Accepted Manuscript

Title: THE CO2 ECONOMY: REVIEW OF CO2 CAPTURE

AND REUSE TECHNOLOGIES

Authors: Efthymia Ioanna Koytsoumpa, Chistian Bergins,

Emmanouil Kakaras

PII: S0896-8446(17)30069-4
DOI: http://dx.doi.org/doi:10.1016/j.supflu.2017.07.029
Reference: SUPFLU 3996

To appear in: J. of Supercritical Fluids

Received date: 23-1-2017

Revised date: 21-7-2017
Accepted date: 23-7-2017

Please cite this article as: Efthymia Ioanna Koytsoumpa, Chistian

Bergins, Emmanouil Kakaras, THE CO2 ECONOMY: REVIEW OF CO2
CAPTURE AND REUSE TECHNOLOGIES, The Journal of Supercritical
Fluidshttp://dx.doi.org/10.1016/j.supflu.2017.07.029

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THE CO2 ECONOMY: REVIEW OF CO2 CAPTURE AND REUSE TECHNOLOGIES

Efthymia Ioanna Koytsoumpaa,b,*, Chistian Berginsa, Emmanouil Kakaras a,b

a
Mitsubishi Hitachi Power Systems Europe GmbH, Schifferstrae 80, Duisburg, Germany
b
National Technical University of Athens, Laboratory of Steam Boilers and Thermal Plants, 9
Heroon Polytechniou, Zografos 15780, Athens, Greece

Corresponding author:

* Efthymia Ioanna Koytsoumpa

Tel.: +49 203 8038 2872

E-Mail: e_koytsoumpa@eu.mhps.com

Address: Mitsubishi Hitachi Power Systems Europe GmbH, Schifferstrae 80, Duisburg,
Germany

Graphical abstract

1
Highlights

Review of global commercial CO2 capture applications in thermal sector

Review of global commercial CO2 capture applications in industrial sector

Review of global CO2 capture utilisation potential

Assessment of power to fuel technology

Review on the development of supercritical CO2 Brayton cycles

Abstract

The continuously increasing share of Renewable Energy Sources (RES) and EU targets for CO2
reduction and energy efficiency necessitate significant changes both on technical and regulatory
level. Environmental challenges of CO2 emissions are assessed in a review of CO2 capture and
utilisation technologies, offering new opportunities in CO2 economy. Commercial applications in
the thermal power and industrial sector for pre and post combustion capture as well as the
potential of direct air CO2 capture are reviewed. The potential of Carbon Capture and Utilisation
(CCU) is assessed focusing on the use of CO2 for fuel as well as for combined heat and power
production. Combining CCU with energy storage as an evolutionary measure for balancing RES
with thermal power under the power to fuel concept presents high market potentials for fuel and
chemical production. Moreover, the recent progress in supercritical CO2 cycles for combined
heat and power production is reported.

1 Abbreviations

BOF Basic Oxygen Furnace

BTX Benzene, Toluene, Xylene
CAES Compressed Air Energy Storage
CCS Carbon Capture and Storage
CCU Carbon Capture and Utilisation
CHP Combined Heat and Power
DAC Direct Air Capture
DEA Diethanolamine

2
DEPG Dimethyl Ether of Polyethylene Glycol
DGA Aminoethoxyethanol
DME Dimethyl-ether
DOE Department of Energy, US
DPA Diisopropanolamine
EJ Exajoules
EOR enhanced Oil Recovery
EPPSA European Power Plant Suppliers Association
ESA Electrical Swing Adsorption
ESI Emirates Steel Industries
EU European Union
FQD Fuel Quality Directive
GHG GreenHouse Gas
GJ Gigajoules
Gt/y Gigatonnes per year
HECLOT High-Efficiency Calcium Looping Technology
HTHP High Temperature Heat Pump
ICEs. Internal Combustion Engines
IGCC Integrated Gasification Combined Cycle
kg kilogramms
LAES Liquid Air Energy Storag e
LHV Lower Heating Value
M100 Pure methanol fuel
M15 15% blend of methanol in gasoline fuel
M50 50% blend of methanol in gasoline fuel
M95 95% blend of methanol fuel
MDEA Methyldiethanolamine
MEA Monoethanolamine
MeOH Methanol
MHI Mitsubishi Heavy Industries
MJ Megajoules
MTBE Methyl tert-butyl ether
MTG Methanol-To-Gasoline process
Mtpa Million tonnes per annum
MWe Megawatt electric
MWhe Megawatthours electric
MWhth Megawatthours thermal
MWth Megawatt thermal
NMP N-Methyl-2-Pyrrolidone
OECD Organisation for Economic Co-operation and Development

3
 OMEs Oxy-methylene ethers
PC Propylene Carbonate
PCC Post-Combustion Capture
PPI Pulp and Paper industry
ppm parts per million
PSA Pressure Swing Adsorption
PtM Power to Methanol
RED Renewable Energy Directive
RES Renewable Energy Sources
SMP Systems Market Price
SNG substitute natural gas
SOFC Solid Oxide Fuel-Cell,
TEA Triethanolamine
TOU Time-of-use pricing
TSA Temperature Swing Adsorption
TTGR-BF Top Gas Recycle Blast Furnace
TVS Temperature Vacuum Swing
US United States
vol%, Volume percentage
VPSA Vacuum Pressure Swing Adsorption
VSA Vacuum Swing Adsorption

Keywords: CO2 capture, CO2 utilization, power to methanol, CO2 cycles

Contents

1 Introduction ......................................................................................................................... 5
2 CO2 Capture ....................................................................................................................... 7
2.1 CO2 Capture in thermal sector ..................................................................................... 8
2.2 CO2 Capture in industry ............................................................................................... 9
2.3 Direct CO2 Capture from air ........................................................................................13
3 CO2 Utlisation ....................................................................................................................14
3.1 CO2 utilization and energy storage under Power to Fuel Technologies .......................15
3.2 CO2 as working medium .............................................................................................18

4
 3.3 Supercritical CO2 Brayton Cycles ................................................................................18
4 Conclusions .......................................................................................................................21
5 Acknowledgements ............................................................................................................21
6 References ........................................................................................................................23
7 Abbreviations ...................................................................................................................... 2

2 Introduction

The European Union (EU) energy strategy for 2030 and 2050 sets specific targets for the
transition of the current European energy system towards a low carbon energy system with
decreased GreenHouse Gas (GHG) emissions, increased energy efficiency and increased
share of Renewable Energy Sources (RES). Especially for 2030 a 40% reduction in carbon
emissions and at least a 27% EU-wide share for renewables in primary energy consumption is
foreseen. The overall electricity generation mix in EU has been following a decreasing trend
over the last few years, as a result of dwindling fossil fuel generation (mainly coal and gas), with
stagnating shares of nuclear and hydro, and a continuously increasing share of renewables.
Different velocities are observed in energy transition of EU Member states with Germany and
Austria to adopt more ambitious targets towards the increase of installed capacity and
production of RES, while other straggle to meet EU targets. After the 21st United Nations
Climate Change Conference in Paris in 2015, COP21 agreement sets a new benchmark limit
the rise in global average temperature to well below 2C in order to mobilise international
political response and measures to climate change. It vindicates the EUs early efforts and
associated legislation to reduce carbon emissions, and the thermal power industry is ready to
tackle the associated challenges. The old fleet of thermal power plants is not optimised for
flexible operation. The existing plants are operated now at very low part-load efficiencies, and
therefore both emissions and resource consumption are high. So the fleet is not able to
contribute to policy goals. Simultaneously, the increasing of RES cannot be continued without
safety measures and careful considerations. Decreasing fossil fuel- fired power plant capacity
without any countermeasures endangers the security of energy supply, which is challenging in
an industry-based society like EU [1, 2]. An insufficient network infrastructure represents an
important barrier for RES, increasing penetration leading to increased levels of curtailment or
requiring additional back up capacity, which can be provided by thermal power and
combinations of thermal power and energy storage. On the other hand, the coupling of
electricity markets leads to a better utilization of the energy sources and lower electricity prices,
the Systems Market Price (SMP) reduction is a fact with profound examples that of Germany
and Spain due to the merit order effect. All effects of energy policy, including rising electricity
prices in the consumers side, might lead to awakening of the European economies if no prompt

5
political counter measures are taken either by Member States or, preferably, on the EU-level.
The increasing share of intermittent RES comes with technical and market challenges, which
need to be faced with flexible thermal plants, improved RES-technology and reactive power, a
Pan-European overlay grid, transmission technologies with improved grid monitoring, control
and effective energy storage. Although the coupling of electricity markets in Europe leads to a
better utilization of the energy sources and lower electricity prices, technical challenges need to
be faced. The technology portfolio for high RES Systems is depicted in Figure 1.

