2 hydrolysis reaction, which results in
bicarbonate formation, instead of carbamation.
The released reaction heat in bicarbonate formation is lower than that of carbamate
formation, thus resulting in lower solvent regeneration costs. Moreover, DEEA has a high CO2
loading of 1 mol of CO2/mole of amine.
Therefore the study of P. D. Vaidya and E. Y. Kenig has highlighted the importance of the
aqueous blend consisting of EEA and DEEA in gas purification applications.

30
 S. Ma’mun et al. [22] have studied 2-(2-aminoethyl-amino) ethanol (AEEA), a diamine with
one secondary and one primary amine group.
AEEA seems to be a potentially good absorbent for capturing CO2 from low pressure
gases. It offers a high absorption rate combined with high absorption capacity compared to the
other absorbents as MEA, MDEA, and PZ. In addition, the vapour pressure of AEEA is much lower
compared to that of MEA (e.g., PsMEA = 15.9 kPa and PsAEEA = 0.969 kPa at 120°C).
The maximum net cyclic capacity of AEEA is somewhat higher than that of MEA and
maintains its absorption power at higher loadings.
Moreover it is a chain molecule and should, therefore, be an environmentally relatively
acceptable absorbent.

Sterically hindered amines

Recently, some researchers are devoting to the use of aqueous solutions of sterically
hindered amines due to their high cyclic capacity, relatively high absorption rates at high CO2
loadings, and loading capacities nearing up to 1 mol of CO2/mol of amine in concentrated amine
solutions.
Due to the bulkiness of carbon groups attached to the amino group, the sterically hindered
amines form unstable carbamates; thus the hydrolysis of carbamates forms bicarbonate and
restores free amines that can react again with CO2 allowing a higher CO2 absorption.
D. Le Tourneux et al. [29] have studied aqueous solutions of 2-amino- 2-hydroxymethyl-1,3-
propanediol (AHPD), a primary sterically hindered amine; whereas B. P. Mandala et al. [30] have
investigated aqueous blends of AMP (2-amino-2-methyl-1propanol) and MEA.
Since, as partially above said, sterically hindered amine does not form stable carbamate,
bicarbonate and carbonate ions may be present in the solution in larger amounts than the
carbamate ions. The researchers speculated that the regeneration energy costs, when aqueous
solutions of AMP is used, may be lower as in the case of using aqueous MDEA solutions.
Therefore AMP/MEA appears to be an attractive new blended amine solvent in addition to
MDEA/MEA.

Sodium carbonate

In order to decrease energy penalty and to avoid environmental pollution other absorbents
as sodium carbonate have been studied.
Normally sodium carbonate is considered unsuitable for CO2 capture from low CO2 partial
pressure sources, because of the limited solubility of both carbonate and bicarbonate.
Thus H. Knuutila et al. [31] have circumvented this problem by allowing the systems to work
in a slurry phase.
Since the CO2 absorption produces sodium bicarbonate, which has lower solubility than the
carbonate, the solubility limit is exceeded and solid bicarbonate is precipitated thereby increasing
the capacity of the solvent.
The overall reaction which occurs in the absorber can be divided into the following
reactions:

Dissolution of CO2 in the liquid: CO2(g) ↔ CO2 (l)

Dissociation of water: H2O ↔ OH- + H+

Dissociation of CO2: CO2 (l) + H2O ↔ HCO3- + H+

Dissociation of bicarbonate ion: HCO3- ↔ CO32- + H+

Dissociation of solid: Na+ + HCO3- ↔ NaHCO3(s)

According to the researchers, sodium carbonate system requires less regeneration energy
than MEA capture system: 3.22 MJ/kgCO2 instead of 3.9-4.3 MJ/kgCO2.
Moreover using the slurry sodium carbonate process the loss in electricity production was
found to be 9 percentage points, lowering the efficiency from 39% to 30%, whereas typically with
MEA-based CO2 capture processes the power plant efficiency decreases from 11–15 percentage
points.

31
 In addition sodium carbonate is non-hazardous, non-volatile, its corrosion rate is low and its
price is lower than that of MEA. It is also non-fouling and do not degrade, apart from the reactions
with SO2 and NOx.
Also sodium based chemicals are already used in power plants for SO2 removal from flue
gases and the possibility of combining CO2 and SO2 removal makes sodium chemicals very
attractive as even though the reactions with SO2 and NOx are non-reversible they provide a cheap
outlet for these contaminants.

However the main drawback with sodium carbonate is the low absorption rate compared to
amines, leading to high absorption towers. To overcome the problem, additives will be needed, but
most of these can affect the CO2 capture energy requirement negatively since they most of
therated-increasing additives have higher heat of reaction than the carbonate.

Potassium carbonate

Potassium carbonate (K2CO3) is used for CO2 removal in high-pressure applications.

However these processes are limited by selectivity and slow rates of absorption under the
conditions present in coal-fired power plants (low CO2 concentration: 12-15% vol).
Some studies have been done to improve the performance of CO2-capture promoting
potassium carbonate by an amine.
J. Oexmann et al. [32] have analysed a CO2-capture process using piperazine-promoted
potassium carbonate. This blended solvent has the potential for a higher CO2 capacity. In addition
piperazine is less sensitive to oxidative degradation than MEA.
In a preliminary comparison between K2CO3/PZ and MEA process it was shown that the
first process could reduce the specific investment costs for absorber and desorber columns by
around 18% in comparison to a CO2-capture process using MEA.

Ammonium

In order to avoid the drawbacks of the MEA processes some studies have been devoted to
use aqueous ammonia as CO2 sorbent.
Flue gas needs to be pre-treated by oxidizing SO2 and NO to SO3 and NO2, respectively.
The flue gas then reacts with aqueous ammonia in a wet scrubber.
It is estimated that the regeneration of ammonium requires less energy than MEA process:
this process could saved energy up to 60% compared to MEA process.
The major by-products from this process include ammonium sulphate, ammonium nitrate,
and ammonium bicarbonate. Ammonium sulphate and ammonium nitrate are well-known fertilizers.
The ammonium bicarbonate can be thermally decomposed to recycle ammonium.

American Electric Power is working with Alstom Power Inc. on a CO2 capture project using
Chilled Aqueous Ammonia Process.
The flue gas is chilled (∼1.5 °C), ammonium carbonate absorbs CO 2 to make ammonium
bicarbonate. This process significantly reduces the amount of energy required to capture CO2
compared to other technologies [33].
Furthermore this system offers high removal of residual pollutants such as SO3.
Also the European CO2 Test Centre Mongstad (TCM) is testing and developing a CO2
capture technologies where the main objective is reducing cost and risk. These technologies
include both amine and carbonate (“chilled ammonia”) process (see § 7.6.4.3).

Amino acids

Other types of chemical absorbent can be amino acids. They have the same functional
groups as alkanolamines and can be expected to behave similarly towards carbon dioxide, but do
not form precipitates with CO2 and do not deteriorate in the presence of oxygen.
In addition they do not have a corrosive behaviour and seem to require less energy.

32
 A further advantage of amino acids is the possibility of adding a salt function. The
carboxylate group can be neutralized with potassium or lithium hydroxide, in order to produce the
corresponding salts of the amino acids. This salt function ensures the non-volatility of the
substance which is extremely helpful in the stripper [34].
Moreover the aqueous solutions of amino acid salts have high surface tension, which
makes them interesting for applications of membrane contactors (see below).

2.2.1.2 Physical absorption

As previously said, in the physical absorption the gas is dissolved in the liquid forming a
solution and the bond between solvent and absorbed is weaker than that is formed in the chemical
absorption.
Anyway the physical absorption is similar to chemical absorption process.
The gas to be treated is injected at the bottom of the absorption column after it is cooled,
while the solvent is injected at the top to absorb the CO2 from the gas. The rich-solvent is then
heated by exchanging heat with the lean-solvent coming from the desorption column. The solvent
is regenerated in the desorption column using low-pressure steam condensation in the reboiler and
it is then recirculated to absorption column after it is cooled, whereas CO2-rich stream is sent to
compression (see Fig. 2.2.1.2/1).

Fig. 2.2.1.2/1 Typical absorption process [35]

The physical solvents are commonly used for high-pressure gas streams. It is in fact known
that using physical absorbent alone is ineffective for low-pressure gas flows. Therefore this method
is not suitable for post combustion CO2 capture process as in the flue gas the CO2 concentration is
low (3-15% by volume), whereas in the pre-combustion system CO2 is present at high
concentration (15-60% by volume on a dry basis) and high pressure.
The main physical absorbents are:

Propylene carbonate;

Methanol;

33

Chilled methanol (Rectisol);

N-methyl-2-pyrrolidone (NMP);

Dimethylether of polyethylene glycol (SelexolTM).

They are known for their chemical stability, their high absorption capacities and for a non-
induced corrosion effect.
Moreover as in the physical absorption process the bonds are weaker, the thermal
consumption is lower than for chemical absorption process, thus the solvent regeneration requires
less energy.
However some of them as methanol and NMP need low temperature.
Methanol has to operate at low temperatures (-30°C) because of its higher volatility which is
a disadvantage with regard to the potential solvent losses. Furthermore it is necessary to add to
the CO2 compression unit a wash water column to capture methanol with water from the CO2
stream and also a dehydration system as the water content should not exceed 20 ppm to avoid
corrosion problems during the CO2 transportation (see Fig. 2.2.1.2/2).

Fig. 2.2.1.2/2 Methanol process for CO2 capture [35]

NMP also requires a refrigeration system to meet relatively low temperatures. The
refrigeration system uses electricity for the compression of the refrigeration media, which means a
higher energy penalty for the process than using cooling water [35].

The solvent regeneration is usually done by a pressure swing step. It is also possible to
use a thermal swing step, but vapour pressure and thermal degradation of the solvent could
become an issue.
However some research has been done to find a solvent could operate with a thermal
swing step, so that the CO2 could, in principle, be released at the pressure of the fuel gas itself,
reducing the energy penalty connected with CO2 compression.

34
 K. L. Jones et al. [36] have investigated perfluorinated compounds (PFCs). These
compounds have high chemical stability due to the high energy of their C–F bonds, high boiling
points, medium vapour pressures, and high molecular weights.
These properties lead to high gas solubility, medium vapour losses, and low forces required
for expelling the gas molecules (and regenerating the solvent) upon decreasing pressure or
increasing temperature. Thus, PFCs showed a high potential for selective CO2 capture from fuel
gas streams at elevated pressures and temperatures.

In order to combine the advantages of physical and chemical solvents it is possible to mix
the two types of absorbents. These blends could provide some benefits for CO2 capture under low-
pressure conditions. They allow an increased CO2 absorption capacity compared to chemical
solvent alone.
For example the solubility of CO2 in primary or secondary amines is improved by the
addition of NMP.
The blend of sulphinol-D (sulpholane and diisopropanolamine) and sulphinol-M (sulpholane
and MDEA) are found effective for the removal of CO2 and sulphur compounds from gas streams.
These mixed solvents also allow reducing the corrosion rate and foaming problems [19].

2.2.1.3 Membranes

Membrane separation processes have been widely used in various industrial separations
for the last two decades. For example they have emerged as a promising alternative to some
traditional separation processes for the upgrading of “low-quality” natural gas that contains
significant amounts of CO2 and H2S [37].
A membrane functions as a selective barrier. It is a layer of material which is permeable to
specific substances and impermeable to other group of particles.
The membrane separation process is based on the different permeabilities of membrane
with respect to different chemical gaseous compounds and it is realised by applying an external
pressure difference.
The gaseous stream to be purified (feed gas) enters on one side of the membrane (FS) at a
given pressure and some components are allowed to pass through the membrane into a permeate
stream. Thus the permeate fraction exits from the other side (PS) of the membrane unit which is
maintained at a lower pressure with respect to the feed gas side.
The other components of feed gas are retained by the membrane and accumulate in the
retentate stream.

Feed gas Retentate gas

FS

PS
Purge gas Permeate gas

Fig. 2.2.1.3/1 Membrane scheme

Membranes are characterized based on solute permeability, the solute flux, and the
selectivity of the membrane for the target species relative to other components in the feed stream.
The permeability of species i, Pi, is:

Pi = JTi / (∆Pi/l)

where JTi is the total flux of species i, ∆Pi is the differential partial pressure of species i across the
membrane, and l is the membrane thickness.

35
 The separation factor of species i with respect to species j, αij is:

αij = (yi/xi)/ (yj/xj)

where yi is the mole fraction of i on the permeate side and xi is the mole fraction of i on the feed
side.
The selectivity, α*ij, is the ratio of the two species’ permeabilities:

α*ij = Pi/Pj

Therefore, in order to separate CO2 from flue gases, it is necessary to use membranes with
high CO2 permeability and high CO2 selectivity with respect to other components.

Other parameters that influence the degree of separation and CO2 purity and should be
taken into account in the choice of membrane are:

• CO2 molar fraction in the feed gas;

• Membrane area;
• Pressure ratio: generally the compression of the feed gas facilitates the achievement of the
same degree of separation with a relatively small membrane area in comparison to using a
vacuum pump at the permeate side [38];
• The stage cut, θ = Qp/Qf: the ratio of permeate flow rate to feed flow rate;
• R= θ  (yp/xf): recovery ratio, where yp is the mole fraction of CO2 in the permeate and xf is the
mole fraction of CO2 in the feed, thus R is the percentage of the CO2 in the feed which is
effectively captured in the permeate stream.
R and yp behave in an antithetical fashion: to obtain the highest CO2 content in the permeate
stream, it is necessary to use a small stage cut, thus a recovery ratio which approaches zero.
Conversely, a high recovery value does not allow a sufficient permeate enrichment, as 100%
recovery corresponds to a permeate composition exactly equal to the feed composition xf, thus
no separation is achieved [39].

As above mentioned CO2 concentration strongly influences the membrane separation

process. In fact membranes could offer significant advantages over absorption processes for CO2
content above 10% [40].
For low CO2 content, the energy requirement associated to membranes is much larger than
that of absorption, the low pressure difference of CO2 provides a low driving force for the
separation.
Therefore employing membrane as carbon capture process is difficult in post-combustion
due to the low CO2 content as well as the low total pressure that prevails in flue gases.
On the other hand membrane separation processes are considered particularly promising
for oxycombustion and precombustion applications; they could also be used as post fuel cells
applications. However the problem consists in finding membranes with an adequate CO2/H2
selectivity values: generally high CO2 permeability is accompanied by low CO2/H2 selectivity.
Nevertheless membrane technologies can offer some advantages, for example:

• Membrane devices operate continuously, lacking sorbent materials that require regeneration,
circulation and replenishment;
• High packing density, therefore relatively small installations;
• Non-moving parts.

For these reasons much research is devoted to find a suitable membrane to CO2 capture.

For example in order to improve the performances of membrane units in post combustion
scheme it is possible to operate with two (or even more) stages of serial membrane with
recirculation of the permeate from the second stage back to the first stage. This configuration

36
allows increasing the CO2 concentration in the first stage and, hence, its partial pressure and its
removal with respect to the single membrane unit [41].
Or even as the one stage membrane process alone cannot fulfil the task owing to the trade-
off relation between membrane permeability and selectivity, it is possible to operate with a multi-
stage gas separation membrane system, which combines the advantages of membranes with high
permeability and membranes with high selectivity and may help to reach the target more easily.
A multi-stage system obviously consumes more energy than a single-stage process;
however through optimization and integration of CO2 capture and liquefaction it can be expected
that membrane separation will become more competitive [38].

Among the different types of membrane studied to CO2 capture could be included:

polymeric membranes;

inorganic membranes;

mixed membranes;

hybrid membranes;

high temperature membranes;

facilitated transport membranes:
- fixed-carrier facilitated transport: swollen chitosan membrane;
- mobile-carrier facilitated transport: supported liquid membrane, immobilized liquid
membrane, bulk flow liquid membranes;

capillary membranes.

Polymeric membranes

Polymeric membranes present low capital investment costs compared with other types of
membrane. Moreover, the process equipment for the polymeric membrane operation is also simple
and easy to handle. They are used to remove CO2 from natural gas, but few commercially
available polymeric membranes have both high permeability and high selectivity [42].
Generally, gas molecules are transported through a polymeric membrane by a solution-
diffusion mechanism. Other mechanisms include a molecular sieve effect and Knudsen diffusion.

Fig. 2.2.1.3/2 Transport mechanism through micro porous membranes [43]

Gas molecules tend to move through free volumes – gaps – between polymeric structures.
Because of the movement of the polymer chains, a channel between gaps can be formed allowing
gas molecules moving from one gap to another and thus gas molecules can effectively diffuse
through the membrane structure. Selective transport of gases can be achieved by use of a polymer
37
which forms channels of a certain size. Large channels will thus allow faster diffusion of gases
through a membrane at the cost of less selectivity [43].
The high temperature of flue gas rapidly destroy polymeric membranes, so the gases need
to be cooled to below 100°C prior to membrane separ ation and it is difficult to integrate this
separation process into the already existing power generation plants.
Additionally the membranes need to be chemically resistant to the chemicals compounds
contained within flue gases, or these chemicals need to be removed prior to the membrane
separation.

Main polymers studied are: polyacetylenes, polyaniline, poly (arylene ether)s, polyarylates,
polycarbonates, polyetherimides, poly (ethylene oxide), polyimides, poly(phenylene ether),
poly(pyrrolone)s and polysulfones. Fig. 2.2.1.3/3 shows molecular structures of some commonly
used polymers.

Fig. 2.2.1.3/3 Examples of polymer molecular structures used for CO2 separation[43]

Polyimide membrane is the more attractive gas separator because it offers high selectivity
(CO2/N2:43) and high permeability (735 m3/m2⋅Pa⋅s) compared to membranes derived from other
polymers.

38
 Permeance Selectivity
Material
(m /m ⋅Pa⋅⋅s) αCO2/N2
3 2

Polymide 735 43
Polydimethylphenylene 2750 19
Polysulfone 450 31
Polyethersulfone 665 24.7
Poly(4-vinylpyridine)/polyetherimide 52.5 20
Polyacrylonitrile with poly (ethylene glycol) 91 27.9
Poly(amide-6-b-ethylene oxide) 608 61
Tab. 2.2.1.3/1 Performance of polymeric membranes separating CO2/N2 [43]

Inorganic membranes

Inorganic membranes can be classified into two categories based on structure: dense and
porous.
The dense inorganic membranes consist of a thin layer of metal, such as palladium and its
alloys, or solid electrolytes, such as zirconia.
Gas transport occurs via solution-diffusion mechanism or charged particles in dense
membranes. The low permeability across the dense inorganic membranes limits its wide
applications as compared to porous inorganic membranes.
The porous inorganic membranes consist of a porous thin top layer casted on a porous
metal or ceramic support, which provides mechanical strength but offers minimum mass-transfer
resistance.
The main porous inorganic membranes are alumina, carbon, glass, silicon carbide, titania,
zeolite, and zirconia membranes supported on different substrates, such as α- alumina, γ-alumina,
zirconia, zeolite, or porous stainless steel.
Carbon membranes have high thermal and chemical stability, thus they could be use for the
CO2 separation from flue gas emissions of power plants.
Silica is a viable starting material for the fabrication of CO2 selective membranes, mainly
because of its innate stability and easy modification of its structures.
On the contrary, some attempts have been made to modify alumina membranes to facilitate
CO2 surface diffusion, however with limited success.
Zeolites membranes are crystalline alumino silicates with a uniform pore structure and a
minimum channel diameter range of 0.3 to 1.0 nm. The presence of molecular-sized cavities and
pores make the zeolites suitable for a wide range of separation applications, as CO2 capture.
Carbon dioxide in fact preferentially permeates in CO2/N2, CO2/CH4, and CO2/H2 mixtures at
low temperatures, because CO2 is adsorbed more strongly on zeolites than the other gases.
For the CO2/N2 and CO2/CH4 mixtures, CO2 is smaller in size and thus permeates faster at
elevated temperature. However, the selectivity is the same for the CO2/N2 or CO2/CH4 systems at
elevated temperatures due to the absence of competitive adsorption.
In porous inorganic membranes there are four main gas transport mechanisms: Knudsen
diffusion, surface diffusion, capillary condensation, and molecular sieving (see Fig. 2.2.1.3/2).
It is also possible increasing the membrane performances. One of the more convenient
ways is modifying the membrane surface by covalently bonding a layer of selected compounds
with appropriate functional groups. Such modification in fact changes the mean pore size and
promotes a specific interaction between the surface of the membrane and the permeating
molecules to enhance permeation [43].

Mixed membranes

Mixed membranes have molecular sieves with superior gas transport properties, but have
significant problems with their processibility. Many researches have been devoted to mixed-matrix
membranes such as the polymer-zeolite pair.
It is known that the permeability of a gas through zeolite-filled polymeric membranes
depends on the intrinsic properties of the zeolite and the polymer. However, their performance
suffers from defects caused by poor contact at the molecular sieves/polymer interface.

39
 This can lead to the gases to flow non-selectively around the solid particles.
Therefore the successful implementation of this membrane development depends on both,
the selection of polymeric matrix and inorganic zeolite, and the elimination of interfacial defects
[43].

Hybrid membranes

In the hybrid membranes a porous inorganic support material is surface-modified with

chemicals which have good affinity with CO2.
This helps CO2 separation in two ways: porous inorganic materials allow large flux while the
chemical provides selectivity [43].

High temperature membranes

As previously mentioned, polymeric and inorganic micro porous membranes for CO2
separation are limited by either low selectivity or permeability, and at elevated temperatures they
lose both selectivity and permeability.
Since it would be desirable to have efficient CO2 separation membranes that can operate at
high temperature (400–1100 °C) particularly with so lid fuel gasification or hydrogen production
systems, some studies have been devoted to find this type of membrane.
Some attempts at creating selective membranes at high temperatures (450–650 °C) have
made use of dense, molten carbonate membranes that operate by transporting CO2 with O2 as a
carbonate ion, CO32−. An external circuit is connected to the membrane through electrodes where
an applied voltage can pump CO2 and O2 across.
Another approach has internally closed the electronic current by creating a dual-phase ionic
membrane where molten carbonate is immobilized into a metallic phase. However this technology
is limited by the requirement of having oxygen in the feed stream to convert the CO2 to CO32− [44].
In order to overcome this issue, J.L.Wade et al. [44] have modelled a dual-phase
membrane which is made from two separate ionically conducting phases, derived from a
combination of molten carbonate and solid oxide electrolytes.
On the surface of the membrane, conversion between gaseous CO2 and CO32− occurs
through the donation of an oxide ion, O2−, from a conductive solid oxide phase.
The reverse occurs where the partial pressure of CO2 is low. Carbonate ions converts back
into CO2, releasing the oxide ion back into the solid oxide phase to complete the circuit.

Fig. 2.2.1.3/4 Dual phase membrane

Thus the driving force is the partial pressure gradient of CO2 established across the
membrane and the flux can be accelerated by a greater CO2 partial pressure ratio.
The CO2 partial pressure ratio depends on the process gas mixtures upstream, the
mechanical strength of the overall membrane structure and the minimum partial pressure that can
be managed in the permeate stream which is set by the chemical stability of the membrane.
In conclusion this application involves a fuel gas mixture rich in CO2 and a permeate stream
that essentially is pure CO2 but at a lower partial pressure than in the feed.

40
Facilitated transport membranes

Facilitated transport membranes (FTMs) have received attention in gas separations

because of their high selectivity and high permeability achieved by incorporating a carrier agent
into membrane, which reacts reversibly with the permeating species.
In addition to the solution diffusion mechanism of the polymeric membranes, FTMs also
involve a reversible complexing reaction.
The permeating species dissolves in the feed side of the membrane and reacts with the
carrier agent inside the membrane to form a complex. This complex diffuses across the
membrane, and then releases the permeants on the other side of the membrane, while the carrier
agent is simultaneously recovered and it diffuses back to the feed side [43].
FTMs can be divided in two types: mobile carrier membranes and fixed carrier membranes.
In the first type a carrier can move freely in the membrane and in the other one a carrier is
fixed to the matrix of the membrane.
In CO2 capture by facilitated transport membranes there is the formation of chemical
complexes between CO2 and a carrier, typically immobilized as a liquid solution in the pores or
void spaces of the membrane. Molecules of CO2 dissolved on the feed side of the membrane can
become ionized to CO32− or another species, diffuse through the liquid solution, and evolve on the
permeate side.
The carrier can be an amino group. In this case, CO2 is transported in the form HCO32; the
carrier in the membrane acts as a catalyst of the CO2 hydrated reaction.
If the carrier has a faster hydrated reaction, membrane performance can improve, and the
order of catalysis efficiency is tertiary amine > second amine > primary amine. Thus, the
hydrophilic materials containing the tertiary amine might further improve membrane performance.
[42].
For example a variety of Chitosan amides can be used as a fixed-facilitated transport
membrane for carbon dioxide separations because of the amino group in its repeating unit.
Chitosan, a derivative of chitin, forms clear, dense and tough films with good thermal
properties. Gas permeation tests have been performed on chitosan membranes for the separation
of CO2/N2 and CO2/O2. Swollen chitosan membranes seem to be effective in separating CO2 from
mixtures also containing N2 and H2.
In this system each type of water (total, free and bound) appears to facilitate the
complexing of CO2 with the polymer.
Free water is lost from the polymer at temperatures slightly above its boiling point (above
110 ◦C at atmospheric pressure). Bound water, which is thought to be hydrogen bonded to various
groups on the chitosan repeating unit, is lost at temperatures greater than 140 ◦C.
In order to increase further the facilitated transport of CO2, L. A. El-Azzami and E. A. Grulke
[45] have studied chitosan membranes modified with amino acid salts (arginine–sodium).
They have found that this membrane has CO2 transport properties about three times more
favourable than those for simple swollen chitosan membrane.
However similar to the latter, the arginine salt–chitosan membrane has a maximum CO2
permeability at 110 ◦C; above this temperature, all free water is lost from the membrane, reducing
the facilitated transport pathway.

As regards mobile carrier membrane a typical instance is a Supported Liquid Membrane

(SLM) or Immobilized Liquid Membrane (ILM). It is usually prepared by impregnating a micro
porous membrane with a carrier solution.
However, this type of membrane has several drawbacks:

• Instability caused by the loss of a carrier solution due to evaporation and the transmembrane
pressure difference;
• Low permeance due to the difficulty of preparing very thin membranes with high stability;
• Chemical degradation of the carrier due to irreversible reactions with some components in the
feed gas.

41
 In order to overcome these disadvantages it is possible to use an ion exchange membrane
as the support for SLMs or a gel-type swollen support membrane.
There are several important points in designing efficient mobile carrier transport membrane
using an ion exchange substrate [46]:

• The mobility of the permeant in the membranes: the complex with the carrier through the ion
exchange membrane is moved by electrostatic interaction with the ion sites on the membrane
matrix. This interaction of the complex with ion sites usually leads to the lower mobility of the
complex. The mobility is related to the water content of the membrane, and the usage of the
swollen membrane with high water content is favourable to obtain a high mobility.
• The enhancement of the permeation rate by the chemical reaction between the permeant and
carrier. Usually, the high carrier concentration leads to increase both high permeability and
selectivity.
• The stability of SLMs: the hydrophilic water swollen membrane is suitable to retain the
membrane solution and the high ion site concentration is desirable to prevent the loss of the
ionic carrier by the washout.

Some authors have proposed a new type of liquid membrane system for gas separation to
overcome FTMs drawbacks.
In this membrane system, as shown in Fig. 2.2.1.3/5, a carrier solution is continuously
supplied to the feed side (high pressure side) of the membrane and is allowed permeating to the
receiving side (low pressure side). This convective flow, or bulk flow, of the membrane liquid is
driven by the transmembrane pressure difference.
The transferred membrane liquid is continuously recycled to the feed side by a pump.

Fig. 2.2.1.3/5 Bulk Flow Liquid Membrane (BFLM).

Therefore, the membrane surface is always covered with a thin layer of the membrane
liquid and the membrane is always wetted with the liquid, which prevents the drying-up of the
membrane.
In addition this membrane system, Bulk Flow Liquid Membrane (BFLM), has a much higher
permeation rate than the conventional SLMs, since a solute gas is transported by the molecular
diffusion and also by the convective flow of the membrane liquid, dissolving the solute gas through
the membrane.
If the recycling or circulation rate of the liquid to the feed side is larger than its permeation
rate, the excess liquid leaves the feed side with the retentate gas. Then it is separated and sent to
the receiving side to strip the dissolved gas. Therefore, the proposed type of liquid membrane is

42
considered as a hybrid of membrane separation and gas absorption and it is expected to have
higher efficiency than the conventional SLMs [47].
Moreover the BFLM process compared to absorption process needs only one unit. Another
advantage may be that a part of heat liberated in gas absorption is transferred to the permeate
side through the membrane and effectively used for stripping.
This means that the membrane also acts as a heat exchanger, which makes this
membrane system very efficient in energy utilization. In addition the membrane pores act as the
pipeline from the absorber to the stripper. Thus, the BFLM system is simpler than the conventional
gas absorption process.
Even when the membrane liquid degrades, it can easily be replaced by a new one or it can
be regenerated outside the membrane module.
Moreover the gas permeance is independent of the membrane thickness, thus thick porous
membranes with sufficient mechanical strength and durability can be used unlike in the
conventional FTMs where thinner membranes are desirable for faster permeation rate.
Another advantage is that it is possible to use conventional micro porous membranes, not
specially membrane.
However BFLM requires a liquid circulation pump, which makes the process a little
complicated compared to FTMs, and also requires much larger amounts of carrier compared to the
FTMs [48].

Capillary membranes

M. Teramoto et al. [49] studied a novel gas separation method using capillary for
simultaneous separation and enrichment of CO2 from flue gases.
In this method both a feed gas and a carrier solution are supplied to the lumen side
(absorption side) of the capillary membrane module and the carrier solution is forced to permeate
the membrane to the shell side (stripping side) maintained at a reduced pressure to strip and
enrich a solute gas.

Fig. 2.2.1.3/6 Concept of facilitated transport of gas using capillary membrane module

43
 The energy consumption was estimated as 0.28 kWh kg CO2 −1 at the optimal condition.
This value is about 55% of the lowest value reported for the conventional gas absorption process
consisting of a gas absorber and a stripper.
Moreover the energy consumption may be further reduced by the optimization of the
experimental conditions, module design and the process design [48].

Membrane flash process

A novel membrane process called membrane flash process was proposed to overcome the
instability problems of a facilitated transport membrane.
K. Okabe et al. [50] have been studying the modification and improvement of this process
to apply it for practical use in the field of CO2 separation and recovery.
In this process the rich solution that absorbes CO2 in the absorber is supplied to the inside
of hollow fibres and it is forced to permeate the membrane.
The rich solution releases CO2 during permeating through the membrane to the out side of
hollow fibres in which the pressure is reduced.

Fig. 2.2.1.3/7 Principle of membrane flash process.

The advantages are high CO2 concentration, membrane stability, and the possibility to use
conventional micro porous membranes, low energy consumption. In fact the electric energy for
CO2 recovery in a membrane flash process is lower (< 0.3 kWh/kgCO2) than the thermal energy of
the chemical absorption process.
However, in the membrane flash process only a small amount of absorbent solution works
well in CO2 desorption, so that a large amount of solution is necessary, and thus the energy of a
liquid circulation pump become higher. Therefore the authors studied to solve this problem utilizing
low temperature energy or waste heat which is not available for other uses.

44
Membrane contactors

There is a further CO2 separation method which combines chemical absorption with use of
membranes. In this particular case the membrane is gas-liquid contactors (ceramic hollow fibre
membrane).
The hollow fibres adopted in this kind of membrane are generally not selective, unlike the
gas membrane separation process (without using solvents) which depends on the membrane
selectivity. The absorbent liquid offers the selectivity instead.
In a hollow fibre membrane contactor, hydrophobic micro porous membranes are always
used to form a permeable barrier between the liquid phase and the gas phase, which permits the
mass transfer between the two phases without dispersing one phase into the other.

