FlexibleCarbonCaptureandUtilization2019 PDF

Renewable and Sustainable Energy Reviews 114 (2019) 109338
Contents lists available at ScienceDirect
Renewable and Sustainable Energy Reviews

journal homepage: www.elsevier.com/locate/rser
Flexible Carbon Capture and Utilization technologies in future energy T

systems and the utilization pathways of captured CO2
⁎
Hrvoje Mikulčića,b, , Iva Ridjan Skovc, Dominik Franjo Dominkovićd,
Sharifah Rafidah Wan Alwie, Zainuddin Abdul Manane, Raymond Tanf, Neven Duićb,
Siti Nur Hidayah Mohamade, Xuebin Wanga
a
MOE Key Laboratory of Thermo-Fluid Science and Engineering, Xi'an Jiaotong University, Xi'an, Shaanxi, 710049, China
b
Faculty of Mechanical Engineering and Naval Architecture University of Zagreb, Zagreb, Croatia
c
Aalborg University, Department of Planning, Copenhagen, Denmark
d
Technical University of Denmark, Department of Applied Mathematics and Computer Science, Lyngby, Denmark
e
Process Systems Engineering Centre (PROSPECT), Research Institute for Sustainable Environment/ School of Chemical and Energy Engineering, Faculty of Engineering,
Universiti Teknologi Malaysia, Johor Bahru, Johor, Malaysia
f
Chemical Engineering Department, De La Salle University-Manila, Manila, Philippines
A R T I C LE I N FO A B S T R A C T
Keywords: Future 100% renewable energy systems will have to integrate different sectors, including provision of power,
Carbon capture heating, cooling and transport. Such energy systems will be needed to mitigate the negative impacts of economic
Carbon utilization development based on the use of fossil fuels, but will rely on variable renewable energy resources. As two-thirds
Variable renewable energy sources of global greenhouse gas emissions can be attributed to fossil fuel combustion, decarbonization of energy sys-
Future energy systems
tems is imperative for combating the climate change. Integrating future energy systems with CO2 capture and
Flexibility
utilization technologies can contribute to deep decarbonization. As these technologies can be operated flexibly,
100% renewable energy systems
they can be used to balance the grid to allow for high levels of variable renewable energy in the power mix. The
captured CO2 can be either utilized as a feedstock for various value-added applications in the chemical industry
and related sectors such as the food and beverage industries. This paper reviews the state-of-the-art literature on
CO2 capture and utilization technologies, with an emphasis on their potential integration into a low-carbon,
high-renewables penetration grid. The potential market size for CO2 as raw material is also elaborated and
discussed. The review paper provides an insight to the development and the technological needs of different
energy system sectors, as well the limitations, challenges and research gaps to the integration of the variable
renewable energy sources and flexible carbon capture and utilization technologies.
1. Introduction Storage (CCS) are envisioned to play complementary roles within an

integrated system that can approach zero emissions that are needed for
According the Intergovernmental Panel on Climate Change (IPCC) climate stabilization in the medium-term future. CCU focuses on re-
[1], global carbon dioxide (CO2) emissions need to be reduced to zero source efficiency, and is aligned with the concept of Circular Economy
by mid-century in order to ensure that temperature rise is limited to (CE) that is currently being advocated from a policy standpoint in many
1.5 °C C by 2100. Carbon Capture, Utilization, and Storage (CCUS) can regions and countries, including the European Union (EU) and China
play an important role as a major technological wedge for achieving [2]. Engineering methodologies can be applied to facilitate the im-
such deep reductions in emissions, along with other options such as plementation of CE which can lead to resource conservation and cli-
energy conservation, use of renewable energy, and deployment of ne- mate change mitigation co-benefits [3]. Most CCU options do not result
gative emissions technologies (NETs) such as bioenergy with carbon in permanent sequestration of carbon, so these benefits arise through
capture and storage (BECCS) and direct air capture (DAC). other means. In particular, there is significant potential in the near
Carbon Capture and Utilization (CCU) and Carbon Capture and future for flexible CCU systems to play a major grid balancing function
⁎
Corresponding author. MOE Key Laboratory of Thermo-Fluid Science and Engineering, Xi'an Jiaotong University, Xi'an, Shaanxi, 710049, China.
E-mail addresses: [email protected] (H. Mikulčić), [email protected] (I. Ridjan Skov), [email protected] (D.F. Dominković), [email protected] (S.R. Wan Alwi),
[email protected] (Z.A. Manan), [email protected] (R. Tan), [email protected] (N. Duić), [email protected] (S.N. Hidayah Mohamad),
[email protected] (X. Wang).
https://doi.org/10.1016/j.rser.2019.109338
Received 22 January 2019; Received in revised form 31 July 2019; Accepted 10 August 2019
Available online 22 August 2019
1364-0321/ © 2019 Elsevier Ltd. All rights reserved.
H. Mikulčić, et al. Renewable and Sustainable Energy Reviews 114 (2019) 109338
Nomenclature HRSG Heat recovery steam generator

IEA International Energy Agency
APC Aromatic polycarbonates IGCC Integrated gasification combined cycle
ASU Air separating unit IL Ionic liquid
BECCS Bioenergy with carbon capture and storage IMF International Monetary Fund
BEV Battery electric vehicle IPCC Intergovernmental Panel on Climate Change
BDCL Biomass direct chemical looping IS Industrial symbiosis
BIGCC Biomass-based integrated gasification combined cycle LT PEM EC Low-temperature proton exchange membrane electro-
CaO Calcium oxide lysis cell
CC Carbon capture MEA Monoethanolamine
CCGT Combined cycle gas turbine N2O nitrous oxide
CCS Carbon capture and storage NET Negative emissions technology
CCU Carbon capture and utilization NG Natural gas
CCUS Carbon capture, utilization, and storage PEM Polymer electrolyte membrane
CE Circular economy PHEV Plug-in hybrid electric vehicle
CH4 Methane PSA Pressure swing adsorption
CHP Combined heat and power PtL Power-to-Liquid
CLC Chemical looping combustion PtX Power-to-X
CO2 Carbon dioxide PV Photovoltaics
COP Coefficient of performance RES Renewable energy sources
CUT Carbon utilization technologies SGC Series gas cooler
DAC Direct air capture SNG Syngas
EOR/EGR Enhanced oil and gas recovery SOEC Solid-oxide electrolysis cells
EU European Union TRL Technology readiness levels
EV Electrical vehicle USA United States of America
FCEV Fuel cell electric vehicle UK United Kingdom
GDP Gross domestic product VRES Variable renewable energy sources
GHG greenhouse gas WHO World Health Organization
GWP Global warming potential
via Power-to-X (PtX) pathways. Such PtX schemes can reduce the need On the other hand, CCS (including BECCS and DAC) contributes to
for direct electricity storage with batteries by using virtual storage in the climate picture through permanent geological sequestration of CO2.
the form of secondary products such as liquid or gaseous fuels [4]. This In order to have a significant contribution to mitigation efforts, se-
grid balancing function can enable higher levels of penetration of re- questration needs to occur at much larger scale in comparison to the
newables in the power grid, which will allow emissions to approach level of CO2 utilization in potential chemical and energy markets.
near-zero level without undue volatility. Sequestration will be vital to enable negative emissions to be achieved
Fig. 1. Integrated VRES based energy system and CCUS system.
2
in specific sectors or regions; such negative emissions will be needed to 3.1. Power generation
offset positive emissions that may occur elsewhere on the planet [5].