The main question for the future development of power industry and electricity markets is the
security of supply, the energy efficiency and the decarbonisation. In the decarbonisation efforts
and energy efficiency, the EU Commission has already set up a roadmap towards 2030 and
2050. The thermal power generation sector has already performed considerable steps towards
reduction of carbon footprint and increase of energy conversion efficiency and is expected to
have a considerable share in the European generation mix until 2030 [1, 2].The security of
supply and the market model are still under investigation. Two aspects can be highlighted here.
First, taxes and policy costs make electricity artificially expensive to end users, thus hampering
decarbonisation not only via shifting the costs to end users but also by hindering market
incentives for the necessary investments either as capacity investments or as the deployment of
storage technologies which support both energy efficiency and avoidance of energy curtailment.
Secondly, todays demand side management should be enriched for the future high RES
system. Additional measures are considered such as integration of wholesale markets with day-
ahead market coupling and cross-border intraday and balancing electricity markets. These
measures together with grid upgrading, which requires high investments (transmission lines),
cannot currently assure and guarantee a successful and advanced market design due to the
complexity of the algorithm with the combination of centralised, decentralised and smart grid
systems. Although price incentives (time-of-use pricing -TOU) are provided to consumers for the
reduction of their energy self-consumption and/or moderation of their peak demand and shift of
it over time, clearly indicates that shifting the choice to single consumers provides no answer to
the security of supply. From the technical point of view, the existence of dispatchable flexible
and back-up capacity in combination with energy storage technologies is the future technology
responses to secure an efficient energy transition. In this context, dispatchable and flexible
thermal power will provide primarily back-up to RES and will be able to simultaneously provide
primary and secondary control services, supporting grid stability and also heat to heat grids.
Capacity remuneration markets with stand-by thermal power plants and their balancing with a
cross-sectorial approach of energy shift to heat grids and storage technologies would allow the
development of regional adequacy assessments with cross-border participation.

The need for energy storage has received significant attention with several roadmaps to arise in
European level as well as in Japan and China, in California and US [3-7]. Energy storage
technologies can be categorized as electric to electric, electric to heat, electric to chemicals as
well as according to their installed capacity and time response ranging from seasonal, to day, to
hour or minute. Energy storage, when directed to electricity grid, can provide arbitrage services,
frequency regulation, load following, voltage support, transmission and distribution services,

6
back up reserve services with basic technologies being represented by pumped hydro, flywheel
and compressed air energy storage (CAES) transform, Liquid Air Energy Storage (LAES) and
batteries. However, there is also a variety of energy storage technologies acting as energy
adsorbents and directing the end product to heat and chemical market. Electric to heat energy
storage technologies include thermal and solar thermal storage either in large scale such as
combined heat and power plants, small scale decentralized heat applications or LAES
technologies for heat recovery and electricity generation in different scales. Electric to chemicals
energy storage technologies or power to fuel technologies include power to hydrogen, power to
substitute natural gas (SNG), power to methanol as well as many other derivatives directing
their end products to chemical market or the global transportation sector. Focusing on power to
fuel, any fuel or chemical requiring at least one carbon and one hydrogen molecule enables the
combination of energy storage and Carbon Capture and Utilisation (CCU).

The present work assesses the environmental challenges of CO2 emissions as new business
opportunities in a CO2 trans-sectorial economy. A review of commercial applications in the
thermal power sector and industrial sector for pre and post combustion capture, the potential of
direct air capture as well as the potential of Carbon Capture and Utilisation (CCU) options are
presented. Among those, a special focus on power to fuel technology is given for the conversion
of CO2 to fuels and chemicals, while the use of CO2 in supercritical cycles for combined heat
and power production is reviewed.

3 CO2 Capture

Carbon dioxide can be captured from different sources according to its partial pressure,
operating conditions and composition of the gas mixture. Higher concentrations of carbon
dioxide allow relatively inexpensive separation. Carbon dioxide can be primarily available in
every combustion process, being its main product. In thermal power generation, including fossil
fuels, biomass, municipal waste and other waste to energy plants, carbon is captured after the
combustion process (Post-Combustion Capture-PCC). There are in general two other capture
categories: the oxyfuel combustion capture, where almost pure oxygen is used in combustion
CO2 is recirculated in the oxygen combustion process and the pre-combustion capture [8, 9]. In
addition, gasification technology, when used in Integrated Gasification Combined Cycles (IGCC)
is also included in thermal power generation, offering the opportunity of both post and pre-
combustion capture [9]. The thermal power sector has the biggest potential for cutting
emissions, whereas the CCS could play a decisive role. Total OECD (Organisation for
Economic Co-operation and Development) CO2 emissions in the thermal sector accounted for
40%, while in the transportation sector for 29%. Total OECD CO2 emissions from fuel
combustion fell by 1.4% to 11.9 Gt CO2 in 2014 compared to 2007, having remained stable in
2013, from which oil was responsible for the largest share of CO2 emissions from fuel
combustion (40%) in 2014, followed by coal (33%) and gas (26%) [10]. Carbon dioxide
concentration in air coal combustion may vary from 12-15 vol%, in natural gas combustion from
3 to 10 vol%, while in fuel oil and biomass from 3-8 vol% [11]. Post Combustion capture of flue
gas streams at atmospheric pressure can be achieved by several physical and chemical

7
separation methods, such as absorption, membranes, adsorption and cryogenic processes.
There are several technologies available for post-combustion capture, which are based on
biological, physical, chemical methods and combination of those [8]. In the present work, the
commercial technologies of post- and pre- combustion capture are assessed.

3.1 CO2 Capture in thermal sector

Post-combustion carbon with amine solvents is the most cost effective and mature technology,
which has been demonstrated at full commercial scale [8, 9, 12, 13]. Solubility of CO2 in solvent
with high cyclic capacity and optimum heat of absorption are required for the energy intensive
post-combustion process with low atmospheric partial pressures of CO2 in flue gas streams. The
general trend of amines in order of loading capacity is Primary amines < Hindered amines <
Secondary amines < Tertiary amines < Diamines [13]. There is several progress made on
increasing the energy demand for these solvents based on the use single conventional
monoethanolamine with approximately 4.1 GJ per tonne of CO2 captured in the 1980s. The
current commercial processes have significantly reduced the energy demand to 2.6 GJ per
tonne of CO2 [13].The state of the art Mitsubishi Heavy Industries (MHI) process, KM-CDR
Process developed together with Kansai Electric Power Co., Inc., since 1990, has already
been implemented in 8 commercial operating plants in 2011, while this number has been
increasing. KM-CDR Process with the developed absorption solvent, KS-1TM has an optimum
energy consumption of 2.44 MJ/kg CO2 from natural gas boiler flue gases as reported in [14],
while the advantages of KS-1TM, KS-2TM, KS-3TM developed solvents are presented in [15, 16].
The largest commercial post-combustion capture plant in power industry in Petra Nova Carbon
Capture Project in Texas, United States uses KM-CDR Process by MHI as depicted in Table
1. MHI has also operated a CO2 capture demonstration test facility with a capacity of 500 tonnes
per day from coal derived flue gases, constructed at Southern Company subsidiary Alabama
Powers Plant Barry in Mobile county, Alabama, and attained a cumulative CO2 underground
storage amount of 100,000 tonnes. MHI continues technological development for the
deployment of the large scale CO2 capture plants reporting an improvement of 30 percent or
more of efficiency in power generation compared to competitors existing technologies with
implementation of 90 percent CO2 capture, waste-heat recovery and MHIs advanced flue-gas
treatment system [17, 18]. Other commercial processes are the Econamine FG PlusTM
technology based on MEA solvent for high oxygen content flue gases, the Hitachi H3-1 solvent
with advantageous anticorrosion behavior and 2.4 MJ/kg CO2 energy demand for coal fired flue
gas as well as the Shell Cansolv Technology with the DC-101, DC-103 and DC-103B tertiary
amine solvent (simultaneous SO2 and CO2 removal) implemented in today s second largest
capture plant in Saskatchewan, Canada as presented in Table 1 [19-22]. Sinopec has also
developed a MEA based post-combustion capture which is used at Shengli power plant,
Dongying, Shangdong Province, China [23]. In addition, the Alstom Chilled Ammonia Process,
the Aker Clean Carbon, the OASE blue BASF process, and the Praxair amine have been
developed [12, 24-29]. There is a continuous research effort on the development on more
efficient solvents to reduce the energy demand to around 2-1.1 MJ/kg CO2, on the heat
integration and optimization of the process components (eg. modifications in tower packing,

8
optmising water balance, installation of expanders etc) and to reduce the operational and capital
costs [12, 13, 29, 30].
According to [31], in 2016 15 large-scale CCS projects around the world, with a CO2 capture
capacity of close to 30 million tonnes per annum (Mtpa) were in operation, while in 2017 further
three large-scale projects, all in the US, will increase the CO2 capture capacity to 35 Mtpa. It is
expected that by the end of 2017, the total CO2 capture capacity will increase to approximately
40 Mtpa with 21 projects. Table 1 presents the three largest CCS projects in the thermal sector
incorporating post-combustion capture technologies.