Fig.2.2.1.3/8 CO2 removal in a hollow fibre membrane contactor. [51]

The gas and liquid phases always flow in parallel (either counter currently or concurrently)
to each other on the opposite side of the fibres, and the gas preferentially fills the hydrophobic
membrane pores and meets the liquid at the opposite side of the membrane, thus avoiding the
problems often encountered in the conventional apparatus such as flooding, foaming and
entrainment [52].
Moreover the membrane contactors are operational flexibility, high mass transfer rate and
easy linear scale-up.
In addition they offer a much larger contact area per volume unit than conventional
absorbers (1500-3000 m2/m3 vs 100-800 m2/m3) and the volumetric mass transfer is several times
higher, thus the size of the absorber can considerably be reduced. Especially for offshore
applications this offers tremendous advantages [53].
So that the operation of the hollow fibre membrane contactor is long-term stable, the pores
of the membrane have to remain completely gas-filled over prolonged periods of operational time.
If membranes are wetted, even if partially wetted, the gas to be absorbed has to diffuse
through the stagnant liquid inside the pores, and it will considerably increase the overall mass
transfer resistance. Thus, the prevention of wetting is an important criterion determining the
contactor operability. So it is important to select a solvent with suitable surface tension.
Unfortunately the conventional reactive solvents like aqueous alkanolamine solutions are
found to wet polyolefin membranes under some particular operating conditions. It is possible
overcome wetting, using more hydrophobic membranes like Teflon (PTFE). However this type of
membranes is not available in small diameters (a few hundred microns) and it is more expensive.
Thus, there is a need for the development of new absorption liquids that can offer stable
performance with relatively cheap polyolefin membrane.
Amino acid salts can be a possible alternative to alkanolamines. As previously mentioned,
they, although more expensive, have suitable physical properties to avoid wetting problem of

45
polypropylene micro porous membranes and they also have better degradation properties than
alkanolamine solutions.
TNO has developed and patented a range of absorption liquids based on amino acid salts
and given them the trade name CORAL (CO2 Removal Absorption liquid) [53].

2.2.2 Innovative technologies

The technologies to capture the CO2 that are currently being developed are:

• Adsorption onto solids;

• Carbonation/calcination;
• Molten carbonate fuel cells;
• Cryogenic separation;
• Hydrate-based separation.

2.2.2.1 Adsorption onto solids

Adsorption processes are used for the removal of CO2 from natural gas or biogas, from
recycled reducing gases in the iron and steel industry and for H2 purification from various syngas
type streams (removal of heavier components such as CO2, CH4, H2O, CO and N2).
The adsorption can be classified as physical and/or chemical adsorption on the solid
sorbents.
Physical adsorption implies relatively weak van der Waals forces and a significant decrease
in CO2 capture capacity with increasing temperature.
Chemical adsorption promotes chemical bonding between specific functionalities in the
solid sorbent and CO2, thus being more stable to temperature.
CO2 capture on a commercial activated carbon represents a pure physisorption process.
On the contrary, polyethylenimine based adsorbents show the influence of the chemistry in
the process presenting constant CO2 capture capacities up to approximately 90 ° C.
There are two main methods for sorbent regeneration: Temperature Swing Adsorption
(TSA) and Pressure Swing Adsorption (PSA).
The first one consists of reducing the overall temperature, whereas the second one consists
of using vacuum with or without heating.
Since the captured CO2 would need to be pressurised before transportation and storage,
resulting in a large energy penalty, PSA could not be suitable.
However considering the sensitivity of the surface amino groups to temperature, the PSA
operation would seem to be more suitable for the impregnated sorbents [54].

At this time adsorption process seems to be a promising technology if effective and

selective CO2 adsorbent will be developed.
Therefore the success of CO2 capture by means of solid sorbents is dependent on the
following sorbents characteristics:

• High CO2 selectivity and adsorption capacity also at high temperatures;

• High sorption and regeneration rate;
• Long-term regeneration and lifetime;
• Low cost;
• Low energy requirement for regeneration.

The main types of adsorbents studied are:

Activated carbons;

Zeolites;

Mesoporous silicas;

46

Fly ash carbons;

Metal oxides:
- Alumina;
- Lithium compounds;
- Calcium compounds;

Alkali metal carbonates;

Carbon Fiber Composite Molecular Sieve (CFCMS).

Activated carbons

Activated carbons as well as other porous materials, like molecular sieve and zeolites, are
suitable candidates for CO2 capture by physical adsorption, due to their highly developed porous
structure.

Activated carbons are sorbents with micro and mesopores that are used in a wide range of
applications, including gas-phase and liquid-phase processes.
The activation process and the intrinsic nature of the precursors strongly determine the
characteristics of the resulting activated carbons.
They can be produced from different precursors, including coals of different rank, and
lignocellulosic materials, by physical or chemical activation processes.
Recently, increasing attention has been focused on using anthracites as a feedstock for
activated carbons, due to their inherent chemical properties, fine structure, high surface area and
relatively low price that make them excellent raw materials for the production of activated carbons
with highly developed micro porosity.
The porous structure (surface area and pore size distribution) and surface chemistry control
the adsorption properties of the activated carbons, thus the CO2 adsorption capacity of activated
carbons is a function of their pore structure and surface chemistry properties.
It has been reported that the CO2 adsorption capacities of activated carbons decrease with
increasing adsorption temperature due to the physical nature of the adsorption process where both
the surface adsorption energy and the molecule diffusion rate increase with increasing
temperature. As a consequence, the adsorbed gas on the surface of the activated carbon becomes
unstable, resulting in the desorption of adsorbed CO2 molecules.
Therefore, different surface treatments have been developed to improve the CO2
adsorption capacity at high temperatures. For example, it has been shown that the CO2 capture
capacity can be increased by introducing nitrogen functional groups on the surface either by NH3
heat treatment or polyethylenimine (PEI) impregnation [55]
Amine addition is expected to offer the benefits of liquid amines in the typical absorption
process, with the added advantages that solids are easy to handle and that they do not give rise to
corrosion problems.
However the introduction of additives through impregnation results a dramatic decrease of
the surface area of the activated carbons, probably due to pore blockage in the structure of
adsorbent by chemical additives.
On the other hand chemical impregnation can increase the CO2 capture capacity of the
activated anthracites at higher adsorption temperature, due to the introduction of alkaline nitrogen
groups on the surface.
As regards NH3 heat treatment, this surface modification makes activated carbon more
alkaline, thus the adsorbability of acid agents like SOx, NOx, or CO2 is expected to increase.
Additionally, strong fixation of the groups on the surface of activated carbons is believed
[56].
In fact the NH3 treatment increases the surface area of the activated carbons, especially at
lower temperatures [55].

In order to improve the CO2 adsorption capacity of activated carbons it is also possible to
add metal oxide species.
M. R. Mehrnia et al. [57] have studied the effect of impregnation with Cr2O and Fe2O3 and
promotion by Zn2+.

47
 They have found that Cr2O is an effective metal oxide species which can increase adsorbed
CO2 amount on the impregnated activated carbon. Moreover the activated carbons impregnated by
both Cr2O and zinc carbonate hydroxide led to 25% increase in CO2 capture capacity.
Among slurry and solution impregnation methods, the first one was found more effective
than other one.
Furthermore washing the adsorbent with distilled water after impregnation caused an
increase adsorption capacity attributed to the removal of metal oxides covering the surface
physically and the increase in surface area.

Zeolites

Zeolites are micro porous materials with high surface area and specific sites of adsorption.
At lower temperatures they have generally high adsorption capacity. However, as well as activated
carbons, their adsorption capacity rapidly declines with increasing temperature above 30 °C.
Moreover gas diffusion in these small pore systems is difficult; therefore adsorption rate
may be inhibited.
In addition zeolites are difficult to regenerate entailing low productivity and high costs.

Mesoporous silicas

Recently the chemical treatment of moleculare sieve surface to improve the CO2 adsorption
is of particular interest as this technology is believed to be cost-effective and can be adapted to a
variety of carbon sequestration schemes [43].
Molecular sieves are a range of specially designed sieves that separate molecules based
on their molecular weight or molecular size.
Hence many research activities has been devoted to find adsorbents based on high surface
area inorganic supports that can incorporate basic organic groups, usually amines, improving CO2
capture.
Ordered mesoporous silicas, such as MCM-41 (Mobile Crystalline Material) and SBA-15
[58], are ideal solid supports because of their uniform and large pores, tuneable pore sizes, high
surface areas as well as a large number of highly dispersed active sites (the hydroxyl groups) on
the pore walls and surface. The hydroxyl groups are essential for surface modification because
only the silanol can anchor the organic molecules to the silica surface to form the functional
groups.
J.H. Zhu et al. [58] have investigated a novel CO2 capture system with a high efficiency
obtained through dispersing the amine mixture of tetraethylenepentamine (TEPA) and
diethanolamine (DEA) or glycerol within the as-synthesized mesoporous silica SBA-15.
The amine could promote the CO2 capture through changing the interaction mechanism.
In the presence of hydroxyl group the formation of carbamate type zwitterions is promoted,
each molar amine group can capture two molar CO2, twice of that no presence of hydroxyl group
theoretically.
In addition, the presence of hydroxyl group promotes the formation of the intermediate
between CO2 and the amine with a lower thermal stability, thus it is easier to regenerate the
adsorbent as the CO2 trapped by the composite is facilitated to be desorbed.
Therefore, using this mixed amine (TEPA and DEA) modified as-synthesized SBA-15 has
three advantages:

• Saving energy and time to remove CO2;

• Cutting down the cost of adsorbent;
• Promotion of CO2 capture by the hydroxyl group.

C.Song et al. [59] have developed a novel CO2 ‘‘molecular basket’’ adsorbents based on
polyethylenimine (PEI)-modified mesoporous molecular sieve of MCM-41 type (MCM- 41-PEI).
The CO2 ‘‘molecular basket’’ adsorbents can selectively ‘‘pack’’ CO2 in condensed form in
the mesoporous molecular sieve ‘‘basket’’. To make the ‘‘molecular basket’’ adsorbent and to

48
capture a large amount of CO2 gas, the adsorbent needs to have large-pore volume channels to
serve as the basket.
The CO2 adsorption capacity of the MCM-41-PEI is 30 times higher than that of the MCM-
41 and more than twice that of the pure PEI, in fact the experiment results showed that, although
the dispersion of PEI on the high surface area materials could already increase the adsorption
capacity, it was the synergetic effect between PEI and MCM-41 pore channels (CO2 ‘‘molecular
basket’’) that contributes to major increase in the CO2 adsorption capacity.
The researchers have also noted that the MCM-41-PEI adsorbents prepared by one-step
the impregnation method showed a higher CO2 adsorption capacity (112 mgCO2/g adsorbent) than
the adsorbent prepared by the mechanical mixing method (99 mgCO2/g adsorbent) and the two-
step impregnation method (96.8 mgCO2/g adsorbent).
Moreover adding PEG into the MCM-41-PEI adsorbent can increase the CO2 adsorption
rate, desorption rate and adsorption capacity.

Fly ash carbons

Fly ash carbons represent a potential alternative for CO2 capture to the existing methods
which use specialized activated carbons and molecular sieves and tend to be very expensive.
Fly ash carbons are less expensive and can be easily converted into high surface area
materials.
Firstly, they can be obtained from the utility industries as a by product. Secondly, the
conventional production of activated carbons consists of a two-step process, which includes a
devolatilization of the raw materials, followed by an activation step. In contrast, for fly ash carbons
only a one-step activation process is required, since they have already been subjected to a
devolatilization process in the combustor.
In addition the carbon in the fly ash can be concentrated to contents >97% by using acid
digestion methods. This de-ashing process removes the inorganic ash from the carbon and also
changes the porous structure and surface properties of the resultant carbon [60].
C. E. Snape et al. [61] have found that low cost carbon materials derived from fly ash and
subjected to an impregnation with organic bases (polyethylenimine aided by polyethylene glycol)
show a high CO2 adsorption capacity (up to 4.5%wt) especially at high temperatures (75 °C),
where commercial active carbons relying on physisorption have low capacities.

Metal oxides

Alumina

In order to find potential applications in high temperature CO2 recovery, metal oxide
sorbents have been studied.
Carbon dioxide, which is an acidic gas, is expected to adsorb more strongly on basic sites.
A metal oxide with a low value of the charge/radius ratio is more ionic in nature and presents more
basic sites. Carbon dioxide molecules can be adsorbed on positive and negative surface sites of
metal oxides. When carbon dioxide is adsorbed in some particular types of metal oxides (such as
CaO and MgO), this CO2 adsorption capacity can be reversibly removed.
Recently alumina PSA systems have been proposed. Alumina adsorbents have high
adsorption capacity and resistance to steam, good mechanical and thermal stability properties.
In addition the alumina system includes lower adsorbent cost and a vessel design which
does not need screens to separate the two different adsorbents.
When alumina is chemically modified by introducing alkaline metal oxides (such as Li2O,
K2O, Na2O) or alkaline metal carbonate (such as Li2CO3, K2CO3, Na2CO3), its reversible adsorption
capacity for carbon dioxide at high temperature can be greatly enhanced.

49
Lithium compounds

In order to find potential applications in high temperature CO2 recovery, basic metal oxides
obtained from naturally abundant minerals such as dolomite and synthetic reactive capture agents,
such as lithium zirconate and lithium silicate attract significant interest.
The latter class of materials offers selective capture of carbon dioxide, based on the
formation of solid carbonates and high capacity of sorption. Most physical sorbents have limited
CO2/N2 selectivity, while the lithium zirconate does not absorb nitrogen at all, thus it would result in
an infinitely large CO2/N2 selectivity.

The following reaction occurs in the temperature range of 450–550 ◦C and the reversible
reaction of decomposition of lithium carbonate and the formation of lithium zirconate is starting
above 650 ◦C.

Li2ZrO3(s) + CO2(g) ←→ Li2CO3(s) + ZrO2(s)

The main drawback of all mineral that can adsorb CO2 is the very high energy requirement
of the regeneration process due to the high temperature of decomposition of the carbonates.
Moreover these minerals have a slow reaction rate. However the rate of CO2 mass transfer
can be improved by establishing a eutectic mixture of alkaline carbonates with a minimum of
melting point below the process temperature of sorption, via doping the starting lithium zirconate
material with, for example, potassium carbonate.
Diffusion of CO2 through the molten carbonate is much faster than in the solid lithium
carbonate, which results in a faster rate of reaction. The acceleration effect was found to be even
greater in the case of tertiary carbonates (lithium, potassium and sodium carbonates) [62].
The faster sorption rate on the doped lithium zirconate can be explained by the double shell
model. During the sorption process, CO2 molecules react with K-doped lithium zirconate to form a
liquid shell of potassium–lithium carbonate (which is molten at temperature above 500 ◦C) on the
outer surface and a dense zirconium oxide shell in the middle covering the unreacted lithium
zirconate core as shown in Fig. 2.2.2.1/1.

Fig. 2.2.2.1/1 Illustration of the double shell model for CO2 sorption on lithium zirconate.

The carbonation reaction can continue by the diffusion of Li+ and O2− through zirconium
oxide shell and the diffusion of CO2 through the molten carbonate shell which is several orders of
magnitude faster than that in the solid carbonate [63].
A further improvement in the reaction rate can also be achieved by decreasing the particle
size, thus decreasing the diffusional length.
Nakagawa et al. have studied lithium silicate and have found that its CO2 adsorption
capacity is much larger than that of lithium zirconate.
Lithium silicate adsorbs CO2 below 720°C and releases CO 2 above 720°C by the following
mechanism:

Li4SiO4 + CO2 ←→ Li2SiO3 + Li2CO3

50
 This compound could become a strong candidate for developing commercially competitive
CO2 adsorbent for its large capacity, rapid absorption, wide range of temperature and
concentrations of CO2 and stability. [43].

Calcium compounds

C.G. Lee et al. [64] have investigated the Ca2SiO4 properties for CO2 adsorption.
Ca2SiO4 can absorb CO2 fast at a broad temperature gap ranging from 500°C to 800°C.
Reaction in CO2 sorption and desorption of Ca2SiO4 was found to be reversible. CO2
sorption efficiency increases with increasing temperature within the temperature range below
800°C.
Thus Ca2SiO4 can capture CO2 at 500°C with a high efficiency, temperature which is much
lower than that of CaO (690°C) and lithium silicate s (750°C), saving much energy.
It was seen that the decaying rate is 1.92% per cycle with 40 min, a little higher than that of
CaO. However, the cycle property of Ca2SiO4 is better than that of lithium silicates and lithium
zirconates, the two latter groups of compounds showed scarcely cycle properties.
Furthermore the Ca2SiO4 specimen maintains its constant solid block shape, rather than
powder like CaO, even after so many reactions. Thus Ca2SiO4 could be more favourable than CaO
for industrial application.

Alkali metal carbonates

S.C.Lee et al. [65] have studied alkali metal carbonate that could be applied to CO2
absorption at low absorption temperatures, with thermal regeneration easily occurring at a low
temperature.
Therefore one of the objectives of their work was to develop a potassium-based
regenerable solid sorbent for use in the CO2 absorption/regeneration process, at temperatures
below 150°C.
The potassium-based sorbents were prepared by the impregnation of K2CO3 on porous
supports such as activated carbon (AC), TiO2, MgO, SiO2, Al2O3.
K2CO3/MgO showed the highest CO2 capture capacity: 119 mgCO2/g adsorbent (the CO2
capture capacities of all adsorbents were about 83–119 mgCO2/g adsorbent). However it also
showed the highest temperature for sorbent regeneration.
The CO2 capture capacities of K2CO3/Al2O3 and K2CO3/MgO, after regeneration at
temperature of less than 200°C, decreased due to th e formation of KAl(CO3)2(OH)2, K2Mg(CO3)2,
and K2Mg(CO3)2-4(H2O), which were not completely converted to the original K2CO3 phase.
On the contrary, in the case of K2CO3/AC and K2CO3/TiO2, it was possible to regenerate
even within a low temperature range (130–150°C), du e to the formation of a KHCO3 crystal
structure during CO2 absorption.
In particular, the rate of regeneration of the K2CO3/TiO2 was a little more than that of
K2CO3/AC even at low temperature. Considering that the regeneration capacity is an important
factor in addition to the CO2 capture capacity, K2CO3/TiO2 could be a potential sorbent for CO2
absorption.

Carbon Fiber Composite Molecular Sieves (CFCMS)

Another type of adsorbent which has been analysed is CFCMS (Carbon Fiber Composite
Molecular Sieves). It is a monolithic adsorbent carbon material composed of petroleum pitch-
derived carbon fibre and phenolic resin-derived carbon binder.
The CFCMS material is a rigid, strong, monolith with open structure that allows the free-flow
of fluids through the material.
It is found that CFCMS is the best one for adsorption of carbon dioxide in carbon-based
adsorbents, because it has a CO2 high affinity compared with conventional carbon-based
adsorbents.

51
 As the other carbon-based adsorbents, the adsorption capacity of CFCMS is reduced with
increasing temperature. However, even in this case, the adsorption capacity for CO2 at high
temperature can be enhanced greatly by using chemical modification [66].
Moreover the monolithic CFCMS allows certain equipment variations not possible with
granular materials. For example the use of the CFCMS would permit the employment of
horizontally oriented vessels with controlled flow of the gas to be adsorbed without risk of
channelling and bypass flows.

2.2.2.2 Carbonation/calcination

As previously seen, metal oxides demonstrated high CO2 capture capacity. In addition,
metal oxides, which are abundant in naturally occurring rocks, present the cheapest option to CO2
capture.
Therefore calcium-based sorbents have recently attracted renewed attention as possible
sorbents for cyclic calcination/carbonation processes due to their potential for regeneration.
The carbonation/calcination of CaO from limestones or dolomites to separate CO2 from coal
gasification gases is already used. However in these processes, the release of CO2 during
calcination was not an issue and the heat for calcination was supplied by combustion of part of the
fuel with air. The need to obtain a purified stream of CO2 from the calciner is in fact relatively new.
This process can be applied both to pre combustion and post combustion technologies, it
can be applied to new and existing coal-based power plants.
In the carbonation/calcination process CO2 is adsorbed by using CaO as regenerable
sorbent.
The reversible reaction which occurs is the following:

CaO + CO2 ↔ CaCO3

In this system calcium oxide serves as a CO2 carrier passing back and forth between the
combustor and the calciner.
The flue gases enter the carbonator and CaO can react with the CO2 at atmospheric
pressure and temperature around 650 oC, to produce CaCO3. Then the flue gases leave the
system depleted in CO2, whereas all the solids including the carbonate carrying the CO2 are sent
to a calciner. The calcination occurs at temperature over 900°C. This process produces a stream
of CO2 suitable for storage and calcined solids that are continuously cycled to the carbonation
reactor.
Due to the endothermic reaction of calcination and the need to heat up solid streams, a
large heat flow has to be supplied to the calciner. Several options could be feasible, but oxyfuel
combustion of coal seems the most suitable option as the source for the calcination heat.
The carbonation/calcination loop normally takes place in a reactor similar to a circulating
fluidized bed combustor. Thus this configuration involves two interconnected fluidised beds,
mechanically similar to other interconnected systems operating in the chemical industry at large
scale configuration.

52
Fig. 2.2.2.2/1 Scheme of the process for CO2 capture using the carbonation–calcination loop of CaO.

Furthermore the operation of oxy-fired combustion using circulating fluidized bed

combustors (CFBCs), should be easier (in terms of temperature control in the bed at high O2
concentration) when there is an endothermic reaction like calcination of CaCO3 taking place in the
combustor [67]. In addition the energy requirements could allow the integration of the system into a
supercritical steam cycle combining a post-combustion capture system and oxyfuel. Thus the CO2
captured proceeds from both post-combustion and oxyfuel combustion with additional power
production which leads to reduced CO2 capture costs [68].
Moreover this technology has an other important advantage; the affinity of CaO towards
sulphur compounds makes unnecessary a flue gases desulphurization unit, so it is very useful
when the power plant uses high sulphur coals.
With this technology the limiting requirements of SO2 in amines absorption (about 10 ppmv)
that increase drastically the capture cost for these types of coals also disappears.
In addition the sorbent cost (e.g. crushed limestone) is cheaper than other sorbent utilized
for CO2 capture. The solids purged of the process, mainly consisting in deactivated CaO and
CaSO4, can be used by the cement industry [69].

However the CO2 capture systems using CaO as regenerable sorbent has some
drawbacks. Several experimental studies showed the carbonation reaction is far from reversibility.
The CO2 capture reaction is characterised by an initial rapid kinetically-controlled phase,
which passes abruptly to a slower diffusion-controlled phase.
In addition the maximum conversion achieved during carbonation of a fixed duration
decreases with cycle number as it is limited by the rate of conversion during the (slow) diffusion-
controlled phase due to a change in the particle morphology resulting from sintering [70].
Sintering leads to a decrease both in the porosity and in the surface area of the adsorbent.
It is favoured both by high temperatures and time at temperature, and is accelerated by the
presence of CO2 and H2O.
During sintering, necks develop between adjacent grains and continue to grow. The
material for this growth is supplied from the rest of the grain, so that the distance between grain
centres is decreased. This causes both the void and the surface area to decrease.
The sorbent deactivation is manly caused by the presence of common impurities of calcium
carbonate and ash from a fuel that can react to form other calcium compounds and sulphates
decreasing the amount of active CaO available to carbonation. These compounds also tend to
block access to the interior of the pores [71].
Moreover deactivation of the sorbent carbonation activity with an increasing number of
cycles influences on cost and heat requirements. To compensate for these losses in sorbent
activity, a make-up flow of fresh CaCO3 has to be introduced in the calciner and a controlled solid

53
purge flow (mainly CaO deactivated and CaSO4) has to be done to counterbalance the mass
balance in the reactor. However high make-up flow improves the carbonation conversion and
hence the CO2 capture, but increases the heat demand at calciner and the fresh sorbent amount.
Large CaO/CO2 also enhances carbonation conversion, but increases the cost of the system due
to intensive solid circulation.
Furthermore not only the process cost will go up, but also the abrasion and erosion in
reactors will be aggravated and more spent sorbents discharged will contaminate the environment.
As previously said sorbents should:

• exhibit high reactivity within a temperature range from 550 to 750 ◦C;
• be resistant to physical deterioration due to attrition or sintering;
• be resistant to decay in reactivity through multiple CO2 capture and release reactions;
• not be highly vulnerable to chemical poisoning of the active sites from combustion/gasification
by-products.

In order to improve the durability of sorbent during the multiple calcination/carbonation

cycles, modified limestone and dolomite with acetic have been studied as CO2 sorbent.
Some researchers [72] revealed that the dolomite had better multicycle CO2 carrying
capacity than limestone during the calcination/carbonation cycles.
In fact although MgO, also contained in calcined dolomite, is inert and does not absorb
CO2, it enhances the dispersion in the CaO, thereby reducing its sintering and increasing its
accessibility.
The acetic acid solution can be replaced by the industrial wastes with acetic acid and the
acetone can be released from modified dolomite at about 380–400°C, so it can be reclaimed in
terms of dry distillation process:

CaMg(CH3CO2)4  CaCO3 + MgCO3 + 2C3H6O

Therefore, the cost of the process could be significantly reduced.

The modified dolomite with acetic acid solution seems maintain higher carbonation
conversions than unmodified sorbent at the same reaction conditions as the number of
calcination/carbonation cycles increases. The acetification of dolomite improves its sintering
behaviour at high temperature. The surface area and pore volume for calcined modified dolomite
are much higher than those for calcined original sorbent after the same cycles, as well as the pore
volume and pore area distributions are superior over the entire pore size range measured.

Other strategies for enhancing multi-cycle performance have been investigated including
steam hydration, thermal treatments and using of high surface area solids – alumina (Al2O3) or
mayonite (Ca12Al14O33) – as support of active material [70].
Steam hydration of CaO with ethanol/water solution was found to improve its carbonation
conversion during multiple calcination/carbonation cycles.
It was also found that Precipitated Calcium Carbonate (PCC) was more reactive than CaO
obtained from the calcination of naturally occurring limestone [72].

In order to take advantage of the large quantities of energy released in the carbonation and
the sensitive heats of the different mass streams, a Supercritical Steam Cycle (SCSC) has been
studied. Carbonator exothermic reaction at 650 °C a nd CO2 from calciner are used to generate
supercritical steam at 280 bar and 600 °C. The stea m expands in a very-high-pressure steam
turbine. Clean flue gases from the original power plant at carbonator exit, carbonator and nearly
pure CO2 stream from calciner are used also to reheat steam to 600 °C before entering a high
pressure turbine and being led to the condenser though the steam turbine [69].

CO2 capture using CaO has also been investigated to directly obtain high H2 contents by
selective carbon removal during reforming and shift reaction, thus even during steam gasification
of biomass.

54
 C.M. Kinoshita and S.Q. Turn [73] have found that the gas exiting the reactor contains ~
95% H2 versus only 67% theoretically producible without the aid of sorbent.
Nearly pure H2 stream is very important with regards to end-use applications, for example
to fuel cell applications.

2.2.2.3 Molten Carbonate Fuel Cells (MCFCs)

As mentioned in § 2.1.2.3, Molten Carbonate Fuel Cells (MCFCs) are high temperature
systems – they work at 650°C – and have an electrol yte of alkali carbonates, which are fluid at the
fuel cell operating temperature.
O2 and CO2 are fed to the cathode side and form carbonate ion which passes through the
electrolyte and reacts with H2 to the anode side. Thus at the anode side H2O and CO2 are formed.
The reactions that occur respectively to the cathode and to the anode are the following:

CO2 + 1/2O2 + 2e− → CO3 2− (cathode);

H2 + CO3 2− → H2O + CO2 + 2e− (anode).

Fig. 2.2.2.3/1 Molten Carbonate Fuel Cells Scheme

Therefore at the anode side CO2 can be concentrated. It could be possible to install a
MCFC downstream to a gas turbine or coal-fired power plant, in which the exhaust gases, that
contained CO2, could be fed at the cathode side. Such gas mixture may be mixed with air in order
to add the amount of oxygen required for the formation of carbonate ions.
As above mentioned these ions across the electrolyte from cathode to the anode, where the
CO2 is released and mixed with the components from the reforming process (H2, CO and a small
quantity of unconverted CH4). On a dry basis the CO2 concentration content can be ~85%wt.
This anode exhaust, composed mainly of H2O and CO2, with some CH4, H2 and CO, is
directed to a CO2 separation unit; the steam can be readily condensed, the other components can
be separated and the relatively pure CO2 is thus available for sequestration.
The residual gas (CO, H2, and CH4) from CO2 separation process can be recombined with
the cathode off-gas in the catalytic burner, before release to the atmosphere. The combustion of
CO in the catalytic burner generates additional CO2 in this exhaust stream, which obviously
diminishes the overall reduction of the emissions. Nevertheless, in this un-optimized scheme, the
CO2 released to the atmosphere can be reduced by circa 40% [74].
Moreover this technology could be applied to existing power plants without changing plant
electrical efficiency, but even adding power output.

55
 However the concentration of CO2 at the cathode is critical to the performance of the fuel
cell, particularly if level falls too low. In fact cell voltage decreases by decreasing CO2
concentration; it decreases most drastically when the CO2 concentration becomes 10% or less.
Neverthless M.B. Wilkinson et al. [74] have found that it would be possible to reduce the
CO2 emission per kWh produced by circa 45% at the 4%vol CO2 and by circa 50% at the 3%vol
CO2. Only at CO2 levels of 2%vol the power density falls away dramatically and therefore has a
significant and deleterious effect on overall performance.
Another relevant difficulty in the MCFC application could be the necessity of cleaning the
exhaust gases which will feed the MCFC.
Usually, in fact, exhaust gases contain also some trace substances like CO, NOx, and SOx.
CO burns at the cathode side of the MCFC, producing some additional CO2 and heat. With
regard to NOx, normally the maximum admissible level is not reached.
While sulphur compounds have to be eliminated, thus if they are present, a
desulphurisation stage should be necessary upstream from the MCFC because they damage the
electrode catalyst.

2.2.2.4 Cryogenic separation

Great advantages of cryogenic CO2 capture are that no chemical absorbents are required
and that the process can be operated at atmospheric pressures [75].

Distillation

Distillation is a process which allows separation of liquids based on their different boiling
points. This process can be used to extract CO2 from the flue gases.
However, since the boiling point of CO2 is very low (- 79°C), cooling the gas stream has a
high energy requirement.
Nevertheless it offers a good separation of CO2 from flue gases containing high CO2
concentration (typically 50-70%). It is also more effective for CO2 separation under high pressure.
Moreover, it needs no further compression for transportation as it produces liquid CO2 [76].

Anti-sublimation

Anti-sublimation of CO2 consists of transforming the carbon dioxide directly from its
gaseous phase into a solid phase frosted on the cold surface. Anti-sublimation allows CO2 capture
at a pressure slightly above atmospheric pressure therefore preventing any disturbance of the
power unit operation.
The process starts by cooling the flue gases from their initial temperature (around 60°C)
down to the CO2 frosting temperature (dependent on the CO2 concentration). The triple point of
CO2 is at 518 kPa, 56.36 °C. At a pressure lower than the triple point pressure, CO2 goes directly
from the gas phase to the solid phase.
Cooling of the flue gases continues until the corresponding exiting frosting temperature
(around -120°C; depending on the desired capture ef ficiency) is reached. This change of frosting
temperature is due to the decrease of the CO2 concentration in the flue gases during capture.
The energy recovered from the CO2 sublimation and fusion improves significantly the global
energy efficiency of the process. This cold energy is recovered by the refrigerant circulating at a
higher temperature inside the tubes of the heat exchanger (around -45°C at the inlet) thus
permitting the defrosting of the solid CO2.
Moreover it is possible to integrate the flue gases desulphurisation in the CO2 capture
process at low temperature. In this way, the cost of flue gases desulphurisation could be avoided
[77].
However since the CO2 freezing temperature is significantly lower than the water triple point
(0.6116 kPa and 0.01°C), water has to be captured i n the most efficient way, otherwise water
vapour will freeze on the low temperature evaporators and thereby block the flue gases passage.
Therefore several costly steps are required to remove all water traces from the flue gas.