Both CCU and CCS can coexist in an integrated CCUS framework The main drivers in decoupling CO2 emissions and GDP growth are
that results in mutual benefits from shared infrastructure. By providing an increase in the grid share of low-carbon power generation sources, as
value-added end use of CO2, CCU can also act as a catalyst for the initial well as the utilization of more efficient energy generation and utiliza-
development of distribution infrastructure that can be scaled up later as tion technologies.
economic barriers to permanent geological storage of CO2 are overcome Greater public concern about the adverse impacts of energy systems,
(e.g., via imposition of carbon tax in the future). Dual benefits accrue coupled with technological changes that have made alternative energy
from direct reduction of CO2, and from the role of the system in en- sources increasingly more affordable, has led to a notable shift towards
abling higher levels of utilization of variable renewable energy systems the use of renewable energy [14]. From 2008 to 2017, the global in-
(VRES). The framework can be visualized as shown in Fig. 1. stalled capacity of renewable energy sources increased from 1.06 TW to
This review paper is intended to provide a survey on background 2.18 TW [21]. In 2017, the worldwide share of renewable energy
issues, component technologies, and system-level integration of CCUS generation in total power generation sector was 25% [22]. Out of the
to achieve future energy systems that approach zero emissions. While total renewable energy capacity installed, hydropower capacity
other review papers on CCUS have been published, many of these amounted to 1.27 TW in 2017. Wind capacity increased more than fi-
previous papers are either technology-specific (Merino-Garcia et al., vefold from 2008 to 2017, from 0.1 TW to 0.51 TW, while photovoltaics
[6]) or geographically defined (Liu et al., [7]) in their scope. Recent (PV) capacity increased more than 20 times in the same period, from
review papers of comparable breadth of scope are listed in Table 1, and 0.015 TW to 0.39 TW. The main driver behind the dramatic increase in
brief descriptions are given of the aspects that they emphasize. While installed capacity of PV and wind turbines has been a significant price
Koytsoumpa et al. [8] also discuss PtX as a measure for grid stabiliza- drop. Between 2010 and 2017, the price of PV dropped by 80%, while
tion, we provide a more in-depth analysis of integrating operations of the price of wind turbines reduced by 50% over the same period [23]. It
CCUS with zero-emissions VRES through measures such as flexible is expected that these technologies will continue to dominate the re-
capture and PtX. newable energy installation portfolio in the future [24].
Increase in power generation demand under the current policies
scenario is set to increase by more than 25% until 2040 according to the
2. Method
International Energy Agency (IEA) [22]. However, by implementing
different policy measures, it is possible to achieve 100% renewable
The research method is based on a three-step procedure, comprising
energy systems by the year 2050. Use of 100% renewable energy for all
(i) literature search and systematic review, (ii) grouping of studies and
sectors, and not only renewable power sectors, was shown to be both
(iii) assessment of study relevance to flexible CCUS technologies, 100%
technically and economically feasible, among other countries and re-
RES energy system and CO2 utilization. The literature search on CCUS,
gions, in South-east Europe [25], the EU [26] and the USA [27].
100% RES energy system and CO2 utilization was done by searching a
Energy systems based on 100% renewable energy sources have been
scientific database. Results of the advanced search of the Scopus [13]
the subject of extensive debate in the scientific literature. One paper
databases by keywords, abstract and title that attempted to reflect these
criticized renewable energy models as not having fine enough spatial
research topics are depicted in Fig. 2. It can be seen that during the last
resolution and potentially having erroneous assumptions in energy
decade research interest for CCUS, 100% RES energy system, and CO2
models [28]. A rebuttal claiming that the original modelling assump-
utilization has resulted with large numbers of published documents.
tions were correct was later published [29]. Another review paper of
These data can be interpreted as a sign that academic community, due
renewable energy system based research papers claimed that papers
to the climate change effect and need for lowering GHG emissions, is
they reviewed are technically unviable, mostly due to unrealistic en-
becoming increasingly aware of the significance of decreasing CO2
ergy-demand forecasts [30]. However, the latter paper was disputed in
emissions and even going for negative CO2 emissions.
an article pointing out the misunderstanding of the energy conversion
processes in energy systems, as well as accounting methods for the
3. Future energy systems primary energy supply of renewable energy sources [31]. The latter
paper explicitly answered point by point all the concerns raised by
Combustion of fossil fuels to generate electricity and to provide Hearda et al. [30], by referring to the relevant literature. It has con-
heating, cooling and transportation services is a major contributor to cluded that energy systems based on renewable energy sources are
emissions of greenhouse gases (GHGs) and air pollutants. Energy sys- feasible, and already economically viable.
tems account for about two-thirds of global GHG emissions [14]. More
than 80% of the world urban population live in areas with air quality Table 1
levels below World Health Organization (WHO) recommendations Recent review papers on carbon capture and utilization.
[15]. Although carbon dioxide (CO2) is responsible for 77% of radiative Review Paper Areas of Focus
forcing [16], other GHGs are also generated by energy systems. In
particular, methane (CH4) and nitrous oxide (N2O) may be generated at Marocco Stuardi et al. [9] • Post-combustion capture
various points (resource extraction, processing, transportation, storage • InValue
situ utilization transformation
Jarvis and Samsatli [10] • Physicalchains
and combustion) along fossil energy supply chains.
• Techno-economic
infrastructure
Although energy demand tends to increase with rising standards of
living, CO2 emissions and Gross Domestic Product (GDP) growth can be
• utilization optionsaspects of conversion and
decoupled, as illustrated in the case of Chinese households [17], in Al-Mamoori et al. [11] • Capture techniques
• Utilization as feedstock for chemical processes
• Decarbonization
energy-intensive industry in Scandinavia [18], as well as for eight
Koytsoumpa et al. [8] of energy systems through
Western European countries [19]. However, this seems not to be the sequestration
case for the transport sector [20]. The International Monetary Fund • Utilization for fuel and energy production
(IMF) showed that four advanced countries (i.e., Italy, Germany, the • Integration of CCUS with energy storage
United States of America - USA and the United Kingdom - UK) de- Norhasyima and Mahlia • Different classes of utilization options
coupled GDP growth from CO2 emissions. However, four emerging

[12] • Literature survey covering 3000 patents over four
decades (1980–2017)
economies that they assessed still have a strong coupling effect (i.e.,
Brazil, China, India and South Africa).
• Trend analysis
3
Fig. 3. Smart energy system concept, adapted from Ref. [37].
as power and heat [32], power and gas [33], and power and mobility
[34], as well as within different sectors, such as within distributed
district heating grids [35]. This cross-sectoral approach also identified
as smart energy system [36] maximises interconnections between the
sectors, resources and demands with the use of storage technologies in
order to improve the energy system flexibility and enables higher in-
tegration of renewable energy (see Fig. 3).
Simulations have shown the possibility of achieving energy systems
with zero carbon emissions by 2050. Mathiesen et al. [36] carried out a
pre-feasibility study showing that the 100% renewable energy system
could be achieved for the whole European Union by integration of
different energy sectors. Similarly, 100% renewable energy systems
were simulated for the case of Denmark [38], Portugal [39], Ireland
[40], and Croatia [41]. Moreover, a zero-carbon energy system was
simulated for the whole South-east Europe [25]. All of those papers
showed that future energy systems will be based on variable renewable
energy sources, mostly onshore and offshore wind, and photovoltaics
(PV). The same papers showed that in the last phase of energy transi-
tion, a certain capacity of electrolysers will be needed in order to
provide additional flexibility to the energy system. In two studies for
Denmark, the capacities of electrolysis must reach up to 9000 MW in
order to provide fuels for the transport sector and industry in 100%
renewable energy systems [42]. Similar behaviour can be seen in
smaller island-states or city-states. For the case of Singapore, one of the
scenarios showed that future energy system could meet 80% of final
electricity demand by variable renewable energy sources, while 6% of
the final electricity demand was used for solid-oxide electrolysis cells
(SOEC) [43]. Similarly, for the case of Aruba, an island state located in
the Caribbean, 78% of the final electricity demand could be met by
variable renewable energy sources by 2020 [44].