3.2 CO2 Capture in industry

In industry, there is a high amount of direct CO2 emissions, which the industries have been
trying to tackle with. Industrial energy consumption grew to 152 exajoules (EJ) in 2013, 35% of
the global total, while chemicals and petrochemicals, cement, iron and steel, aluminium, and
pulp and paper industry accounted for 68% of industry emissions [32]. CO2 emissions can vary
from 20-30% vol dry in Iron and Steel industry, 14-33% vol dry in cement industry, while in
hydrogen refineries, it can be found in typical concentrations of 15-20% vol dry [33]. There are
processes such as natural gas processing, ammonia production and other fertilizer production
but also bio-ethanol fermentation and biogas plants, where CO2 is an inherent component of the
process. [11,32]. Especially in biogas upgrading, the CO2 concentration reaches 40-50 vol%,
which enables a pre-combustion capture and separation of CO2 and a high valuable methane
rich gas. In bioethanol and fermentation processes as well as urea/ammonia synthesis, a nearly
pure CO2 stream of around 100 vol% can be found. [32-35].

The pre-combustion capture refers to separation of CO2 generated as a co-product of a

conversion process. In natural gas reforming and gasification, pre-combustion is associated with
the water gas shift reaction for converting the carbon monoxide and water to carbon dioxide and
hydrogen and the removal of carbon dioxide. There are several absorption, adsorption,
membrane and cryogenic processes but absorption processes are the most widely used in
commercial applications. According to the content and composition of the treated gas different
methods for removal are applied usually also used as acid gas removal for simultaneous
separation of carbon dioxide and sulfur species. Depending on the solvent used, the gas
components can be simply dissolved physically or are bound chemically to the solvent
characterized as physical or chemical absorption or a mixture of those [36-38]. At low carbon
dioxide content, the absorption capacities of chemical solvents are much higher presenting
higher affinity when compared with absorption capacities of physical solvents, whereas physical
solvents provide better results at high partial pressures. Thermal energy requirements for
chemical solvents are much higher than those for physical solvents due to the addition of heat
through the reboiler of the stripper column [37]. In physical solvents, the loading capacity of the
solvents is in a virtual linear dependency between the partial pressure of the component to be
removed and the solvent loading according to Henrys law, allowing its regeneration by pressure
throttling. The dissolution of carbon dioxide in the physical liquid solvent is attributed to the van
der Waals or electrostatic interaction and is optimal at high pressure and low temperature

9
[37,38]. Depending on the presence of sulphur species, the regeneration of the physical solvent
might also demand heat for the reboiler duties [39-41]. Two stage processes are also used for
the chemical solvents such as the HiPure Process [42]. Among the physical processes, solvents
such as DEPG (Dimethyl Ether of Polyethylene Glycol), MeOH (Methanol), NMP (N-Methyl-2-
Pyrrolidone) and PC (Propylene Carbonate) are used. The state of the art processes are
Selexol, Rectisol, Purisol, Morphysorb, Fluor [37-42]. Among chemical solvents, primary
amines such as monoethanolamine (MEA), secondary amines Diethanolamine (DEA),
Aminoethoxyethanol (DGA) and Diisopropanolamine (DPA) and tertiary amines such as
Triethanolamine (TEA) and Methyldiethanolamine (MDEA), Ucarsol as well as alternatives to
amines such as hot potassium carbonate are used. Among hot potassium carbonate processes,
Benfield, Catacarb, Giammarco-Vetgrocoke and Vacasulf processes exist. In addition,
mixtures of chemical solvents or physical and chemical solvents can be also used such as in
commercial solvents OASE (aMDEA), Amisol, Sulfinol-D and Sulfinol-M. Flexsorb also
uses hindered amines [37-43]. The composition of the treated gas, the selected operating
process parameters of the scrubbing technologies as well as their stages and heat integration
may present significant differences in the energy demand. In [37], an energy penalty of 7.64 to
14% is reported for natural gas pre-combustion technology based on commercial CO2
separation systems. Minimum electricity demand as reported in [36] for DEPG and MeOH
solvents at 97% CO2 capture without pre-compression from coal steam gasification at 20 bar is
around 0.3 MJ/kg CO2, while in [39] and [40] for DEPG without considering CO2 compression
and at 90% CO2 capture from coal gasification at 35 bar an electric demand of around 0.16
MJ/kg CO2 is reported. For the heat demands for DEPG around 0.12 and 0.29 MJ/kg CO2 is
reported respectively in [39] and [40]. For potassium carbonate and MDEA at 97% CO2 capture
from coal steam gasification at 20 bar, a heat duty of 1.99 and 1.77 MJ/kg CO2 and an electricity
consumption of around 0.05 MJ/kg CO2 is reported in [36]. Due to the wide field of applications
and the diversity of conditions, no further review on the energy demand is presented.

Chemical and petrochemical industry generates as basis olefins (C2-C4) such as ethylene,
propylene, generally obtained from hydrocarbon feedstocks using steam cracking, aromatics
(C6-C8) such as benzene, toluene, xylene (BTX), generated using steam cracking of catalytic
reforming which are further processed into a wide range of plastics, rubbers, resins, solvents
and other petrochemical products, and also synthesis gas based chemicals such as ammonia,
methanol, hydrogen, carbon black, sulphur etc. For the production of synthesis gas based
chemicals as well as for hydrogen production, pre-combustion capture is often used after water
gas shift reaction which moderates the hydrogen to carbon ratio for the subsequent synthesis
[36-38]. According to [31], among the operating commercial CCS projects, the majority has
found application in natural gas processing, fertiliser and hydrogen production implementing
pre-combustion technologies. The initial volume fraction in syngas derived via solid fuel
gasification may vary according to the fuel, the stoichiometric ratio, the operating pressure and
temperature and the oxidation agent but typical values are in the range of 5 to 30 vol dry%
before the water gas shift reaction [36, 44-47]. Natural gas reforming is conventionally
performed via steam reforming, partial oxidation, autothermal reforming, dry reforming of
methane, but also via combined reforming of methane, reforming with membrane, tri-reforming
of Methane. In dry reforming, waste carbon dioxide is used to reform natural gas to syngas with

10
a low H2/CO ratio (1.0) which can be preferentially used for production of liquid hydrocarbons
in Fischer-Tropsch and DME synthesis with the aim of reduction in thermal energy consumption
required by steam generation [48]. In ethylene production from gaseous, liquid or other
feedstocks, carbon dioxide is reduced down to 2 ppm and hydrogen sulfide is removed
simultaneously from the cracked gas by acid gas removal systems (such absorption in caustic
wash and regenerative alkanolamines solvents) in order to avoid formation of ice and hydrates
in the subsequent fractionation steps. In steam crackers, depending on the raw feedstock 1
1.6 ton of CO2 per ton of ethylene is produced, while in comparison to bioethanol derived
ethylene, CO2 emission per ton of ethylene are lower by 60% [49]. In Canada, Shell, on behalf
of the Athabasca Oil Sands Project venture is capturing more than 1 million tonnes of CO 2 per
year using ADIP-X process. The Scotford upgrader turns thick heavy oil from the oil sands
bitumen into synthetic crude for further refining to gasoline and jet fuel cell using hydrogen to
upgrade to lighter oil from the Scotford oil sands bitumen. This is the largest capture and
storage project in oil industry operating since 2015 reducing Scotford plants direct CO2
emissions by up to 35% [50, 51]. In the Tomakomai project, CO2 capture with amine scrubbing
is operating at an oil refinery, which produces high purity hydrogen for hydrotreating via PSA
system. The PSA offgas, contains H2, CH4, CO and a large amount of CO2 in 44-59% volume.
This is Japans first CCS project capturing 100.000 tons of CO2 per year lead by Japan CCS Co.
Ltd which group of major companies with expertise in CCS-related fields, including electric
power, petroleum, oil development, and plant engineering [52]. The Gorgon project has started
operation in 2016 capturing CO2 from the Gorgon Field gas (14 % vol CO2) and the Jansz-Io
field gas (0.15% CO2) in order to be separated from the natural gas stream prior to further gas
processing and liquefaction. This is the world's largest operating sequestration project in gas
industry capturing 3.4-4 million tonnes CO2 per year using ADIP-X [53]. In Coffeyville project,
1 million tonnes per annum (Mtpa) are captured using the Selexol process at a petroleum coke-
based nitrogen fertiliser production process at Kansas, US. Synthetic gas is produced from the
petroleum coke gasification, from which ammonia and urea ammonium nitrate (UAN) fertilisers
are subsequently synthesised. The capture CO2 after compression and dehydration is injected
into the North Burbank Unit for enhanced Oil Recovery. In the Enid project in Oklahoma US,
ammonia, liquid fertiliser and Urea are produced providing a high purity CO2 using Selexol
process which is dehydrated, compressed and transported for enhanced Oil Recovery in a
capacity of 680,000 tonnes of CO2 per annum [54]. An overview of the largest CCS projects in
the industrial sector according to [54] is presented in Table 2.