56
 In addition the increasing layer of solid CO2 onto heat exchanger surfaces during the
capture cycle adversely affects the heat transfer, reducing the process efficiency.
Furthermore, in order to avoid excessive mechanical stresses of heat exchangers, the
regeneration cycles, which operate at a different temperature, should be carried out with great
care.
M. van Sint Annalanda et al. [75] studied a novel cryogenic CO2 removal process using
packed beds, with which the before mentioned drawbacks can be circumvented.
In this process hot flue gas (at Tin) containing CO2, H2O and inert gases is feed to an initially
uniformly refrigerated packed bed (T0) so that a separation between CO2, H2O and the permanent
gases is achieved on the basis of differences sublimation points as schematically illustrated in
2.2.2.4/1.

Fig. 2.2.2.4/1 Typical evolution of axial temperature in a packed bed refrigerated.

The packing material is heated up and the gas mixture is cooled down until H2O starts to
condense. Condensation takes place until the packing material (and the gas phase) reaches an
equilibrium temperature (TS1). Due to this change in phase, a front of condensing H2O moves
through the bed toward the outlet of the bed.
However, at the same time, the packing material closer to the inlet of the bed is heated up
from the equilibrium temperature TS1 to the inlet temperature of the gas mixture Tin. This increase
in temperature causes the evaporation of the previously condensed H2O. Thus another front of
evaporating H2O moves through the bed toward the outlet of the bed. The velocity of the
condensing front is faster than the velocity of the evaporating front, due to the opposed enthalpies
involved in the condensation/evaporation.
After the water being condensed at the packing surface, the gas mixture is further cooled
until CO2 starts to desublimate and a new equilibrium temperature (TS2) is reached. Again fronts of
sublimating and desublimating CO2 develop and move toward the outlet of the bed.
The amount of condensed H2O and the amount of desublimated CO2 per unit volume solid
packing reach a maximum, which is related to the maximum amount of cold stored in the solid
packing. Thus, problems with plugging during the capture cycle can be intrinsically circumvented.
Moreover the outlet gas temperature is at the very minimum temperature of the refrigerant
during almost the entire capture cycle, so that the maximum possible amount of CO2 is actually
captured.
When the third temperature front reaches the end of the bed, CO2 starts to breakthrough.
At this point, the bed is switched to a regeneration cycle, where a pure gaseous CO2 flow is
used to recover the frosted CO2. The heat stored during the capture cycle in the first zone of the
bed can be used to evaporate condensed H2O and desublimated CO2.

57
 After the regeneration the bed is again switched to a cooling cycle, where it is cooled using
a refrigerated inert gas.

2.2.2.5 Hydrates-based separation

Hydrates are structures in which gases are trapped in a crystalline solid similar in
appearance to ice.
It is possible to trap CO2 by means to dissolve flue gases in water under suitable conditions
to allow the CO2 hydrates formation. This typically occurs at temperatures around 0°C and
pressures from 1 to 7 MPa.
The CO2 can be released by heating or lowering the pressure. This technology could be
useful in removing CO2 from pressurised gas streams with very low energy loss [76].
Moreover N. H. Duc et al. [78] have found that the CO2 selectivity in the hydrate phase is at
least four times better than in the gas phase.
In addition the presence of some additives as TBAB (Tetra-n-Butyl Ammonium Bromide –
C16H36NBr) can considerably decrease the formation pressure of simple hydrates (CO2 or N2) and
mixed hydrates (CO2–N2).

2.2.3 Risks

Power plants with CO2 capture emit a CO2-depleted flue gas to the atmosphere and liquid
wastes. In some cases solid wastes can also be produced.
However the concentrations of most harmful substances in the flue gas as acid gas
pollutants (SOx and NOx) would be similar to or lower than in the flue gas from plants without CO2
capture, because CO2 capture processes remove some impurities and some other impurities have
to be removed upstream to enable the CO2 capture process to operate effectively.
For example, post-combustion solvent absorption processes require low concentrations of
sulphur compounds in the feed gas to avoid excessive solvent loss.
Nevertheless in the case of post-combustion solvent capture, the flue gas may also contain
traces of solvent produced by its decomposition. In fact solvent scrubbing processes produce
degraded solvent wastes, which would be incinerated or disposed of by other means [79].
Moreover the NOX emissions likely increase when carbon capture technologies are
implemented on a large scale, due to the reduced efficiency of power plants that capture CO2. The
increase of NOX emissions from natural gas and coal plants will be rather low, estimated at 5% and
24%, respectively, while at least 80% of the CO2 generated will be captured [80].
Post-combustion capture processes normally produce more degraded solvent than pre-
combustion capture processes and IGCC technology is characterized by lower acid gas emissions
than pulverized coal plants with carbon capture.

With regard to technical risks related to CO2 capture, they are very similar to those related
to known industrial gas processes with in addition the fact that CO2 is basically inert.
It is easy to monitor and control the potential leakages. Moreover their magnitude cannot
reach high levels.
CO2 capture technology does not constitute in any way a sizeable risk needing special
attention beyond the present regulation in industrial gases handling [79].

58
 UNIVERSITÀ DEGLI STUDI DI GENOVA
DICAT
Dipartimento di Ingegneria delle Costruzioni, dell’Ambiente e del Territorio
16145 GENOVA - Via Montallegro, 1 - Tel. 39 - 010 3532491 - Fax 39 - 010 3532546

SUMMARY OF SEPARATION TECHNOLOGIES

CO2 SEPARATION EFFICIENCY CO2

TECHNOLOGIES T P ENERGY PENALTY
CONCENTRATION FROM CAPTURE
40°C absorber 0.9-1 bar absorber
MEA 3-15% mainly N2 90% 10-15%
100-140°C stripper 2-3 bar stripper
40°C absorber 0.9-1 bar absorber
Blended amines 3-15% mainly N2 90% 6-10%
100-120°C stripper 2-3 bar stripper
40°C absorber
CHEMICAL ABSORPTION Sterically hindered amines 3-15%
100-120°C stripper
90% (with 20%
40-70°C absorber 0.9-1 bar absorber
Sodium carbonate (slurry) 10-15% mainly N2 NaCO3 9%
100-120°C stripper 2 bar stripper
concentration)
Ammonium 10-15% 1.5°C absorber

24-27 bar or more 10%

-30 °C absorber
PHYSICAL ABSORPTION Methanol > 15% absorber mainly H2 85% 9% if pressure is
35°C stripper
1.4 bar stripper higher

> 80% like the best

1 bar feed
Polimeric membranes >20% 70°C H2/N2 (if xCO2<10% → absoprtion
30 mbar permeate
80%) permformances
High temperature membranes 800°C

MEMBRANE 1.5-2.5 bar feed

Facilitated transport membranes 10% 50-100°C H2/N2
1 bar permeate

Membrane contactors 15% 25 °C 0.5-1 bar H 2/N2

PERT – Process Engineering Research Team

16145 GENOVA - Via Opera Pia, 15 - Tel. 39 - 010 3536504 - Fax 39 - 010 3532589
 CO2 SEPARATION EFFICIENCY CO2
TECHNOLOGIES T P ENERGY PENALTY
CONCENTRATION FROM CAPTURE
75 °C adsorption
PEI (polyetthylenimine) 15% mainly N2
110-150°C desorption
450-650 °C adso rption
ADSORPTION Lithium zirconate N2
>650°C desorption

Activated carbon 30°C

650°C carbonator
CARBONATION/CALCINATION CaO-CaCO3 10-15% 1 bar H2/N2 70%
900-930°C calcination

MCFC generates
power in addition to
FUEL CELLs MCFC > 7% 650°C 3 bar N2
the classical power
plant

high CO2
Distillation -80°C
concentration
CRYOGENIC SEPARATION
< 5.2 bar (CO2
Antisublimation -45°C (inlet)/-120°C N2
triple point)

HYDRATES Hydrates 15-20% 0°C 10-70 bar H 2/N2

60
 TECHNOLOGIES POSSIBLE USE PROJECT RESULTS COSTS

Achievment of only 2.5

Sleipner % CO2 goal in the
natural gas

In Salah
MEA Mainly after post combustion
Project of ENEL/ENI (Brindisi) Under study

Technint Under study

Validation plant at Mongstad (Norway) Under study

CHEMICAL ABSORPTION
Blended amines Mainly after post combustion

Sterically hindered amines Mainly after post combustion

Sodium carbonate (slurry) Mainly after post combustion

Validation plant at Mongstad (Norway)

Ammonium Under study
and at Mountaineer (USA)

Mainly after precombustion

PHYSICAL ABSORPTION Methanol
and oxyfuel

MEMBRANE CAPTECH research programme Under study

Polimeric membranes

CCP programme
High temperature membranes Under study
DECARBit European project
Facilitated transport membranes

Membrane contactors
TNO has developed and patented a range of
absorption liquids
61
 based on amino acid salts

CESAR European project Under study

TECHNOLOGIES POSSIBLE USE PROJECT RESULTS COSTS

PEI (polyetthylenimine) Mainly after post combustion

ADSORPTION Lithium zirconate

Activated carbon

CARBONATION/CALCINATIO After post combustion or with

CaO-CaCO3
N steam reforming or WGS

FUEL CELLs MCFC After post combustion Studies of Ansaldo Fuel Cells

Distillation
CRYOGENIC SEPARATION
Antisublimation

HYDRATES Hydrates

62
 UNIVERSITÀ DEGLI STUDI DI GENOVA
DICAT
Dipartimento di Ingegneria delle Costruzioni, dell’Ambiente e del Territorio
16145 GENOVA - Via Montallegro, 1 - Tel. 39 - 010 3532491 - Fax 39 - 010 3532546

References

[1] IPCC, 2005. IPCC special report on carbon dioxide capture and storage. Prepared by working group III
of the Intergovenmental Panel on Climate Change.
[2] M. Bryngelsson, E. G. Lindfeldt, J. Heller, The modelling of a hybrid combined cycle with pressurised
fluidised bed combustion and CO2 capture; 2008.
[3] C. Descamps, C. Bouallou, M. Kanniche, Efficiency of an Integrated Gasification Combined Cycle
(IGCC) power plant including CO2 removal; Energy 33 (2008) 874–881.
[4] Y. Huang, S. Rezvani, D. McIlveen-Wright, A. Minchener, N. Hewitt, Techno-economic study of CO2
capture and storage in coal fired oxygen fed entrained flow IGCC power plants; fuel processing
technology 89 (2008) 916-925.
[5] Martin Pehnt, Johannes Henkel, Life cycle assessment of carbon dioxide capture and storage from
lignite power plants; 2008.
[6] Chao Chen, Edward S. Rubin, CO2 control technology effects on IGCC plant performance and cost;
2008.
[7] The European Technology Platform for Zero Emission Fossil Fuel Power Plants (ZEP), The final report
th
from Working Group 1 Power Plant and Carbon Dioxide Capture, 13 October 2006.
[8] E. Croiset, K.V.Thambimuthu, NOx and SO2 emissions from O2/CO2 recycle coal combustion; Fuel 80
(2001) 2117-2121.
[9] Franz Heitmeir, Wolfgang Sanz, Emil Göttlich, Herbert Jericha, Graz University of Technology, The Graz
Cycle – a Zero Emission Power Plant of Highest Efficiency; 2003.
[10] Hanne M. Kvamsdal, Gas Technology Center NTNU – SINTEF, Power Generation with CO2
th
management; CO2 seminar 22 February 2005.
[11] P. Mathieu, R. Nihart, Zero-Emission MATIANT Cycle; Transaction of the ASME, vol. 21January 1999.
[12] The European Technology Platform for Zero Emission Fossil Fuel Power Plants (ZEP), draft final report
th
from Working Group 4 on Markets, Policy and Regulation, 26 September 2006.
[13] Kay Damen , Martijn van Troost, Andre´ Faaij, Wim Turkenburg, A comparison of electricity and
hydrogen production systems with CO2 capture and storage. Part A: Review and selection of promising
conversion and capture technologies; Progress in Energy and Combustion Science 32 (2006) 215–246.
[14] K. Foy, J. McGovern, Comparison of Ion Transport Membranes; Fourth Annual Conference on Carbon
Capture and Sequestration DOE/NETL, May 2005.
[15] http://www.airproducts.com.
[16] Rehan Naqvi, Jens Wolf, Olav Bolland, Part-load analysis of a chemical looping combustion (CLC)
combined cycle with CO2 capture; Energy 32 (2007) 360–370.
[17] Tobias Mattisson and Anders Lyngfelt, Applications of chemical-looping combustion with capture of CO2;
Second Nordic Minisymposium on Carbon Dioxide Capture and Storage, Göteborg, October 26, 2001.
[18] S. Campanari, Carbon dioxide separation from high temperature fuel cell power plants; Journal of Power
Sources 112 (2002) 273–289.
[19] B. Thitakamol, A. Veawab, A. Aroonwilas, Environmental impacts of absorption-based CO2 capture unit
for post-combustion treatment of flue gas from coal-fired power plant; International journal of greenhouse
gas control 1 (2007) 318–342.
[20] Mohammad R.M. Abu-Zahra, L.H.J. Schneiders, J.P.M. Niedere, P. H.M. Feron, G.F. Versteeg, CO2
capture from power plants Part I. A parametric study of the technical performance based on
monoethanolamine; International journal of greenhouse gas control 1 (2007) 37–46.
[21] P. Keshavarz, J. Fathikalajahi, S. Ayatollahi, Mathematical modeling of the simultaneous absorption of
carbon dioxide and hydrogen sulphide in a hollow fiber membrane contactor; Separation and Purification
Technology 63 (2008) 145–155.
[22] S. Ma’mun, H. F. Svendsen, K. A. Hoff, O. Juliussen, Selection of new absorbents for carbon dioxide
capture; Energy Conversion and Management 48 (2007) 251–258.
[23] I. R. Soosaiprakasam, A. Veawab, Corrosion and polarization behavior of carbon steel in MEA-based
CO2 capture process; International journal of greenhouse gas control 1 (2007) 553–562.
[24] M. Pehnt, J. Henkel, Life cycle assessment of carbon dioxide capture and storage from lignite power
plants; International journal of greenhouse gas control (2008).

PERT – Process Engineering Research Team

16145 GENOVA - Via Opera Pia, 15 - Tel. 39 - 010 3536504 - Fax 39 - 010 3532589
[25] A. Aroonwilas, A. Veawab, Integration of CO2 capture unit using single and blended-amines into
supercritical coal-fired power plants: Implications for emission and energy management; International
journal of greenhouse gas control 1 (2007) 143–150.
[26] Q. Zhou, C.W. Chan, P. Tontiwachiwuthikul, A monitoring and diagnostic expert system for carbon
dioxide capture; Expert Systems with Applications 36 (2009) 1621–1631.
[27] R. Notz, N. Asprion, I. Clausen and H. Hasse, Selection and pilot plant tests of new absorbents for post-
combustion carbon dioxide capture; Trans IChemE, Part A, Chemical Engineering Research and Design,
2007, 85(A4): 510–515.
[28] P. D. Vaidya, E. Y. Kenig, Absorption of CO2 into aqueous blends of alkanolamines prepared from
renewable resources; Chemical Engineering Science 62 (2007) 7344–7350.
[29] D. Le Tourneux, I. Iliuta, M. C. Iliuta, S. Fradette, Faïçal Larachi, Solubility of carbon dioxide in aqueous
solutions of 2-amino-2-hydroxymethyl-1,3-propanediol; Fluid Phase Equilibria 268 (2008) 121–129.
[30] B. P. Mandala, M. Guha, A. K. Biswas, S. S. Bandyopadhyay, Removal of carbon dioxide by absorption
in mixed amines: modelling of absorption in aqueous MDEA/MEA and AMP/MEA solutions; Chemical
Engineering Science 56 (2001) 6217–6224.
[31] H. Knuutila, H. F. Svendsen, M. Anttila, CO2 capture from coal-fired power plants based on sodium
carbonate slurry; a systems feasibility and sensitivity study; International journal of greenhouse gas
control (2008).
[32] J. Oexmann, C. Hensel, A. Kather, Post-combustion CO2-capture from coal-fired power plants:
Preliminary evaluation of an integrated chemical absorption process with piperazine-promoted
potassium carbonate; International journal of greenhouse gas control 2 (2008) 539–552.
[33] www.aep.com
[34] J. Van Holst, G.F.Versteeg, D.W.F.Brilman, J.A.Hogendoorn, Kinetic study of CO2 with various amino
acid salts in aqueous solution; Chemical Engineering Science 64 (2009) 59–68.
[35] M. Kanniche, C. Bouallou, CO2 capture study in advanced integrated gasification combined cycle;
Applied Thermal Engineering 27 (2007) 2693–2702.
[36] H. W. Pennline, D. R. Luebke, K. L. Jones, C. R. Myers, B. I. Morsi, Y. J. Heintz, J. B. Ilconich, Progress
in carbon dioxide capture and separation research for gasification-based power generation point
sources; Fuel Processing Technology 89 (2008) 897–907.
[37] J. Hao, P.A. Rice, S.A. Stern, Upgrading low-quality natural gas with H2S- and CO2-selective polymer
membranes Part I. Process design and economics of membrane stages without recycle streams; Journal
of Membrane Science 209 (2002) 177–206.
[38] L. Zhao, E. Riensche, R. Menzer, L. Blum, D. Stolten, A parametric study of CO2/N2 gas separation
membrane processes for post-combustion capture; Journal of Membrane Science 325 (2008) 284–294.
[39] R. Bounaceur, N. Lape, D. Roizard, C. Vallieres, E. Favre, Membrane processes for post-combustion
carbon dioxide capture: A parametric study; Energy 31 (2006) 2556–2570.
[40] E. Favre, Carbon dioxide recovery from post-combustion processes: Can gas permeation membranes
compete with absorption?; Journal of Membrane Science 294 (2007) 50–59.
[41] A. Corti, D. Fiaschi, L. Lombardi, Carbon dioxide removal in power generation using membrane
technology; Energy 29 (2004) 2025–2043.
[42] J. Shen, L. Wu, L. Zhang, Y. Dong, H Chen, C. Gao, Selective permeation of CO2 through a composite
membrane with a separation layer of 2-N,N-dimethyl aminoethyl methacrylate and acrylic acid
copolymer; Desalination 193 (2006) 327–334.
[43] H. Yang, Z. Xu, M. Fan, R. Gupta, R. B. Slimane, A. E. Bland, I. Wright, Progress in carbon dioxide
separation and capture: A review; Journal of Environmental Sciences 20(2008) 14–27.
[44] J. L. Wade, K. S. Lackner, A. C. West, Transport model for a high temperature, mixed conducting CO2
separation membrane; Solid State Ionics 178 (2007) 1530–1540.
[45] L. A. El-Azzami, E. A. Grulke, Carbon dioxide separation from hydrogen and nitrogen. Facilitated
transport in arginine salt–chitosan membranes; Journal of Membrane Science 328 (2009) 15–22.
[46] H. Matsuyama, M. Teramoto, H. Sakakura, K. Iwai, Facilitated transport of CO2 through various ion
exchange membranes prepared by plasma graft polymerization; Journal of Membrane Science 117
(1996) 251-260.
[47] M. Teramoto, N. Takeuchi, T. Maki, H. Matsuyama, Facilitated transport of CO2 through liquid
accompanied by permeation of carrier solution; Separation and Purification Technology 27 (2002).
[48] M. Teramoto, S. Kitada, N. Ohnishi, H. Matsuyamaa, N. Matsumiya, Separation and concentration of
CO2 by capillary-type facilitated transport membrane module with permeation of carrier solution; Journal
of Membrane Science 234 (2004) 83–94.
[49] M. Teramoto, N. Ohnishi, N. Takeuchi, S. Kitada, H. Matsuyama, N. Matsumiya, H. Mano, Separation
and enrichment of carbon dioxide by capillary membrane module with permeation of carrier solution;
Separation and Purification Technology 30 (2003) 215–227.

64
[50] K. Okabe, H. Mano, Y. Fujioka, Separation and recovery of carbon dioxide by a membrane flash
process; International journal of greenhouse gas control 2 (2008) 485–491.
[51] N. Boucif, E. Favre, D. Roizard, CO2 capture in HFMM contactor with typical amine solutions: A
numerical analysis; Chemical Engineering Science 63 (2008) 5375–5385.
[52] S. Yan, M. Fang, W. Zhang, S. Yuan Wang, Z. Xu, Z. Luo, K. Cen, Experimental study on the separation
of CO2 from flue gas using hollow fiber membrane contactors without wetting; Fuel Processing
Technology 88 (2007) 501–511.
[53] P. S. Kumara, J. A. Hogendoorna, P. H. M. Feronb, G. F. Versteega, New absorption liquids for the
removal of CO2 from dilute gas streams using membrane contactors; Chemical Engineering Science 57
(2002) 1639–1651.
[54] M.G. Plaza, C. Pevida, A. Arenillas, F. Rubiera, J.J. Pis, CO2 capture by adsorption with nitrogen
enriched carbons; Fuel 86 (2007) 2204–2212.
[55] M. M. Maroto-Valer, Z. Tang, Y. Zhang, CO2 capture by activated and impregnated anthracites; Fuel
Processing Technology 86 (2005) 1487– 1502.
[56] J. Przepiorski, M. Skrodzewicz, A.W. Morawski, High temperature ammonia treatment of activated
carbon for enhancement of CO2 adsorption; Applied Surface Science 225 (2004) 235–242.
[57] A. Somy, M. R. Mehrnia, H. D. Amrei, A. Ghanizadeh, M. Safari, Adsorption of carbon dioxide using
impregnated activated carbon promoted by Zinc; International journal of greenhouse gas control (2008).
[58] M. Bo Yue, L. B. Sun, Y. Cao, Z. J. Wang, Y. Wang, Q. Yu, J. H. Zhu, Promoting the CO2 adsorption in
the amine-containing SBA-15 by hydroxyl group; Microporous and Mesoporous Materials 114 (2008).
[59] X. Xu, C. Song, J. M. Andresen, B. G. Miller, A. W. Scaroni, Preparation and characterization of novel
CO2 ‘‘molecular basket’’ adsorbents based on polymer-modified mesoporous molecular sieve MCM-41;
Microporous and Mesoporous Materials 62 (2003) 29–45.
[60] M. M. Maroto-Valer, Z. Lu, Y. Zhang, Z. Tang, Sorbents for CO2 capture from high carbon fly ashes;
Waste Management 28 (2008) 2320–2328.
[61] A. Arenillas, K.M. Smith, T.C. Drage, C.E. Snape, CO2 capture using some fly ash-derived carbon
materials; Fuel 84 (2005) 2204–2210.
[62] A. Iwan, H. Stephenson, W. C. Ketchie, A. A. Lapkin, High temperature sequestration of CO2 using
lithium zirconates; Chemical Engineering Journal 146 (2009) 249–258.
[63] J. Ida, R. Xiong, Y.S. Lin, Synthesis and CO2 sorption properties of pure and modified lithium zirconate;
Separation and Purification Technology 36 (2004) 41–51.
[64] M Wang, C. Lee, C. Ryu, CO2 sorption and desorption efficiency of Ca2SiO4; International journal of
hydrogen energy 33 (2008) 6368–6372.
[65] S. C. Lee, B. Y. Choi, T. J. Lee, C. K. Ryu, Y. S. Ahn, J. C. Kim, CO2 absorption and regeneration of
alkali metal-based solid sorbents; Catalysis Today 111 (2006) 385–390.
[66] Z. Yong, V. Mata, A. E. Rodrigues, Adsorption of carbon dioxide at high temperature—a review;
Separation and Purification Technology 26 (2002) 195–205.
[67] N. Rodriguez, M. Alonso, G. Grasa, J. Carlos Abanades, Heat requirements in a calciner of CaCO3
integrated in a CO2 capture system using CaO; Chemical Engineering Journal 138 (2008) 148–154.
[68] L. M. Rome, Y. Lara, P. Lisbona, J. M. Escosa, Optimizing make-up flow in a CO2 capture system using
CaO; Chemical Engineering Journal (2008).
[69] L. M. Romeo, J. C. Abanades, J. M. Escosa, J. Paño, A. Giménez, A. Sánchez-Biezma, J. C.
Ballesteros, Oxyfuel carbonation/calcination cycle for low cost CO2 capture in existing power plants;
Energy Conversion and Management 49 (2008) 2809–2814.
[70] N. H.Florin, A.T.Harris, Reactivity of CaO derived from nano-sized CaCO3 particles through multiple CO2
capture-and-release cycles; Chemical EngineeringScience64(2009)187–191.
[71] B.R. Stanmore, P. Gilot, Review—calcination and carbonation of limeston during thermal cycling for CO2
sequestration; Fuel Processing Technology 86 (2005) 1707–1743.
[72] Y. Li, C. Zhao, L. Duan, C. Liang, Q. Li, W. Zhou, H. Chen, Cyclic calcination/carbonation looping of
dolomite modified with acetic acid for CO2 capture; Fuel Processing Technology 89 (2008) 1461–1469.
[73] C.M. Kinoshita, S.Q. Turn, Production of hydrogen from bio-oil using CaO as a CO2 sorbent;
International Journal of Hydrogen Energy 28 (2003) 1065–1071.
[74] A. Amorelli, M.B. Wilkinson, P. Bedont, P. Capobianco, B. Marcenaro, F. Parodi, A. Torazza, An
experimental investigation into the use of molten carbonate fuel cells to capture CO2 from gas turbine
exhaust gases; Energy 29 (2004) 1279–1284.
[75] M.J. Tuinier, M.van Sint Annaland, G.J.Kramer, J.A.M.Kuipers, Cryogenic CO2 capture using
dynamically operated packed beds; Chemical Engineering Science (2009).
[76] Can Europe Climate Technology Sheet #1: Carbon Capture Technologies.
[77] The European Technology Platform for Zero Emission Fossil Fuel Power Plants (ZEP), The final report
th
from Working Group 1 Power Plant and Carbon Dioxide Capture, 13 October 2006.
[78] N. H. Duc, F. Chauvy, J.M. Herri, CO2 capture by hydrate crystallization – A potential solution for gas
emission of steelmaking industry; Energy Conversion and Management 48 (2007) 1313–1322.

65
[79] European Technology Platform for Zero Emission Fossil Fuel Power Plants, Working group n. 4: Making
Carbon Capture and Storage happen in Europe, CO2 Use and Storage, September 2006.
[80] E. Tzimas, A. Mercier, C.-C. Cormos, S. D. Peteves, Trade-off in emissions of acid gas pollutants and of
carbon dioxide in fossil fuel power plants with carbon capture; Energy Policy 35 (2007) 3991–3998.

3. CARBON DIOXIDE TRANSPORT

3.1 Transport
Normally the power plants and industrial production plants that are large point-sources of
CO2 are located a long distance away from storage locations.
Therefore captured CO2 has to be transported from the point of capture to a storage site [1].
CO2 can be transported by pipelines, ships, trains or trucks. Industrial CO2 has been safely
and efficiently transported for many years by truck, train and small ships. However to transport
large volume of the CO2 envisaged by CCS&T, pipelines or large ships will be the optimum choice.
The best transport system depends on the CO2 volumes, the distance between CO2 source
and storage location and the geography and geology of the route where CO2 will be transported
[2].
For instance pipelines are used for large volumes over shorter distances and ships can be
used for small volumes over longer distances.
Therefore it is necessary to identify the optimal transport system, to determine the best
infrastructure routing, to build these infrastructure and to establish necessary regulations for cross
country CO2 transportation. The aim of these studies will be minimize both the cost and
environmental impact [3].

CO2 properties

It is very important to know the physical properties of CO2 in order to understand the
technical issues and the potential environmental and safety hazards of CO2 transport.
CO2 is a highly compressible gas that in supercritical or “dense” phase exhibits a very low
viscosity and the density of a liquid. It can be transported in all of its physical states (gaseous,
supercritical, liquid and solid).

Properties of CO2
Tc 304.6 K
Pc 73.8 bar
3
ρc 467 kg/m
T at triple point 216.8 K
P at triple point 5.18 bar
3
ρsolid at triple point 1512 kg/m
Table 3.1/1 Proprieties of CO2

Properties Gas Supercritical Liquid

3
Density (g/cm ) 0.001 0.2-1.0 0.6-1.6
2
Diffusivity (cm /s) 0.1 0.001 0.00001
Viscosity (g/cm⋅s) 0.0001 0.001 0.01
Table 3.1/2 Proprieties of CO2 in different phases

The gas phase is not convenient for CO2 transport as the gas density is very low, thus the
pipeline diameter should be very large.
For transport solid CO2 (called “dry ice”), the problem is that at normal temperature the solid
sublimates, so it does not go through the liquid phase. Therefore the solid CO2 transport demands
specially insulated and pressurized vessels.
66
 For the above the CO2 is transported in liquid or supercritical phase.
Another important problem in the CO2 transport is its corrosive behaviour.
Dry CO2 is not corrosive for the carbon-manganese steels customarily used for pipelines,
even if the CO2 contains contaminants such as oxygen, hydrogen sulphide, and sulphur or nitrogen
oxides.
However if water is present, CO2 is highly corrosive. In fact CO2 reacts to form carbonic
acid, which is quite corrosive to pipeline steels.
Moreover even if the H2O concentration is significantly low, the combination of SO2 (it can
be present in the flue gases from power plants) and small amounts of H2O can be highly corrosive
leading to potential materials performance issues. Therefore a CO2 pipeline would have to be
made from a corrosion-resistant alloy, or be internally clad with an alloy or a continuous polymer
coating [4].
Obviously the cost of materials is several times larger than carbon-manganese steel.

Pipelines

Fig. 3.1/1 Gas pipelines

CO2 pipeline transport is well known as it has been widely used in USA since 1970s
transporting large volumes of CO2 to oil fields for enhanced oil recovery (EOR). Every year over
than 40 MtCO2 from natural and anthropogenic sources are transported through a 3,100 km long
onshore infrastructure of high pressure (100-200 bar) carbon steel pipelines.
A significant example of this is the CO2 pipeline from the Gasifier in Beulah, North Dakota
to the Weyburn Oil Field in Saskatchewan, Canada.
In the last years CO2 pipeline options have come into existence in Europe. One is offshore
at Statoil’s Snohvit LNG project and the other is Linde’s onshore CO2 line in the Netherlands [2].
Furthermore there is an extensive knowledge of the natural gas and liquid propane gas
(LPG) transport, thus the experience in hydrocarbon pipeline transportation can be transferred
directly to CO2 transport [5].
Records maintained by the regulatory authorities in the USA of incidents involving CO2
pipelines indicate that the frequency of incidents is similar to that of natural gas pipelines, but the
degree of incidental damage caused is significantly lower than that for natural gas pipelines.
In addition, there are no records of serious injuries or fatalities associated with incidents
involving CO2 pipelines from records dating back to the 1970s. The principal causes of incidents
have been outside intervention and corrosion.
Natural gas transport is regulated by the EIA (Environmental Impact Assessment) Directive
for pipelines of diameter greater than 800 mm and a length more than 40 km. There is also a
Pressurised Vessels Directive that provides standards for the materials to be used to transport gas
at various pressures.
Since potential hazards of CO2 transport are broadly comparable to those of natural gas
transport (moreover CO2 is not inflammable or explosive unlike natural gas), it is possible to
believe that the risk framework applied to natural gas transport by pipeline is adequate to regulate
also CO2 transport [6].