The increasing penetration of variable renewable energy sources
(VRES) has shown the increasing need for a flexible energy system. As
old fossil fuel plants are retired, flexible power plants will need to be
Fig. 2. Results of advanced Scopus [13] database search by year: a) (TITLE- built to supply electricity when VRES is not available. Due to VRES
ABS-KEY: (carbon AND capture AND utilization AND storage)); b) (TITLE-ABS- penetration, in certain time periods there is an excess of electricity that
KEY (100% AND res AND energy AND system)); c) (TITLE-ABS-KEY (co2 AND is not exportable, and the spot market electricity prices become very
utilization)). low or even negative. The economically valuable utilization of such
surplus electricity presents an important opportunity [45]. One of the
Future energy systems will continue to utilize ever increasing levels most promising and appropriate solution for such electricity is energy
of renewable energy sources. Moreover, the future energy systems are storage. A crucial aspect is that conversion systems must be market
set to a more integrated pathway both between different sectors, such controlled [46], and that different types of stakeholders can participate
4
in that market [47]. 3.2. Transport

It has been long debated if carbon capture is a sustainable solution.
Carbon capture from stationary CO2 emitting installations is a tech- Transport is a sector that is responsible for a large share of primary
nology that can drastically reduce the emissions to the atmosphere. energy demand, as it accounts for 22% of end-use energy demand
There are two ways the captured CO2 can be handled. One is to geo- worldwide [52]. While it is expected that energy demand for cars and
logically store it via Carbon Capture and Storage (CCS), and the other is trucks will grow slowly until 2040, energy demand for aviation trans-
to reuse it as a new resource via Carbon Capture and Utilization (CCU). port is expected to rise significantly until the year 2040, by up to 63%
It is arguable that CCS as a technology can enable the prolonged use of according to one of the scenarios [52]. With EU-28 goals to reduce the
fossil fuels. Additionally, CCS is not very suitable for a 100% RES en- GHG emissions in transport by 67% in 2050 [53], commercialization of
ergy system that is based on VRES since these plants operate as base- new technologies that can offer high-efficiency improvements, low
load production, and require increased fossil fuel consumption for carbon liquid fuels and modal shift will be necessary. Decreasing
capture processes [48]. Compared to CCS, CCU provides different and transport demand and modal shifts are an essential part of the long term
more sustainable products/services, and integrates different systems transport sector planning. Decreasing transport demand by changes in
using waste from one as a resource to the other. CCU can be viewed the transport infrastructure and via car-sharing is a necessary step to a
from the perspective of being an enabling technology component for 100% renewable energy in transport sector [54]. According to Anable
future 100% RES carbon-free energy systems. Viewed from the per- et al. [55], radical changes in lifestyle can lead to a 74% reduction in
spective of the energy generating system, power-to-gas and power-to- distance travelled by cars in 2050.
fuel CCU options provide the electrofuels that are long term high Electrification of transport is the most promising technological so-
density energy storage. The electrofuels can be used by heavy-duty lution for the sector, because the electric motor is much more efficient
vehicles, ships, airplanes, and by Combined Cycle Gas Turbine (CCGT) than the internal combustion engine; electric cars are 3.5 times more
or engines operating in Combined Heat and Power (CHP) mode to efficient, and electric buses are 2.5 times more efficient than their in-
provide electricity and heat when there is no other renewable energy ternal combustion counterparts [44]. The advantage is further com-
source available. pounded because electricity can be generated using various low-carbon
The deployment of CCU as a technology depends on the penetration sources. However, not all transportation modes can be directly elec-
of RES in the power system. In the EU, it was 16.7% in 2015 [50]. The trified by the currently available technology. One study showed that for
penetration of around 30% of RES can be balanced by the grid. Up to the case of the European Union, 72.3% of the transport energy demand
approximately 80% of VRES penetration, the volatility can be balanced could be directly electrified by the existing technology [56]. Elec-
by demand response, which includes short term storage, thermal sto- trification of road transport can bring demand reductions of ~70% with
rage and batteries in electric vehicles [51]. Increasing penetration the use of battery-driven vehicles [52]. In the period from 2010 to
further presents a greater challenge (see Fig. 4.), as they need to be 2017, electric car stock (BEV and PHEV) has increased more than 200
handled by long term energy storages. Long term energy storage tech- times [57]. For the case of Denmark, the authors assumed that 50% of
nologies include the chemical energy stored in electrofuels produced by the transport sector could be directly electrified, although they did not
CCU, together with hydro and biomass. Hydro and biomass offer the carry out a detailed technical assessment of the transport sector [36].
best option for storing renewable energy when it is produced and re- Another positive aspect of electrification of the transport sector is that it
leasing it, with simple and affordable technology, when there is a de- can serve as an integration point for other energy sectors, such as power
mand. However, using only hydro and biomass is not always sufficient and gas. One paper showed that smart charging and vehicle-to-grid
for covering this remaining 20% gap, as there may not be enough of usage can reduce CO2 emissions and the amount of curtailed renewable
these resources in some countries or regions (e.g., the whole EU) [36]. energy by half, in an energy system with large penetration of VRES
This gap can be solved by flexible CCU; however, CCU should be used [58]. At the city level, Šare et al. [59] showed that smart charging can
only as a last energy storage option since it has the highest marginal reduce curtailed renewable energy by 7.5% in an urban energy system
cost. The precondition of CCU use is that there is an excess of zero- with a large share of VRES. However, the high penetration of electric
carbon electricity, meaning that CCU is to be used only with electricity vehicles can be achieved only with the right policies and incentives in
generated by RES sources. Due to the expected increased penetration of place [60]. Electric ferries are emerging in the Scandinavian area,
VRES, CCU needs to operate in a flexible manner. Dual benefits accrue where the market share of current domestic ferry market could reach up
from both direct removal of CO2 from exhaust gases, as well as its role to 80% [61]. According to Connolly [62], implementation of eRoad
as an enabler of high penetration of renewables into the grid power technology in combination with BEV for road transport can offer in-
mix. vestment savings.
Fig. 4. Penetration of RES into EU28 power system over time, adapted from Ref. [49].
5
For long distance transportation, heavy-duty transportation, share of agriculture in the total global anthropogenic GHG emissions
marine, and air transportation, direct electrification is not a feasible was 11.2% ± 0.4% in 2010, compared to 11.5% ± 0.3% in 2000 and
solution with currently available technology, different alternatives will 12.3% ± 0.6% in 1990. For the EU, in order to meet the 2 °C target, the
play a role in future transport energy systems. For the remainder of the EU will need to focus on nitrous oxide (N2O) and methane (CH4)
transport sector that is not suited to electrification, several alternatives emissions reduction in the agriculture sector [84]. Some of the tech-
have been proposed, such as biofuels, hydrogen, electrofuels, or a nological advancements and increased efficiencies that could help
combination of these technologies [56]. The use of hydrogen will most curbing GHG emissions in the agriculture sector are nitrification in-
likely emerge as the range extender option FCEVs [63]; however, the hibitors, feed additives for ruminants, and covering and flaring of slurry
maturity of the vehicle technology, costs and need for infrastructure facilities [84]. Another opinion paper claimed that the currently plau-
expansion coupled with renewable production of hydrogen are the sible technologies will not be enough to meet the climate targets and
main barriers for large scale implementation. The projected share of that the development of such as methane inhibitors will be needed [85].