Among the three leading technologies in Steel Industry, Basic Oxygen Furnaces (BOF) with
Blast Furnace (BF) shares the 69% of worldwide steel production and will remain dominant as it
is the most cost-effective route of virgin ore steel production for high added value products.
Other technologies are FINEX and COREX processes, the smelting reduction (SR), coal
based Direct Iron Reduction (DRI) and gas based DRI (Midrex, HYL/Energiron). Worldwide,
there are few pilot scale facilities using CO2 capture in Steel Industry (HYL/Energiron) [55]. In
2003, the World Steel Association launched the CO2 Breakthrough Programs, with research
and development being done in the EU (ultra-low CO2 steelmaking, or ULCOS I and ULCOS II),
in the US, in Canada, in South America, in Japan (Course 50), in Korea, China and Taiwan, and
Australia [55-57]. Blast Furnace Technology is directly connected with the use of coal which is

11
processed in the coke plant, while studies on substituting coke in a certain extend via pulverized
coal or natural gas or even oil, tar, biomass and waste plastics have been performed. In ULCOS
BF, Top Gas Recycle Blast Furnace (TGR-BF), the Hisarna technology (combination of a hot
cyclone and bath smelter HIsarna based on HIsmelt process), the direct reduction process
ULCORED as well as two electrolysis variants ULCOWIN and ULCOLYSIS were investigated.
The TGR-BF involves the replacement of host blast with oxygen and the recycle of top gas with
the CO2 removal. The technologies for CO2 removal involve Pressure Swing Adsorption (PSA),
Vacuum Pressure Swing Adsorption (VPSA) and amines. The total energy demand required
including compression work as reported in [55] is 1.12, 1.05 and 3.81MJ/kg CO2 for Pressure
Swing Adsorption (PSA), Vacuum Pressure Swing Adsorption (VPSA) and amines respectively.
The worlds first commercial carbon-capture steel project, the Al Reyadah - Masdar Abu /Dhabi
National Oil Company project, has started operation in Abu Dhabi. Amine scrubbing is used to
capture CO2 from an off stream from the Emirates Steel Industries (ESI) Factory with a capacity
of 0.8 million tonnes per annum. After compression and dehydration at Al Reyadah, it is injected
into onshore oil fields for enhanced oil recovery [38, 54].

CO2 is a by-product of the cement manufacturing process as the raw material (limestone) used
in cement manufacturing accounts for roughly two thirds of the total CO2 emitted from the
cement plant. The other third derives from the combustion of fossil fuels to obtain the heat
required for the limestone decomposition process [58]. Pre-combustion, post-combustion and
direct capture as well as oxyfuel are currently being considered [59-62]. Pre-combustion is
related to new integrated gasification technologies for produce syngas production and hydrogen
firing in the cement kiln without CO2 capture from the calcination process. On the other hand,
post-combustion capture has many retroffitting options with lower costs and higher emission
reduction, while the replacement with new highly efficient power plants is also a considered
configuration [61]. Pure oxygen combustion in oxyfuel requires major modifications to burner
design, kiln, and new plant configuration [59-62]. In [61], a categorization according to the
technology readiness level has been made for 5 different technologies, with post-combustion
capture to has the highest level due to its existing applications in thermal power industry. Post-
combustion capture in cement industry has a considerable advantage compared to the thermal
power sector due to the higher CO2 concentration of 14-33% [62]. The pilot plant in Brevik,
Norway with different capture technologies is the most developed project in cement industry
[61]. The main infrastructure includes amine scrubbing from Aker Solutions, whereas Alstoms
regenerative carbonate cycle and sorbents from the Research Institute Triangle and Membrane
technology have been developed [58]. In addition, the High-Efficiency Calcium Looping
Technology (HECLOT) capture project by the Industrial Technology Research Institute (Taiwan)
and Taiwan Cement is in operation capturing 1 ton CO2 per hour [63], while Skyonic has an
operational pilot facility in San Antonio, Texas, US. Capitol SkyMine is expected to capture
75,000 tons annually from the coal-fired Capitol Aggregates Cement plant and utilising the CO2
towards the production of hydrochloric acid, baking soda (sodium bicarbonate) and bleach. The
SkyMine process claims a 30% energy reduction compared to amine-based CO2 capture [64].

In pulp and paper industry, mechanical mills and integrated Kraft mills are commonly used. Kraft
mills in Europe have the highest share of European PPI emissions and thus the Kraft PPI plants
and thus the largest potential for capture of CO2. Emissions can arise from the bark boiler, the

12
black liquor and from the lime kiln, thus it can be biogenic or not depending on the fuels used
[65]. Depending on the installation, CO2 emissions from pulp and paper mills are scattered
around the site in several stacks, but emissions from the recovery boiler are usually considered
with concentrations varying from 10 to 20 vol% [66]. The advantage of capture in Kraft mills is
the biogenic emissions from the recovery boiler [66] considering post-combustion technologies,
while pre-combustion can be used in the gasification of the black liquor [67-68].

3.3 Direct CO2 Capture from air

Carbon dioxide is also available in air with concentration in the range of 399 ppm in 2015
according to [68]. Although the low concentration of CO2 in air requires the treatment of high
volumes, there has been several interest [70]. Direct carbon dioxide (DAC) absorption from
atmospheric air has been investigated since half a century [71, 72] and has been applied in
cryogenic oxygen separation plants, space craft, and submarines [73]. DAC can be achieved
with organic capture, with production of metal carbonates and with the use of sorbents

Organic carbon reduction with organisms, which naturally capture CO2 through photosynthesis,
is fundamentally limited to one-time reductions. Alternative solutions such as ocean flora
creating plankton has also been investigated with limited success [74]. Steel slag and waste
concrete with calcium and magnesium oxides, have also been suggested as air carbon
sequestration materials forming solid carbonates [74, 75]. According to [75], the total annual
production of concrete and steel could capture less than 1% of U.S. emissions. For larger
quantities, regenerative materials are investigated for direct air capture. Fans driving air
counter-currently through convective towers and packed scrubbing towers with sodium
hydroxide solutions have been suggested for the direct carbon dioxide absorption from
atmospheric air [76-78]. In [79], spray towers have also been suggested. The main principal is
the absorption of CO2 into a solution of sodium hydroxide and its conversion to an aqueous
solution of sodium hydroxide and sodium carbonate focusing on optimum conditions at the
contact of the components. However, the sodium carbonate has to be regenerated in a closed
loop process and converted again into sodium hydroxide, via the causticization processes using
lime. In [77] the capture ratio is only 50% capture rate based on CO2 concentration of 380ppm in
air. In [80] and [81], a comparison of air capture and post combustion capture is made. In [80],
for a capture ratio of 25% for both processes the cross sectional area required for air is higher
by a factor of 3.6, while the amount of air processed would be over 1000 times that of flue gas
capture for an equivalent amount of CO2. This provides an indication on the capital costs and
energy requirements. Respectively in [81], the DAC reference plant with a capacity of 1 MtCO2
annually or equivalent to a 150 MWe supercritical power plant based on a scheme published by
[78], requires around 330 absorbers, resulting in a total absorber cross section of 37,000 m2.
Comparing the energy demand, the afore mentioned process, requires a minimum
thermodynamic energy limit of 179 kJ/mol CO2 for the conversion of calcium carbonate to lime
and 109.4 kJ/mol CO2 for the conversion of sodium carbonate to sodium hydroxide [82]. In [81],
the net thermal energy requirement for the DAC plant is estimated at 6.1 GJ for each ton of CO 2

13
captured, which means that combusting natural gas with 75% thermal efficiency for providing
high temperature heat results in a total thermal energy input of 8.1GJ per ton of CO 2 captured.
In addition, the total electricity requirement is also reported in [81] equal to 1.78 GJ per ton of
CO2 captured. However, the authors in [82] suggest the regeneration of NaOH via direct
causticization using titanate. They report that half of the energy is required, as the heat
requirement of the proposed process is equal to 135 kJ/mol and similar to MEA requirements. In
[83], energy requirements as high as 500 -800 KJ/mol CO2 are reported.