67
 As regards the way to transport CO2, the most efficient is transporting it as a supercritical
phase which occurs at a pressure greater than 73.8 bar and a temperature higher than 304.6 K
(see Table 3.1/1 and Table 3.1/2). Therefore CO2 will be transported at supercritical pressure,
most likely in the range of 80–150 bar.
The CO2 must be compressed to a pressure high enough to overcome the frictional and
static pressure drops. Moreover in order to avoid two-phase flow, liquid slugs in the pipeline and
liquids in the injection compressor, the CO2 should be delivered at a pressure higher than the
critical pressure [7]. Thus whenever the pressure falls below 80 bar it is necessary to repump the
CO2 [8].
Z.X. Zhang et al. [9] have studied the possibility of transport CO2 as a sub cooled liquid.
It is necessary a cooling utility of 15 °C or less so that the CO2 can be kept below its critical
temperature.
Refrigeration could be added along the pipeline using CO2 as the working medium, but this
will obviously increase the capital and operating costs and reduce the overall energy efficiency.
Actually the refrigeration compressors that would be required for this purpose are quite
small capacity as the quantity of heat that needs to be removed from the liquid CO2 in that
pipelines is limitated. Moreover, the refrigeration plants do not need to run continuously, for
example when ambient temperature is low as at night or in winter.
In additional, especially for environmental, security and safety reasons most new pipelines
will be buried, despite the higher initial costs. Underground temperatures are much more stable
than surface temperatures. For example in direct sunshine, the ground surface temperature at
noon is about 65°C., while at one meter underground , the temperature was found to be below
30°C.
The researchers said that, although no buried pipelines may need to be insulated in order
to maintain CO2 as a liquid in warmer climates, CO2 transportation in the sub cooled liquid state
has some advantages over supercritical state transport.
In fact it is possible:

- to use smaller pipe sizes or to have lower pressure losses because of the lower compressibility
and higher density of the liquid within the pressure range considered;
- to use pumps rather than compressors to boost pressure along the line or for injection at the
well end.

For building pipelines transport of CO2, studies have to perform to identify the suitable
material with respect to corrosion resistance, volume flow rate, pressure, temperature. The
pipelines also need protection from damage and appropriate monitoring facilities and safety
systems.
As above said, CO2 is highly corrosive in presence of water, so the transported CO2 must
be treated to a very low water content or a relative humidity of less than 60% in order to prevent
hydrate formation and internal corrosion of the carbon and low-alloy steel pipelines.
The concentration of H2S should also be kept very low to prevent sulphide stress corrosion
cracking and because of safety reasons where pipelines pass populated areas.
The pipeline routes must be carefully planned. Rural areas will be first priority for safety
reasons. The context of geography and geological activity has to be carefully studied.
For offshore transportation, the seabed stability for installation of the transport infrastructure
must be ensured [2].
Existing infrastructure originally designed for transport of natural gas or petroleum products
may be retrofitted for CO2 transport. However existing compressors, offshore platforms, wellheads,
and control systems will require modification for use in a CO2 transport system.
In order to guarantee human safety in urban areas, extensive use of pipeline modelling and
gas modelling dispersion technology will be essential.

68
Ships

Fig. 3.1/2 LNG ship

Nowadays a small amount of CO2 is already transported by ship to service the food and
drink industry, but the CCS&T technology needs to transport large volume of CO2.
However the transport of liquefied gas by ship is very similar to CO2 transport. Liquefied
Natural Gas (LNG) transportation has been established for over forty years with almost fifty
thousand cargoes delivered and Liquefied Petroleum Gas (LPG) is routinely transported
throughout the world. Moreover transportation of liquefied gases by sea has a very good safety
record, despite the number of cargoes carried; LNG carriers have not suffered any significant
losses. Thus large scale transport of CO2 can employ similar technologies to LPG.
CO2 transport by ships will be in liquid form. CO2 exists in liquid form at pressures between
triple point, 5.18 bar and critical point, 73 bar; the density of saturated liquid ranges from 1200 to
600 kg/m3. So in a fixed volume vessel almost two times more CO2 can be transported at low
pressure near the triple point than at high pressures near the critical point. Moreover, the cost of
the pressure vessels is lower if the pressure is lower.
Even if the required energy to liquefy CO2 increases with decreasing pressure, the marginal
penalties for the decreased pressure is small compared to the benefits of higher transport
capacities and less expensive vessels.
Therefore it is likely that the CO2 will be transported at a pressure near the triple point
although operating near this point can lead to operational problems because of the formation of dry
ice below the triple point.
In semi-pressurized ships the gas to be transported is kept in liquid phase on the saturation
line by a pressure higher than atmospheric pressure and a temperature lower than ambient
temperature, around -55°C and 6 bar [10].
Since the corrosive behaviour of CO2, material technology research is necessary to develop
optimal materials for CO2 vessels.

Intermediate storage

A pipeline transport allows a continuous flow from the emission source to the storage site.
The other means of transportation must include appropriate intermediate storage facilities to
handle the reloading of CO2, e.g. at harbours.
There are two main technologies for intermediate storage of LPG: underground in great
rock and salt caverns or above ground in large steel tanks.
At present, only the steel tank technology is used for CO2 applications. As regards to the
salt caverns there are some uncertainties with respect to the dissolution behaviour of CO2.
Rock caverns for the LPG industry are constructed in two different ways, either as
pressurised or as cooled caverns. If the caverns are intended for storage of CO2, these techniques
must be combined to create favourable conditions with respect to pressure and temperature for the
CO2. The cost for building a rock cavern depends mainly on the rock quality. Poor rock quality
increases the need for lining and reinforcement of the rock, which obviously increases costs [11].

69
3.2 Risks
As every transport system, the CO2 transport could cause damage on humans and the
environment.
At ambient temperatures, CO2 gas is heavier than air and disperses mainly horizontally.
At concentrations in air above than 10%, CO2 is an asphyxiant, and at smaller
concentrations it causes nausea, vomiting, and diarrhoea and skin lesions.
Some hazard of CO2 transport could be:

• A release of CO2 from a ship which would impact on the surrounding ocean. The CO2 would
dissolve in the water, forming carbonic acid (H2CO3) that could acidify the water, improving its
ability to solubilise sources of calcium carbonate present in form of coral and the
carbonaceous shells of clams and other shellfish;
• A failure in a supercritical phase CO2 pipeline due to the energy released when compressed
CO2 suddenly expands to atmospheric conditions;
• An accidental release from pipe or tank rupture, although they are highly unlike;
• A leak of CO2 during loading or unloading operations, though the impact may be smaller than
that of pipelines and storage tanks, it may pose a significant hazard to workers in the
immediate vicinity of the release.

In order to prevent or minimize the environmental impacts and safety hazards it is

necessary to do hazard identification (HAZID), hazard and operational analyses (HAZOP) and
manage carefully the process [10].
For instance specific crack arrestors can be installed on the pipelines to reduce the hazard
from cracks; seals can be manufactured out of specialized polymers that resist the CO2 corrosive
effects; gas detector system should be required; gas masks and protective clothes should be used
from workers during loading and unloading operations [8].

3.3 Conditioning

Gas conditioning is a required process in the interface between CO2 capture and transport.
In fact it is necessary to remove water and other unwanted components from CO2 stream.
The energy requirement for the conditioning processes is normally between 90 and 120
kWh/tCO2; however, this depends on the pressure and composition of the captured CO2-rich
stream. Basically, it is possible to treat CO2 to near 100% purity, however in most cases it is
preferable to have less rigid specifications in order to reduce both energy and capital costs.
Moreover the required specifications may depend on the end target (EOR, storage, etch.).
Some methods of CO2 gas conditioning are [7]:

• removal of water and other liquids in vapour-liquid separator drums;

• removal of volatile gases in the volatile removal column;
• removal of unwanted components by chemical or physical treatments.

Removal of water and other liquids

Water must be removed to avoid gas hydrates, freezing of water and corrosion. Vapour-
liquid separator drums ensure no liquid entrainment to the CO2 compressors. They allow
separation by gravity of components with higher density than gaseous CO2, so they are the
simplest and most cost and energy effective way to remove these components.
Moreover components with high solubility in water or with higher boiling point than CO2 can
also be removed in separator drums.

70
 Most of the water is removed in the first vapour-liquid separator drums and with proper
design this technology can remove water down to roughly 400-500 ppm.
In order to decrease the water content, after the separator drums the CO2 gas can be dried
by regenerative adsorption columns.
The purge gas from the adsorption column should be cooled and recycled into one of the
first vapour–liquid separator drums to avoid purging of CO2.
After this process, based on industrial experience, the CO2 product could contain maximum
50 ppm water. As regards to corrosion and ice problems this level of water content is very low as
they will probably not occur before the water content is more than 10 times higher than this
specification. On the contrary for ship transportation the water should be removed to 50 ppm to
avoid operational problems in the liquefaction process.
However for processes with pressures higher than 20–30 bar, the specification could be
achieved using only separator drums.

Removal of volatile gases

Volatiles gases, like nitrogen or argon, will usually not cause any safety or operational
problems for the pipeline transport process or the final storage. However as transport is both
energy and cost intensive, it is better not to process and transport the inerts.
Furthermore in ship transport in which CO2 is near the triple point most volatiles must be
removed to avoid dry ice formation during liquefaction or transport. At transport pressures of 6–7
bar, only small fractions of volatiles, typically 0.2–0.5 mol% can be allowed to insure that dry ice is
not formed.
In addition if the CO2 is used for EOR immiscible components may increase the miscible
pressure in the reservoir and thereby decrease the efficiency of the CO2. Oxygen may cause
precipitation reactions and thus reduce the permeability of the reservoir. It may also lead to
overheating at the injection point reacting exothermally with oil.
Therefore nitrogen content should be under 300 ppm and oxygen content under 50 ppm.
The problem is that oxygen cannot easily be removed to such stringent specifications using
conventional separation without increasing the re-boiler and condenser duty significantly.
Therefore a balance between stringent specifications and costs for achieving them must be
evaluated.
It is preferable to remove the volatiles in a column instead of a flash separator to reduce the
CO2 amount in the volatile purge stream.

Removal of unwanted components

Components as propane, ethane, H2S and SO2 cannot be easily separated from CO2 by
flashing or simple distillation. Small quantities of propane and ethane do not cause any operational
problems; on the contrary H2S could be a safety hazard, so it must be removed.
Unwanted components that cannot be removed in the vapour–liquid separator drums or in
the volatile column must be removed by chemical or physical treatments as absorption or
adsorption towers, rigorous distillation, membranes or catalytical processes.

Therefore based on composition, the CO2-rich streams can be divided into three categories
[7]:

1) Streams with only CO2 and water (and possible traces of amines and minor fractions of inerts):
pre- and post- combustion capture process using amines;
2) Streams containing CO2, water and non-combustible volatiles: oxyfuel process that employ a
cryogenic air separating unit (ASU). In this case the process with volatile purge removal
generates a purge gas consisting of non-combustible volatiles and CO2. In order to avoid CO2
emissions, either the entire purge stream may be recirculated back to the power cycle or the
stream may be fed to an advanced separation system, after which the CO2 may be recycled in
the gas conditioning and the volatiles may be vented to the atmosphere or be recovered as
saleable products;

71
3) Streams containing CO2, water, inert and combustible volatiles: Methane Steam Reactor
(MSR), pre-combustion with Authotermal Reforming Reactor (ATR) as it contains some H2 and
the group of reactors as membrane reactors, sorption enhanced reactors, fuel cells and
chemical looping reactors in which full fuel conversion is virtually impossible. It could be more
beneficial to optimize the CO2 capture process at a lower fuel conversion rate than the highest
possible one, and integrate the capture process with the gas conditioning process with
recirculation of the combustible volatiles. There are two possible ways of recycling the
combustibles. The purge gas, containing both combustibles and noncombustibles can be
recycled directly to the capture process or it can be sent to an advanced separation, which
separates the combustibles from the CO2 and other volatiles, before the combustibles are
recycled.
The most effective way to treat the purge gas and where in the process the recycle should
occur could be a topic for future studies.

Fig. 3.3/1 Recycle possibilities in the interface between capture and transport [7].

72
References

[1] IPCC, 2005. IPCC special report on carbon dioxide capture and storage. Prepared by working group III
of the Intergovernmental Panel on Climate Change.
[2] Strategic Research Agenda (SRA) of European Technology Platform for Zero Emission Fossil Fuel
Power Plants, Working group n. 3: Infrastructure and Environment, May 2006.
[3] Strategic Deployment Document (SDD) of European Technology Platform for Zero Emission Fossil Fuel
Power Plants, Working group n. 3: Infrastructure and Environment, May 2006.
[4] U.S Department of Energy (DOE) Project: Materials Performance Issues in CO2 Transport.
[5] Strategic Research Agenda (SRA) of European Technology Platform for Zero Emission Fossil Fuel
Power Plants.
rd
[6] Impact Assessment, Commission of European Communities, 23 January 2008.
[7] A. Aspelund, K. Jordal, Gas conditioning—The interface between CO2 capture and transport;
International journal of greenhouse gas control 1 (2007) 343-354.
[8] D.Golomb, Transport systems for ocean disposal of CO2 and their environmental effects; Energy
Conversion and Management 38, suppl. (1997) S279-S286.
[9] Z.X. Zhang, G.X. Wang, P. Massarotto, V. Rudolph, Optimization of pipeline transport for CO2
sequestration; Energy Conversion and Management 47 (2006) 702-715.
[10] A. Aspelund, M. J. Mølnvik, G. De Koeijer, Ship transport of CO2,Technical Solutions and Analysis of
Costs, Energy Utilization, Exergy Efficiency and CO2 Emissions; Institution of Chemical Engineers, Trans
IChemE, Part A, September 2006, Chemical Engineering Research and Design, 84(A9): 847-855.
[11 R. Svensson, M. Odenberger, F. Johnsson, L. Stromberg, Transportation systems for CO2––application
to carbon capture and storage; Energy Conversion and Management 45 (2004) 2343-2353.

73
4. CARBON DIOXIDE STORAGE

After capture, CO2 can either store or re-used. Since the market for re-use of CO2 is limited,
the majority of captured CO2 must be stored.
Geological formations can be the main CO2 storage options; in fact they offer a huge
storage capacity. They include:

Sequestration option Worldwide capacity [GtC]

Deep saline aquifers 100-1000
Depleted oil and gas reservoirs 100
Unminable coal seams 10-100
Tab. 4/1 Estimated world sink capabilities of CO2 disposal options [1]

Since the world CO2 emissions are 25 GtCO2/year, despite the broad ranges in the storage
capacity, it can be concluded that the capacity could be sufficient to store worldwide man-made
CO2 emissions for tens and possibly hundreds of years.

Fig. 4/1 Different geological formations for CO2 storage

It is also possible to inject CO2 in the deep ocean that can be storage roughly 1000 GtC [1].
Moreover in order to avoid emissions into the atmosphere, there are some other ways to
capture or fix CO2:

• mineral carbonation;
• forestation;
• biofixation.

4.1 Geological formations

The majority of geological formations are layers of porous rock underground that are
covered by a layer of non-porous rock, called cap-rock.
The CO2 is compressed and pumped into a porous layer, around a kilometre underground
and there are different trapping mechanisms to retain CO2 for a very long time: physical and
geochemical trapping.

74
 Figure 4.1/1 CO2 density vs depth of geological formation [2]

At first CO2 injected at high pressure can move through geological formation as a fluid.
CO2 is more buoyant than water and tends to flow upward until it encounters a cap-rock,
which can trap the CO2 and forms a continuous primary seal. It is the same cap-rock that has
trapped oil, gas and CO2 underground for millions of years.
In stratigraphic trapping, cap rock, sometimes coupled with impermeable rocks forms a
closed container which traps CO2. In structural trapping, impermeable rocks shifted by a fault or
fold in the geologic strata retain the CO2. In addition, CO2 storage rocks are generally separated
from the surface by other thick layers of impermeable rock, called secondary seals.
Therefore injection pressure must be high enough to force the liquid CO2 into porous rock,
but not so high to break the cap rock.
Usually after injection stop, another trapping mechanism begins, it is called residual
trapping. Water from surrounding rocks moves back into the tiny pores containing CO2, thus the
CO2 is trapped by the capillary pressure of water [2].
For the long-term entrapment of the injected CO2, geochemical trapping mechanism is
important. Much of CO2 injected dissolves in the saline water or in the oil that remains in the rock.
The primary advantage of this mechanism, called solubility trapping, is that the dissolved
CO2 no longer exists as a separate phase; the buoyant forces do not act anymore and CO2
saturated water tends to sink to the bottom of the storage formation.
Depending on the rock formation and on the fluid types and interactions that occur the
dissolved CO2 may react chemically with the surrounding rocks to form stable minerals (mineral
trapping), the most permanent form of geological storage. Mineral trapping is a slow process,
potentially taking 10,000s of years.
Therefore two distinct time periods in CO2 storage has been defined: active or injection
period and the passive storage period.
The first, around 50 years, is used to inject the gas. In this period the dominant trapping
mechanism is the physical type. Whereas the second period is much longer, possible 1000 to
10,000 years, and is the actual storage period. In this period the geochemical trapping takes place
and the CO2 has to stay in the intended location and has to be stored safely [3].
For well-selected, designed and managed geological storage sites, the vast majority of the
CO2 will gradually be immobilized by various trapping mechanisms and could be retained for up to
millions of years. Observations from engineered and natural analogues as well as models suggest
that the fraction retained in appropriately selected and managed geological reservoirs is very likely
to exceed 99% over 100 years and is likely to exceed 99% over 1,000 years [4].
Therefore it is very important to evaluate a good geological storage site. It must possess
the following characteristics [2]:

• the location should be economically accessible from the CO2 source;

• the storage capacity should be adequate to serve the large volumes of captured CO2;

75
• storage formation must have adequate porosity (a measure of the space in the rock for storing
fluids) and permeability (a measure of the ability of the rock to allow fluid flow) to store CO2;
• the formation can store CO2 at the rate required to serve the intended sources, so it should
have adequate injectivity;
• the CO2 should be stored deep enough to be supercritical;
• cap rock must have low porosity and permeability to trap stored CO2 below;
• the geologic environment must be adequately stable to ensure the integrity of the storage site;
• pathway faults or uncapped wells should not penetrate the cap rock and storage formation.

4.1.1 Depleted oil and gas reservoirs

Oil and gas reservoirs are considered to be safe storage site for CO2, since they have held
oil, gas and often also CO2 for millions of years.
Moreover CO2 injection can increase the oil production. A small amount of the injected CO2
dissolves in the oil, increasing the bulk volume and decreasing the viscosity, thereby facilitating
flow to the wellbore. As part of CO2 is pushed out with oil, it is recaptured and reinjected until as oil
as is feasible has been extracted. CO2 injection allows recovery of an additional 10–15 percent of
the oil.
This process, known as enhanced oil/gas recovery (EOR), is not a new technology, it has
been performed in the USA using CO2 for some years, not with the purpose of CO2 storage, but to
obtain additional oil. In Canada, injection of acid gas (a residual product of natural gas refining
consisting of mainly CO2 and H2S) into oil/gas fields and deep saline aquifers has been practiced
for many years [5].
The use of CO2 in oil fields either onshore or offshore has two main advantages [3]:

the geology of most of oil and gas fields has been widely studied in oil exploration and
operations. In addition the oil and gas industry uses accurate models of the underground
behaviour of these fluids that could be adapted to CO2;

EOR may mitigate storage costs.
However it is important to take into account that in existing commercial CO2-EOR projects,
so far, the main purpose is to maximise oil recovery with a minimum quantity of CO2. In fact, at the
moment, this storage modality is not conceived to maximise the CO2-storage, but to produce the
maximum enhanced oil recovery.
Recent efforts are devoted to the optimization of CO2 storage and improved oil recovery at
the same time.
In addition the economic viability of EOR projects depends on the price of oil and the
proximity of a relatively pure carbon dioxide flood. As the CO2 removal process requires large
amounts of energy, EOR project could not always be profitable. Furthermore when oil prices are
low, EOR projects may be uneconomical [1].
Similar to EOR, it is possible to apply Enhanced Gas Recovery (EGR), but this process is
not yet a commercially viable technology. There still are some open questions, mostly about the
early mixing at depth between the two gaseous components, CO2 and CH4, and software
simulations are not always optimistic.

4.1.2 Unminable coal seams

CO2 can also injected into coal-beds which are too deep or too thin to be economically
mined. This process is known as Enhanced Coalbed Methane (ECBM). In fact all coals have
varying amounts of methane adsorbed on pore surfaces and the injection of CO2 allows additional
recovery of methane.
CO2 can enter into very small pores of coal and compete with the absorbed methane
molecules. The latter detach from adsorption sites when CO2 is injected into the coal due to a
decrease in methane partial pressure in the free gas phase. The displaced methane is then free to

76
flow towards the wells while the injected CO2, which has a greater adsorption affinity than CH4, is
adsorbed onto the coal [6].
For store CO2 in coal beds, sites must possess the following characteristics [7]:

have sufficient capacity for injecting large volumes of CO2;

have adequate permeability (at least 1–5 millidarcy);

have simple structure (minimal faulting and folding);

be homogeneous and confined (the presence of an overlying seal will prevent upward leakage
of mobile CO2 that is not adsorbed onto the coal matrix);

have low water saturation (coals with low water saturation are preferable because the coal
seam has to be dewatered before it can be used for storage);

have high gas saturation (from a methane-production perspective);

be unmineable, now and in the future;

have concentrated coal deposits with preferentially few, thick (> 1m) rather than multiple,
thinner seams. However recently this criterion has been changed as thick coals could be
mined in the future, thus, rather than sterilize a potential resource, multiple thin coal seams
should be used.

The advantages of storing CO2 in a coal bed are [7]:

coalfired power plants are often situated close to coal deposits, thus the transport distances to
the target formations are small;

coal bed methane represents a hydrogen-rich fuel, practically free of toxic products;

efficient sorptive storage of CO2 in coal seams may occur at 200-800 m, unlike of geogical
storage that should be performed at higher depth (> 800 m);

many states have coal basins and, thus, operations could be carried out in many countries;
India and China have extensive coal reserves and also a great need for technological
expertise.

However there are also some drawbacks:

in Europe most coal basins are located in fractured areas, with risks of leakage;

when coal adsorbs CO2, it swells in volume and permeability drops. Therefore the flow of CO2
in the formation is restricted and the recovery of methane is impeded;

as the current lack of understanding of adsorption or absorption processes for liquid and
supercritical CO2 and the potential for coal plasticization in the presence of CO2 at high
pressure and temperature, unless significant advances in science and technology are made,
only coals at in situ temperature and pressure conditions where CO2 is in gaseous phase
should be considered suitable for storage. These constraints reduce the depth window to a
range of a few hundred metres to less than 1000 m;

coal seams are lower capacities compared to deep saline aquifers, so the amount of CO2
sequestered is small and does not significantly contribute to the need to store CO2 in large
quantities [6].

Some research has been made to understand and optimise this process. For example
some studies have been devoted to evaluate the theoretical, effective and practical CO2 storage
capacity in coal beds in Alberta, Canada [8].
S. Bachu found that it is highly unlikely that all the effective CO2 storage capacity in coal
zones will be utilized because it is uneconomic to build the necessary infrastructure (pipelines,
compressors and a high density of injection and production wells) for areas with low storage
capacity.
In fact in Alberta coal basins among three coal zone analysed, only one could be become a
suitable CO2 storage site. It has large practical capacity (800 Mt CO2) in a forested area of 3300
km2 that is unlikely to become the object of land-use conflicts. In addition large stationary CO2
sources are located within close distance of this area.

77
4.1.3 Deep saline aquifers

Deep saline formations are layers of porous rock that contain water unusable because of its
high salt or mineral content.
As mentioned, they have much more capacity than oil and gas reservoirs or coal seams
and are widely dispersed throughout the world, including in areas with no appreciable oil and gas
production, in addition they are often present close to industrial CO2 sources. Therefore deep
saline formations represent an enormous potential for CO2 geological storage and could likely
become the most widely used type of geologic storage site.
However as deep saline aquifers have no alternative uses, very often too little is known
about these formations, thus there is an amount of uncertainty regarding the suitability of them for
CO2 storage.
Through petroleum or geothermal exploration, the morphology of some of the structures in
saline aquifers is known, but many of the parameters that are required to fully evaluate their CO2
storage capacity are not known yet [3].
There are aquifer formations bounded by whole or individual compartments. The upper
boundary must be a good seal capable of confining the CO2, but the fluid must be able to pass
through at least part of the lateral boundaries of the formation otherwise there will be a rapid
pressure rise within a relatively small percentage of the pore space in the aquifer (or
compartment). Therefore, heavily compartmentalised aquifers, or overpressurized aquifers are not
suitable as CO2 storage sites [3].
Nowadays there are some active geological storage projects in saline aquifers. The first
commercial injection project in the world is the Norwegian Sleipner project, where annually circa 1
million tons of CO2 is injected into an aquifer under the North Sea. This project demonstrates that
CO2 can effectively be stored in large quantities.

4.2 Deep ocean

The ocean carbon reservoir is larger than other two main reservoirs (terrestrial and
atmospheric). A doubling of the carbon concentration levels in the atmosphere represents an
increase of 2% in the ocean carbon concentration. Over a period of 100 years, it is estimated that
around 80% of today’s anthropogenic emissions of carbon dioxide will be absorbed by the ocean
[1]. This natural process can be enhanced by direct injection of CO2 into the ocean.
Different ocean disposal scenarios have been proposed to date:

dissolution of gaseous CO2 in shallow waters (200 – 500 m);

dissolution of liquid CO2 at intermediate depths (500 – 1500 m) or in deep waters (3000 m);

injection of denser, concentrated CO2 aqueous solution in shallow waters;

disposal in the form of dry ice;

disposal in the form of CO2 hydrate.

Dissolution at intermediate depths or deep water

Direct carbon injection can cause a pH level decrease of surrounding areas and it is known
that marine animals are, in general, intolerant to changes in the pH of the water in which they live.
In order to minimise the environmental impact, CO2 should be injected at depths of at least
1500 m. Models suggest that, with careful site selection, retention times of several hundred years
would be achieved by injection at this depth. Several studies have modelled the dissolution of an
ascending plume of liquid CO2 droplets emerging from a diffuser. These models predict that, with a
suitably designed diffuser, all the CO2 would be dissolved in the surrounding seawater within a
height of 100 m above the injector. Then the CO2-rich seawater would be diluted because it
disperses horizontally, aided by currents.
Injecting CO2 through a pipe hung vertically from a moving ship, it is possible to achieve a
rapid dispersion of the CO2-rich water.

78
 Injection at depth > 3000 m allows a retention time of CO2 in the ocean greater than at
lower depths. The density of liquid CO2 exceeds that of water, so a pool of CO2 could be formed in
a hollow or trench on the seabed, thereby confining the impact to a small area, although this
impact would be severe. Moreover dissolution of CO2 into the overlying seawater would be
reduced significantly by CO2-hydrates, forming an ice-like combination of CO2 and water.
The problem is that a vertical pipe, attached to a platform, would be required to reach this
depth. However design calculations indicate that, for pipe diameters of up to 1 m, a pipe length of
up to 5000 m would be possible [9].

Figura 4.2/1 Methods of dispersing CO2 and injecting liquid at depth [9]

Disposal in the form of CO2 hydrates

Some studies indicate that disposal of CO2 hydrate may cause the least marine-
environmental disturbance [10].
Hydrate formation condition would normally be satisfied in the ocean at depths greater than
500 m. Since the hydrate particles are denser than seawater, the released hydrate particles should
descend to the seabed and be sequestered there.
However, as the hydrate film so formed is very thin, the apparent density of the CO2 drop
covered with the hydrate film is not affected by the hydrate formation. Thus, the CO2 drops with
hydrate film should have positive buoyancy when they are released into the ocean at depths
shallower than 3000 m. Therefore, the released CO2 will ascend in the ocean, and eventually be
released to the atmosphere.
As a consequence of this, hydrates should be produced via a reactor on land or at the
ocean surface, and then it is disposed of in the deep ocean. Since surface seawater cannot satisfy
the conditions for hydrate formation, considerable energy is required for hydrate production in this
way, and to prepare low-temperature and high-pressure conditions. Moreover, hydrate particles
are easily agglomerated to form clusters which may cause a pipeline blockage as often
encountered in natural-gas pipelines.

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4.3 Mineral carbonation
Mineral carbonation is a natural CO2 fixation process that occurs whereby the chemical
weathering of rocks, such as silicates, containing calcium and magnesium.
The silicate rocks reacting with CO2 produce magnesium carbonate and calcium carbonate
(known as limestone) following this mechanism:

(Mg,Ca)xSiyOx+2y + xCO2 → x(Mg,Ca)CO3 + ySiO2

The products are thermodynamically stable and environmentally inert, thus mineral
carbonation results a safe storage of CO2 avoiding the risk of any accidental release of stored CO2
underground. So the disposal side needs no monitoring system.
Besides the storage capacity exceeds all possible CO2 emissions from (known) fossil fuel
reserves and the minerals in question are worldwide available in huge amount.
However the weathering process happens very slow, therefore artificial ways have been
studied to acceralate this process. Research in the field of mineral carbonation focuses on finding
process routes that can achieve reaction rates viable for industrial purposes and make the reaction
more energy-efficient.
Two methods are possible to accelerate the reaction rates: to enhance the dissolution of
mineral ions using stronger acids, or to react under higher CO2 pressure. But the use of acid can
cause problems in both the reaction facilities and in the environment, and higher CO2 pressure
requires energy [11].
Furthermore large-scale sequestration of CO2 as mineral carbonate will require huge
amounts of mineral with significant environmental impact because of mining and generate large
amounts of solid waste.
The carbonation process energy required would be 30 to 50% of the capture plant output.
Considering the additional energy requirements for the capture of CO2, a CCS system with mineral
carbonation would require 60 to 180% more energy input per kilowatthour than a reference
electricity plant without capture or mineral carbonation.
Besides some silicates as serpentine often contain chrysotile, a natural form of asbestos
[4].
In order to reduce the energy requirement and environmental impact, the utilization of
alkaline wastes material as oxide mineral sources for CO2 mineral sequestration has been
investigated [12].
Waste materials provide several advantages:

they supply a readily available source of calcium or magnesium mineral matter without the
need for pre-processing;

they are typically fine-grained with high reactive surface areas;

many fine-grained industrial wastes, such as cement kiln dust, coal fly ash, and steel slag,
have high mass percentages of CaO;

the environmental quality of the waste materials can be improved through pH-neutralization
and mineral transformation;

the end product of the sequestration may re-used in products such as road base or other
construction material;

alkaline industrial wastes are typically generated at or near point sources of CO2.

Figura 4.3/1 Mineral carbonation process scheme

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4.4 Forestation
The CO2 can also be captured increasing forestation, reforestation of arid lands and
deserts. In fact it is estimated that 1.4±0.7 Gt-carbon is captured by terrestrial systems from
atmosphere via photosynthesis. At the beginning of this sequestration, the carbon flow to terrestrial
vegetation is positive and the “stock” of carbon is increased. When fully developed, the net capture
becomes zero because the balance of capturing and release. The potential capacity for carbon
sequestration in terrestrial systems is estimated to be 5-10 Gt-carbon annually [11].
Some researchers [13] say that removal of atmospheric CO2 by plants and storage of fixed
C as soil organic matter, called “Soil C sequestration” (SOC), could at the same time increase
agricultural productivity especially in developing countries, and mitigate climate change. Adoption
of a restorative land use and recommended management practices on agricultural soils (i.e
integrated nutrient management with compost, biosolids and nutrient cycling and restoration of
degraded soils through land use change) can reduce the rate of enrichment of atmospheric CO2
and have positive impacts on food security, agro-industries, water quality and the environment.
Although SOC sequestration has much less capacity than geological and ocean
sequestration, it is the most cost-effective strategy during the first half of the 21st century and it
does not cause adverse effects on ecosystems and risks of leakage as the other sequestration
processes.