hydrogen fuel in EU-28 in 2050 is only 5% [64]. According to Jacobson More efficient use of nitrogen fertilizers will needed to be achieved, as
et al. [65], hydrogen can meet the residual transport demand left after one large meta-analysis showed that N2O emissions grow exponentially
high electrification share. Biogas or liquefied methane can be used for as nitrogen inputs exceed crop needs, and not linearly as it was often
supplying heavy-duty trucks, buses and ships. Even with improvements assumed [86]. Reduction of GHG emissions from agriculture has several
in gas vehicles, the direct use of biogas for electricity or heat production difficulties, mostly connected to quantification of actual levels of
is more beneficial [66]. Second-generation biofuels for road transport emissions [87].
by gasification of woody biomass in form of methanol and syngas (SNG) Literature on relations between carbon emissions, economic growth
show good cost-performance according to Ref. [67]. The scarcity of and energy consumptions is very limited [88]. Study by Liu et al. [89]
sustainable biomass resources will inevitably be an issue that will limit looked into the impact of renewable energy and agriculture on the
the use of traditional biofuels in the transport sector [34]. Biomass carbon emissions showing that organic agriculture systems have posi-
scarcity, coupled with the increased level of variable renewable elec- tive impacts on reduction of CO2 emissions. Somewhat contrary, one
tricity, will increase the need for chemical storage of electricity in form large meta-analysis of life cycle emissions that included 742 agri-
of liquid or gaseous fuels so-called electrofuels [68], which can increase cultural systems showed that organic agriculture require more land, use
the flexibility of the overall energy system and help the integration of less energy but have similar GHG emissions as conventional systems
variable renewable sources. Biojet fuels are most commonly suggested [90]. Qiao et al. [91] shows that agriculture significantly increases CO2
alternatives for the aviation sector [69] and can contribute to the CO2 emissions in G20 countries, while confirming the positive effect of re-
emission reductions [70]. Other option is production of jetfuels for newable energy on the CO2 emissions. Bidirectional causality has been
aviation [71] via power-to-liquid (PtL) pathway [72]. shown between agricultural emissions and agricultural economic
growth [92]. Moreover, renewable production of ammonia by PtX for
3.3. Industry fertilization purposes can further decrease the emission levels [93].
In order to reduce the emissions, changes in the diets from the
The industrial sector accounts for 21% of global GHG emissions consumer side are a necessary step, as the highest pollutants are the
[73]. Reduction of emissions from industry is challenging due to the production of meats [94]. In the EU, reducing the GHG emissions in the
existence of many different subsectors. Process efficiency and energy agriculture sector alone will not be enough to meet the climate targets,
efficiency improvements in the industry are important first steps in and changes in diet will be unavoidable [84]. Switching to lower im-
transitioning the industry to a more sustainable and low-carbon future. pact foods offer the largest potential for reducing GHG emissions in the
Electrification of the industrial sector and production of hydrogen and agriculture sector, which includes avoiding ruminant meats and in-
hydrocarbons with power-to-liquid and power-to-gas technologies creased use of plant-based foods [90]. Ruminant meats have around
could be one of the transitional pathways [74]. Luh et al. [75] showed 100 times the impact of the plants food [90]. Although the agriculture
that single measures have a limited impact on the decarbonization of is an important sector from the climate change point of view and re-
the industrial sector, but the integrated approach can make a greater lated emissions, it has limited potential for using in connection with
difference. CCUS, as its most important GHGs include CH4 and N2O.
The large demand for conventionally produced ammonia in the
petrochemical industry, which is mainly used in fertilizers, could be 4. Carbon capture
displaced by green ammonia produced by using electrolytic hydrogen;
this technology can also serve as a form of electricity storage [76]. The This section describes the major technologies for CO2 capture, in-
fossil-free iron and steel production by using hydrogen-based fuels has cluding pre-combustion capture, oxyfuel combustion, chemical looping
potential, once the required technology matures [77]. Brown et al. [78] combustion (CLC), post-combustion capture, capture from fermentation
gave an overview of mitigation technologies that can be implemented processes, and direct air capture (DAC). There has been extensive
in order to reduce CO2 emissions from heavy industry. Implementation growth in CO2 capture technology, as evidenced by a 2013 analysis of
of the circular economy (CE) can play an important role in the future of the patent landscape by Li et al. [95]. This paper covered over 1000
the manufacturing industry with the right framework in place [79]. patents (including more than 600 from the year 2000 onwards), in-
Concepts such as industrial symbiosis (IS), where the exchange of re- dicating accelerating commercial interest in these technologies. Of
sources across multiple industries in the same geographic area can re- these patents, 37.5% were on solvent-based systems, 35.5% on sorbent-
duce the dependence of primary raw materials, and help enhance in- based systems, and 27% on membrane-based systems. Although the
dustrial sustainability [80]. The cement industry is particularly bulk of the initial existing scientific and patent literature applies to CO2
problematic due to inherent CO2 emissions. Cement industry dec- capture from fossil fuel combustion [96], many of the same techniques
arbonizing pathways are given in Ref. [81]. can be adapted to systems involving combustion (or co-combustion) of
biomass in Bio-Energy with Carbon Capture and Storage (BECCS) sys-
3.4. Agriculture tems, with consequent changes in performance levels. BECCS can be
implemented via direct firing of biomass in dedicated plants, or co-
In 2015, agriculture represented (crop and livestock production) firing of biomass with fossil fuels as an interim measure [97]. Bhave
9.58% of the EU-28 GHG emissions, of which the biggest contributors et al. [98] reported a techno-economic assessment of eight mixed and
were enteric fermentation and agricultural soils [82]. Using the largest dedicated BECCS schemes. The four dedicated biomass schemes were
three available global datasets, the authors in Ref. [83] showed that the based on pre-, post-, oxy-, and chemical looping combustion systems.
6
Capture cost was estimated for 50 MW plants at € 145–185/t, with CLC CLC has also been explored [113]. Song and Shen [114] review dif-
being the least expensive and pre-combustion systems being the cost- ferent configurations of CLC reactor systems designed for solid fuels.
liest. For these options, technology maturity was assessed at Tech- Typical problems in such systems include mechanical attrition of carrier
nology Readiness Levels (TRL) of 4–5 [98]. In Table 2, the technology particles and carbon residue deposition. Techno-economic analysis by
readiness level of carbon capture technologies is given. Cormos [115] of a biomass direct chemical looping (BDCL) scheme
using wood as fuel indicated that thermal efficiency of 42% can be
4.1. Pre-combustion CO2 capture achieved in a highly integrated process, even at CO2 capture rate of
99%. This level of performance was shown to be clearly superior pre-
Pre-combustion capture of CO2 in integrated gasification combined and post-combustion BECCS plants to in the same work.
cycle (IGCC) plants is one of the major technology options for “green-
field” projects (i.e., new power plants). Gasification products are made
4.4. Post-combustion CO2 capture
to undergo the water-gas shift reaction to give a mixture of CO2 and H2.
The former gas is then separated for capture and subsequent use or
Currently post-combustion capture involves capture of CO2 from
storage, while the latter is used as fuel in a CCGT plant [100]. For such
flue gas via a scrubbing process, membrane CO2 capture, cryogenic CO2
plants, parasitic energy losses are incurred for the generation of O2 in
capture and other niche capture options for specific industries. For
an air separating unit (ASU) and for CO2 removal from the syngas. In
example, high-quality CO2 is a byproduct of bioethanol production, and
addition to electricity, IGCC plants can also be used for polygeneration
its capture is already commercially viable [116]. Techno-economic
of various chemical or fuel products [101]. Process simulations invol-
analysis of CO2 capture in bioethanol plants with gas-fired boilers
ving multiple biomass feedstocks co-fired in IGCC plants for electricity
shows that reduction in CO2 can be doubled by integrating CO2 capture
generation and biofuel production via Fischer-Tropsch synthesis in-
from the boiler flue gas, at the expense of a 40% increase in fossil fuel
dicated significant opportunities for optimization via fuel blending
consumption due to parasitic consumption of the capture system [117].