Adsorption technology for CO2 capture receives more and more attention due to its potential of
lower energy consumption. Temperature swing adsorption (TSA), temperature-vacuum swing
(TVS), pressure swing adsorption (PSA), vacuum swing adsorption (VSA), and electrical swing
adsorption (ESA) are considered for treatment of feed gases with various CO2 concentrations
[84]. As the adsorption material plays a key role, a lot of research is going on different materials
with zeolites, metal-organic frameworks (MOFs), amine modified adsorbents to receive
significant attention. DAC with adsorption of CO2 has also been investigated. The adsorption
capacity of carbon-based materials and MOFs is strongly pressure dependent and decreases
with at low partial pressures as the CO2 concentration in air [85]. The adsorption capacity of
activated carbons is low, while the presence of water highly influences the selectivity of zeolites
[86]. The combination of chemical and physical adsorption in amine functionalized mesoporous
supports has received several attention for DAC [84-91]. In [89], the specific energy
requirements of the TVS adsorption process studied vary according to the air relative humidity
and are estimated to be 12.5 kJ/mol CO2 of mechanical work and between 493 and 640 kJ/mol
CO2 of heat for operation below 100 C. In [90], capture ratios of 90% and 99% purity are
reported. In [91], the authors have tested amine-grafted mesoporous adsorbents and reported
the formation of urea groups which decreased the adsorption capacity due to thermal
desorption. New startups such as Climeworks, Global Thermostat and Carbon Engineering
have been emerged deploying air CO2 capture technologies [92-94].

4 CO2 Utilisation

Carbon Capture and Utilisation (CCU) explores the use of carbon dioxide in applications other
than storage. Carbon dioxide is already used in a variety of sectors and processes as presented
in Table 3. Especially the enhanced oil and gas recovery has the highest potential for near term
CCS in specific areas [95]. Although, it imposes geographical constrains the same as the
storage sites which are not viable for all CO2 emitters, thus other options are investigated [96].
The European Commission has launched several relevant calls within Horizon 2020 (SPIRE,
BIOTEC, LCE 25, NMBP 19 and 20) to support research on CO2 utilisation as a viable approach
for sustainable production of fuels, chemicals and intermediates [97]. Several European
initiatives have been started to develop CO2 reuse technologies [98], while in US the
Department of Energy support also the research within the Carbon Use and Reuse technology
areas [96]. Utilization of CO2 finds applications in the chemical, oil and power sector, in the food,
pharmaceutical sector, in pulp and paper industry, in steel industry as well as other uses. Its use
can be categorized to resource recovery (e.g. Enhanced Oil and Gas Recovery, Enhanced

14
Coal-Bed Methane Recovery), captive (process integrated) using CO2 as an intermediate
product in the manufacturing chain without external sources and the non-captive or merchant
use [95-96, 99-101]. As reported in [95], the order of magnitude for CO2 reuse is very pertinent
with the global non captive consumption to be estimated at approximately 80 Mtpa, while only
urea production in the global captive consumption reaches 113 Mtpa. The worldwide urea
production required 112-120 Mtpa CO2 and was estimated to grow up to 176 Mt by 2016 as
given in [102,103]. CO2 utilisation has an estimated potential of at least 3.7 Gigatonnes per year
(Gt/y), which is equal to about 10% of the worlds current annual. It is expected to produce
revenues coupled with favourable CCS projects in developing economies, releasing some of the
pressure on the energy costs and abatement and aiming at value-added products that create
jobs and economic benefits [99]. In [104], CO2 utilisation potential has been evaluated at around
300 Mtpa. The Global CO2 Initiative presents an annual market on CO2-based products of 0.8 to
1.1 trillion dollars via using over 10% of annual global CO2 emissions.

The highest potential and market size for CO2 utilisation is identified in the chemical and oil
industry, with the Enhanced Oil Recovery (EOR) to have the greatest potential for non captive
demand (estimated up to 300 Mtpa in [95]), the urea production, the polymer processing as well
as in fuel and chemical synthesis such as renewable methanol, formic acid. The cement sector
has also a great uptake potential of up to 300 Mtpa in [95, 104], In the food sector, a medium
potential exists basically for beverage carbonation, packaging, decaffeination and horticulture.

In the power sector, if supercritical CO2 cycles are not only limited to todays existing
applications of geothermal plants and heatpumps, a broad market is to be expected for future
potential applications ranging from nuclear, coal, biomass and natural gas, waste incinerator
plants as well as in small combined heat and power applications [95-96, 99-101]. In the present
work, a focus is made on the CO2 utilisation related to the power sector focusing on chemical
and fuel synthesis via power to fuel technology and on using CO2 in supercritical cycles.

4.1 CO2 utilization and energy storage under Power to Fuel Technologies

Power to fuel refers to Power to gas, either hydrogen or SNG or in the production of other liquid
fuels such as methanol, dimethyl-ether (DME), oxy-methylene ethers (OMEs), other chemicals
and derivatives. As a mean of energy storage, the electrolyser technology simultaneously
converts water to hydrogen via use of electricity and also provides grid balancing services.
Although the electrolyser technology of alkaline electrolysers is mature, the lack of existing
infrastructure and its capital intensity as well as safety issues are prohibiting its wide use for
power to hydrogen applications. The combination of CO2 utilisation and energy storage is
realized under Power to Fuel technology, where captured CO2 and the produced hydrogen are
mixed and compressed before inserted in catalytic reactors [105]. Power to SNG includes the
production of methane in catalytic reactors [11]. The prices of fossil natural gas prohibit the
merge of electricity market with natural gas market as a high utilisation factor reflect operation in
high electricity prices mitigating the elevated costs to the end product [105].

15
Methanol production via the use of carbon dioxide and hydrogen produced via water electrolysis
has been demonstrated at the production plant of 4,000 tons of methanol from CO2 per year,
George Olah plant at Svartsengi, Iceland, built and operated by Carbon Recycling International.
The process for the conversion was described before [104] and can reach conversion
efficiencies of >60% from electricity to CO2 derived methanol lower heating value depending on
the application. The integration of the methanol technology with a power plant and flexible
operation will be further demonstrated in an ongoing EU funded project, MefCO2 (Grant
agreement 637016) [105]. The wide application of power to methanol (PtM) technology in
power, chemical and steel industry and its high potential of use in large automotive market
contributes to CO2 emission reduction and offers grid balancing services. A large-scale
commercial methanol plant connected to the grid, able to produce 50,000 to 100,000
tonnes/annum methanol (based on 8500 full load hours) requires thermal energy of 1.01
MWhth/tonne methanol and electric energy of 9.74 MWhe/tonne methanol based on alkaline
electrolyser with an efficiency from an Alternating to Direct Current of 4.4 kWhe/Nm of H2
produced. If the heat is provided from a power or Combined Heat and Power (CHP) plant, the
corresponding amount of electricity not produced but consumed as heat for covering the thermal
demands of the CO2 Capture is 0.15 MWhe/tonne methanol (based on 15% losses at the
specific heat extraction conditions for covering the thermal demands of the CO2 Capture). The
total energy demand in units of electrical energy is therefore 9.89 MWhe/tonne methanol. The
configuration of the existing power plant and the PtM plant is shown in Figure 2. Integration with
power or CHP plants can involve only extraction of flue gas and provision of heat extracted from
the steam cycle in order to cover the reboiler needs of post-combustion capture. The techno-
economics of this scale are highly influenced by a) the final methanol price as well as by b)
regulations concerning electricity market, c) fuel and chemical market and specifically by d) the
Renewable Energy Directive (RED) and e) Fuel Quality Directive (FQD) for non-biological
sources. Both the original RED and FQD set ambitious targets on the decarbonisation of the
transport sector which put pressure on the fuel market to fulfil the stricter sustainability criteria
on a scale that matches fossil fuels. Therefore, low carbon electricity should be used for the
production of the low carbon fuel.

On the other hand industrial must-run CHP plants in industry and connected to heating grids
suffer from decreased demand for electricity while they have to burn by-products like off-gases
from steel industry or wood waste from wood and pulp and paper industry and/or have to deliver
steam or heat to industry and the heating grids. In such cases, optimum boundary conditions
exist for implementation of power to fuel as except from the available CO2, the necessary
infrastructure also exists such as heat source/sink and connections to the grid. If other low
carbon electricity is available, the heat export can be increased by using electrolyser waste heat
and a high temperature heat pump (HTHP) for steam production increasing the efficiency [106].
This way must-run power plants can create new business by providing methanol and in parallel
enable more renewables to be installed and/or avoid curtailment in conjunction with new
transmission lines and optimally designed grid upgrades. Additional advantages arise from the
sales of grid services, nearby consumers of oxygen like steel-industry. In Figure 3, the

16
integration of power to fuel technology -focusing on methanol production- in CHP systems for
future applications is presented.