4.5 Biofixation

A biological and ecological CO2 sequestration is biofixation by microalgae: utilization of

cyanobacteria and microalgae to capture CO2 by photosynthesis process. These biological
organisms grow converting light, heat and carbon dioxide to useful products, such as
carbohydrates, and oxygen by the following reaction:

6CO2(aq) + 6H2O(l) + light + heat → C6H12O6(aq) + 6O2(g)

Aquatic biomass presents a more photosynthetic efficiency (6-8%) than that of terrestrial
(1.8-2.2%). In addition aquatic biomass has an easy adaptability to grow in different conditions,
either in fresh or marine waters, and in a wide enough range of pH.
Therefore some research has devoted to study the CO2 biofixation. This system consists in
a bioreactor operating in such conditions that ensure an optimal microalgae growth using CO2
emitted by power plants and wastewater which supply the amount of required nutrients [14].
J. A. V. Costa et al. [15] have studied the photosynthetic microorganisms Scenedesmus
obliquus and Spirulina sp. in serial tubular photobioreactors for determining carbon dioxide fixation
and their resistance to carbon dioxide limitation and excess.

Figure 4.5/1 Spirulina sp.

They found that both Spirulina sp. and S. obliquus can grow in media supplied with air
containing 12% of CO2, thus these organisms could be used to sequester the CO2 produced by
flue gases from power stations.

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 It is very important to find the correct CO2 concentration for the microalgae growth. In fact
the concentration of carbon dioxide in a culture media should never be less that required for the
maximum growth rate of the culture but should not be so high as to exceed the maximum tolerated
by a particular organism.
E.Arato et al. [16] have also considered the case of the alga Spirulina Platensis (S.P.)
which is used in the production of beauty cream.
The ability of S.P. to grow on carbon dioxide or a mixture of bicarbonate/carbonate has
been compared under light irradiation conditions. Inorganic carbon is preferentially assimilated in
the form of bicarbonate and its utilization efficiency depends on the pH (8.5–10.5) of the final
biomass level.
Feeding Spirulina with a greater quantity of CO2 allows it to grow better. Besides, this type
of feeding requires a pH correction only during the start-up, because afterwards the growing
Spirulina neutralises the acidity caused by CO2 bubbling.
Another important parameter in a bioreactor is the distribution of light flux which affects the
CO2 uptake rate.
The plants consume CO2 for photosynthesis until saturation point, when there is equilibrium
between photosynthesis and breathing, but a higher light intensity requires a higher CO2 molar
concentration to reach saturation. Therefore, if there is a higher light intensity, a plant can absorb a
higher CO2 molar concentration.
A great advantage of biofixation is that the produced biomass by this system can be used to
obtain products used in pharmacy or in cosmetic, biodiesel, biogas, etc.
Moreover the isolation of microalgae from lakes or ponds close to coal or oil fired power
plants could be a useful strategy for obtain microorganisms tolerant to the conditions prevalent in
the area, so they could be able to grow in the presence of combustion gases [17].
It could be possible to feed to bioreactor CO2 gas separated from flue gas or flue gas as it
is directly. The latter is an advantageous method because of energy saving, however normally
there are problems of high temperature and the presence of NOx and SOx.
K. Maeda et al. [18] have found a microalgae (Chorellu sp. T-I) which can be successfully
cultivated even in a severe environment with the presence of SOx and NOx.
However despite 50 years of development of closed-system photo-bioreactor systems,
commercial viability has not yet been achieved. At present the costs are still high, for example
open pond systems produce around 100 t of biomass annually at a cost of around USD
$10,000/metric ton [11].

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4.6 Risks

CO2 storage is not well-known system yet. The diffusion of CO2 via various pathways
cannot be fully excluded.
A very limitated part of CO2 will neither dissolve in underground water nor will it chemically
or physically combine with the caprock. This part will then exist as a separate phase which might
escape from geological formations through the following pathways:

the pore system in low-permeability cap rocks such as shales, if the capillary entry pressure at
which CO2 may enter the caprock is exceeded;

openings in the cap rock or fractures and faults;

wells which penetrate the storage formations.

Figure 4.6/1 Some potential escape routes for CO2 injected into saline formations [19]

Since the CO2 will be stored in rock formation that were able to retain fluids for millions of
years, the main risk of leakage is that CO2 escapes from poorly completed and/or abandoned pre-
existing wells, typically used for oil and gas. Therefore these wells must be sealed in order to
ensure that they do not provide pathways for the leakage of CO2.
For this reason research is currently underway to better determine the effect of CO2 on
materials such as cement used to seal such wells [2].
The consequences of CO2 escape can be on local or global scale:

local scale damage:

- direct effect in the terrestrial and marine ecosystem;
- effect of dissolved CO2 on groundwater;

global scale damage: leakage of large amount of CO2 from storage into the atmosphere might
impede the decrease of greenhouse gases level.

Impacts to ecosystem

Stored CO2 may affect the flora and fauna with which it comes into contact. Impacts may be
expected both on microbes in the deep subsurface and on plants and animals in shallower soils
and at surface.
Elevated CO2 concentration for long time in vegetation areas cause death. Concentrations
above 5% may be dangerous for vegetation and when concentration is higher than 20%, CO2
becomes phytotoxic. Carbon dioxide can cause death of plants through ‘root anoxia’, together with
low oxygen concentration [3].

83
Impacts to groundwater

As CO2 migrates from a storage formation to surface, increase in dissolved CO2

concentration may occur and potentially affect the shallow groundwater used for potable water and
industrial and agricultural needs.
Dissolved CO2 forms carbonic acid, alters the solution pH and can mobilize toxic metals,
sulphate or chloride. In the worst case, water contamination could reach so high dangerous levels
that the use of groundwater for drinking and irrigation must be interdict.
However the contamination of shallow groundwater is very rare. Moreover in the unlikely
event that CO2 would migrate until shallower groundwater, seismic monitoring, groundwater
analysis, and chemical tracers can detect it [2].

Seismicity

Storage sites should be selected because they are inherently stable, have effective seals
and are located away from areas of seismic instability. Therefore CO2 storage will be sited away
from earthquake faults, but even earthquakes appear unlikely to cause leaks. Seals in a properly-
designed project are very effective and most of the energy of earthquakes tends to spread at
depths much shallower than where CO2 would be stored.
For example in October 2004, a major earthquake measuring 6.8 on the Richter scale
occurred 20 kilometres from the injection site of a CO2 geologic storage site at Nagaoka, Japan.
This project stored CO2 in a saline formation at 1100 meters of depth. The storage
formation was monitored before, during and after the earthquake and no leakage has ever been
detected [2].
Moreover the results of seismic monitoring of CO2 injection into the Sleipner field
demonstrate that the gas has accumulated in thin layers, and that these have so far remained
localised [20].
Further evidence that earthquakes would not cause leaks is that a large number of
producing oil and gas fields in California are near seismically active faults. They have much the
same trapping mechanisms as CO2 storage and earthquakes over many years have not caused
them to leak.
However underground injection of CO2 into porous rock at pressures higher than formation
pressure could cause fracturing and movement along faults. CO2 storage might induce structural
changes in geological formations and alteration in thermodynamic proprieties causing micro-
seismic activity.
Induced local fracturing and fault activation could create or enhance fracture permeability,
so providing pathways for CO2 migration and could also provoke earthquakes large enough to
cause damage.
In the early 1960s low levels of seismic activity induced by fluid injection was noticed in
underground natural gas storage facilities. Since then, most natural gas storage facilities have
been sited away from potentially active faults [2].

Monitoring

Since CO2 is to be stored in reservoirs for many years, it is fundamental to ensure that
there is a low risk that it could migrate out of the storage site.
It is necessary a geologic analysis of the storage site, safe operating practices, careful
monitoring of the underground CO2 during injection and continued monitoring for some time
afterward so that any undesirable CO2 movement can be readily detected and fixed.
Reliable geological surveys can prove the presence of impermeable rock barriers and the
capability of deep rock formations to hold fluids.
It is also taken into account that techniques and equipments for injection are already widely
used in the oil and gas industry, although more advanced technologies for CO2 injection are also
being developed.
Besides, CO2 is safer to handle than the oil and gas because it is not flammable, explosive
or toxic. Since CO2 is colourless and odourless, however, instrumentation is required to detect it.

84
 In any case industry already has substantial experience handling it and using such
instrumentation.
A number of reservoir modelling studies have been carried out and new developments on
monitoring are being done in order to satisfy a requirement for low-cost, long-term observations by
instruments that can be left in place for a number of decades and will operate semi- autonomously,
including borehole and sub-sea CO2 sensors and pH sensors. There is also a need to develop
passive seismic monitoring using multiple long-term sensors, such as resistivity or gravimetric
monitoring.

References

[1] C. Stewart, M. Hessami, A study of methods of carbon dioxide capture and sequestration–the
sustainability of a photosynthetic bioreactor approach; Energy Conversion and Management 46 (2005)
403-420.
[2] Geological Storage of Carbon Dioxide, published by IEA Greenhouse Gas R&D Programme (2008).
[3] European Technology Platform for Zero Emission Fossil Fuel Power Plants, Working group n. 2: CO2
Use and Storage, May 2006.
[4] IPCC, 2005. IPCC special report on carbon dioxide capture and storage. Prepared by working group III
of the Intergovernmental Panel on Climate Change.
[5] A “down-to-earth” solution to climate change, European Carbon Dioxide Network (CO2net).
[6] E. P. Robertson, Economic analysis of carbon dioxide sequestration in powder river basin coal;
International Journal of Coal Geology 77 (2009) 234-241.
[7] A. Kronimus, A. Busch, S. Alles, D. Juch, A. Jurisch, R. Littke, A preliminary evaluation of the CO2
storage potential in unmineable coal seams of the Munster Cretaceous Basin, Germany; International
journal of greenhouse gas control 2 (2008) 329-341.
[8] S. Bachu, Carbon dioxide storage capacity in uneconomic coal beds in Alberta, Canada: Methodology,
potential and site identification; International journal of greenhouse gas control 1 (2007) 374-385.
[9] Ocean Storage of CO2, produced by IEA Greenhouse Gas R&D Programme (1997).
[10] A. Yamasaki, M. Wakatsuki, H. Teng, Y. Yanagisawa, K. Yamada, A new ocean disposal scenario for
anthropogenic CO2: CO2 hydrate formation in a submerged crystallizer and its disposal; Energy 25
(2000) 85–96.
[11] H. Yang, Z. Xu, M. Fan, R. Gupta, R. B. Slimane, A. E. Bland, I. Wright, Progress in carbon dioxide
separation and capture: A review; Journal of Environmental Sciences 20(2008) 14–27.
[12] D. N. Huntzingera, J. S. Gierkeb, L. L. Sutterc, S. K. Kawatrad, T. C. Eisele, Mineral carbonation for
carbon sequestration in cement kiln dust from waste piles; Journal of Hazardous Materials (2009).
[13] R.Lal, Soil Carbon sequestration to mitigate climate change, review; Geoderma 123 (2004) 1-22.

[14] M. Aresta, A. Dibenedetto, G. Barberio, Utilization of macro-algae for enhanced CO2 fixation and biofuels
production: Development of a computing software for an LCA study; Fuel Processing Technology 86
(2005) 1679– 1693.
[15] M. G. de Morais, J. A. Vieira Costa, Biofixation of carbon dioxide by Spirulina sp. and Scenedesmus
obliquus cultivated in a three-stage serial tubular photobioreactor; Journal of Biotechnology 129 (2007)
439–445.
[16] M. Lusardi, B. Bosio, E. Arato, An example of innovative application in fuel cell system development:
CO2 segregation using Molten Carbonate Fuel Cells; Journal of Power Sources 131 (2004) 351–360.
[17] M. G. de Morais, J. A. Vieira Costa, Isolation and selection of microalgae from coal fired thermoelectric
power plant for biofixation of carbon dioxide; Energy Conversion and Management 48 (2007) 2169–
2173.
[18] K. Maedal, M. Owadai, N. Kimura, K. Omata, I. Karubd, CO2 fixation from the flue gas on coal-fired
thermal power plant by microalgae; Energy Conversion and Management 38, (1995) 717-720.
[19] European Technology Platform for Zero Emission Fossil Fuel Power Plants, Working group n. 4: Making
Carbon Capture and Storage Happen in Europe: Markets, Policy and Regulation, September 2006.
[20] A Vision for Zero Emission Fossil Fuel Power Plants, report by European Technology Platform for Zero
Emission Fossil Fuel Power Plants, 2006.

85
5. COSTS

Since power plants with CCS&T technology have not been built yet at a full scale, the cost
estimation of these systems cannot be made with a high degree of confidence at this time. The
performance and cost of current and future CCS&T technology components and integrated system
still remain uncertain.
In addition CCS&T costs vary considerably from country to country. In general the wide
range of costs for CCS&T components is due to different conditions:

the design, operating and financing characteristics of the power plants;

the type and costs of used fuel;

the required distances, terrains and quantities involved in CO2 transport;

the type and characteristics of the CO2 storage.

Some studies of CCS&T costs are reported in the following tables.

CCS&T system components Cost range Remarks

Capture from a coal or gas-fired Net costs of captured CO2, compared
15-75 US$/tCO2 net captured
power plant to the same plant without capture.
Per 250 km pipeline or shipping for
Transportation 1-8 US$/tCO2 net transported mass flow rates of 5 (high end) to 40
-1
(low end) MtCO2 yr .
Excluding potential revenues from
Geological storage 0.5-8 US$/tCO2 net injected
EOR or ECBM.
Including offshore transportation of
Ocean storage 5-30 US$/tCO2 net injected
100-500 km.
Range for the best case studied. It
Mineral carbonation 50-100 US$/tCO2 net injected includes additional energy use for
carbonation.
Tab. 5/1 2002 Cost ranges for the components of a CCS&T system applied to a power plant [1]

NGCC PC IGCC
Power plant system
(US$/kWh) (US$/kWh) (US$/kWh)
Without capture (reference plant) 0.03-0.05 0.04-0.05 0.04-0.06
With capture and geological storage 0.04-0.08 0.06-0.10 0.05-0.09
With capture and EOR 0.04-0.07 0.05-0.08 0.04-0.07
Tab. 5/2 Costs of CCS&T: production costs of electricity for different types of power generation [1]

86
 NGCC plant PC plant IGCC plant
Cost measures Range Rep.(*) Range Rep. (*) Range Rep. (*)
Low–High value Low–High value Low–High value
Plant efficiency with capture (%) 47-50 48 30-35 33 31-40 35
Capture energy requirement
11-22 16 24-40 31 14-25 19
(% increase input/kWh)
Total capital requirement
515-724 568 1161-1486 1286 1169-1565 1326
without capture (US$/kWh)
Total capital requirement
with capture 909-1261 998 1894-2578 2096 1414-2270 1825
(US$/kWh)
Percent increase in capital cost
64-100 76 44-74 63 19-66 37
with capture (%)
Percent increase in cost of
electricity production (COE) 37-69 46 42-66 57 20-55 33
with capture (%)
Cost of net CO2 captured
37-74 53 29-51 41 13-37 23
(US$/tCO2)
(*)Representative value is based on the average of the values in the different studies.
Tab. 5/3 Summary of CO2 capture costs for new power plants based on current technology [1]

Scenario Module combination Distance [km] Quantity [MtCO2/y] Cost [€/tCO2]

Pipeline on shore 110 1.0 1.03
Railway 100
Intermediate storage 1.0 8.58
Water carrier 500
Small-scale
Pipeline on shore 100
start-up
Intermediate storage 1.0 5.61
Water carriers 500
Pipeline on shore 100
1.0 17.75
Pipeline off shore 500
Pipeline on shore 110 10 0.95
Pipeline on shore 100
Large-scale
Intermediate storage 10 1.52
single-source
Water carriers 500
Pipeline on shore 100
10 2.93
Pipeline off shore 500
Pipeline network on shore 230
40 1.96
Pipeline network off shore 500
Coordinated
Pipeline network on shore 230
network
Intermediate storage 40 1.79
Water carriers 500
Tab. 5/4 Module combinations evaluated in the different scenarios [2]

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 Tab. 5/5 Storage costs by depths of reservoir (in €/tCO2) [3]

As above seen the cost of capture is the largest cost component. Among power plants, the
most expensive depends on vary condition. If the fed fuel is natural gas, it is more efficient to apply
the post combustion technology than the pre-combustion capture, whereas if the feed is coal, an
IGCC plant with pre-combustion technology instead of equipping a PC plant with post-combustion
capture could be lead to lower avoidance cost.
Anyway capture costs can be minimised by utilising exhaust gas streams with high-purity
CO2, which are emitted by several industrial processes and transport costs can be minimised if the
reservoir is close to the source.
In addition where it is possible applied CO2-EOR and the injection of CO2 into oil reservoirs
can enhance oil recovery, storage could be realised at small (or even negative) cost [4].
Whereas CO2-ECBM often results unprofitable without some additional economic incentive,
above all when unmineable coal basin has low methane content. The low volumetric recoveries are
not sufficient to offset the costs of CO2 capture and injection [5].
However in the future the costs of CCS could be reduced by research and technological
development and as result of “learning-by-doing”.
The capture costs could decrease by 20-30% thanks to new technologies that are still in the
research or demonstration phase [1].
For a European scenario that assumes 80 to 120 CCS&T projects in 2030, the total CO2
abatement cost for the CCS&T mature commercial plant could be around € 30-45 per tonne.
Alternatively, for a global scenario with 500 to 550 CCS&T projects in 2030, this would be
reduced by around € 5 per tonne CO2 [6].

* Carbon price for 2015 from 2008-15 estimates from Deutsche Bank, New Carbon inance, Soc.Gen, UBS, Point Carbon,
assumed constant afterwards.
Fig. 5/1 Forecast of development of CCS&T costs and carbon price [6]

88
 Although most studies suggest that CCS&T systems begin to deploy at a significant level
when CO2 prices begin to reach approximately 25–30 US$/tCO2, low-cost capture possibilities (e.g.
in hydrogen and ammonia processes) in combination with short (<50 km) transport distances and
storage options that generate revenues (such as EOR) can lead to the limited storage of CO2 (up
to 360 MtCO2 yr-1) with low or no incentives.
Furthermore CO2 capture can be applied to power plants fuelled with biomass or fossil-fuel
plants with biomass cofiring, leading to lower or negative CO2 emissions which could reduce the
costs for this technology, depending on the market value of CO2 emission reductions [1].
In addition the European Union is evaluating a number of incentives to allow the CCS&T
deployment such as including it within EU Emission Trading Scheme (see § 6.1).

References

[1] IPCC, 2005. IPCC special report on carbon dioxide capture and storage. Prepared by working group III
of the Intergovernmental Panel on Climate Change.
[2] R. Svensson, M. Odenberger, F. Johnsson, L. Stromberg, Transportation systems for CO2––application
to carbon capture and storage; Energy Conversion and Management 45 (2004) 2343-2353.
[3] S. Bode, M. Jung, On the Integration of Carbon Capture and Storage into the International Climate
Regime; Hamburgisches Welt-Wirtschafts-Archiv (HWWA) Hamburg Institute of International
Economics, Discussion Paper 303, 2004.
[4] K. Damena, A. Faaija, F. van Bergen, J. Gale, E. Lysen, Identification of early opportunities for CO2
sequestration—worldwide screening for CO2-EOR and CO2-ECBM projects; Energy 30 (2005) 1931–
1952.
[5] E. P. Robertson, Economic analysis of carbon dioxide sequestration in powder river basin coal;
International Journal of Coal Geology 77 (2009) 234-241.
[6] Carbon Capture & Storage: Assessing the Economics, report written by McKinsey&Company.

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6. INSTITUTIONS AND RESEARCH CENTRES

6.1 European Union

Recently European Commission is very interested on carbon capture and storage.
The Commission has proposed the realization of 12 large-scale demonstration plants by
2015 so that CCS&T technology could become commercially viable by around 2020. It will
determine the most suitable way to support the design, construction and operation of these
demonstration plants.
The Commission considers that a clear long-term framework is necessary to facilitate a
smooth and rapid deployment of CCS&T process and to ensure that CO2 capture, sequestration
and transportation is an available mitigation option and it is done safely and responsibly.
In addition in Europe a coordinated CO2 infrastructure that serves a number of capture and
storage operations may be more efficient than leaving transport logistics to each individual project
or country. Therefore the role of EU could be very important to coordinate a development of a CO2
pipeline network.
Moreover in the projects demonstration and up-scaling phase incentives are needed to
allow the technology deployment.
In the demonstration phase incentives bring down production costs while increasing
adoption, whereas in the up-scaling phase, the technology have gained a certain momentum, and
incentives can induce more users and investors to take on the technology. At this stage, the costs
of the technology are sufficiently low, but incentives are needed to advance the diffusion of the
technology.

For these reasons, in January 2007 the European Commission presented a Communication
to the Council and European Parliament on Sustainable Power Generation from Fossil Fuels:
” Aiming for Near- Zero Emissions from Coal after 2020”.
The Commission had noted that “it believes that by 2020 all new coal-fired plants should be
built with CCS” and it explored three possible incentives:

Establishing a more favourable long-term investment framework by ‘‘ensuring the relative

perpetuity of the emissions trading scheme and by facilitating commercial financing and risk-
sharing instruments’’;

Developing EU CO2 storage sites and pipelines for multi-user access or projects for CO2
infrastructure development at Member State level;

‘‘Adopting legally binding measures to regulate maximum allowed CO2 emissions per kWh
after 2020 and/or introduce a timed phase-out (for instance by 2050) of all high CO2 emitting
(i.e. non-CCS) electricity generation’’.

In November 2007 the Commission presented a Communication entitled: "A European

strategic energy technology plan (SET Plan) - Towards a low carbon future". This plan aims to
accelerate the development and deployment of cost-effective low carbon technologies. It
comprises measures relating to planning, implementation, resources and international cooperation
in the field of energy technology [1].
And yet in January 2008 the Commission produced a draft of proposed legislative
measures called the ‘‘climate action and renewable energy package’’. As part of this package the
Commission proposed a Directive on the geological storage of carbon dioxide, along with a
detailed Impact Assessment and a statement on supporting early demonstration of sustainable
power generation from fossil fuels. The proposed Directive could establish a legal framework to
regulate the storage of captured CO2 in the EU. It aims to cover the entire life-cycle of a geological
storage site, from site selection and operation requirements, through to closure obligations and the
transfer of post-closure responsibilities to competent authorities of Member States, but only after
there is near certainty that the possibility of leakage has been reduced to zero.

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 The Impact Assessment used a range of analytical tools to assess the costs and benefits of
different policy options for CCS&T deployment [2]:

• No policy change;
• Including CCS&T in the EU Emission Trading Scheme (ETS);
• Realizing CCS&T obligation at:
- new coal power plant from 2020;
- new coal and gas plant from 2020;
- new coal from 2020 and retrofit of coal built from 2015;
- new coal and gas from 2020 and retrofit of plant built from 2015;
• Including CCS&T in EU ETS with a subsidy.

The Commission came down in favour of the option of inclusion of CCS&T within the EU
ETS, and argues against a CCS&T mandate or subsidy. The conclusion relies upon the ability of
the EU ETS to provide a sufficiently strong economic incentive for CCS&T development.

In the Impact Assessment it was also discussed the way to ensure right implementation of
the framework requirement for a safe and secure CO2 storage.
The competent authority, responsible for the issues of permit, would submit the draft permit
decision to the Commission, which would refer it to a Scientific Panel.
The Scientific Panel (SP) shall provide an opinion on whether the assessment of the
security of the storage site is robust, and whether also all other relevant permit requirements
specified in the Directive are met. Thus, the SP will consider the site selection, the proposed
operation, monitoring and control plan, the proposed plan for closure and after-care, the adequacy
of financial securities, and the competency and reliability of the storage site management.
Based on its assessment, the Commission will issue an opinion to the member state on
draft permit, which shall be taken into account in making the permitting decision.
The Scientific Panel is intended to have 8 permanent and 2 associated members and would
include geological experts, as well as people with experience in permitting analogous activities (for
instance landfills, natural gas storage and mining).

In realizing a legal framework, the Commission also intended to clarify existing legislation
and remove barriers that currently restrict the large-scale development of CCS facilities,
particularly in relation to waste, water and industrial emissions legislation [2].
For instance the Water Framework Directive 2000/60/EC prohibits injection into saline
aquifers except in certain cases and in the Landfill Directive 1999/31/EC the prohibition on injection
of liquid waste could be interpreted as prohibiting CO2 injection into geological formations (CO2 is
injected as a supercritical liquid).
Removing these barriers will complement similar work in the international context. The
London Convention (on dumping of wastes and other material in the marine area) was amended in
November 2006 and the OSPAR Convention on the protection of the North East Atlantic is been
amended to allow CO2 storage offshore.
At the same time there is some legislation that could serve – via modification – to enable
the development of risk assessment and management controls for CCS&T activities [3]:

EIA Directive (Land use planning legislation);

IPPC Directive and Emissions Trading Directive (Industrial pollution control legislation);

Seveso II Directive (Major-accident hazard legislation);

Environmental Liability Directive (Liability legislation);

Landfill Directive, Transfrontier Shipment of Waste Regulation (Waste management
legislation);

Indirectly via legislation such as the Habitats Directive and Worker Safety Directive.

European Commission has also set up to some project or research programs in order to
contribute to CCS&T development.

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 Acceptance of CO2 Capture, Storage, Economics, Policy and Technology (ACCSEPT)
project is funded under the Sixth Framework Programme. From January 2006 to December 2007 it
identified and analysed the main factors which have been influencing the emergence of CO2
capture and geological storage within the European Union.
These factors have been analysed through interviews, a large-scale questionnaire and
discussions in two stakeholder workshops.
The ACCSEPT project studied a number of critical questions which need to be addressed
before CCS&T could be reliably, effectively, efficiently, equitably and safely implemented within the
EU [2].

As previously mentioned, the Commission has proposed the construction of some

demonstration plants.
Therefore in order to move in research, development and demonstration activities, in 2005
Technology Platform for Zero Emission Fossil Fuel Power Plants (ZEP) was funded.
ZEP includes European energy industry, research community, Non-Governmental
Organisations, Member States and the European Commission.
It aims to use fossil fuels in a sustainable way and to lead to the successful deployment of
Zero Emission Fossil Fuel Power Plants over the next fifteen years.
The activities of ZEP take into account time, funding, the environment, public acceptance,
and the fiscal and regulatory issues [4].
It should be primarily useful to avoid duplication of effort and to allow coordination and
knowledge sharing, both among activities undertaken in Europe as well as between European
activities and those in third countries.
ZEP has developed by means of Working Group a Strategic Research Agenda (SRA) and a
Strategic Deployment Document (SDD) to guide the research and demonstration activities needed
to achieve the platform's goals.
In 2007 ZEP presented a vision for an EU Flagship Programme of large-scale CCS&T
demonstration projects which will ensure the implementation of complete CCS&T value chains –
from the capture of CO2 at large emission sources to storage sites.
In 2008, ZEP has made an in-depth study into how such a demonstration program could
work in practice, from every perspective – technological, operational, geographical, political,
economic and commercial – backed up by robust R&D activity [5].

Moreover for stimulating the effective demonstration of sustainable fossil fuel technologies
in commercial power generation, the Commission has launched a European Industrial Initiative on
CO2 capture, transport and storage starting in 2008. This Initiative will also aim at addressing in an
integrated manner the need for continuous research and for increasing public awareness and
acceptance [6].
To secure the effectiveness of the Initiative and to create and animate a network of CCS&T
demonstration projects, the Commission set up a Support Action under the Framework Programme
7 (€ 1.85 billion between 2007 and 2013) [7].
Public awareness actions and interaction with partners in third countries undertaken in a
coordinated manner will be more cost-efficient and have higher impact, providing clear benefits for
all projects.
In addition since project characteristics such as the portfolio of capture and storage
technologies, geographical distribution, and costs are important in demonstrating CCS&T, the
Commission considers very useful to have among the demonstrations combinations of various
capture and storage activities [8].

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 Country Power plant Capacity Storage Start Capital Project Parties
(MWe)
IGCC 1000 Aquifer? 2011 € 1.7bn Siemens Siemens
Germany PC + oxyfuel 300 Aquifer? 2102-2015 ? Schwarze Vattenfall
Pumpe
IGCC 450 Aquifer? 2014 < € 1bn RWE RWE
Netherlands IGCC multifuel 1200 Gas field/EGR 2011 1 G€ Magnum Nuon
NGCC 385 EOR? 2009 ? Karsto Naturkraft
Norway NGCC 860 EOR 2011 ? Tjeldbergod Shell,
den Statoil
IGCC 1000 Aquifer 2012 ? GE GE, Polish
Poland
utility
IGCC 800 EOR? 2009 $ 1.5bn Teeside Progressive
Energy
IGCC 900 EOR? 2010 ? Hatfield Powerfuel
NG to H2 350 EOR 2010 $0.6bn Peterhead BP, SSE
UK Miller
IGCC 450 Aquifer/gas 2011 ? Killingholme E.ON
field/EGR
SCPC, retrofit 500 EOR/EGR? 2011 ? Ferrybridge SSE
SCPC 1000 EOR? 2016 £0.8bn Tilbury RWE
Tab. 6.1/1 Proposed large-scale commercial projects of CO2 capture
from power plants and storage (OECD/IEA, 2006) [8]

Since it is estimated that the demonstration plants could cost € 7-12 billion, they obviously
need incentives.

Fig. 6.1/1 Additional funding required for EU Demonstration Programme

of 10-12 CCS&T projects.

Five groups of incentives are discussed [8]:

• the EU Emissions Trading Scheme (see below);

• Member-State-based public financial support through investment support, feed-in subsidies or
a CO2 price guarantee;
• an EU-level low carbon portfolio standard with tradable certificates. It could also be an effective
instrument to stimulate the introduction of CCS&T in the EU and it guarantees that
environmental targets will be achieved if regulations are designed well. In addition a trading
component could be introduced to add flexibility and lower overall system costs, e.g. for
Member States with limited CO2 storage capacity. The disadvantages of this system are the
complexity of the standard and the trading regime;
• an EU-wide CCS&T obligation for all new fossil-fuel-based power capacity from 2020 onwards;
• public-private partnerships fed predominantly by national budgets and private sector
investment. They could be used for realizing large pipeline infrastructure for the transportation
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 of CO2. Partnerships for CO2 piping may be modelled on Trans-European Energy Networks.
Financial institutions as the European Investment Bank (EIB) and the European Bank for
Reconstruction and Development (EBRD) for Eastern Europe, could assist in financing a
network. The EIB already finances, through loans up to 50% of the total cost, many projects in
the Trans-European Energy Network (TEN). The latter aims to interconnect and develop trans-
European networks for transporting electricity and gas.

However the choice for any form of aid may be made on a case-by-case basis, depending
on the viability of a particular project and the magnitude of required funding.

Emission Trading Scheme (ETS)

The European Directive 2003/87/EC established a scheme for greenhouse gas emission
allowance trading within the Community in order to promote reduction of greenhouse gas
emissions in a cost-effective and economically efficient manner. This Directive entered into force
on 25 October 2003.
Therefore it is possible an emission allowance trading in relation to own targets. A company
which will produce less greenhouse gas emissions respect to its target could sell its allowance to a
company that, on the contrary, will increase its emissions.
Traded allowances in the EU ETS will not be printed but held in accounts in electronic
registries set up by Member States. All of these registries will be overseen by a Central
Administrator at EU level who, through the “Community independent transaction log”, will check
each transaction for any irregularities. In this way, the registries system keeps track of the
ownership of allowances in the same way as a banking system keeps track of the ownership of
money [9].
There are three trading period in ETS, the first one from 2005-2007, the second one from
2008-2012, and the third one will start in 2013.
As above said, the EU ETS is considered to be one of the principal policy instrument to
incentivise CCS&T. Thus in the Phase II of ETS, CCS&T has became to be recognized as system
of emissions reduction.
In the “Proposal for a Directive of the European Parliament and of the Council amending
Directive 2003/87/EC” it can be read: “In view of the long-term potential for emissions reductions
from CCS, and pending the entry into force of Directive 2008/xx/EC on the geological storage of
carbon dioxide, installations undertaking the capture, transport and geological storage of
greenhouse gases should be included in the Community system. While Article 24 offers the
appropriate legal framework for unilateral inclusion of such installations pending the entry into force
of the said Directive, activities concerning capture, transport and geological storage of greenhouse
gas emissions should be explicitly mentioned in Annex I of the Directive, in order to provide clarity.
With a view to providing the necessary incentives for geological storage of emissions, there
would be no need to surrender allowances for emissions stored. However, no free allocation
should be given for capture, transport or storage of greenhouse gas emissions”. [10].
However, there are some issues to consider for including CCS&T in the ETS, they mainly
are the following [3]:

to recognise captured CO2 as non-emitted and thus absolve the responsibility of the operator
to surrender allowances for non-emitted CO2 which is transferred outside of the installation
boundary;

to ensure that any emissions of CO2 across the chain is accounted for in order to maintain the
environmental integrity of the scheme.