[102]. Techno-economic analysis of a biomass-based integrated gasifi-
cation combined cycle (BIGCC) plant using air and with an amine-based
capture process for removing CO2 from syngas was recently reported by 4.4.1. Amine scrubbing
Ref. [103]. Their results show that efficiency can be optimized by using Amine scrubbing is the mature and commercially viable technique
air to eliminate the need for an energy-intensive Air Separation Unit for capturing carbon dioxide. It is widely used method for the post
(ASU), and by introducing a heat recovery steam generator (HRSG). combustion treatment of the flue gas [118]. Procedure is based on the
chemical absorption where amino-based absorbents are added from the
4.2. Oxyfuel combustion top of an absorber to react with CO2 from the flue gas. Solution en-
riched with the CO2 molecules is then introduced to the stripper column
Oxyfuel combustion is a technique for generating CO2-rich flue gas to release captured CO2 [119]. As an absorbents metal carbonates can
by burning fuel in the absence of nitrogen [104]. This approach re- be used as well, but their price significantly affects wider usage of them
quires the use of an ASU to produce the oxygen needed for combustion; [120]. Process is highly efficient in terms of capturing CO2 and effi-
operation of the ASU, which is usually based on cryogenic separation or ciency can be up to 98%. Nevertheless, heavy consumption of amino-
pressure swing adsorption (PSA), is highly energy intensive and creates based solvents enhances the corrosion processes on the used equipment
a parasitic electric power load that leads to reduced power plant output and even more, high energy input is required for the solvent re-
and efficiency. Part of the CO2-rich flue gas is recycled and mixed with generation [118]. High energy input for the solvent regeneration im-
the oxygen stream to simulate the thermal ballast effect that would plies high energy penalty and decline of the power plant efficiency,
normally be played by N2, keeping the flame temperature and radiative which can be up to 30%. For example, for a baseline efficiency in a coal-
profile close to conventional flame conditions [105]. Oxy-fuel com-
bustion has been extensively studied for use with fossil fuels [106], Table 2
although the technique has also been tested for coal-biomass blends Technology readiness level of Carbon capture technologies, adopted from Ref.
[99].
[107]. Höltl et al. [108] point out that the oxyfuel combustion can
provide favourable conditions for burning fuels of low calorific value, Technology readiness level TRL Proposed technology
such as biomass from agricultural or municipal wastes. The rate of flue
Concept TRL1
gas recycling can be adjusted to account for the effect of reduced flame Formulation TRL2
temperature during biomass combustion [109]. Proof of concept TRL3 • Post-combustion Ionic liquids
• BECCS power
4.3. Chemical looping combustion • Pre-combustion treatment
• Membranes dense inorganic
Chemical Looping Combustion (CLC) systems make use a solid

Lab prototype
Lab-scale plant
TRL4
TRL5
• Oxy-combustion gas turbine
oxygen carrier which recirculates between air and fuel reactors to
achieve combustion in the absence of nitrogen without excessive energy
Pilot plant TRL6 • Membranes
plants)
polymeric (power
penalties [110]. In a CLC system, the carrier is typically based on metal • Post-combustion biphasic solvents
• Chemical looping combustion
oxides, which oxidizes in contact with air in the air reactor; its oxygen
• Calcium carbonate looping
content is then used to burn the fuel in the fuel reactor, as it is reduced
back to its initial state [111]. However, recirculation of the carrier re-
Demonstration TRL7 • Membranes
industry)
polymeric (NG
sults in eventual deterioration through mechanical attrition. As fuel • Pre-combustion IGCC + CCS
• Oxy-combustion coal power plant
• Post-combustion
combustion occurs without direct contact with air, the resulting com-
adsorption
bustion products consist mainly of CO2 and water vapor. Removal of
• BECCS industry
this moisture content leaves a high-purity CO2 stream which is ready for
transport for subsequent storage or utilization. While CLC was origin- Commercial refinement TRL8
• Direct Air Capture (DAC)
ally proposed for use with gaseous fuels, particularly natural gas (NG), required
the scheme can also be used in BECCS systems. One option is to first
Commercial TRL9 • Post-combustion
plants)
amines (power
gasify the biomass, and then to use the resulting volatile product in
conventional CLC systems [112]. Direct use of particulate solid fuels in
• Pre-combustion NG processing
7
fired power plant of about 38%, CO2 capture reduces efficiency. to only NOx and SO2) is a major obstacle to their application for CO2 capture
31% [121]. This energy penalty provides the basis for flexible operation from combustion products [135].
of capture systems, and will be discussed in the next section. In addi-
tion, degradation of the solvent leads to the decrease of the absorption 4.4.3. Cryogenic CO2 capture system
capacity and increment in overall operating costs [118]. Flexibility and Cryogenic CO2 capture is also a competitive technology for in-
economic feasibility of an amine scrubbing can be achieved if the de- dustrial sites where there is available excess cold energy, and offer
graded solvent is stored when the electricity prices are high and solvent advantages of giving a high purity product stream that may be needed
regeneration is performed when electricity prices are lower. In general, by downstream CO2 utilization sinks [135]. In the absence of a ready
it can be stated that decoupling of the power generation and CO2 source of cold energy, electricity demand will typically be double the
capturing will result with reduced energy penalty and better economic cooling duty [136]; another thermodynamic disadvantage is the high
performance of the system [121]. level of exergy loss due to temperature drop from of combustion pro-
Chemical absorption processes for CO2 capture that make use of ducts down to cryogenic temperatures [135]. Examples of cryogenic
amines, such as monoethanolamine (MEA), have been extensively stu- capture techniques include dynamic packed-bed systems [136], me-
died and is considered to be the most promising near-term technolo- chanical coolers using the Stirling cycle [137] and hybrid membrane/
gical option [122]. A major technical challenge in amine-based systems cryogenic process [138]. The latter hybrid process is reported to have
is the parasitic energy consumption in the recovery loop. Process in- an energy consumption of 1.7 GJ/t CO2, which is 50% lower than that
tegration principles have been used to optimize heat recovery and of systems based on Stirling coolers [139].
minimize energy losses in MEA-based systems [123]. For example, Le
Moullec and Kanniche [124] studied different flowsheet configurations 4.5. Other CO2 capture systems
and identified options that can reduce power plant efficiency penalty by
as much as 30%. Amine degradation under normal flue gas conditions is There are also other niche capture options for specific industries.
also known to be a major issue [125]. Puxty et al. [126] did a screening For example, ethanol-based biorefineries produce high-quality CO2
study of 76 candidate amines, of which seven compounds were found to streams that can be readily captured with minimal need for further
have good properties for CO2 capture applications. It should be noted treatment. This industry represents an attractive and technologically
that amine-based post-combustion capture for BECCS is less efficient mature capture option. Although its potential scale is ultimately limited
than CCS with fossil fuels (and also less so than oxy-fuel based BECCS) in magnitude to approximately a 1:1 mass ratio with ethanol output, it
and is also highly sensitive to biomass moisture content [127]. In ad- can serve as an initial catalyst for the development of CCUS infra-
dition to amines, CO2 capture using aqueous ammonia solution is in- structure which will be needed as other capture techniques become
herently more efficient due to the low energy requirement for re- commercialized [116]. Techno-economic analysis of CO2 capture in
generation; for this reason, coupled with the widespread use of bioethanol plants with gas-fired boilers shows that reduction in CO2 can
ammonia, this option also has lower costs than amine-based capture be doubled by integrating CO2 capture from the boiler flue gas, at the
systems. On the other hand, disadvantages include higher potential for expense of a 40% increase in fossil fuel consumption due to parasitic
fugitive ammonia emissions and equipment corrosion [128]. Ionic li- consumption of the capture system [117]. System-level integration
quids (ILs) are alternatives to amines, and offer significant advantages schemes for post-combustion capture may also have significant poten-
such as better chemical stability; use of ILs in the absence of water can tial for carbon management. For example, Dean et al. [140] proposed a
also reduce parasitic energy requirement of capture systems [129]. calcium-looping scheme using calcium oxide (CaO) to simultaneously
reduce CO2 emissions from a power plant integrated with a cement
4.4.2. Membrane CO2 capture plant. Such a scheme can readily be extended to biomass-fired plants to
Membranes are among the most promising environmentally friendly achieve negative emissions.