Although methanol is already used for fuel blending, for Methyl tert-butyl ether (MTBE)
production for biodiesel production, other pathways for the introduction of low carbon fuel are
available such as the conversion of methanol to drop-in fuels. Drop-in fuels can be used pure or
can be blended with gasoline for use in existing internal combustion engines (ICEs). Examples
are oxygenates like dimethyl-ether (DME) and oxy-methylene ethers (OME) [107]. DME can
easily be manufactured from methanol with proven technology, but is not liquid at ambient
temperature and therefore requires a separate distribution infrastructure with pressurised tanks.
OME production processes are still under development. The methanol-to-gasoline process
(MTG) on the other hand is well developed and used in large scale but as also mentioned for
OME-, it has lower overall efficiency than direct use of methanol or DME [107-110].

Direct methanol use as blend with high methanol content 50-85%, in ICEs is possible in flex-fuel
engines or as M100 (pure methanol) in dedicated methanol engines. After fleet tests of
methanol cars in Europe and the US [111] in the 80s triggered by the oil crisis, the R&D
activities slowed down in a phase of low oil prices. Having urgent need today for the reduction of
emissions in the transport sector new activities are started for methanol as a clean alternative
[105]. Due to the absence of carbon-carbon bonds in the methanol molecule, soot formation is
avoided, resulting in virtually zero values. The absence of sulphur in the fuel leads to inherently
zero sulphur emissions from pure methanol combustion. The lower flame temperature of
methanol also results in inherently lower NOx emissions. Even at higher compression rates
enabled by methanols wider knock limits and allowing highest ICE efficiency, lower levels of
NOx emissions are achievable compared to gasoline [112]. In Europe, a 3% blend of methanol
in gasoline is standardized for SP95 gasoline in DIN EN228. Some countries incentivise
blending or use of low carbon methanol in biodiesel production, and in the UK no road taxes are
applied to M95 (95% methanol). Australia has a similar initiative with reduced road taxes for
methanol. In Sweden, unblended methanol is also utilised as zero sulphur marine fuel. China
has sold a 15% blend of methanol in gasoline (M15) as automobile fuel in several provinces and
fleet tested 100% methanol (M100) in eleven major cities. In Iceland, Carbon Recycling
International has conducted fleet testing of at 50:50 blend of methanol and gasoline (M50) in
flexible fuel vehicles from Ford and is now testing M100 with vehicles from Chinese automobile
manufacturer Geely [106,113].

In future fuel cell cars based on methanol can enable the highest well-to-wheel efficiencies
compared to all other synthetic fuels with Ballard, SFC Energy and Serenergy to have already
commercialized the technology. Serenergy in Denmark is delivering methanol fuel cell systems
as range extenders for electric cars [114-115]. Nissan started testing of bio-ethanol fuel cell
(Solid Oxide Fuel-Cell, SOFC) cars in 2016 [116].

Although the final value of the carbon footprint reduction depends on the specific application
and the CO2 footprint of the electricity used, there are several aspects of environmental
protection and economic benefits associated with PtM. Carbon dioxide is captured and reused

17
for replacing fossil fuels and their respective emissions from exploration, transport and
processing reducing NOx, SOx and soot emissions in the transportation sector as well as the
energy dependency in Europe in a sustainable and economic way.

4.2 CO2 as working medium

Waste heat streams are generated mainly by exhaust gases in boilers, ICES, kilns, furnaces,
ovens, turbines, engines, and other equipment in the thermal and process industry, as well as in
mines and other sites including residential sites [117]. The EU Energy Efficiency Directive
includes a comprehensive assessment of the national potential of cogeneration and district
heating and cooling in each EU member state. According to 2012, a target of 20% energy
efficiency target by 2020, while since November 2016, an update was proposed for a target of
30% energy efficiency target by 2020 [118]. Waste heat can be utilized to produce electricity
(waste heat to power) or mechanical work, to produce warm water or steam increasing the
energy efficiency. The economic feasibility for waste heat recovery declines as the temperature
and flow rate decline. Thermodynamic cycles such as Rankine, steam Rankine cycle (SRC),
organic Rankine cycle (ORC), Kalina cycle, and supercritical carbon dioxide (CO2) cycle are
used [117].
Another application of CO2 is its use as a working fluid in cycle processes. Carbon dioxide has
been used as a working medium in transcritical and supercritical processes. In transcritical
processes, CO2 has been used in refrigeration and heat pumps in commercial scale with
increasing market in households and industry applications. A review of different transcritical
cycles and applications is presented in [119]. Especially domestic scale CO2 heat pumps have
found many applications in the water heating industry because of their ability to deliver
significantly more heat for the same amount of electricity compared to traditional electric storage
water heaters installations. The market share of CO2 as a natural refrigerant was 35% in 2012,
with Japan to have established a mature market with Ecocute system [120, 121]. According to
[122], the ESA30-25 CO2 refrigerant heat pump water heater has achieved the industrys
highest COP of 4.3 for a 30 kW application. Modular heat pump units can be assembled
together to reach higher scales. In industrial heat supply, todays heat pumps can produce hot
air up to a temperature of 120 C and steam up to 165 C replacing boilers in many industrial
processes [123].

4.3 Supercritical CO2 Brayton Cycles

In supercritical processes, CO2 has been used in supercritical CO2 Brayton cycles for producing
electricity in industrial medium scale applications. Different pilot plant systems are being tested
in in the US, Japan and Korea [124]. Echogen and Dresser Rand have commercialized the
technology developing a compact system with a maximum net electricity output of 8 MWel and a
process efficiency up to 30 % [125]. NET Power is commercializing a new thermodynamic cycle,
the Allam Cycle, named for its lead inventor, Rodney Allam- using a high-pressure, highly
recuperative, oxyfuel, supercritical CO2 cycle with incorporated CO2 capture. NET Power, CB&I,

18
Toshiba, and Exelon have partnered to develop a 50MWth NET Power demo plant in La Porte,
Texas which is expected to be completed in 2017. NET Power is aiming at the design and
development of plants with an electrical power output of 295 MWel until 2022 and efficiency of
58.9 % [126, 127]. In [128], supercritical CO2 cycle system of 10 MWe with upscaling potential
to 33 MWe using GEs prototype CO2 turbine claim to reach efficiency of 50% at 700C. The
use of CO2 in supercritical Brayton cycles has considerable advantages related to the high
density of supercritical CO2 which results in smaller and compact equipment sizes. Except its
stability and relative inertness, non-toxicity, abundance and its low cost, its compressibility factor
around the critical point decreases resulting in lower pressure ratios in the cycle and less energy
consumption [124, 129].

The critical parameters for CO2 reaching the supercritical region of state are a pressure of 7.38
MPa and a temperature of 30.98C [129]. The basic design of supercritical CO2 Brayton Cycle
in closed system includes the compression step, a heating source where enthalpy increase is
realized via a heat exchanger, a turbine for pressure reduction and simultaneous power
generation and a cooler for heat rejection. There are many different configurations to the basic
cycle. A selection is presented in Figure 4. The most efficient layout depends on the specific
conditions of the heat source as well as the required power and heat demand. A comparison of
numerous process layouts is presented in [124] and in the literature presented in Table 4 [129-
153]. In [124, 129, 139], the recompression supercritical Brayton Cycle configuration has
presented the highest efficiency.

The highest theoretical efficiencies have been reported with the following conditions at the inlet
of the turbine: a temperature of 700 C and pressure of 20 MPa with an efficiency of 53% [129,
138], a temperature of 620 C and pressure of 20 MPa with an efficiency of 52.4% [144], a
temperature of 700 C and optimal pressure ratio of 4.4 with an efficiency of 52.1% [139] and a
temperature of 750 C and pressure of 20 MPa with an efficiency of 52% [150]. The difference
in the results is attributed to the configuration used and the assumptions made on the isentropic
and mechanical efficiencies of the compressor and turbine, on the temperature approach,
effectiveness and pressure losses in the heat exchangers and recuperators and on the cooling
temperature. Selected isentropic efficiencies for the compressor are in the range of 80%[129],
85% [138, 145], 86%, [131], 87% [149], 88%[124], 89%[141,142, 144, 147].
Moreover, selected isentropic efficiencies for the turbine are in the range of 90%[131, 138, 143,
145], 92% [124], and 93%[141,142, 144, 147]. Indicatively the effectiveness for the recuperators
is in the range of 86 to 95% [124, 129-153]. More research is required for testing the power
production, the efficiency of its machinery component and rotor dynamics, the fluid properties
also in mixtures, the material corrosion and stresses at higher pressure and temperatures and
the design of heat exchangers [129, 151]. It has to be mentioned that there is a lot of research
and development required to achieve the theoretical efficiencies as also the pilot facilities
presented in [124] are still on the research stage for achieving the targeted efficiencies.
However, a process with an electrical power output of more than 10 MWel is necessary to
determine the challenges and opportunities that are related to this technology [124]. The current

19
research efforts are summarized in Table 5 according to the application, heat source and scale
[154].