Furthermore in the second phase combustion, capture, transport, and storage installations
would be opted in as a single installation. However for the post-2012 it will better to opt-in capture,
transport and storage operations as distinct installations under the ETS, so that being able to
immediately take account of leakage in the ETS should be advantageous.

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 In fact the issue is that emissions may leak from the transport and storage network, thus the
quantity of emissions safely isolated from the atmosphere is not necessarily equal to the quantity of
emissions passed from the capture plant to the storage plant.
There are four options for handling this issue [11]:

1) regulate CO2 emissions from transport and storage outside the ETS only;
2) include CO2 emissions from transport and storage within the ETS, but do not regulate
otherwise;
3) combine (1) and (2);
4) combine (1) with another means of compensating for CO2 emissions from capture and storage.

Option 3 would combine the advantages of Options 1 and 2. It would provide regulation on
the selection and management of storage sites so as to minimise leakage, and requirements to
rectify leakage if it occurred. Inclusion under the ETS would ensure that any emissions from
transport and storage, including those from injection and from booster stations, were properly
accounted for, and would provide an incentive to reduce them.
Finally, any leakage that occurs would be accounted for under the ETS, thus avoiding any
overcompensation for CCS&T installations. Thus this option was preferred.

In the EU-ETS exists the Clean Development Mechanism (CDM) which allows to developed
countries to realize an environmental-friendly project in the developing countries, obtaining
greenhouse gases emission credits.
The CDM is, at this time, the only structural incentive for reducing greenhouse gas
emissions in the developing world. Without the potential incentives given by the CDM, CCS&T in
developing countries will only take place sporadically in niche sectors.
Some people consider inclusion of CCS&T within the CDM to be ‘important’ for the future
development of CCS&T; however there are also some opponents.
In fact CCS&T is not ready for market-based deployment; therefore, it is unsuitable for a
market-based mechanism like the CDM and technology should be developed and tested in
industrialised countries first and only after that be implemented in developing countries.
In addition allowing CCS&T within the CDM could risk using developing countries as
‘guinea pigs’ for testing new technologies [2].

Although the EU-ETS is the most cost-effective instrument to reduce greenhouse gas
emissions, at this moment it is very difficult to predict what level of incentives it will provide for
future CCS&T activities. It is also difficult to know whether the “weak” ETS scenario will lead to
sufficient development of CCS&T in the short term because of low incentive levels and the
“innovation market failure”.
If the “strong” ETS scenario would be politically unfeasible, additional instruments on the
EU and the Member State level can be effective in correcting this failure [8].

6.2 Carbon Dioxide Knowledge Sharing Network (CO2NET)

Carbon Dioxide Knowledge Sharing Network (CO2NET) [12] was set up under the 5th
Framework Programme of European Commission. This Network comprises more than 30 of the
major companies and organisations, across Europe, USA and Australia, who are extensively
involved in the development of CCS&T.
The key drivers for CO2NET are the development of CCS&T as a safe, technically feasible,
socially acceptable option to help reduce the effects of human influenced climate change and to
meet the CO2 emission reduction target set by the Kyoto agreement.
The members of CO2NET recognise that knowledge and skills are required and that
building the “people capability” in CCS&T is necessary.
CO2NET now has a niche role in providing education to understand CCS&T in detail across
all its disciplines, to enable sharing of crucial lessons learned and transfer skills to personnel
incoming to CCS&T.
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 Every year the CO2NET Annual Seminar is realized. It has been established as the flagship
event for CCS&T networking in Europe, particularly to share the newest CCS&T knowledge.
The CO2NET thinks it is important that CCS&T engineers, geologists and technologists
meet and talk to present and discuss their actual work.

6.3 Geological Storage of CO2 – European Network (CO2GeoNet)

CO2GeoNet is the European Network of Excellence [13] on geological storage of CO2,
sponsored by the European Commission under the 6th Framework Programme, promoting
research integration within the scientific community to help enable the implementation of CO2
geological storage.
It comprises more than 150 established researchers and postgraduate students, engaged
in enabling the efficient and safe geological storage of CO2 as a solution for clean and climate-
friendly energy production and consumption.
It is a partnership between 13 research institutes that represent 7 European countries, with
a high international profile and critical mass in CO2 geological storage research.
Therefore it is the largest group of researchers in Europe working together on CO2
geological storage.
The Network researchers work together to improve their knowledge about geological CO2
and the tools needed for its safe deployment.
They are involved in many research activities which are structured by Joint Research Areas
and Sub-Areas:

Predictive numerical modelling: to simulate the CO2 fate and storage behaviour during the
injection period and long term abandonment period;

Rock and fluid behaviour experiments: to provide crucial data from laboratory and field
experiments for a better understanding of processes;

Enhanced hydrocarbon recovery: to develop combination of CO2 storage with EHR for
economic viability and early applications;

Monitoring techniques: to develop tools and strategies to control the storage behaviour, give
early warning, and verify the quantities of stored CO2;

Risks and uncertainties: to develop assessment and remediation methodologies of possible
local impacts on ecosystems and humans;

Geological models: to integrate all the site data from the reservoir up to the surface into a
geological earth model, with visualisation facilities.

In addition CO2GeoNet can also:

offer training and capacity building for the scientists and engineers who will be needed to
enable CO2 storage;

provide scientific advice and project proposal audits;

engage with stakeholders and help address their concerns and needs.

Moreover the Network deals of raising public awareness about the geological storage of
CO2.

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6.4 Intergovernmental Panel on Climate Change (IPCC)

The Intergovernmental Panel on Climate Change (IPCC) [14] was set up by the World
Meteorogical Organization (WMO) and the United Nations Environment Programme (UNEP) in
1988. Its tasks are:

to assess available scientific and socio-economic information on climate change and its
impacts and on the options for mitigating climate change and adapting to it;

to provide, on request, scientific/technical/socioeconomic advice to the Conference of the
Parties (COP) to the United Nations Framework Convention on Climate Change (UNFCCC).

From 1990, the IPCC has produced a series of Assessment Reports, Special Reports, and
Technical Papers. Its latest major report is the “Climate Change 2007”; it leads the organization to
be honoured with the Nobel Peace Prize at the end of that same year.
At COP7, a draft decision was taken to invite the IPCC to write a technical paper on
geological storage of carbon dioxide. Thus, at its 20th Session in 2003 in Paris, the IPCC decided
to develop a Special Report on Carbon dioxide Capture and Storage.
This volume has been produced by Working Group III of the IPCC and focuses on carbon
dioxide capture and storage (CCS) as an option for mitigation of climate change.
As is usual in the IPCC, this report has achieved by the knowledge, enthusiasm and
cooperation of many hundreds of experts worldwide, in many related but different disciplines.

6.5 National Energy Technology Laboratory (NETL)

The National Energy Technology Laboratory (NETL) [15], part of DOE’s national laboratory
system, is owned and operated by the U.S. Department of Energy (DOE). NETL supports DOE’s
mission to advance the national, economic, and energy security of the United States.
NETL implements a broad spectrum of energy and environmental research and
development (R&D) programs that will return benefits for generations to come.
NETL has expertise in coal, natural gas, and oil technologies, contract and project
management, analysis of energy systems, and international energy issues.
In addition to research conducted onsite, NETL’s project portfolio includes R&D conducted
through partnerships, cooperative research and development agreements, financial assistance,
and contractual arrangements with universities and the private sector.
NETL manages a portfolio of laboratory and field R&D focused on technologies for reducing
greenhouse gas emissions and controlling global climate change. Most efforts focus on capture
and storage of carbon dioxide.
In 1997 NETL gave rise to Carbon Sequestration Program. It is helping to develop
technologies to capture, purify, and store CO2 in order to reduce greenhouse gas emissions
without adversely influencing energy use or hindering economic growth.
By 2012, NETL envisions having a technology portfolio of safe, cost-effective, commercial-
scale greenhouse gas capture, storage, and mitigation technologies, leading to substantial
deployment and market penetration.
NETL’s primary Carbon Sequestration research and development (R&D) objectives are:

lowering the cost and energy penalty associated with CO2 capture from large point sources;

improving the understanding of factors affecting CO2 storage permanence, capacity, and
safety in geologic formations and terrestrial ecosystems.

The Carbon Sequestration Program Goal is: “By 2012, develop fossil fuel conversion
systems that offer 90% CO2 capture with 99% storage permanence at less than a 10% increase in
the cost of energy services.”

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 Fig. 6.5/1 Carbon Sequestration Program Goal

The Carbon Sequestration Program involves three key elements:

• Core R&D: it is driven by technology needs and is accomplished through laboratory and pilot-
scale research aimed at developing new technologies and new systems for GHG mitigation. It
contains five focal areas for research and technologies development:
- Capture;
- Geological Storage;
- Monitoring, Verification and Accounting;
- Simulation and Risk Assessment;
- CO2 Use/Reuse;
• Infrastructure: it includes the Regional Carbon Sequestration Partnerships (RCSPs) and other
large-scale projects where validation of various CCS&T technology options and their efficacy
are being confirmed. RCSPs is a government/industry cooperative effort aimed to develop
guidelines for the most suitable technologies, regulations, and infrastructure needs for CCS&T
in different regions of the U.S. and Canada. The RCSPs consists of three phases:

- the Characterization Phase (2003): potential sites for pilot-scale testing were identified;
- the Validation phase (2008): pilot-scale CO2 injections are being conducted;
- the Development phase: large-volume sequestration tests are scheduled, to begin to
demonstrate the potential to store CO2 emissions for hundreds of years.

Technologies are being validated at test sites in the United States and Canada, and ongoing
data collection is confirming geologic and terrestrial sequestration capacity and effectiveness;
• Global Collaborations: DOE participates in international projects and also in other international
efforts to advance CCS&T such as the Carbon Sequestration Leadership Forum (CSLF), North
American Energy Working Group, and Asian-Pacific Partnership.
U.S. technological advances and expertise in sequestration are also being shared in initiatives
such as the Australian Otway Basin project, the European Union CO2SINK project in Germany,
the Algerian In Salah industrial-scale CO2 storage project, and the IEA GHG Weyburn-Midale
CO2 Monitoring and Storage Project in Canada.
Moreover there is also DOE/NETL’s Existing Plants, Emissions and Capture (EPEC)
program (known as Innovations for Existing Plants - IEP). It is conducting research to develop
post- and oxy-combustion CO2 capture technologies for new and existing coal-fired power plants
that will achieve 90 percent CO2 capture at less than a 35 percent increase in COE and will be
available for commercial deployment beginning in 2020.
The R&D program targets include:

• laboratory-scale testing of advanced concepts for post- and oxy-combustion technologies in

2009;
• multiple pilot-scale field tests in 2010-2012;

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• full-scale field testing of the most promising advanced CO2 capture technologies by 2014-
2016.

Prior to IEP, CO2 emissions control R&D effort was conducted under the Carbon
Sequestration Program, now the latter continues to focus on pre-combustion CO2 emissions
control and geological sequestration.
NETL's pre-combustion CO2 capture R&D goals are:
• initiate at least two slipstream tests of novel CO2 capture technologies that offer significant cost
reductions by 2014;
• initiate large-scale field testing of promising novel CO2 capture technologies by 2018.

Near-term applications of CO2 capture from pre-combustion systems will likely involve
physical or chemical absorption processes (e.g glycol-based solvent: Selexol).

6.6 Carbon Sequestration Leadership Forum (CSLF)

The Carbon Sequestration Leadership Forum (CSLF) [16] is a Ministerial-level international
climate change initiative that is focused on realization of cooperation in order to facilitate
development of cost-effective techniques for capture and safe long-term storage of CO2.
The CSLF is currently comprised of 22 members, including 21 countries and the European
Commission. Membership is open to national governmental entities that are significant producers
or users of fossil fuels and that have a commitment to invest resources in research, development
and demonstration activities in CO2 capture and storage technologies.
The role that the CSLF can play in worldwide effort of deployment of CO2 capture, transport
is stated in Article 1 of its Charter:

to facilitate the development of improved cost-effective technologies for the separation and
capture of carbon dioxide for its transport and long-term safe storage;

to make these technologies broadly available internationally;

to identify and address wider issues relating to carbon capture and storage.

The CSLF is neither a funding agency nor research council. It intends to add value to on-
going and future activity in the field of CO2 capture, transport, and storage through facilitative and
collaborative efforts to close implementation gaps.
The major topics for CSLF projects are:

lower costs;

secure reservoirs;

measurement, monitoring and verification (MMV) technologies.

In 2006 and 2007, the CSLF and the International Energy Agency (IEA) held three
workshops for invited experts from around the world on the topic of near-term opportunities for
CCS&T. Resulting recommendations from these workshops were formally adopted by the CSLF
and were sent forward to G8 leaders.

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6.7 International Energy Agency (IEA)

The International Energy Agency (IEA) [17] is an intergovernmental organisation which was
founded in 1974 during the oil crisis within the framework of the Organization for Economic
Cooperation and Development (OECD) to implement an international energy programme.
This agency includes 28 member countries.
The IEA focuses its efforts to increase energy security by improved energy efficiency,
development of alternative energy sources and research, development and demonstration on
matters of energy supply and use.
With a staff of around 190, mainly energy experts and statisticians from its 28 member
countries, the IEA conducts a broad programme of energy research, data compilation, publications
and public dissemination of the latest energy policy analysis and recommendations on good
practices.
The IEA attends also to Carbon Capture and Storage, for instance it has been working
since 2004 to analyse legal issues surrounding CO2 storage in national and international law. In
the 2007 IEA made a publication, “Legal Aspects of CO2 Storage: Update and Recommendations”,
which provided a compilation of up-to-date information regarding the legal, policy and regulatory
principles for CCS&T.
In 1991 an Implementing Agreement of the IEA was founded, it is called IEA Greenhouse
Gas R&D Programme (IEA GHG) [18].
It is one of the major international research collaborations which assess technologies
capable of achieving significant reductions in greenhouse gas emissions.
The IEA GHG has produced vary information sheets on CCS&T:

Capture and storage CO2;

CO2 capture in Power Generation;

Geological storage of CO2;

Ocean storage of CO2;

CO2 storage in deep salt water reservoirs;

Depleted oil and gas fields for CO2 storage;

Storing CO2 in unmineable coal seams.

In addition the IEA GHG has also produced a topical summary report on the subject entitled
“Putting Carbon Back in the Ground” and has prepared a number of summary reports on CCS&T
that aim to provide more general information on the topic for both stakeholders and the lay public:

Carbon Capture and Storage;

Storing CO2 Underground;

Capturing CO2;

Geologic Storage of Carbon Dioxide;

Natural Releases of CO2.

The IEA GHG has also created a website [19] which provides a collection of resources
related to the Carbon Capture and Storage and aims to:

provide a central source of information on CO2 Capture and Storage Research, Development
and Demonstration (R, D & D);

promote awareness of the extent of R, D & D that is now underway;

facilitate co-operation between projects.

Moreover the IEA, in association with the IEA GHG, University College London’s Carbon
Capture Legal Programme and the Carbon Sequestration Leadership Forum, has created the CCS
Regulators Network to provide policy makers with opportunities to interact with peers in an
objective, neutral forum. The Network involves policy practitioners with a huge variety of expertise,
from local, national and international levels. Network participants present case studies and status

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updates, ask questions, and discuss possible solutions to develop adequate CCS legal and
regulatory frameworks.

6.8 Italian National Institute of Geophysics and Volcanology (INGV)

The Italian National Institute of Geophysics and Volcanology (INGV) [20] is a big European
Institute of geochemical and geophysical monitoring of so-called "CO2 analogues": geological sites
where naturally there is CO2.
INGV was involved in the largest IEA-EU geological storage of CO2 project IEA-EU in
Weyburn, Canada.
INGV in Italy is one of the main promoters of CCS&T and national and international projects
of the highest level for the geological storage of CO2.
Recently INGV has created a specific Functional Unit, called "Fluid geochemistry,
geological storage and geothermal energy", almost exclusively devoted to the geological storage of
CO2 .
INGV is involved in the survey of CESI Ricerca SpA to make a list of areas for the storage
of CO2.
INGV is also involved in many Italian projects of geological storage of CO2 such as ECBM
research at Sulcis coal basin (Sardinia) and geological investigation in Upper Lazio with ENEL.

6.9 SINTEF
The SINTEF Group [21] is an independent research organisation in Scandinavia. Every
year, SINTEF supports the development of many Norwegian and overseas companies via its
research and development activity.
The SINTEF Group solves customers’ problems through research contracts in the following
fields:

health;

information and communications technology;

marine activities;

materials science and applied chemistry;

petroleum and energy;

technology management and building/construction.

SINTEF has approximately 2000 employees, 1300 of which are located in Trondheim
and 450 in Oslo. It has offices in Bergen, Stavanger and Ålesund, in Houston, Texas (USA),
Skopje (the former Yugoslav Republic of Macedonia), Rio de Janeiro (Brasil) and a laboratory in
Hirtshals (Denmark).

In 1986, SINTEF launched the idea of fossil-fuelled gas power plants with integrated CCS
facilities on the Norwegian continental shelf.
Now SINTEF enjoys the status of being one of the world’s leading research centres in CO2
scrubbing technology for gas- and coal-fired power stations.
Scientists at SINTEF Energy Research, SINTEF Materials and Chemistry and SINTEF
Petroleum Research can boast of expertise throughout the entire value chain related to carbon
dioxide capture, transport and storage in geological formations.
These research groups have been awarded important competence-building projects by the
Research Council of Norway, Gassnova and industry.
SINTEF is also one of the most important research centres in the field of CO2 capture and
storage in the EU’s 6th and 7th Framework Programmes, via its management of and participation in
most of the EU’s projects in this area.

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 SINTEF, the Norwegian University of Science and Technology (NTNU) and Aker Clean
Carbon signed an agreement for an eight-year science and development programme called
SOLVit.

SINTEF Energy Research has been involved in CO2-transport research projects since
2000. The research activity spans from in-depth and long-term research addressing fundamental
issues of CO2 behaviour in pipelines to industrially focused conceptual studies related to large-
scale ship and pipelines for CO2 transport. The aim of all the projects is to enable a safe and
efficient design and operation of CO2 transport and injection systems.
In a new project called “CO2 Dynamics”, SINTEF Energy Research will conduct in-depth
research on the single-phase (liquid) and two-phase (gas-liquid) flow of CO2 with impurities.

6.10 CanmetENERGY (Natural Resources Canada)

Natural Resources Canada's CanmetENERGY [22] is the Canadian leader in clean energy
research and technology development with over 450 scientists, engineers and technicians and
more than 100 years of experience.
CanmetENERGY supports Natural Resources Canada's priorities to promote the
sustainable and economic development of natural resources.
It is an energy science and technology organization which works on clean energy research,
development, demonstration and deployment. Its goal is to ensure that Canada is at the leading
edge of clean energy technologies to reduce greenhouse gas emissions and improve the health of
Canadians.
CanmetEnergy manages science and technology programs and services, supports the
development of energy policy, codes and regulations, acts as a window to federal financing and
works with partners to develop more energy efficient and cleaner technologies.

As Canada has an abundant supply of coal, natural gas, and oil reserves, CanmetENERGY
is exploring ways to lessen the environmental impact of fossil fuel combustion technologies, which
currently comprise a substantial portion of the Canadian energy supply. For this reason it is
studying CCS&T technologies.
CanmetENERGY is actively pursuing the research and development of:

• near-zero emissions oxy-fuel technologies for pulverized coal-fired power plants;

• oxy-fuel circulating fluidized bed combustion;
• high-pressure oxy-fuel combustion;
• feasibility studies of oxy-fuel combustion;
• gasification for CCS&T;
• computational fluid dynamics (CFD) modelling of oxy-fuel combustion;
• CO2 capture and compression technologies;
• CO2 post-combustion capture processes;
• advanced power cycles;
• advanced fuel cell research and development.

CanmetENERGY is also involved in funding and collaborative research in the following

areas of CO2 storage:

• CO2 injection;
• monitoring, measurement, and verification;
• CO2 storage sites and opportunities;
• storage integrity;
• capacity estimation through the Technology & Innovation program, PERD, the ecoENERGY
Technology Initiative, and other funding programs.

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 The CCS&T program at CanmetENERGY has many linkages with academia, research
institutions, and industry, and it is supported by pilot-plant facilities, which are utilized by
CanmetENERGY's research groups and by clients from the public and private sectors.

CanmetENERGY is actively searching for partners to further advance the High Pressure
Oxy-fuel (HiPrOx) technology. In the immediate future, a back-end portion of a HiPrOx pilot plant
will be designed to study gas and liquid properties, solids segregation, CO2 capture, and heat
transfer under various operating conditions.
CanmetENERGY is seeking support and funding to construct a fully functional pilot-scale
HiPrOx test facility. Discussions are currently under way with various potential government agency,
industrial and university partners to form a pressurized oxy-fuel combustion consortium to further
develop the HiPrOx process and to advance its business case.
The High Pressure Oxy-Fuel process is a natural evolution of the ambient oxy-fuel process.
HiPrOx uses oxygen to combust fuels at elevated pressures in a boiler. The HiPrOx
process consists of mostly off-the-shelf industrial components including furnaces, steam/gas heat
exchangers, air separation units (ASU), and pumps. In addition, two condensing heat exchangers
are employed to recover flue gas latent heat and to liquefy CO2.
CanmetENERGY said that the cost of electricity associated with CO2 capture is only about
25% higher than without capturing CO2 for HiPrOx process, whereas for air-fired combustion with
amine scrubbing or ambient pressure oxy-fuel, these cost are more than 60%.

6.11 Dutch research programmes

CAPTECH

CAPTECH [23] is a research programme of 6 Dutch consortium partners. The programme

runs from 2006 until 2009 and is coordinated by Energy research Centre of the Netherlands (ECN).
The aim of the consortium is the qualification of CO2 capture technologies with power plant
efficiency losses less than 5% points, resulting in capture costs not higher than 20-30 €/tonne.
This research programme covers the entire field of CO2 capture technologies. This includes
a variety of projects, such as Dutch CATO programme and the European projects such as
CASTOR, ENCAP and CACHET, and several projects funded by industrial partners (e.g. CCP).
The consortium aims to work in close cooperation with these programmes.
The Subprojects of CAPTECH programme are listed in the Table 6.11/1.

Title Short description Partners

SP1 Polymer New low-temperature polymer CO2 membranes for partial CO2 Kema, ECN
membranes removal from flue gases
SP2 New advanced chemical and hybrid solvents with low Shell, Procede,
Advanced
regeneration energy consumption for post- and pre-combustion TNO
solvents
CO2 capture
SP3 ZEPP oxyfuel Novel air separation technologies for oxy fuel Zero-emission ECN, Kema
power plants (e.g Oxygen Transport Membranes)
SP4 IGCC SEWGS Pre-combustion CO2 capture (Sorption-enhanced water-gas shift Kema, ECN
and membrane reactors) for IGCC
SP5 Integration & Integration of CO2 capture in power stations, technical and Kema, ECN, Shell,
assessments economic evaluation and infrastructure aspects Procede, Univ
Utrecht
SP6 Dissemination & Dissemination and co-ordination with CATO project Utrecht Center of
coordination Energy research
(UCE), ECN
Tab. 6.11/1 subprojects of CAPTECH programme

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CATO

The first CATO programme (CO2 Afvang, Transport en Opslag) [24] was initiated in 2001
and continued until the end of 2008. It “de facto” became the Dutch national CCS&T programme.

The aim of CATO (in future CATO-1) was to identify whether and how from an economical,
technical, social and ecological point of view CCS&T would contribute to a sustainable energy
system in the Netherlands. And under which conditions CCS&T could be implemented in the Dutch
energy system.
A prime characteristic of the programme was that all major stakeholders and a number of
research groups from very different fields of expertise worked together within an integrated
framework.
Later the Dutch government has decided to start two large scale CCS&T demonstration
projects in 2015 and set up the CATO-2 programme.
This national CCS&T programme includes a consortium of nearly 40 partners working
together to help realise the governments plans. CATO-2 is expected to be running from 2009 until
2014 and it has an extensive budget provided by the Dutch government and CATO consortium
partners.
The CATO-2 programme will focus a significant part of its applied research efforts on the
port of Rotterdam area (off-shore included) and the Northern Netherlands regions where large
scale demonstration sites will be realized.
CATO-2 research will be performed in six Sub Programme lines:

CO2 Capture;

Transport and CCS chain integration;

Subsurface storage of CO2 and monitoring storage;

Regulation and safety;

Public perception;

Dissemination.

Participants in the CATO-2 programme are also involved in many projects and networks
regarding CCS&T which are funded by the Sixth and Seventh Framework Programs of European
Union. This will help to ensure coordination with ongoing and envisaged research efforts in these
programs.

6.12 SOLVit

SOLVit [25] is an eight-year programme which was launched in 2008 by Aker Clean Carbon
together with Sintef and the Norwegian University of Science and Technology (NTNU).
In 2009, the energy companies E.ON, ScottishPower and Statkraft all joined the
programme.
The SOLVit programme aims to generate better and more cost-effective processes and
chemicals to manage CO2 emissions from the process industry and from coal and gas-fired power
stations.
The programme particularly aims to make the amines more effective and cheaper to use.
The programme also includes building a new laboratory at Tiller in Trondheim, which will be
a unique test centre for pilot projects, including a 30 metre tall tower and processing column that
reached 25 metres high.
The lab will also be available for other of SINTEF’s domestic and international customers
and partners.
The SOLVit-programme will also involve the testing of chemicals and processes in a mobile
capture facility, which has been developed by Aker Clean Carbon and is currently being built at
Aker Verdal. The mobile facility is large enough to process parts of emissions from power stations
and industrial sites in periods of several months.

104
References

[1] http://ec.europa.eu/energy/technology/set_plan/set_plan_en.htm.
[2] H. de Coninck, T. Flach, P. Curnow, P. Richardson, J. Anderson, S. Shackley, G. Sigurthorsson, D.
Reiner, The acceptability of CO2 capture and storage (CCS) in Europe: An assessment of the key
determining factors Part 1. Scientific, technical and economic dimensions; International journal of
greenhouse gas control (2008).
[3] Technical support for an enabling policy framework for carbon dioxide capture and geological storage.
Task 2: Discussion paper - Choices for regulating CO2 capture and storage in the EU; April 2007.
[4] Proposal for a Directive of the European Parliament and of the council on the geological storage of
carbon dioxide and amending Council Directives 85/337/EEC, 96/61/EC, Directives 2000/60/EC,
rd
2001/80/EC, 2004/35/EC, 2006/12/EC and Regulation (EC) No 1013/2006; 23 January 2008.
[5] European Technology Platform forZero Emission Fossil Fuel Power Plants (ZEP), EU Demonstration
Programme for CO2 Capture and Storage (CCS) ZEP’s Proposal, November 2008.
[6] Communication from the Commission to the European Parliament, the Council, the European Economic
and Social Committee and the Committee of the Regions, Supporting Early Demonstration of
rd
Sustainable Power Generation from Fossil Fuels; 23 January 2008.
[7] http://ec.europa.eu/research/infrastructures/framework_prog_en.html.
[8] Technical support for an enabling policy framework for carbon dioxide capture and geological storage.
Task 3: Incentivising CO2 capture and storage in the European Union; April 2007.
[9] http://ec.europa.eu/environment/climat/emission/index_en.htm.
[10] Proposal for a Directive of the European Parliament and of the Council amending Directive 2003/87/EC
so as to improve and extend the greenhouse gas emission allowance trading system of the Community;
rd
23 January 2008.
rd
[11] Impact Assessment, Commission of European Communities, 23 January 2008.
[12] www.co2net.com.
[13] www. co2geonet.eu.
[14] IPCC, 2005. IPCC special report on carbon dioxide capture and storage. Prepared by working group III
of the Intergovernmental Panel on Climate Change.
[15] http://www.netl.doe.gov/.
[16] http://www.cslforum.org/.
[17] http://www.iea.org/.
[18] http://www.ieagreen.org.uk/.
[19] http://www.co2captureandstorage.info/.
[20] www.ingv.it/.
[21] http://www.sintef.no/.
[22] http://canmetenergy-canmetenergie.nrcan-rncan.gc.ca/eng/index.html.
[23]www.co2-captech.nl.
[24] www.co2-cato.nl.
[25] www.akercleancarbon.com.

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7. PROJECTS

7.1 First project

7.1.1 Sleipner

Sleipner is the first commercial-scale project, started in 1996, with the purpose of disposing
of CO2 from natural gas production in an aquifer more than 800 metres below the seabed in the
Norwegian sector of the North Sea.
The Statoil-operated Sleipner West field is one of the largest gas producers in the
Norwegian sector of the North Sea and it was discovered in 1974.
During field development planning (1990), tests showed that the natural gas in the reservoir
contained around 9% carbon dioxide. This exceeded the customers' requirements (2.5%) and the
CO2 content therefore had to be reduced.
Moreover in 1991, the Norwegian government introduced a CO2 tax to reduce emissions
offshore.
Statoil therefore planned to separate the carbon dioxide offshore and to inject it into
geological layers deep beneath the Sleipner platform.

Fig. 7.1.1/1 Injection of cabon dioxide into the Utsira Formation from the Sleipner A platform [1]

A conventional amine process was selected for CO2 capture.

After capture, the carbon dioxide is boiled off and transferred to the A platform on the
Sleipner East field for pumping into the base of the Utsira Formation sandstones through a
dedicated, near-horizontal injection well.
One of the greatest challenges was to make the processing equipment compact enough to
be placed on a platform out in the middle of the North Sea, 250 kilometres from land.
In practice it has also been difficult to honour the 2.5 per cent goal, as the process has
proved unstable.
This led to several modifications and the Statoil Research Centre finally found the answer.
Subsequent offshore pilot studies resulted in a stable performance while reducing the
carbon dioxide content to 2.25 per cent.
The new knowledge was implemented during upgrade of the Sleipner T platform in
September 2004 and is incorporated in the Snøhvit plant in 2006.

In order to learn as much as possible about long-term carbon dioxide storage and at the
same time involve a wider group of expertise from many countries, Statoil together with the IEA
Greenhouse Gas R&D Programme took the initiative to start the Saline Aquifer Carbon Dioxide

106
Storage programme (SACS) for monitoring the Sleipner injection (1998-2003).

Fig. 7.1.1/2 Results of seismic monitoring [1]

About 1 million tonnes of carbon dioxide is injected into the Utsira Formation each year and
time-lapse seismic monitoring is showing that there is no observable CO2 leakage through the
storage site, which strongly suggests that the caprocks are sealing.
Sleipner project as well as Snøhvit and In Salah projects show that CO2 geological storage
in saline aquifers is technologically feasible. In addition these operations have been extremely
helpful for testing monitoring and verification technology and have been used to establish best
practice guidelines for future CO2 geological storage sites.
In fact many articles have been published on the basis of data from Sleipner, and
StatoilHydro has proposed guidelines for a legal framework for how the carbon storage is to be
monitored.
However these projects are not necessarily representative of conditions encountered
globally. For example, aquifer permeability at Sleipner is probably unusually high compared to
what could be expected for other sites [1].