technology for the recovery of CO2 emissions [130]. They have been
proven highly efficient when the concentration of CO2 in flue gas is not 4.6. Direct air capture
below 10%, while optimal economic competitive requirements are
achieved for the concentrations of 20% of CO2 in the flue gas [131]. The Direct air capture (DAC) is an emerging technology which can po-
introduction of polymeric membranes resulted in a significant boost in tentially allow for the development of widely distributed CO2 capture
membrane deployment [132]. Use of polymer materials decreased the infrastructure. As the term suggests, DAC involves removing CO2 from
cost of membrane production and simplified handling requirements. air through chemical separation processes. Note that this separation
Nevertheless, polymeric membranes are prone to the degradation, needs to occur at thermodynamically unfavourable conditions because
especially at higher pressures and temperatures. Since the fundamentals of the very dilute ambient levels of CO2 in air, as compared to com-
of this process are based on the pressure difference between inlet and bustion gases [141]. Pritchard et al. [142] argue that, from a systems
exit, several limitations arise when the polymeric membranes are used. perspective, DAC only makes thermodynamic and economic sense after
Firstly, low concentrations of the CO2 in the treated gas will lead to the opportunities for CO2 capture from point sources have been maximized.
low partial pressures, which affects process efficiency [131]. Moreover, Chen and Tavoni [143] ran global simulations that indicated the need
elevated temperatures and higher pressure can cause swelling (plasti- for widespread use of DAC as an important carbon management tech-
cization) of the polymer material, which results in lower selectivity and nology later in the 21st Century. The earliest and most widely studied
increased permeability for all gases. Since the trade-off between per- DAC technique involves the use of aqueous solutions of sodium or
meability and selectivity is a key driver for efficient CO2 capture, pre- calcium hydroxide to skim CO2 from the atmosphere [144]. This re-
cise optimization of those two parameters is essential. Feasibility and action forms carbonates which can later be calcined to release a con-
competitiveness of this technology is expected when the permeability centrated CO2 stream, while the resulting hydroxide stream recirculates
between 1000 and 10000 Barrer and CO2/N2 selectivity between 50 in a closed loop within the system. McLaren [145] rated the techno-
and 200 is achieved [133]. More recently, composite membranes made logical maturity of this DAC technique at 4–6 using the TRL scale, and
of polymer and some inorganic material (ceramic, zeolites) are being estimated potential CO2 capture capacity to be 10 Gt/y. House et al.
investigated since they can be used at elevated temperatures and [146] estimate the energy intensity of future large-scale DAC at 400 kJ/
slightly higher pressures, which can extend overall membranes ap- mol or 9.1 GJ/t CO2, at a cost of US$1000/t. Alternative DAC techni-
plicability [134]. Membrane-based separations processes are used ex- ques include those based on bulk solid alkali carbonate systems. The
tensively in many industrial applications, but their propensity to de- initial work in this area investigated the carbonation of CaO and Ca
grade at elevated temperature and in the presence of acid gases (e.g., (OH)2 at temperatures ranging from 300 to 450 C; moisture in air was
8
also found to accelerate capture [147]. Sodium-based systems were approaches to increase the flexibility of systems based on pre-com-
subsequently reported [148]. Other novel DAC techniques include bustion or oxy-fuel combustion [155]. These options are shown in
electrochemical capture, which utilizes hydroxyl ions generated in the Table 3. The prospect for co-generation of secondary products along
electrolysis of water to react with ambient CO2 [149]. The energy with electricity is one of the advantageous features of pre-combustion
consumption reported was 8.7 GJ/t of CO2, which is 4% below the capture systems. Biomass-based IGCC plants co-producing electricity
benchmark value given by House et al. [146], but which is supplied and hydrogen at different ratios were simulated by Cormos et al. [102]
primarily as electricity. using different fuel blends at CO2 capture rates of 92–93%. A flexible
CL-based system for co-production of electricity and hydrogen using
4.7. Flexible CO2 capture methane as fuel was proposed by Ajiwobowo et al. [156]. Their concept
combines a solid oxide electrolytic cell (SOEL) with a CLC-CC plant;
The energy-intensive nature of most CO2 capture processes results in simulations indicate that a maximum energy efficiency of up to 56%
the potential to use flexible operations as a means to stabilize volatile can be achieved by the system. For cryogenic CO2 capture systems, the
electricity supply in a grid with high penetration of variable renewable product stream can be used as basis for storage of cold energy if there is
energy. In such systems, CO2 capture can be reduced to free up electric demand [135]. In addition, the option for intermediate buffer CO2
power output that would otherwise be lost to parasitic energy re- storage in tanks or naturally occurring geological formations (e.g., ca-
quirements, during periods of high demand or low supply in the grid. verns) is in principle universally applicable regardless of capture
They can be used in conjunction with other stabilization strategies such technique, and may play an important role in large-scale CCUS net-
as energy storage or various Power-to-X (PtX) schemes. A recent review works where there are also market-based variations in downstream CO2
shows that the current literature on such systems focus on amine-based demand. The potential use of pipelines for interim CO2 storage was
post-combustion capture plants, and that there is significant overall recently proposed by Aghajani et al. [157].
potential to have improved profitability relative to non-flexible capture In addition, some early work on flexible DAC systems has been re-
plants because of the low cost of renewable energy during periods of ported by Wohland et al. [158]. Their simulations show that negative
surplus [150]. The two most common flexible operating schemes in emissions amounting to 500 Mt/y can be achieved by running flexible
post-combustion capture are bypassing or venting, in which the flue DAC on surplus electricity with high penetration of renewables in the
gases bypass the capture system entirely, or solvent storage, in which European grid. However, viability requires at least 80% renewables in
case the energy-intensive regeneration units are activated only when power mix. These early results are promising, but further techno-eco-
there is surplus electricity in the grid [151]. Techno-economic analysis nomic assessment is needed to gauge the viability of running flexible
by Cohen et al. [152] at carbon prices in the range of US$20–70/t show large-scale DAC systems at part load for a significant fraction of their
that venting-based systems can increase profits relative to inflexible operating lives.