As reported in [137], the Department of Energy (DOE) Gen-IV S-CO2 Research Program, there
are different sizes and applications investigated. In nuclear applications, direct or indirect
applications in temperature ranges of 350 to 700 C and scales of 10 to 300 MWe are
investigated. In fossil fuel thermal power, indirect applications in temperature ranges of 550 to
900 C and scales of 300 to 600 MWe and direct applications in temperature ranges of 1100 to
1500 C and scales of 300 to 600 M are investigated. In addition, concentrated solar power
applications with temperature range of 500-1000 C and scales of 10 to 100 MWe, waste heat
recovery in the temperature range of 230 to 650 C and scales of 1 to 10 MWe as well as
geothermal applications in ranges of 100 to 3000 C and scales of 1 to 50 MWe [137]. A direct
cycle is the most efficient approach as additional losses associated with the primary loop are
eliminated and indirect cycles have a complicated plant layout and cost increase. However,
direct cycles impose limitations on the range of applicability of the cycle and there is also a
focus on replacing the steam cycle [117]. In the thermal power sector, supercritical CO2 Brayton
cycles have been investigated mainly in [144], [145] and [148] but also in [152] and [153]. In
[144], the coupled coal power plant exhibits a net efficiency in the range of 47.8 0.1%-LHV
(Lower Heating Value) efficiency compared to the state of the art steam Rankine cycle in coal
power plants of 45.4%-LHV based efficiency and they suggest further improvements for
reaching a net efficiency of 48.8%-LHV based 0.1. A recompression cycle with different
recompression and reheating stages, a turbine inlet temperature of 620 C and 30 MPa
pressure was used. The researchers assumed a pinch of 6 Kelvin in the cycle recuperators, a
pinch of 30 Kelvin in the air-gas heat exchanger, a compressors isentropic efficiency of 89 %, a
turbine isentropic efficiency of 93 %, an alternator/motor electrical efficiency of 99.6 % and a
mechanical efficiency of 98.5%. In [145], the cascaded configuration with a supercritical CO2
part flow topping cycle and a simple supercritical CO2 bottoming cycle coupled with a counter-
current radiative-convective biomass boiler has been investigated. Gross efficiency in the range
of 30-36% was achieved with air preheating and a turbine inlet temperature of 550 C and
pressure of 20MPa assuming a temperature difference with the flue gases of 50 C. The
researchers assumed an effectiveness of 90 and 95% in the low and high temperature
recuperators, a compressors isentropic efficiency of 90 %, a turbine isentropic efficiency of
90 %, and a mechanical efficiency of 98%. The researchers claim that the maximum of 36% is
4.7%-points higher than that of the simple cascaded system using the same boiler design. In
[148], the author presents the combination of supercritical Brayton cycle with recompression
and reheating stages into a coal fired power plant with two different carbon capture systems that
deliver the make-up CO2 for the cycle. The net efficiency of the plant without the carbon capture
and supercritical conditions at the inlet of the turbine of 300 bar and 620 C is 50.3 % LHV
based, which is 4 % points above the efficiency of a state of the art hard coal power plant. The
net plant efficiency with MEA-based carbon capture and CO2 compression to 110 bar was
calculated to 41.3% LHV based. It is reported that via increasing the turbine inlet temperature at
700 C, the total net plant efficiency with carbon capture and compression is increased to 44.5%
eliminating the energy penalty imposed by CO2 capture in the net power generation from coal
power plants. In [152], a net efficiency in the range of 43.4% is calculated for a combination of

20
oil and natural gas boilers with a split flow with two turbines and intercooling supercritical
Brayton cycle configuration and turbine inlet temperature of 650 C and 20 MPa pressure. The
researchers assumed an average recuperation effectiveness of 93%, a compressors isentropic
efficiency of 88 %, a turbine isentropic efficiency of 93% and a mechanical efficiency of 98%. In
[153], the researchers have tried to estimate the different combined heat and power efficiencies
in different loads and different combinations of supercritical Brayton cycle. They claim that the
cascaded supercritical CO2 CHP plant with the higher cycle working at 540 C and 21 Mpa and
the lower cycle working at 300 C and 20 MPa can achieve net efficiencies of 39.44% compared
to the conventional CHP configuration with an efficiency of 37.97% Their efficiency results
reported have some inconsistencies.

5 Conclusions

The future energy system has to assure the grid stability, to secure heat and electricity supply in
the power and industrial sector, to integrate highly efficient and environmental friendly
technologies. The operation of the thermal fleet harmonised together with the fluctuating
renewable energy sources and energy storage is a necessity. The flexibility, the efficiency and
emission reduction of thermal plants needs to be addressed taking into consideration an
integrated system of the power and industrial sector in a CO2 circular economy. In the present
paper, CO2 emissions and capture technologies from different industries were reviewed with the
focus on commercial applications. Several commercial projects prove that CO2 capture has
successfully managed to reach a high technology readiness level. However, the incentives for a
wide implementation of the technology in the thermal and industry sector are still missing. CO2
utilization could be the bringing gap for the deployment and geographical constraints of capture
technologies based on boosting legislative schemes. A general review for CO2 utilization
applications has been presented in the present work. Among different applications, the power to
fuel technologies and supercritical CO2 cycles have been assessed focusing on the thermal
sector but having also applications in the process industry. An integrated Industry System
between thermal power, energy intensive industries and the renewable electricity sector
supports decarbonisation of three sectors, electricity, heat and transportation transforming the
European Market.

6 Acknowledgements

The authors would like to acknowledge Philipp Moormann for his contribution to the literature
review for CO2 Cycles which is included in the present work. The authors would like to
acknowledge the EU Commission for the financial support of the MefCO2 Project -Synthesis of
methanol from captured carbon dioxide using surplus electricity" which is funded under the EU
funded SPIRE2 2014: Adaptable industrial processes allowing the use of renewables as
flexible feedstock for chemical and energy applications -Horizon 2020 with the Grant agreement
no: 637016.

21
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35
Figure 1 Technology portfolio in high RES systems

114.5 MWel
+1.8 MWel
100 kt/a 65MW(LHV)
low carbon O2
DPel=1.8 MWel Methanol
H2O
water electrolysis
fuel flue
gas G water
H2
Methanol Methanol
flue gas synthesis distillation
(CO2 lean) CO2

Post combustion
CO2 capture
MWth MWel
flue gas PCC 11.9 1.8
(CO2 rich)
MeOH 0.0 2.4
Electrolyser 0.0 110.3
Bleed -11.9 1.8
Electric Power Pel Thermal Power Qth
Total Dpel = 116.3 MWel

Figure 2 Power to Fuel integrated in thermal plants

Heat storage Transmission Today: Stand-alone CHP power plant

Industry system
(heat consumer) Electric Power Pel Heat
consumers heat Grid heat
Thermal Power Qth
Heat Recovery Qth loss

Power
Fuel Plant

electricity
electricity Grid
HTHP (high temperature heat pump
with COP up to more than 3)
low carbon O2 Future power plant, combined with MeOH plant, exporting additional heat

H2O Methanol
water electrolysis
flue heat Grid
fuel gas G HTHP
water
H2
Methanol Methanol
gas Power Methanol
CO2 synthesis distillation Fuel
(CO2 lean) Plant Plant MeOH
Post combustion
CO2 capture
electricity Grid
gas
(CO2 rich)

Figure 3 Power to Fuel integrated in CHP systems

36
Figure 4 Supercitical Brayton Cycle Configurations

37
Table 1. The three largest CCS projects in thermal power sector [18-22]
Boundary Dam Carbon
CCS Project the Sinopec Shengli
Project Petra Nova Carbon
Saskatchewan Power Plant CCS
Name Capture Project
Government is the sole Project
owner
Shengli power plant,
Project
Saskatchewan, Canada Texas, United States Dongying, Shangdong
Location
Province, China
Power generation
Power generation (lignite / Power generation
Industry pulverized coal boiler (sub-
brown coal) pulverized coal boiler
bituminous coal)
today 40,000 tonnes per
CO2 1 million tonnes per annum 1.4 million tonnes per annum of CO2 ,
Capacity (Mtpa) annum (Mtpa) Scale up to: 1 million
tonnes per annum.
CO2 PCC Amine PCC KM-CDR amine
PCC
Technolog Shell Global, Cansolv scrubbing CO2 developed
SINOPEC
y technology by MHI and KEPCO
Start Date October 2014 2016 2010-2017
Aquistore project Winnipeg
Storage and Deadwood formations at No No
3.4 km / 2.1 mile depth
Frio Formation (sandstone) Injection is at 3 Km
Weyburn Oil Unit oil-
1,6402,066 meters / depth into the Shengli oil
EOR bearing formation at 1.5 km /
5,0006,300 feet below field in the Yellow River
1 mile depth
ground surface delta.