107
7.1.2 Snøhvit

Figure 7.1.2/1 Snøhvit field

The Statoil-operated, unitized Snøhvit complex in the Barents Sea came on stream in 2007.
A liquefied natural gas (LNG) facility has been built at Melkøya, near Hammerfest in
northern Norway.
It comprises a fully subsea offshore development, a 143-kilometre multiphase pipeline to
shore, and a gas liquefaction plant, producing LNG which is exported by ship to the USA and
Continental Europe.
However the gas contains 5 to 8 per cent carbon dioxide, which must be reduced to less
than 50 parts per million prior to liquefaction.
A separate pipeline therefore transports the carbon dioxide from the Hammerfest LNG plant
back to the Snøhvit field. There, it is stored in a suitable geological layer of porous sandstone
called the Tubåen formation.
The Tubåen Formation is about 2 600 metres below the seabed.
The first CO2 was injected into the reservoir in April 2008 and more than 700,000 tonnes of
carbon dioxide will be stored annually in this manner.
A separate monitoring programme has been established to examine how CO2 behaves in
the reservoir [1].

7.1.3 In Salah

Figure 7.1.3/1 In Salah Gas Facility

In 2004 it is launched the CO2 capture and storage project at the In Salah gas field, in the
Algeria desert.
In Salah is a joint venture between Sonatrach, the Algeria national energy company, BP
and StatoilHydro.
The CO2 concentration in the gas is approximately 10%. Rather than venting the CO2, the
project is capturing, compressing and injecting it in wells 1,800 metres deep into a lower level of
the gas reservoir where the reservoir is filled with water.
The separation is based on an amine process.
The amount of CO2 injected has increased from 186,000 tonnes in 2004 to 687,000 tonnes
in 2007, and will rise to 1.2 million tonnes per year [1].

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7.1.4 Weyburn
In 1998 PanCanadian Petroleum Limited, now EnCana Corporation, announced a plan to
implement a large scale EOR project in an oilfield at 16 km south east of Weyburn,
Saskatchenwan, Canada, using CO2 captured from a coal gasification power plant in order to keep
the field viable.

1) CO2 is captured from Dakota Gasification Plant and transported via pipeline to the Weyburn and
Midale oilfields, where it is injected 4,800 meters underground into a depleted oil and gas reservoir;
2) Oil absorbs injected CO2. Combined with water injection, CO2 injection increases reservoir pressure
and oil fluidity enabling oil to escape from rock pores and flow toward production wells;
3) Oil, CO2 and water are extracted. However a significant amount of CO2 remains safely stored;
4) The extracted CO2 and water are separated and re-injected.
Fig. 7.1.4/1 The Weyburn Project schematic [2]

This project allowed to demonstrate and study a large-scale geological storage project and
to provide the data to evaluate the safety, technical and economic feasibility of such storage.
The CO2 injection started in 2000 and the CO2 is produced in the Great Plains synfuel plant
in Beulah, North Dakota, USA, which is operated by the Dakota Gasification Company.
In order to supply the CO2 to Weyburn field, 325 km of pipelines were constructed.

Figure 7.1.4/2 CO2 pipeline in Weyburn project

Therefore this project involves the cross border transfer of CO2 from USA to Canada and so
it is the first time that there has been international trading of “physical” CO2 for the purposes of
emissions reduction.

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 For monitoring Weyburn field, it is set up the IEA GHG Weyburn CO2 Monitoring and
Storage Project which is an international cooperation between industry and research organizations,
with researchers participating from Canada, USA and Europe.
The research was divided in four major themes:

Geological characterization of the geosphere and biosphere: investigation of geosphere by a

variety of methods to determine the integrity of the geological system for long-term storage of
CO2;

Prediction, monitoring and verification of CO2 movements: geochemical and seismic
monitoring in order to predict and verify CO2 movements in the reservoir and physical and
chemical changes induced by CO2 injection;

CO2 storage capacity/distribution, prediction and application of economic limits: demonstration
of the technical and economic feasibility of sequestration of CO2 in geological formations,
primarily oil reservoirs;

Long-term risk assessment of the storage site: establishing whether or not the CO2 injected
leaks to the surface, and if it does, whether or not the leakage impose any environmental risk.

The project found that the CO2 will be safely stored and that its storage can be economic.
Geological settings such as the Weyburn reservoir appear to be suitable for the long-term storage
of CO2 [2].

7.2 European Union projects

European Commission has placed great emphasis on CCS projects in the 5th, 6th and 7th
research framework programs.
The main projects are [3]:

GESTCO;

CO2STORE;

CACHET;

CAPRICE;

CASTOR;

CO2SINK;

COACH;

DYNAMIS

ENCAP;

HYSEPS;

MOVECBM;

CAESAR;

CESAR;

DECARBit;

STRACO2.

5th framework program

GESTCO [4]

The European Potential for the Geological Storage of CO2 from Fossil Fuel Combustion,
GESTCO, project started on March 2000 and ended on February 2003.
The countries participating were Belgium, Denmark, France, Germany, Greece, the
Netherlands, Norway and UK.
The project aimed to determine whether the geological storage of CO2 captured at large
industrial plants is a viable method of reducing greenhouse gas emissions capable of widespread
application in Europe.

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 This was established by a series of case studies that evaluated the CO2 storage potential of
saline aquifers, geothermal reservoirs, coal seams and oil and gas reservoirs.
Moreover the economics aspects and aspects of safety and environment, conflicts of using
underground space and public perception were evaluated.
Another goal of the GESTCO project was to establish a CO2 storage GIS for Europe and a
Decision Support System (DSS) to serve as an economic analysis tool for CO2 storage in Europe.
The GESTCO GIS incorporates the wide range of data provided by the project partners and
allows users to simultaneously view one or more layers of data including the location of the CO2
sources and possible CO2 sinks.
The DSS enables to operator to select a source of CO2 and a potential sink. The DSS
determines if the storage potential of the selected sink is sufficient. In addition the calculation
modules allow the operator to calculate costs of CO2 separation, compression, transport and
injection into the storage site.

CO2STORE

CO2STORE [5] is a research project with 19 participants from industry and research
institutes, partly funded by the European Union.
The project focused on storage of CO2 in aquifers to allow a widespread underground
storage in them in the future.
The project was divided into two parts. Firstly applying the knowledge and experience
gained from the CO2 storage at the Sleipner gas field in the North Sea to develop site-specific
plans for storage operations elsewhere in Europe, both onshore and offshore.
Secondly, in order to establish the long-term safety case for geological CO2 storage,
continuing work on the injection operation at Sleipner, which provides a unique natural
underground CO2 injection laboratory, testing new geophysical monitoring technologies and long-
term flow simulations.
The aim was to:

investigate the feasibility of alternative and smaller CO2 reservoirs;

investigate the final fate of CO2 injected into the Utsira reservoir near the Sleipner field;

investigate alternative cost-effective monitoring techniques;

update documentation needed for dissemination of the technology.

CO2STORE project includes the following studies.

Middle Norway
It has been made a geographical distribution map of geological storage capacity in the
Middle Norway in order to find aquifer where to store CO2 produced by a combined heat and power
(CHP) plant that Industrikraft Midt-Norge (IMN) has been planning to build in this region.
In addition security and stability of CO2 storage in the study area have been investigated
and evaluated. Both the risk and mechanisms for, and effect of, potential leakages from the
identified, prospective storage formations have been studied.

United Kingdom
Suitable sites for underground storage of the CO2 has been evaluated to inject 1-2 million
tonnes per year of CO2 produced by a 450 MW coal gasification combined cycle (CGCC) power
plant that was planning by Progressive Energy Ltd in South Wales.

Germany
Evaluation of a deep saline aquifer in the Northeast German basin.

Denmark
Case-study of the potential future capture and underground storage of CO2 from two point
sources. These are the coal fired power plant Asnæsværket and the Statoil refinery both located in
the city of Kalundborg.

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6th framework program

CACHET

CACHET started in April 2006 and lasts three years.

The project includes 28 participating organizations from 17 countries: oil and gas
companies, electricity utilities, equipment manufacturers, engineering contractors, research
institutes and universities.
The aim of the project is to develop pre-combustion technology to reduce cost of CO2
capture to 20-30 €/ton at 90% capture rate.

CAPRICE

The CAPRICE project objective is the international cooperation and exchange in the area of
CO2-capture using amine processes.
The long-term aim is to contribute to the implementation of these technologies on a large
scale.

CASTOR [6]

"CO2 from Capture to Storage", CASTOR, is a European initiative grouping 30 partners

(industries, research institutes and universities) coming from 11 different European countries and
partially funded by the European Commission.
The overall goal of CASTOR is to develop and validate, in public/private partnerships, all
the innovative technologies needed to capture CO2 and store CO2 in a reliable and safe way.
The main targets of this project are:

a major reduction in post-combustion capture costs, from 50-60 € down to 20-30 € per ton of
CO2 ;

to advance general acceptance of the overall concept in terms of storage performance
(capacity, CO2 residence time), storage security and environmental acceptability;

to start the development of an integrated strategy connecting capture, transport and storage
options for Europe.

CASTOR activities fall into 3 technical sub-projects (SP):

1) “Strategy for CO2 reduction”;

2) “Post-combustion capture”;
3) “CO2 storage performance and risk assessment studies”.

In SP2 and SP3, large-scale field tests (capture facility, injection and monitoring facility) will
be executed to validate the research results.
In all sub-projects innovative methods and tools will be developed, building upon the state
of the art knowledge of participating organisations which are leading in the field of CO2 capture,
transport and storage.

CO2SINK

CO2SINK is a research project dedicated to CO2 storage in a saline aquifer near Ketzin in
Germany.

COACH

The objective of COACH project is to start a strong and durable cooperation between
Europe and China to respond to the fast growing energy demand of China. Among a variety of

112
technologies, CO2 capture and permanent geological storage - including use for enhanced oil or
gas recovery - constitute an important process.

DYNAMIS

The goal of DYNAMIS project, part of the HYPOGEN initiative, is to put the first European
full-scale facility for combined hydrogen and power production from fossil fuels into operation by
2015.

ENCAP

"Enhanced capture of CO2", ENCAP, is a project focused on pre-combustion capture of

CO2.

HYSEPS

"Hybrid Hydrogen - Carbon Dioxide Separation Systems", HYSEPS, is a project devoted to

development of hybrid membranes for H2 and CO2 separation used for the pre-combustion CO2
capture.

MOVECBM

The objective of MOVECBM project is to improve the understanding of CO2 injected in coal
for a long-term reliable and safe storage.

7th framework program [7]

CAESAR

CArbon-free Electricity by SEWGS: Advanced materials, Reactor- and process design,

CAESAR, is devoted to reduce the energy penalty and costs of the SEWGS (Sorption-Enhanced
Water-Gas-Shift) CO2 capture process through optimization of sorbent materials, reactor design,
and process design.
With an optimized SEWGS process CO2 avoidance costs could be reduced to less than €
15/ton CO2.

CESAR

The overall objective of CESAR project is to develop low-cost post combustion CO2 capture
technology to provide economically feasible solutions for both new power plants and retrofit of
existing power plants.
The project aims:

to develop novel (hybrid) solvent systems;

to develop new high flux membranes contactors;

to improve modelling and integration studies on system and plant level;

to test new solvents and plant modifications in a pilot plant.

DECARBit

DECARBit is a research project focused on advanced pre-combustion capture technologies

to enable zero-emission pre-combustion power plants with a capture cost of less than 15 €/ton
CO2, thereby underpinning and promoting implementation of large-scale CCS&T power plants, as
well as retrofit applications and the possible use of new capture technologies in other energy
intensive industries.
The main objectives are:

113

to assess and research new techniques for CO2 separation in pre-combustion schemes by
developing membranes, sorbents and novel solvent systems characterised by improved
capacity and reduced efficiency penalty;

to develop advanced oxygen production techniques using novel sorbents, membranes, new
concepts for large-scale cryogenic systems and optimised process integration in order to lower
power consumption and oxygen cost.

STRACO2 [3]

“Support to regulatory activities for carbon capture and storage”, STRACO2, is a project
which aims to review development and implementation of a regulatory framework in the EU for
CCS&T activities.
Part of the scope is also supporting CCS&T collaboration and implementation in the
international context, particularly in China.

7.3 A USA project: FutureGen

The “FutureGen” is a public-private partnership between the FutureGen Industrial Alliance,

Inc, a non-profit consortium of some of the largest coal producers and users in the world and the
U.S. Department of Energy [8].
This project was announced as part of President Bush’s “National Climate Change
Technology Initiative”. It is intended to demonstrate on a commercial scale the production of
electricity by means of hydrogen obtained from coal with carbon capture and sequestration.
The project provides the design, construction and operation of a 275 MW coal-fired IGCC.
This scale is intended to produce commercially-relevant data, and to capture at least 1
million tonnes CO2 per year to test the sequestration site [9].
On 14th of July 2009 the Department of Energy issued a National Environmental Policy Act
(NEPA) Record of Decision to move forward toward the first commercial scale, fully integrated,
carbon capture and sequestration project in the country.
The Record of Decision and the FutureGen plan allowed to the FutureGen Industrial
Alliance to proceed with site-specific activities for the project. The Alliance will complete a
preliminary design, refine its cost estimate, develop a funding plan, expand the sponsorship group,
and, if needed, will conduct additional subsurface characterization.
Following these activities, which will be completed in early 2010, the Department and the
Alliance will decide whether to continue the project through construction and operation.
When fully operational, the facility will use integrated gasification combined cycle
technology with carbon capture and sequestration into a deep saline geologic formation. It will be
designed to capture 90% of the carbon emissions by the third year of operations but it may be
operated at 60% capture in the early years to validate plant integration and sequestration capability
[10].

7.4 Australian projects

CO2 Cooperative Research Centre (CO2CRC)

In Australia the CO2 Cooperative Research Centre (CO2CRC) [11] has been undertaking
research into the geological storage of carbon dioxide since 1998.
Through the Centre, more than 100 researchers in Australia and New Zealand are
collaborating to develop safe and economical CO2 geosequestration technologies.
The Centre, thus, aims to review a range of capture technologies and applications that
might be used by the fossil fuels industry sectors, selecting those technologies most likely to allow
significant reductions in emissions and developing them.

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 A framework of economic evaluation is used to measure and validate research directions
and integrate both with energy production issues and storage infrastructure.
The CO2CRC works through three main research programs:

Capture of CO2, through which scientists research, develop and aim to demonstrate
technologies that will reduce the costs of capturing CO2 by 75 to 80 per cent;

Storage of CO2, through which researchers are studying sedimentary basins and identifying
regions and sites in Australia and New Zealand that are best suited to the safe, storage of
CO2;

Demonstration and Pilot Projects and Regional CO2 Strategies, which are demonstrating that
geosequestration is a viable option for CO2 mitigation in Australia.

During the year, several research program on CO2 storage were completed:

A detailed study of the CO2 storage capacity part of southeast Queensland. Even if more work
is necessary to turn that potential into a technical and economic reality, this study represents a
very important first step;

A study on the southern part of the Perth Basin, in Western Australia, was carried out between
2004 and 2006. The work for this CO2CRC project was chiefly conducted at Geoscience
Australia with important contributions from the Australian School of Petroleum, CSIRO and the
University of New South Wales;

A number of comprehensive studies have been carried out in the state of Victoria such as the
Victorian Basin Assessment project. In December 2006 the CO2CRC published a Review of
Geological Storage Opportunities for Carbon Capture and Storage (CCS) in Victoria.

The main projects in which CO2CRC is currently involved are:

The CO2CRC Otway Project. This is Australia’s first demonstration of the CO2
geosequestration located in Victoria. Launched in April 2008, the project involves the
extraction, compression, transport and storage of 100.000 tonnes of naturally occurring CO2.
The CO2 is being stored in a depleted natural gas reservoir two km below the earth’s surface.
The project also provides a development and implementation of a rigorous monitoring and
verification program that complements the demonstration of the subsurface geosequestration
technology. The project is also leading the way in defining regulatory requirements for
geosequestration;

Demonstration of post-combustion capture (PCC) in pilot plant settings in the Latrobe Valley
This pilot plant is part of the Monash Energy Project which was developed under a Clean Coal
Energy Alliance formed between Anglo American and Shell in May 2006;

Demonstration of pre-combustion carbon dioxide capture technologies for brown coal power
generation in pilot plant settings in Victoria.

Munmorah PCC Project [12]

At the Munmorah Power Station in New South Wales, a research-scale pilot plant will
capture up to 3000 tonnes of CO2. The focus of the project is to assess the performance of post-
combustion capture under Australian conditions and to evaluate various CO2 absorbents.
It is hoped the Munmorah project will provide the foundation for post-combustion capture
and storage demonstration project, planned for operation by 2013, capturing up to 100,000 tonnes
of CO2 each year.

ZeroGen Project [12]

The ZeroGen project provides two steps. One step will develop a demonstration-scale
IGCC power plant with CCS&T in 2012, the second one will carry out the world’s first commercial-
scale plant using these technologies in 2017.

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 The demonstration plant will capture up to 75% of CO2. Some of this will be transported by
road tankers for sequestration in deep underground reservoirs in the Northern Denison Trough,
approximately 220 km west of the plant.
The commercial plant will be a 450 MW IGCC power plant with CCS&T and will capture up
to 90% of CO2.

Callide Oxyfuel Project [12]

The Callide Oxyfuel Project is an international oxyfuel demonstration plant.

The Oxyfuel boiler is scheduled to be operational in the Callide A power plant by 2011. The
project team is assessing potential carbon storage sites to the west of the power plant and plans to
select the final location this year.
The carbon dioxide will be transported in road tankers.

Gorgon CO2 Injection Project [13]

Gorgon is a project which could be position Australia as a world-leader in commercial-scale

carbon dioxide injection technology, it could potentially become the largest CO2 storage operation
in the world.
This project, planned by Chevron in collaboration with Shell and Exxon, provides the CO2
injection from natural gas production.

Figure 7.4/1 Gorgon project

The CO2 injection location is on the central eastern coast of Barrow Island near the gas
processing plant to a depth of 2.3 km. This site was selected to maximise the migration distance
from major geological faults and limit ground disturbance.
The injection wells will be directionally drilled from discrete surface locations to minimise the
area of land required for the well sites, surface facilities, pipelines and access roads.
A number of monitoring activities are planned, including:

Routine observation and recording of injection rates and surface pressures at the injection
wells;

Surveillance to detect the unlikely leakage of CO2;

Measurement via well and/or seismic surveys to track the migration of the CO2 plume in the
subsurface.

The use of seismic surveys and well pressure data will provide information required to
update the reservoir models used to predict the behaviour of the injected CO2.

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 A Reservoir Management Plan will be developed to integrate the monitoring activities,
reservoir modelling and the management of injection operations.

7.5 Italian projects

7.5.1 Enel

Enel has been conducting research on CO2 capture technologies and some projects are
envisaged [14]:

Pre-combustion technology applied to a 12 MWe combined cycle by hydrogen at Fusina;

Atmospheric oxycoal combustion of 3 MWth already in operation and pressurized oxyfuel
combustion pilot plant of 48 MW under construction in ITEA ‘Federico II’ power plant in south
of Brindisi;

Design and characterization of a 10,000 Nm3/h pilot plant to be mounted, in side-stream, on
one of the 660 MWe units of ENEL's coal-fired plant at South Brindisi with post-combustion
capture technology by means of amine in agreement with ENI (see below). Later on, a 600,000
Nm3/h demonstrative plant will be realized for processing part of the flue gases from a 660
MWe unit of the Torrevaldaliga Nord Power Station;

Exploration of a salt aquifer (named Matilde 1) in Upper Lazio, which is expected to be
characterized for potential storage of CO2 produced by power plant at Torrevaldaliga Nord. At
the same time, characterization of other two areas, in the Upper and Lower Adriatic Sea, will
be started.

Moreover ENEL has been conducting research on new materials for producing more
selective membranes than those presently available on the market.

7.5.1.1 Enel-ENI Project

At the end of 2008 Enel and ENI have signed a cooperation agreement to join forces for
implementing Italy’s first project for the capture, transport and geological sequestration of CO2 [14].
This project allows testing the entire process, from CO2 capture and its injection
underground up to the monitoring and checks of the stability and safety of the deposit.
The pilot project results from the integration of two projects launched independently by both
companies. Enel is building a CO2 capture and liquefaction plant, capable of removing 2.5 tonnes
of gas per hour, at the Brindisi thermal power station.
On the other hand, Eni started to implement a project which is aimed at injecting about
8,000 tonnes of CO2 per year at the Stogit exhausted field at Cortemaggiore (Piacenza).
At the beginning the captured CO2 will be transported by 230 trucks per year. However in
order to gain experience in the pipeline transport of CO2, Enel and Eni have also decided to lay a
pilot dense-phase CO2 transport line at the Brindisi site.
The underground injection is set to start in the autumn of 2010.
The integrated project will allow:

to carry out a detailed feasibility study for the construction of a large integrated CCS&T demo
plant;

to make a field test verification of the forecasted behaviour of injected CO2;

to define a methodology for CO2 injection;

to start to investigate if the CO2 can be used as cushion gas for long-term storage.

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 Figure 7.5.1.1/1 Enel power plant at Brindisi

7.5.2 ENI

In addition to injection project at Cortemaggiore, Eni is involved in other projects [15].

It is studying the geological capture of CO2, in order to examine the technical feasibility of
CCS&T projects in Italy. This project involves using the results of the study carried out during the
period 2005-2007 by injecting CO2 into the subsoil by means of special wells and monitoring
storage techniques.
In this new study, CO2 will be injected into active deposits in order to favour the recovery of
hydrocarbons.

ENI is also studying a CO2 Biofixation project which aims to verify the techno-economic
feasibility of CO2 (produced by refineries) biofixation processes using micro-algae that are able to
assimilate it. This process makes it possible to clean refluent water and at the same time produce
biomass that can be converted into biofuels and/or other energy vectors such as bio-methane,
pirolitic oil and electricity.
The majority of the experiments are being carried out at the Gela refinery, where a small-
scale pilot plant consisting of photo bioreactors and open tanks has been functioning since 2007.
If the project's techno-economic objectives have been reached, a pilot plant covering a
hectare of space and a full-scale plant covering ten hectares will be constructed by the end of
2009.

7.5.3 Techint

Techint is strongly engaged in CCS&T development and is involved in the following projects
[16]:

a pilot plant for carbon capture through pre-combustion technology, which can be applied in a
Integrated Gasification Combined Cycles to reduce the greenhouse emissions and to produce
hydrogen from fossil fuel (in co-operation with ENEA, Politecnico of Milan, Sotacarbo and
University of Cagliari);

laboratory tests to search for a new physical solvent enabling an optimisation of the absorption
process in pre-combustion technology;

a feasibility study for a CO2 capture and sequestration plant to retrofit an existing 120 MW
Natural Gas Combined Cycle located in Northern Italy (Dalmine - Bergamo) in co-operation
with Tenaris Dalmine (owner of the potential hosting plant), ENEA, CESI Ricerca and
Politecnico of Milan. This study has been focused to identify specific solutions to optimize the
process and, therefore, the energy consumption.

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Natural Gas Combined Cycle at Dalmine

The CO2 capture plant will retrofit an existing NGCC composed by two gas turbines and two
heat recovery steam generators where the recovered heat is converted into steam fed to a Steam
Turbine.
The plant has been also designed for cogeneration purposes: some steam extractions from
the steam turbine are used both for supplying heat to a steel factory, nearby the NGCC, and for
district heating (DH) to the Municipality and domestic users close to the plant.
Nominal electrical power is about 120 MWe, while maximum provided heat is about 12
MWth for steel factory and 35 MWth for DH.
The proposed initiative is articulated in several phases:

Phase 1: development of the complete project with the selection of the best technology
suitable for this post-combustion application and detailed engineering, economic evaluation
and financial plan in order to evaluate the full feasibility of the initiative;

Phase 2: realization of a first carbon capture plant module to treat flue gas from one gas
turbine (150,000 tCO2/year, about half of the total quantity of flue gas emissions of the power
plant); in this phase the captured CO2 can be used in industrial applications for few years and
the capture process can be tested while the realization of the geological storage is defined;

Phase 3: realization of a second module of capture plant to treat the total amount of the flue
gas emissions of the power plant (300,000 tCO2/y). In this final phase the geological storage is
supposed to be available and defined in all the related aspects.

With regards to post-combustion technology, the study took into consideration a number of
solvents: MEA, EconamineSM Plus by Fluor, KS-1SM by MHI, and Chilled Ammonia by Alstom.
Since some alternative solutions are not completely described in the available literature and
data are covered by license, a complete process simulation and economic analysis was possible
currently only for the MEA, therefore this solvent has been chosen.
In the MEA absorption/regeneration process specific attention has been devoted to energy
efficiency optimization, therefore particular attention has been dedicated to materials selection,
equipment design and plant configurations.

In order to investigate the captured CO2 utilization, several possibilities have been studied:

geological storage (a potential site is located 25 km from the plant, in a depleted oil & gas
reservoir);

industrial use in food industries, situated in the area of the NGCC;

steel slag carbonation, due to the particular location of the NGCC inside a steel factory.

7.5.4 ECBM project in Sardinia

Sotacarbo [17] and Carbosulcis SpA [18], in collaboration with the Department of
Mechanical Engineering of Cagliari (Sardinia, Italy), ENEA, the National Institute of Geophysics
and Volcanology of Italy, have founded a program of research and development to verify the
application of ECBM technology to the Sulcis coal basin (South-West Sardinia).
The program was activated in December 2004 and it was implemented in stages through
the development of specific projects of research and development, with the aim of:

investigating the chemical-physical and mineralogical proprieties of Sulcis coal through

specialized laboratory analysis, in order to know the capacity of the methane release and the
absorption of CO2 injected underground;

obtaining further geological, hydrogeological and geo-structural knowledge of the Sulcis coal
basin in order to explore the possibility of discovery of coal layers deep (500-1500 m) which
can not be economically cultivated;

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improving ECBM technology;

defining an experimental plant configuration;

realizing a pilot plant and performing the necessary experimental campaigns.

7.6 Other projects

7.6.1 CO2 Capture Project (CCP)

The CO2 Capture Project (CCP) [19] grew out of the BP/International Energy Agency’s
Greenhouse Gas Program/US Department of Energy informational meeting ‘CO2 Capture and
Geologic Sequestration: Progress through Partnership’ in 1999.
It is a partnership of eight of the world’s leading energy companies and three government
organizations undertaking research and developing technologies to help make CO2 capture and
geological storage a practical reality for reducing global CO2 emissions.
Therefore the CCP aims to accomplish the following goals:

Reducing technical and cost uncertainties associated with CO2 capture technologies and
demonstrate that geological storage of CO2 is a secure and viable means of reducing
greenhouse gas emissions;

Reducing CO2 capture costs by 20-30% through choosing the right technologies;

Identifying and addressing critical issues surrounding geological storage of CO2 and
encouraging public awareness and acceptance;

Developing consistent technological standards for the evaluation of the risk, security and well
integrity of storage sites;

Developing a way of sharing information between organizations about both capture and
storage demonstrations.

The CCP Program falls into three Phases.

Phase 1 (CCP1) started in the beginning of 2000 with the goal of bringing candidate
technologies to pilot plant or demonstration stage.
Phase 2 (CCP2) started in 2004 and it is currently reaching the end. The objective of this
phase is the development of technologies which can reduce the costs of capturing CO2 by 50% for
retrofits and by 75% for new-built plants from the baseline established in 2000.
Scaling up technologies by one order of magnitude compared to the scale tested in CCP1
is the main goal of CCP2. Since most technologies achieved “proof-of-concept” in CCP1, the
expected level of development by the end of CCP2 is “ready for pilot testing”.
Table 7.6/1 lists the technologies studied in CCP2.

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 Project Name Participating organizations Co-Funder

Oxy-firing Fluidized Randall Gas Technologies(ABB

CCP2
Catalytic Cracker, FCC Lummus Global, Inc.)

Best Integrated Norwegian Research Council, CLIMIT

GE, Nexant
Technology, BIT ProgrammeCCP2

Chalmers University, Alstom Boilers,

Consejo Superior Investigaciones
Chemical Looping European Union, CLCGASPOWER
Cientificas (CSIC), Shell, Technical
Combustion, CLC ProjectCCP2
University of Vienna (TUV), Tallinn
University

Hydrogen membrane Norwegian Research Council, CLIMIT

StatoilHydro
reformer, HMR Programme; CCP2

Energy research Centre of the

Membrane Water Gas Netherlands (ECN), Sintef, University of
European Union, Cachet Programme
Shift, MWGS, and Dalian, Process Design Center (PDC),
CCP2
Membrane Reforming Chevron, National Technical University
of Athens (NTUA), BP

Sorption Enhanced
BP, Air Products (GB), ConocoPhillips, European Union, Cachet Programme
Water Gas Shift,
ECN, NTUA, PDC, Chevron. CCP2
SEWGS

Chemical Looping
Chalmers, Alstom, CSIC, TUV, NTUA,
Reforming, CLR (two European Union, Cachet Programme
PDC, BP, IFP, Shell, EniTecnologie
concepts)/One Step CCP2
(now Eni - only OSD), Sintef.
Decarbonization, OSD

HyGenSys(Steam,
IFP, Technip, Siemens, NTUA, PDC, European Union, Cachet Programme
Methane Reformer and
BP, Chevron. CCP2
Gas Turbine)
Table 7.6.1/1 CCP2 Program

Phase 3 (2009-2012) is currently in the planning stage and will likely include several pilot
plants and demonstration projects.

The Program is led by and operates through an Executive Board, composed of

representatives from each full member organisation, which selects from the many opportunities
important project for technology improvements and funds those developments. An Advisory Board
composed of sector experts also reviews and recommends changes to the Program and potential
new areas for exploration on a twice-yearly basis.

CCP Activities are carried out through the close cooperation and shared decision-making of
four broad technical teams: Capture, SMV (storage, monitoring and verification), Policy and
Incentives, and Communications.
These teams are composed of experts from CCP member companies and third-party
organizations that investigate technical advances, monitor development of the technologies and
policies, look for ways to integrate the best technology advances from the program, and present
results at technology forums and industry and academic conferences.
In order to enable CCS&T technologies economically and socially acceptable to
stakeholders from industry to government, to NGOs and consumer groups, the CCP holds a series
of biannual meetings and updates for a variety of key stakeholders such a regulators, policy
makers and NGOs that take place in the Europe and America.

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7.6.2 K-12 CO2 Injection Project

K12-B is the first site in the world where CO2 is being injected into the same reservoir from
which it was produced as a by-product of methane production.
In 2004 Gaz de France Production Nederland B.V. and TNO examined the possibility of
CO2 injection, enhanced gas recovery and CO2 storage in depleted natural gas fields on the Dutch
continental shelf; the project was called “Offshore Re-injection of CO2” (ORC).

Figure 7.6.2/1 K-12 offshore site [20]

The mature gas field K12-B is thus selected as a demonstration site for offshore injection of
CO2.
This gas field is situated approximately 150 km north-west of Amsterdam in the Dutch
sector of the North Sea. Since 1987, the field has been producing natural gas with a relatively high
CO2 content (13%). Prior to transport to shore the CO2 is separated from the natural gas on the
platform, where it was vented to the atmosphere until 2004.

Figure 7.6.2/2 K-12 gas field [20]

Since the start of the CO2 injection, 50,000 tonnes of CO2 have been injected into the
Rotliegend sandstone reservoir at nearly 4 km depth.

In January 2007 a new project, called “Monitoring K-12 CO2 Storage” (MONK), started.
The monitoring activities are carried out by Gaz de France Production Nederland B.V., the
operator of the K12-B platform and TNO.
The aim of the monitoring programme is to investigate research topics such as well
integrity, storage mechanisms in the deep subsurface and the potential of enhanced gas recovery
[20].