systems by as much as 10%. They also found that solvent storage sys-
tems are only viable for periods of up to 30 min, beyond which capital
5. CO2 utilization pathways
costs for storage units become prohibitive. There has been significant
interest in developing techniques to enhance capture plant flexibility
CO2 is an important source of carbon for making organic chemicals,
[150]. Tait et al. [153] reported pilot-scale dynamic tests using syn-
materials, and carbohydrates apart from being a greenhouse gas. There
thetic flue gas with 30% MEA as capture solvent. They determined that
have been numerous studies done on CO2 utilization pathways. One of
response lag was determined mainly by the total inventory of circu-
the pathways that have gained great interest is the utilization of CO2 in
lating solvent. Fast-response power output maximization schemes they
chemical industry via chemical conversion into many useful products
tested were (a) bypassing the capture plant entirely and (b) stopping
by carboxylation and reduction reactions. Besides the utilization of CO2
steam feed into the solvent recovery reboiler. Conversely, ramp-up of
in chemical industry, CO2 has also been used in the agriculture sector in
steam feed into reboiler was also determined to be an effective transient
China as fertilizer for over 30 years, and have led to marked im-
strategy during periods of excess energy availability. In principle, the
provements in plant nutritions. These are among the proof of applica-
venting strategy should also be feasible for use in post-combustion CO2
tions that CO2 utilization in chemical industry and agricultural sectors
capture using other techniques such as cryogenic or membrane tech-
are mature technologies. In 2009, electrofuel was introduced and be-
nology.
came an emerging technology for CO2 utilization pathway by means of
Although flexible capture systems are often envisioned to compen-
converting CO2 feed stock into synthetic fuel such as methanol, me-
sate for volatility of a renewables-intensive grid at relatively short
thane, biodiesel and petrol [36]. These three pathways have shown
timescales measured in minutes or hours, they also offer the prospect of
great potential for CO2 emission reduction by transforming it into other
risk mitigation for long-term energy deficits. For example, Haszeldine
useful products, including for clean energy storage.
[154] suggested venting as a strategy to free up electricity in a grid with
high wind energy penetration, during extended periods of low wind
speed. Similar crisis may occur at the seasonal scale, as in the case of 5.1. Chemical industry
droughts reducing hydroelectricity supply over the span of multiple
weeks or months. For such long-term variations, other flexible capture There are two common pathways for CO2 utilization in chemical
schemes based on solvent storage will clearly not be physically viable. industry. Due to its inert properties, CO2 could be used as an efficient
Although, as previously noted, the bulk of the literature on flexible CO2 extractor and solvent [159], or could be directly used for various pur-
capture deals with post-combustion capture, it is possible to implement poses as been discussed in section 4.1.1.
Table 3
Flexibility enhancement techniques for CO2 capture systems, adapted from Domenichini et al. [155].
Technique Pre-combustion Post-combustion Oxy-fuel combustion
Storage of CO2 capture solvent Yes No No

Storage of liquid O2 Yes No Yes
Co-production and storage of H2 Yes No No
Switching off capture system Yes Yes No
Buffer CO2 storage Yes Yes Yes
9
5.1.1. Direct utilization based on physico-chemical properties size are lower as well [168]. Refrigeration capacity of CO2 is around
CO2 can either be used directly or as a raw material for manu- 22 600 kJ/kg at 0 °C, which is 5–22 times higher than those of com-
facturing chemical products. Table 1 gives examples of direct uses of mercial synthetic refrigerants. In addition, CO2 has a small decline of
CO2. Direct usage of high purity CO2 in either liquid or gaseous form is saturation temperature relative to pressure drop, which enhance mass
necessary, especially for applications in the food and beverage in- flux in evaporator and suction pipes. This feature is especially pro-
dustries. Lately, microalgae production has been marked as a potential nounced in temperature range of −30 to −50 °C, where higher system
CO2 sink. The microalgae industry is growing due to products that can efficiencies have been noted [169]. Sharma et al. [170] found that the
be utilized for a wide range of applications [159]. Potential products implementation of CO2 transcritical booster systems or cascade/sec-
include pharmaceuticals, human and livestock food, and biofuels [160]. ondary loop systems in supermarkets using optimized operating con-
Another interesting and potential utilization of CO2 is to produce suc- ditions lead to reduced direct GHG emissions while achieving com-
cinic acid [161]. Succinic acid is used as a pH modifier, a flavoring parable energy consumption. Abas at el [169]. stated that when CO2 is
agent and as an anti-microbial agent in the food industry, along with used as a refrigerant for the supermarket systems, the coefficient of
other applications as a detergent/foaming agent, pharmaceutical, che- performance (COP) is often higher than those of HFC based systems.
mical intermediate [162]. CO2 is also one of the most popular natural refrigerant for ground
The food and beverage industries today consume about 11 Mt CO2 source heat pumps [171]. Additional work on its utilization in such
annually [163]. The amount of 6 Mt CO2 is used as process gas in applications have been reported using carbon dioxide direct-expansion
various applications such as for industrial gas, and oil and gas recovery ground source heat pump (CO2-DX-GSHP) [172], carbon dioxide direct-
(EOR/EGR) [164]. expansion geothermal heat pump [173], transcritical CO2 heat pump
Another potential application is the use of CO2 as a commercial integrated with thermal energy storage [174], geothermal heat pump
refrigerant. Selection of the refrigerant strongly depends on the system working with different zeotropic and azeotropic mixtures [175]. Wang
requirements which need to be fulfilled. It should be noted that its et al. [176] investigated a novel CO2 heat pump system with Series Gas
critical unique point is at 31 °C and 74 bar. Usage of CO2 as a refrigerant Cooler (SGC) for the application in an electrical vehicle (EV). System
implies dealing with pressures up to 10 times higher compared to the using CO2 as a refrigerant, offers a great heating advantages in a cold
commercial hydrofluorocarbons [167]. Because the Global Warming climate. At the temperature of −20 °C, the proposed heat pump system
Potential (GWP) of CO2 is several orders of magnitude lower of some achieved 5.6 kW maximum heating capacity and 1.8 COP, which
commercial hydrofluorocarbons utilized today (see Table 4), climate greatly outperforms the conventional PTC heating supplement for an
implications of leaks and fugitive emissions are significantly reduced. EV.
In refrigerant applications, the liquid density of CO2 is lower than
that of other alternatives; hence, requirements for system design and
Table 4
Direct usage of CO2.
Application Description References
Solvent • Solvent for chemical reactions and process [165]

• Results in more efficient process than conventional solvent
• Quick development from supercritical dissolvable with non-dissolvable process
• Miscibility or solubility switch
• Mobile phase in continuous flow catalyst for a new chemical synthesis initiative.
Refrigerant • The old version of refrigerant that have been used before World War 2 [165]
• Have been displaced with synthetic refrigerant due to high pressure needed for CO refrigerant
• Natural
2
and safer refrigerant compared to synthetic refrigerant
Protecting gas • Exploitation of non-oxidizing and inert properties of CO [165]
• Use
2
in fire extinguisher and safety special equipment
• Exhibits high CO concentration atmosphere in museum
• degradation.
2
To preserve paper of historical manuscript from acidification that could cause mechanical
Enhanced oil and gas recovery • Largest direct CO application that have been used since 1980 [166]
• economically
2
attractive
• enhance oil recovery up to 15% for each reservoir
• mature technology for EOR but not mature for enhanced gas recovery (EGR)
Cleaning and extracting agents • supercritical carbon dioxide extraction [166]
• Extracted product residues freed from undesired substance
• Non-polar impurities cleaning agent
• Dry cleaning agent in archaeology and arts
• Separation of heavy metal in wastewater treatment using nuclear technology
Enhanced coal bed methane • Assist trapped methane extraction [166]
Techniques for reversible adsorption and assimilation of • Could absorb CO using reversible amine solution technology [166]
• Could
2
carbon dioxide also use membrane resins and inorganic systems
Impregnating operator • Invert procedure of extraction [165]
• Impregnation of a framework with low sub-atomic weight mixes
• Improved the heat and mechanical stabilities of polymer and polymeric membranes
Acidity controller for aqueous solution • Acidity or pH adjuster [165]
• Neutralization agent for waste waters from steel industry
Use in food and beverage industries • Used to carbonize beverages [166]
• ToCasein
produce deoxygenated water
• Pre-treatment
precipitation
• Used as acidifierof olives before oil pressing
• Need very high purity of CO
• Enhance the shelf-life, aroma and vitamin retentions of fruits and vegetable by using CO controlled
• atmosphere storage of fruits and vegetables
2
10
5.1.2. Chemical conversion of CO2 Table 6

Chemical conversion of CO2 can be classified into two main types of Products obtained from carboxylation reaction of CO2.