38
Table 2. The largest CCS projects in industrial sector [54]
Capture
Operation
Project name Location Industry Capture type capacity
date
(Mtpa)
Pre-combustion
United Natural Gas
Val Verde Natural Gas Plants 1972 capture (natural gas 1.3
States Processing
processing)
United Fertiliser
Enid Fertilizer CO2-EOR Project 1982 Industrial Separation 0.7
States Production
Pre-combustion
Shute Creek Gas Processing United Natural Gas
1986 capture (natural gas 7
Facility States Processing
processing)
Pre-combustion
Natural Gas
Sleipner CO2 Storage Project Norway 1996 capture (natural gas 0.9
Processing
processing)
Great Plains Synfuel Plant and Synthetic Pre-combustion
Canada 2000 3
Weyburn-Midale Project Natural Gas capture (gasification)
Pre-combustion
Natural Gas
Snhvit CO2 Storage Project Norway 2008 capture (natural gas 0.7
Processing
processing)
Pre-combustion
United Natural Gas
Century Plant 2010 capture (natural gas 8.4
States Processing
processing)
Air Products Steam Methane United Hydrogen
2013 Industrial Separation 1
Reformer EOR Project States Production

United Fertiliser
Coffeyville Gasification Plant 2013 Industrial Separation 1
States Production
Pre-combustion
United Natural Gas
Lost Cabin Gas Plant 2013 capture (natural gas 0.9
States Processing
processing)
Pre-combustion
Petrobras Santos Basin Pre-Salt Natural Gas
Brazil 2013 capture (natural gas 1
Oil Field CCS Project Processing
processing)
Hydrogen
Quest Canada 2015 Industrial Separation 1
Production
Pre-combustion
Uthmaniyah CO2-EOR Saudi Natural Gas
2015 capture (natural gas 0.8
Demonstration Project Arabia Processing
processing)
United
Iron and Steel
Abu Dhabi CCS Project Arab 2016 Industrial Separation 0.8
Production
Emirates
Alberta Carbon Trunk Line
Fertiliser
("ACTL") with Agrium CO2 Canada 2017 Industrial Separation 0.3 - 0.6
Production
Stream
Alberta Carbon Trunk Line
("ACTL") with North West Canada 2017 Oil Refining Industrial Separation 1.2 - 1.4
Sturgeon Refinery CO2 Stream
Pre-combustion
Gorgon Carbon Dioxide Injection Natural Gas
Australia 2017 capture (natural gas 3.4 - 4.0
Project Processing
processing)
Illinois Industrial Carbon Capture United Chemical
2017 Industrial Separation 1
and Storage Project States Production

United Power Pre-combustion

Kemper County Energy Facility 2017 3
States Generation capture (gasification)

39
Table 3. State of the art carbon dioxide utilization [95-100]
Sector Process/Product Potential
Chemical and Oil Enhanced Oil Recovery High
Enhanced Gas Recovery
Enhanced Coal bed Methane Recovery
Stimulation/Fracturing of oil and gas
Urea production
Polymer Processing
Chemicals and Fuels (Methanol, methane, CO, fertilisers etc
and derivatives)
Food Beverage Carbonation Medium
Coffee Decaffeination
Wine production
Food processing
Food preservation
Food packaging (Modified or controlled atmosphere
packaging)
Dry Ice Production
Horticulture (greenhouses)
Refrigeration
Mineralisation Calcium and Magnesium carbonate for use in cement Medium
Baking soda
CO2 concrete curing
Bauxite residue treatment (red mud)
Power Heat pumps Low-
Working medium in other CO2 cycles Medium
Energy crops Algae cultivation (biomass production via photosynthesis) Medium
Pharmacheutical Inerting Low
Chemical synthesis
Supercritical Fluid Extraction
Product transportation
Pulp and Paper pH reduction during Washing Low
Steel Injection to metal casting Low
Bottom stiring agent in BOF furnaces
Chilling medium
Hardening sand cores and moulds
Other Electronics (in printed circuit manufacture) Low
Pneumatics (working medium in hand tools and equipment)
Welding ( shield gas)
Fire extinguishers, fire suspension
Flavors, Fragnaces
Blanket Products
Aerosol can Propelant
Inert gas
Soda ash production for glass industry
Dry gas cleaning
Water treatment
Refrigerant gas

40
Table 4. Efficiencies reported in the literature for different applications.
Efficiency A Efficiency B
Ref. Temperature ( C ) Pressure
(Thermal) % (System) %
129 550 20 Mpa 46 theoritical
129 550 20 Mpa 45.3 calculated
129 650 20 Mpa 50
129 700 20 Mpa 53
130 520 10 to 15 MPa 35 to 40 33.42
130 520 18 to 25 MPa >40 35.14
130 520 25 to 30 Mpa >40 35.3
131 580 8 and 34 Mpa 38
131 700 8 and 34 Mpa 42
132 675 3.2/10 Mpa 44.5
133 732 26,5 48 40
134 600 25 30MPa 51
135 800 12 MPa 50
136 555 20 MPa 41%
137 600-700 20 MPa 50-53
138 538 43
138 700 50
138 800 54
139 700 ratio 4.4 52.1
139 700 ratio 4.5 46.8
140 <750 40-50
141 550-850 25MPa <56%
142 550-900 25MPa 47.9-60.5
143 516.15-579-650 40.88-41.56-33.65MPa 41.35-45.15-49.42
144 550-850 15-40 MPa 41-58
144 620 20 MPa 41.9
144 620 20 MPa 42.1
144 620 20 MPa 46.8
144 620 20 MPa 47.1
144 620 30 MPa 52.4 47.8
145 550 20 MPa 44.18/28.34 36
146 650 7.5 MPa 35.1
147 400 17.5 MPa 36.69
148 550 25 MPa 43.6
148 550 25 MPa 45.7
149 620 20 -35 MPa 47.4-50.8
149 620 35 MPa . 41.4
149 700 35 MPa 44.5
150 550 22 MPa 39.59
150 550 22 MPa 42.67-43.72
151 750 20 MPa 52 40
152 650 20 MPa 43.4
153 540/300 21/20 MPa 39.44

41
Table 5. Research efforts according to different applications, heat sources and scales [154]
Heat Technolo Heat Source Turbine Turbine Press SCO2 Net Cycle Power
Source gy/ Inlet Inlet ure Cycle Output
Quality Investiga Temper Pressure Ratio Efficiency
tor ature (MPa)
(C)
High PWR PFBC 700 20.68 2.6 49.9% 38.3% (plant)
Grade (cycle)
(>500C) NREL Solar Power Tower 700 22 2.6 38.30% 5-10 MWe
Sandia Gas Fast Reactor 650 20 2.7 45 50% 200 MWth
EPRI Coal-fired boiler 600 7.58 2 4 400 800 MWe
KAIST Small Modular 550 20 2.6 40% 330 MWth
Water Cooled
Reactor
KAIST Sodium Fast 550 20 2.08 44.02 264.1 279.9
Reactor 2.64 46.65% MWe
Sandia Immersion Heaters 536 13.98 1.81 52.8 kWe
Barber- Unspecified 400-650 22 2 12.2 MWe
Nichols
Intermed Abengola Solar Parabolic 500 40 2.7 25% 65% (thermal)
iate (power)
Grade Concepts Gas Turbine 480 24.65 2.75 40 50 % (Improvement
(200C NREC Exhaust over GT 20
500C) 24%)
Kumar Concentrated 480 19.8 7.5 32.14% 5.6 kWe
Solar Thermal
Univ. of Molten Carbonate 375 21.6 3 39.90% 583.6 kWe
Seville Fuel Cell (MCFC)
Echogen Waste Heat 200-540
Low Oak Geothermal/Waste 120 30 5 16.5
Grade Ridge / Heat /Solar
(<200C) Univ. S.
Fla

42