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7.6.3 North Sea CO2 transport

In March 2007 the UK Department of Trade and Industry (DTI) commissioned a study on
behalf of the UK, Norway and North Sea Basin Task Force, to examine possible development
pathways for pipeline infrastructure connecting large UK and Norwegian CO2 sources with
appropriate sinks in the North Sea.
The project team developed a comprehensive database of CO2 sources, CO2 sinks, and
existing pipeline infrastructure in the North Sea that may be appropriate to CCS&T.
These datasets are used in a CO2 network model. Given the dynamic nature of the power
and North Sea oil and gas industries, and the requirement to examine the growth of a CO2
infrastructure, the model itself is dynamic, spanning over 25 years of network development, in five
development phases.
The first phase runs from 2013-2017; the final phase runs from 2033-2037. The long lead
times associated with CCS&T planning and execution suggests that 2013 is a realistic start date
for proposed UK and/or Norwegian CCS projects.
The model predicts the costs and benefits (e.g. CO2 abated and enhanced oil recovered)
for networks developed under a range of scenarios as agreed with the DTI [21].

7.6.4 Chilled Ammonia Process

Different size demonstration plants are investigating to validate Almost’s Chilled Ammonia
Process.

Plant Size Companies

Palo Alto (US) – Gas and coal 0.25 MWth EPRI, SRI, Alstom, StatoilHydro
Pleasant Prairie (US) – Coal 5 MWth EPRI, We Energies, Alstom
Karlshamn (Sweden) – Oil 5 MWth AEP, Alstom
Mountaineer (US) – Coal 20 MWth E.ON, Alstom
Mongstad (Norway) – FCCU/Gas 40 MWth StatoilHydro, Alstom
Tab. 7.6.4/1 Pilot plants with Chilled Ammonia process [22]

7.6.4.1 Large bench scale pilot plant

A 0.25 MW plant was carried out in 2006 at Palo Alto, California by SRI.
The goals of this pilot plant were:

to demonstrate potential to achieve 90% CO2 capture efficiency for 3.5, 8, 15% CO2
concentrations;

to demonstrate low ammonia emissions;

to measure mass transfer;

to optimize the absorber design and operating conditions;

to provide data to support the design of the field pilots.

This pilot plant was transferred to Alstom Technology Center Växjö, Sweden during 2008 in
order to further explore enhancements to the chilled ammonia process and to test new
components, advanced process controls and instrumentation.

7.6.4.2 Field pilot plants

Two 5 MW field pilot plants were carried out, designed to capture 1,600 kgCO2/hr.
One is at We Energies Pleasant Prairie Power Plant (USA) and the other one is at E.ON
Karshamn Power Plant (Sweden).
The first one is currently operating since June 2008 and it aims to provide data necessary
to establish “proof of concept”.
The second one is operating since April 2009 and its objectives to test and verify:

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CO2 absorption efficiency;

ammonia emissions;

quality of captured CO2;

quality of liquid by-product streams;

energy optimization and usage.

7.6.4.3 Validation pilot plants

Two validation plants were designed: Mountaineer and Mongstand.

Mountaineer

A 20-MW capture system has been installed at AEP’s 1,300-MW coal-fired Mountaineer
Plant, where it is expected to remove approximately 100,000 tons of CO2 emissions annually from
the flue gas stream of the plant. The captured CO2 will be compressed and injected into two saline
reservoirs located beneath the plant site.
The project will be the first to capture carbon dioxide from a pulverized coal-fired power
plant as well as inject it into a permanent storage site more than 7,800 feet underground.
The Mountaineer project will operate for up to five years and help validate the effectiveness
of Alstom’s patented chilled ammonia process for carbon dioxide capture and the viability of
storage in the local geology. The project has been hailed for its potential to provide the critical
information that could scale up capture and storage technologies for new power plants and for
retrofit of existing facilities [23].

Fig. 7.6.4.3/1 AEP Mountaineer Station

Mongstand

The Norwegian government and StatoilHydro have entered into an agreement to construct
a full-scale carbon capture facility at Mongstad refinery, near Bergen, Norway, where a new
Combined Heat and Power (CHP) station will be constructed.
The new power station, scheduled to start up in 2010, will produce 280 MW of electricity,
350 MW of heat and 1.8 millions of CO2 per year [24].
As the first stage of the agreement with the authorities, a partnership was established in
June 2007 for the European Carbon Dioxide Test Centre Mongstad (TCM). The partnership
consists of StatoilHydro, Dong Energy, Vattenfall, Shell and Gassnova SF.
The goal of the test centre is to further develop and test various technologies relating to
carbon capture from exhaust gases from the combined heat and power station and from other
emission sources at the refinery.
To achieve this, phase one comprises the creation of a smaller-scale absorption plant
which could capture 100,000 tCO2/y.
This plant should remove 85% of CO2 from two flue gas sources:

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Combined Heat and Power (natural gas): 3.5 vol.% CO2;

Residual Catalytic Cracking (RCC) Unit: 12.9 vol.% CO2.

Regarding capture, two absorption systems are being planned in parallel. For the CHP
station the system is based on amine solvents, while for the RCC Unit the process is based on
chilled ammonia.
StatoilHydro has signed an engineering, procurement and construction (EPC) contract with
Alstom for the chilled ammonia CO2 capture plant. This technology will have the capacity to
capture 80.000 ton per year, the equivalent of 40 MWth [25].
The test centre is scheduled to start up in 2011; operation and testing are planned from
2011 to 2013.

The second phase comprises a full-scale facility that is capable of capturing carbon dioxide
from both the combined heat and power station and other relevant emission sources at the refinery
(> 1 milion of ton CO2 per year).
Plans call for a final decision on the size and type of the full-scale facility to be taken in
2012, and engineering and construction work will start immediately afterwards.
The development of the test centre for carbon capture technology followed by full-scale
capture will make Mongstad a forward-looking centre for environmentally friendly industrial activity
[1].

Seawater
CHP

CO2 stack
RCC Amine
Technology

Substation
Utility System

Chilled Ammonia
Technology

Fig. 7.6.4.3/2 Test Centre Mongstad Layout [22]

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7.7 European company activities on CCS&T

7.7.1 Statoil

Statoil [1] has been, and is, both the initiator and active partner in various carbon capture
and storage research and development projects.
Statoil is involved in many important CCS&T projects such as Sleipner, Snøhvit, In Salah
and Mongstad.
Recently Statoil and Shell signed an agreement to work on a project where carbon from a
gas-fired power station at Tjeldbergodden will be used for improved oil recovery at the Draugen
and Heidrun fields in the Norwegian Sea.
Statoil has done much research on the cleaning of flue gas emissions from coal- and gas-
fired power plants. Its initial work was largely centred on a flagship venture, which started in 1992
as a joint industry project with Kværner Process Systems, NTNU and SINTEF.
The main aim of this project was to investigate whether membrane contactors could replace
the bulky amine towers currently used for carbon dioxide absorption and desorption.
W L Gore and Associates (Gmbh) supplied designer membranes for installation at two
major pilot plants – one in Norway (at Kårstø) and one in Japan (Osaka).
In the first plant a conventional amine was used, while in the second one a recently
developed alternative was tested.
Statoil was also involved in CCP1 which included three regional programmes run in the
United States, Norway and the European Union; Statoil headed the Norwegian contribution.

7.7.2 Vattenfall

In 2001, Vattenfall started a research and development (R&D) project with the aim of
developing a commercial concept for CCS&T at power plants by 2015-2020.
A pilot plant was inaugurated on September 9, 2008, near the existing lignite fire power
plant at Schwarze Pumpe in Germany.

Figure 7.7.2/1 30 MW thermal pilot plant at Schwarze Pumpe [24]

This 30 MW pilot plant is designed to capture 95% of carbon dioxide by oxyfuel technology,
for which Alstom is supplying the oxy-boiler technology.
Lignite and hard coal will be combusted in a mixture of oxygen and re-circulated CO2, and
water vapour. The flue gas will then be treated and sulphuroxides, particles and other
contaminants removed. Finally, the water will be condensed and the concentrated CO2
compressed into liquid.

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 Through a co-operation agreement signed between Gaz de France and Vattenfall, the CO2
captured will be used for enhanced gas recovery and storage and will be injected at dephts of 3000
m at Europe's second largest onshore gas field, Altmark, during a three-year trial period.
The purpose of the pilot plant is to validate engineering work, to learn and better
understand the dynamics of Oxyfuel combustion and to demonstrate the capture technology.
The next step is to demonstrate through tests and experiments that the technique can be
scaled up.
The project phases are listed below, each phase is evaluated before the next phase begins.

Test rigs;

Pilot plant;

Demonstrations plants;

Commercial concepts.

The project should result in commercial concepts for carbon capture and storage at coal-
fired power plants by 2015-2020.

Vattenfall also supports a number of Swedish and German universities in their research on
the Oxyfuel technology:

Brandenburg Technical University;

Chalmers University of Technlogy in Gothenburg;

Technical University of Dresden;

Technical University of Hamburg-Harburg;

Institute of Process Engineering and Power Plant Technology at Stuttgart University.

In addition Vattenfall is involved in other CCS&T project.

Oxycoal UK project

The OxyCoal UK project is developing a 40 MWth pilot plant with Oxyfuel technology for the
capture of carbon dioxide in Renfrew, UK.
The pilot plant was inaugurated on the 24th of July, 2009. The project will run until the end
of 2009, with a possible two-year extension.
This involves burning coal in a mixture of high-purity oxygen and recycled gas to produce a
gas rich in carbon dioxide that can be purified and compressed for transportation and storage.
For Vattenfall, the project is an important complement to efforts in the Oxyfuel pilot plant in
Schwarze Pumpe.

Demonstration plant in Jänschwalde

A demonstration plant on Oxyfuel capture technology is investigated at Jänschwalde in

Germany. The new oxyfuel boiler would be of 650 MW thermal (around 250 MW electric), which is
about 20 times more than 30 MW pilot plant at Schwarze Pumpe.
Also post-combustion capture technology will be demonstrated at Jänschwalde.
At Jänschwalde there is lignite fired 3000 MWe power plant. At each of the six blocks of the
power plant, two 250 MW boilers produce steam for a steam turbine. One new 250 oxyfuel boiler
will be built to replace one of the existing boilers. The other existing boiler in the block will be
retrofitted with a post-combustion capture unit and this unit would be possible to operate also
without the capture function.
Furthermore several on-shore storage options have already been investigated and also
possible routes for the pipelines in which the captured CO2 will be transported to the final storage.

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CCS&T demonstration project in northern Denmark

Vattenfall has the intention to develop a full-scale CCS&T demonstration project in

Denmark.
As a first step towards the fulfillment of this demonstration project, Vattenfall has asked a
team of engineers and geologists to start investigations to ensure that CO2 storage is a realistic
possibility at Vedsted in northern Jutland. If the storage proves feasible, the intention is to establish
a full-scale CO2 capture plant in 2013 at Nordjyllandsværket (Aalborg).
The CO2 will be be transported in liquid form to the storage via a 30 km long pipeline. The
CO2 will be stored in a geological reservoir at a depth between one and two kilometres below the
surface.
Based on the results of investigations of the geological structure, an investment decision is
planned for late 2010.

Investigation of storage sites

Together with Verbundnetz Gas and Schlumberger, Vattenfall has initiated exploration of
two different possible storage sites in the German federal state of Brandenburg. The aim is to
investigate the potential of these aquifers to store CO2 from demonstration project in Jänschwalde.
If the exploration is successful, the storage sites will be developed.
The connection system between the injection drill hole and the transport pipeline will be
implemented in the period 2011 to 2015. This will be followed by transport via a gas pipeline from
the demonstration plant in Jänschwalde to the storage site. The pipeline, up to 150 km in length,
will be built with a distribution system but no pressure boosting system.

7.7.3 Total

Total [26] turned its attention early on to the potential of CO2 capture and storage
technology and is involved in a number of national and international R&D projects in this field.
The various studies that Total has undertaken jointly with French and international research
partners focus on:

CO2 capture technologies;

the physical-chemical properties of CO2 in the storage formation;

the long-term integrity of reservoirs and boreholes;

methods of risk analysis.

Total is involved in numerous research projects being pursued under the programs of the
French National Research Agency (ANR) – including the Géocarbone-Picoref project aimed at
identifying potential geological storage sites in France.
In this project, which is coordinated by the French Petroleum Institute, IFP, and involves 14
partners, Total contributes to improved knowledge of the subsoil by providing seismic data and
taking part in simulations and methodology studies on topics such as EOR and long-term CO2
storage. The project also aims to understand regulatory aspects and preparations for seeking the
authorizations that will be required for future demonstration projects.
Total is also participating in European projects, such as ENCAP and CO2ReMove. In
addition it is involved in CO2NET.

In February 2007, Total announced the launch CCS&T first demonstration pilot plant in
France associated with steam generation in the Lacq basin.
This project entails converting one of the five steam boilers of the steam generating plant to
an oxyfuel combustion unit, then capturing and compressing its CO2 emissions, transporting the
gas via a 27-kilometer pipeline, for injection into the nearly-depleted Rousse natural gas reservoir
in the Lacq area, at a depth of 4,500 meters.

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 The pilot plant, which will produce 40 tonnes of steam per hour for use by the industries of
the Lacq complex, will emit up to 150,000 tonnes of CO2 over a two-year period.
The Rousse well will be subject to close monitoring, with detectors located throughout the
surface and subsoil regions to measure the injection flow, pressure, temperature and concentration
of the CO2.

Figure 7.7.3/1 Total project scheme

The project has three main objectives:

to improve knowledge of the oxyfuel combustion process, particularly with a view to

applications in the production of extra-heavy oils;

to halve the cost of carbon capture compared to existing processes;

to develop monitoring methods and instruments to demonstrate on a larger scale the reliability
and sustainability of long-term CO2 storage technology.

Furthermore Total is a partner in a number of other industrial demonstration projects such

as Sleypner and Snøhvit.

Fig. 7.7.3/2 R&D project in which Total is involve [26]

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7.7.4 Siemens

Siemens is developing two technologies for CO2 capture for existing and new power plants.
For pre-combustion capture, the Siemens IGCC technology is ready to implementation.
For post-combustion capture Siemens has been performed tests with different solvents for
more than two years and it has selected a solvent family which provides substantial advantages.
This technology will be ready for the implementation in the upcoming demonstration
projects.
The advantages of this post-combustion technology are:

low energy demand;

low oxygen degradation;

almost zero solvent slip in the scrubber and stripper;

high specific absorption rate;

environmentally harmless solvent.

The new process and the energetically optimum integration into conventional power plants
will be verified in a small pilot plant under real operating conditions [27].
A pilot installation on an E.ON power plant site in Germany will be operational by 2010.
Further developments will follow up until 2014. The mid-term target is to develop this new
CO2 capture process ready for large-scale, commercial deployment by 2020.
In addition Siemens technologies are also used for carbon dioxide transport and storage:
compressors supplying the necessary pressure in the pipelines and the pressure required for
forcing the CO2 deep underground.

In 2000 Siemens started work under a co-operation agreement with Shell to develop and
demonstrate a natural gas fired 0.25 MW Solid Oxide Fuel Cell (SOFC) modified to enable capture
of CO2. In fact, as previously said (see § 2.1.2.3), feeding exhaust gases from power plants to
SOFCs, it is possible to obtain a high CO2 concentration in the anode exhaust flow [28].

7.7.5 RWE

RWE is the biggest power production in Germany. It is active in the generation and
transmission as well as the sale and trading of electricity and gas.
RWE is currently one of the companies worldwide to be developing the entire process chain
of CCS on an industrial scale.
Its project plan for the development of CO2 storage provides for three phases:

Phase 1:
- stock-taking and pre-selection (screening);
- assessment and feasibility study for selected locations;

Phase 2:
- exploration of the locations (2D and 3D seismic, and exploratory wells);
- selection of a suitable depository;
- implementing the approval procedure;

Phase 3:
- extending the selected storage facility by drilling wells;
- erecting above-ground facilities;
- connecting to the CO2 pipeline.

RWE is currently in the second phase.

RWE is also studying the possible use of CO2 for growing algae. The algae pilot plant was
commissioned on 6 November 2008 at Niederaussem/Germany.
For the planning and implementation of this project, RWE Power works with some partners
like the Jacobs University, Bremen, the Jülich Research Centre and the Phytolutions company.

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 The goal is to optimize the entire process chain from algae production to the final product.
In a trial plant, algae are "fed" with flue gas from the power plant.
With regards to the resulting algae biomass, possible uses are to be investigated (e.g. as
biofuel) [29].

7.7.6 Alstom

In 2007 Alstom announced agreements with AEP, Statoil, Vattenfall, E.ON. and PGE
Elektrownia to test CO2 capture technologies in the U.S. and Europe.
In 2008, Alstom and Dow entered into a Joint Development Agreement to develop
advanced amine technology for CO2 capture. Alstom will design, construct and operate the pilot
plant, which is expected to capture approximately 1,800 tons per year of CO2 from flue gas using
Alstom’s and Dow’s advanced amine technology. The flue gas will come from a coal-fired boiler at
the Dow-owned facility in South Charleston, West Virginia. Dow will also provide to the chemicals.
The advanced amine technology should significantly reduce the amount of energy required
for CO2 separation and capture. The West Virginia pilot plant will validate this new technology [25].

References

[1] www.statoilhydro.com.
[2] IEA GHG Weybyrn, CO2 Monitoring & Storage Project, produced by IEA Greenhouse Gas R&D
Programme.
[3] www.co2net.com.
[4] Geological Storage of CO2 from Combustion of Fossil Fuel, European Union Fifth Framework,
Programme for Research & Development, Summary Report, November 2004.
[5] www.co2store.org.
[6] www.co2castor.com.
[7] Caesar, Cesar and DECARBit, Development of pre- and post combustion capture technology in FP7,
newsletter 1-2008 published by SINTEF Energy Research.
[8] www.futuregenalliance.org.
[9] Climate Technology Sheet 2: Pre-Combustion Carbon Capture;Can Europe
[10] http://www.fossil.energy.gov/programs/powersystems/futuregen/
[11] www.co2crc.com.au.
[12] www.newgencoal.com.au.
[13] www.gorgon.com.au.
[14] www.enel.it.
[15] www.eni.it.
[16] www.techint.com/group/it.
[17] www.sotacarbo.it.
[18] www.carbosulcis.eu.
[19] www.co2captureproject.org.
[20] www.k12-b.nl.
[21] Development of a CO2 transport and storage network in the North Sea, Report to the North Sea Basin
Task Force, produced by Element Energy Ltd. with Pöyry Energy, and the British Geological Survey.
th
[22] The 5 Trondheim Conference on CO2 Capture, Transport and Storage, June 2009, Trondheim,
Norway.
[23] EPRI Joins AEP, Alstom in Mountaineer CCS Validation Project, Power News, September 2009.
[24] www.vattenfall.com
[25] www.alstom.com.
[26] www.total.com.
[27] http://w1.siemens.com/entry/cc/en/.
[28] M.R. Haines, W.K. Heidug, K.J. Li, J.B. Moore, Progress with the development of a CO2 capturing solid
oxide fuel cell; Journal of Power Sources 106 (2002) 377-380.
[29] www.rwe.com.

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8. RESEARCH AND DEVELOPMENT (R&D)

The Carbon Capture and Storage process needs further research to become commercially
available in the coming years.
Some CO2 capture and storage technologies are already used in industry, thus there is no
real completely new knowledge required, there are no new inventions which have to be made, and
there are no unknown mechanisms or processes.
However they must be further studied in order to improve their performance, to reduce
costs, to optimize the process.
Some technologies and tools to be studied and developed are shown below.

8.1 R&D in carbon dioxide capture

Separating agents [1]

• Materials research improving the performance and the stability in a flue gas environment of the
separating agents such as adsorbents, membranes, as well as lowering their costs;
• Development of new solvents with high CO2 loading, low regeneration energy requirement and
fast reaction kinetics;
• Reduction or avoidance of thermal and oxidative degradation of sorbents;
• Reduction of impact of flue gas contaminants (particulates, sulphur- and nitrous oxides) on the
solvent process;
• Investigation and analysis of solvent degradation mechanisms;
• Development of new or improved physical or chemical solvents for gas treatment under
pressure;
• Investigation of CO2 hydrates;
• Achievement of the cost-effective cryogenic separation of CO2 and H2;
• Development of membranes for separating CO2 and H2 with better selectivity and durability
than currently used.

Pre-combustion capture [1]

• Development of highly efficient gas turbines for hydrogen combustion;

• Development of fuel conversion technologies with O2 membrane production;
• Development of water gas shift membrane reactors which permit the shifting of CO and H2O
in CO2, with direct separation of the products what would save steps;
• Investigation of CO2 capture by means of calcium oxide during the steam gasification of
biomass to enhance hydrogen production and to obtain a concentrated stream of CO2 as a
byproduct. In this way it could be realized a net removal of CO2 from the atmosphere [2].

Oxy-fuel capture [1]

• Development of mixed conducting ceramic membrane technology for oxygen production;

• Development of large air compressors and new integration possibilities within the heat system
of the power plants;
• Development and implementation of Chemical Looping Combustion (CLC);
• Development of fuel conversion technologies with O2 membrane production;
• Investigation of long-term operational properties of materials for flue gas environment in oxy-
fuel processes;
• Investigation of corrosion under oxy-coal atmosphere.

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Gas conditioning and CO2 compression [1]

• Optimization of CO2 processing and compression system to remove inert gases from the CO2-
product;
• Investigation of CO2 dehydration and clean-up strategies;
• Efficiency improvement and scale-up of CO2 compressors;
• Design of efficient CO2-compressor chain based: e.g. intercooled, axial CO2 compression;
• Analysis and design of pumps to compress CO2 in a liquid state instead of CO2 compression in
a gaseous state for lower energy consumption.

Materials [1]

• Efficiency improvement of supporting technologies such as vacuum pumps and compressors;

• Development and qualification of new materials for high-temperature-loaded areas in steam
generators, piping, valves, and turbines;
• Development of low-cost and compact equipment for the solvent processes;
• Optimised heat integration methods to limit impact on the power production process;
• Development of process modelling and equipment modelling.

8.2 R&D in carbon dioxide transport

Pipelines [3]

• Investigation of influence of variations in temperature, flow rate, gas stream composition and
pH on the corrosion on different materials;
• Research of materials that can withstand all likely conditions such as offshore applications,
unstable geology, large temperature variations, and consistently cold or hot environments;
• Identification and solution of all issues related to the corrosive behaviour of CO2;
• Studies of adequate crack arresters to reduce the hazard from a potential CO2 pipeline cracks;
• Development of new materials for seals that can resist the CO2 corrosive effect and prevent
leakage;
• Optimization of transport solutions between source and sink;
• Investigation of possible re-use of existing pipelines originally designed for other flow systems
that may be converted to CO2 pipelines;
• Development and optimization of use of intermediate storage systems (tanks, depleted gas
fields, salt caverns);
• Identification of transport infrastructure requirements with reference to volume scenarios for
CO2 production and storage capacity requirements;
• Development of multi-fluid models with phase transition;
• Analysis of possible pipeline depressurization and two phases formation: liquid and gas;
• Research on underwater pipeline technology.

Ships [4]

• Efficiency optimization of terminal storage, with particular emphasis on total systems design,
construction and safety, including load and off load port applications;
• Identification of the best storage medium and any environmental impacts where CO2 might
escape during trans-shipment;
• Assurance refrigerated CO2 can be safely, environmentally and economically transhipped and
mixed into a pipeline that carries super-critical CO2;
• Development of optimal materials (stainless steel) for building CO2 ships capable of moving
large volumes of CO2 and resisting its corrosive behaviour.

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Impurity components

• Experiments and simulations to assess the effect of each impurity component in the CO2
stream;
• Studies of the interaction of CO2, water, oxygen, heavy metals, particulates and other acid
gases, as well as varying levels of different impurities;
• Development of low cost materials options to permit CO2 gas stream with higher levels of
contaminants to be transported and stored safely.

Environmental and safety impact

• Risks assessment of CO2 transportation;

• Determination of the environmental footprint of such infrastructure;
• Development of an accurate and verifiable monitoring systems in order to detect potential
infrastructure leakages;
• Investigation of pipeline network construction in densely populated areas.

8.3 R&D in carbon dioxide storage

Geological formation storage [5]

• Determination of the potential demand for CO2 in commercial applications, e.g. enhanced oil or
gas recovery;
• Investigation of CO2 storage capacity in deep aquifers;
• Realization of new Enhanced Gas Recovery test sites in order to fill knowledge gaps about the
behaviour of the injected CO2;
• Investigation in coal beds to clarify the real CO2 adsorption capacity of the coal;
• Up scaling of geochemical and geophysical experimental data;
• Long-term geochemical modelling and knowledge about the basic transport processes;
• Research and investigation into the properties of potential seals for CO2 storage, especially
within the context of alterations in permeability and porosity;
• Investigation in fault characterisation;
• Study of possible fault reactivation due to differential CO2 injection pressure;
• Study of possible CO2 influence on strength properties of faults;
• Development of more advanced assessment tools and databases for prudent forward planning
of large scale storage activities;
• Studies of thermodynamic properties for mixtures of impure CO2 (especially if SOx are co-
injected) and residual natural gas in reservoirs by means of experimental data, geochemical
studies and models;
• Investigation of the impact on fresh groundwater quality from CO2 escaped from storage site;
• Development of policy measures in order to ensure that CO2 emitters/providers are properly
placed with respect to the infrastructure.

Ocean storage [6]

• Research on understanding the impact of CO2 on marine ecology;

• Quantification of the effectiveness and benefits of ocean sequestration;
• Identification of favourable sites;
• Determination of the storage capacity.

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References

[1] European Technology Platform for Zero Emission Fossil Fuel Power Plants, Working group n. 1: Power
Plant and Carbon Dioxide Capture, October 2006.
[2] N. H. Florin, A. T. Harris, Enhanced hydrogen production from biomass with in situ carbon dioxide
capture using calcium oxide sorbents. Chemical Engineering Science 63 (2008) 287–316.
[3] Strategic Research Agenda (SRA) of European Technology Platform for Zero Emission Fossil Fuel
Power Plants, Working group n. 3: Infrastructure and Environment, May 2006.
[4] Strategic Research Agenda (SRA) of European Technology Platform for Zero Emission Fossil Fuel
Power Plants.
[5] European Technology Platform for Zero Emission Fossil Fuel Power Plants, Working group n. 2: CO2
Use and Storage, May 2006.
[6] Ocean Storage of CO2, produced by IEA Greenhouse Gas R&D Programme (1997).

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9. CONCLUSION
The Carbon Capture, Sequestration and Transportation technology is currently a great
challenge.
Important commercial projects such as Sleipner, In Salah, Snøhvit and Weyburn are
demonstrating that, given the right geological and reservoir conditions, injecting industrial-scale
volumes of CO2 into saline aquifers is achievable [1], however there are still some issues to be
solved in order to allow the CCS&T development:

• costs;
• lack of a specific legal framework;
• public acceptance;
• further research.

Costs

There is a high degree of uncertainty in estimating the costs of CCS&T because of

significant variations between projects’ technical characteristics, scale and application.
With the exception of CO2 storage for Enhanced Oil Recovery projects, the only reason why
CCS&t is implemented is to reduce CO2 emissions. Hence, in the absence of measures for limiting
CO2 emissions, there are likely only small, niche opportunities for CCS&T technologies to deploy
[2].
Moreover the development of CCS&T will depend both on the price of the technology and
carbon price. Current CO2 market prices as well as future projections for the 2008 – 2012 period of
the Emission Trading Scheme (ETS) show price levels around 21 €/tCO2. Such price is insufficient
for inducing structural deployment of CCS&T, although it will be high enough for some options [3].
Therefore, in order to realize significant market penetration of CO2 capture, sequestration
and transportation technology, incentives are needed to stimulate the required large investments in
this additional technology by power companies and industries. In addition carbon prices must be
established, in the form of a carbon tax or a trading system [4].

Lack of a specific legal framework

There is uncertainty over that would be responsible for monitoring storage sites, how long
monitoring would be needed and what that monitoring would require over time. In fact even if most
companies express a high degree of confidence regarding the permanence of CO2 storage in
geological reservoirs, they are unwilling to remain liable for those reservoirs for a long time after
site abandonment. The main reason is that the lifetime of private site operators is generally shorter
than the storage duration. Since the lifetime of the State is longer, it could become the more
appropriate organisation for assuming long-term liability [5].
Transport for CCS&T is currently governed by existing natural gas transport regulation;
however obtaining permits for transport where new pipeline routes are required remains a big
challenge, particularly where cross-border needed [6].

However with regards to legal framework, European Union is working to implement

regulations on CCS&T. This year a European Directive was published for the environmentally safe
geological storage of carbon dioxide: Directive 2009/31/EC of 23 April 2009.
This Directive comprises:

• selection of storage sites and exploration permits;

• operation, closure and post-closure obligations;
• third-party access;
• general provisions.

It does not permit the storage of CO2 in the water column.

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 This Directive shall not apply to geological storage of CO2 with a total intended storage
below 100 kt, undertaken for research, development or testing of new products and processes.

Public acceptance

An uncertainty exists around the public support for CCS&T. Public concerns turn on
whether the CO2 captured and stored will remain isolated from atmosphere in the long term and on
whether the CCS&T process presents health or environmental risks.
A Massachusetts Institute Technology (MIT) study showed that levels of public awareness
of CCS&T in US were low; however a possible way of resolving some of scepticism could be
effective public information campaigns that significantly can increase CCS&T acceptance [6].

Further research

The CCS&T technology can effectively eliminate up to 90% of the carbon emissions from
fossil fuels power plants and lead to an overall reduction in EU-27 CO2 emissions of 25-30% by
2030 to 2000 [7].
The consensus of literature shows that CCS&T could be an important component of the
huge portfolio of energy technologies for climate change mitigation with renewable energies,
energy efficiency and nuclear power [2].

Fig.9/1 Illustrative examples of the global potential contribution of CCS as part of a mitigation
portfolio based on two alternative integrated assessment models (MESSAGE and MiniCAM).
a) and b) show global primary energy use, including the deployment of CCS;
c) and d) show the global CO2 emissions in grey and corresponding contributions of main emissions
reduction measures in colour [2].

In order to avoid being too late to fight the climate change, it is extremely important to carry
out demonstration plants by 2015.
It is also necessary to continue to investigate all three main capture technologies and the
various storage options in order to determine which are the best.

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 Moreover looking on countries with an increasing electricity demand and a huge amount of
coal like China and India, the necessity of CCS&T as a strategic climate protection option can be
much more evident. Maintaining the global lead in developing CCS&T technologies, European
Union could generate new commercial opportunities for European business in these countries.

References

[1] K. Michaela, G. Allinson, A. Golaba, S. Sharmaa, V. Shulakova, CO2 storage in saline aquifers II –
experience from existing storage Operations; Energy Procedia 1 (2009) 1973–1980.
[2] IPCC, 2005. IPCC special report on carbon dioxide capture and storage. Prepared by working group III
of the Intergovernmental Panel on Climate Change.
[3] Technical support for an enabling policy framework for carbon dioxide capture and geological storage.
Task 3: Incentivising CO2 capture and storage in the European Union; April 2007.
[4] www.co2net.com.
[5] H. de Coninck, T. Flach, P. Curnow, P. Richardson, J. Anderson, S. Shackley, G. Sigurthorsson, D.
Reiner, The acceptability of CO2 capture and storage (CCS) in Europe: An assessment of the key
determining factors Part 1. Scientific, technical and economic dimensions; International Journal of
Greenhouse Gas Control (2008).
[6] Carbon Capture & Storage: Assessing the Economics, report written by McKinsey&Company.
[7] Communication from the Commission to the Council and the European Parliament - Sustainable power
generation from fossil fuels: aiming for near-zero emissions from coal after 2020; 10.01.2007.

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