reaction, namely, carboxylation and reduction. Aresta and Application
Dinbenedetto [166] reported that 110 Mt CO2 per year have been either
converted into chemicals such as urea (70 Mt CO2 per year), inorganic Urea Fertilizer
Polymer synthesis (melamine and urea-
carbonates (30 Mt CO2 per year) and pigment or additives to methanol
formaldehyde resins) deNOx application for
synthesis (6 Mt CO2 per year). The amount of 20 kt CO2 per year has diesel-engine vehicles
been used to produce salicylic acid together with the production of a Acrylates, lactones and Super absorbents used in diapers (acrylates)
few kt per year of propylene carbonate as side products [177]. Ad- carboxylic acids Solvent, pharmaceuticals, surfactants,
ditionally, 18 Mt of CO2 per year has been used as a fluid that can cosmetic (carboxylic acids)
Fragrance (lactones)
transmit energy, via a process that involves adjustment of the fluid
Monomeric carbonate Alternative to toxic phosgene
pressure [11]. Isocyanate Sealants and adhesives
Polymeric material
Polycarbonate Phosgene-free process to aromatic
5.1.2.1. Carboxylation. Carboxylation involves CO2 reaction that polycarbonates (APCs)
occurs without breaking the carbonyl (C]O) bonds completely. This Ethylene carbonate
category of reaction includes mineral carbonation, use of CO2 as Polyolefin Polypropylene and polyethylene carbonate
initiator of some carbon-based chemicals, and polymer production Polyhydroxyalkanoate Biodegradable resins
Bioplastic
[177]. The ecological advantages of carboxylation include the
Polyether carbonate polyols Polyurethane, elastomers, coatings, sealants
substitution of vitality, outflows of harmful reactants (e.g. epoxides), and adhesives
and long term carbon storage [178]. Table 5 presents the chemicals and Chlorinated polypropylene Degradable CO2 copolymer
final products produced from carboxylation reaction of CO2 (see Tables
6 and 7).
commercially available technology [166]. However, the CO2 captured
from power plant flue gases needs to be purified prior to use, due to the
5.1.2.2. CO2 reduction reaction. In the CO2 reduction reaction, one or
potential presence of impurities such as O2, N2, H2O, H2S, CO, CO2,
both carbonyl (C]O) bonds are broken during the product formation
SO3, NOX, heavy metals (e.g., Hg), and trace hydrocarbons. Certain flue
[179]. The products include methane, methanol, ethanol, carbon
gas impurities may act as catalyst poison [165]. Screening criteria
monoxide, synthetic gas, formic acids and acetone. The CO2 reduction
should be considered when using CO2 from power plant flue gas for
reaction is energy-intensive because it needs a large amount of energy
chemical synthesis applications involving modern catalyst; for example,
to break the bonds [180]. The required energy can be provided by high-
in the case of methanol synthesis, H2S content in the feed gas has to be
energetic reactants such as hydrogen, by heat [181], electricity [182],
less than 0.1 ppm [236].
sunlight [183] or microwaves [184].
The quality of captured CO2 that is distributed via pipeline is usually
suitable to be used as raw material for chemical reactions. The type of
5.1.3. Sources and purity of CO2 contaminant and purity of CO2 may be relevant depending on the ap-
Sources of CO2 can be classified into two categories, namely, CO2 plication. Very high CO2 quality levels are required in food, beverage
captured from the atmosphere and CO2 captured from point sources. and pharmaceutical industry [237]. For example, high purity require-
CO2 can be removed from the atmosphere using the DAC technology ments are stipulated for the licensing of pharmaceutical ingredients
[233]. Due to the low concentration of CO2 in the air, the specific en- such as salicylic acid [165]. For chemical products, heavy metal im-
ergy requirement for its recovery is very high, making DAC less at- purities need to be low, for example when CO2 is converted to urea used
tractive compared to CO2 capture from point sources [233]. as fertilizers [165]. On the other hand, CO2 purity may be less critical in
CO2 point sources include numerous industries such as fermenta- cases where final product refining or purification follows the in-
tion-based processes, cement production, and fertilizer manufacturing corporation of CO2.
[165]. High purity CO2 captured is usually obtained from chemical Ammonia production has been recognized as one of the CO2 point
industries and refineries [234]. 120 Mt per year of pure CO2 are sepa- sources with lower energy requirement, providing 127 Mt per year CO2
rated during the production of H2/N2 gas mixture for ammonia synth- as a co-product [166]. Compared to ammonia production, CO2 recovery
esis [165]. The purity of CO2 captured from ammonia production and from fossil-fuel power plant requires more energy [238]. Other sources
fermentation is practically suitable to be used for all synthesis purposes of CO2 can be obtained from manufacture of ethylene oxide, bioethanol,
[235]. The sources of captured CO2 can be matched with suitable ap- iron and steel, cement, pulp and paper industry, refineries as well as in
plications (demands) depending on its purity requirements [165]. For sweetening of sour natural gas [250].
example, captured CO2 from ammonia plant has been paired with urea
production, while CO2 captured from fermentation has been paired
with beverage industry. 5.2. Use of CO2 in agriculture
CO2 captured from power plants flue gas is considered to be a major
potential source at the global scale [178]. Fossil-fuel power plants re- CO2 can be used in directly gaseous form as a greenhouse fertilizer,
lease approximately 78% of all CO2 from point sources [178]. The stimulating plant growth without requiring more chemical fertilizer
capture of carbon dioxide from the flue gas of coal, oil, or gas-fired input. CO2 fertilizer have been used since 30 years ago in China [239].
power plants, and from industrial processes is a mature and Research shows that CO2 gaseous fertilizers could increase crop yield by
Table 5
Characteristics of the most prominent refrigerators which are in use today and will be dominant in the short term [167].
Refrigerant R717 R744 R290 R600a R22 R134a R410A R32 R404a R1234ze
Group Inorganic CO2 HC HC HCFC HFC HFC HFC HFC HFC

ODP 0 0 0 0 0.055 0 0 0 0 0
GWP100 0 1 3 3 1700 1430 1980 675 3922 6
Atmospheric lifetime (years) Few days Few days Few days Few days 1–20 1–300 4–5 –
11
Table 7
Reduction reaction of CO2.
Routes Method/reaction Product Descriptions
Chemical Fischer Tropsch Methanol, hydrocarbon Reversible Fischer Tropsch process to reduce CO2 to methanol and
hydrocarbon [165]
Dry reforming CO, H2 Reversible drying reforming step to produce CO and H2 [184]
Reverse water gas shift CO, CH4 Reverse water gas shift reaction to produce CO and CH4 [165]
Sabatier reaction Methane Sabatier reaction for methane production [165]
Electrochemical Solid oxide fuel cell
Platinum CO • Initially proposed to produce O2 from CO2 rich atmosphere [185]
• Extended research to identify the Pt stable oxide [186]
• The performance have been improved when gas diffusion was found out to
be the limiting factor [187]
The improvement of efficiency using Pt-YSZ cermet electrode [188].
Nickel CO, methane • Nickel-YSZ electrode [189],
• Electrocatalytic dry reforming process [190]
• Nickel cermet (Ni-YSZ-CeO) electrode [191]
Electrolyser mode at high temperature [192]
Palladium CO Paladium electrode for CO2 reduction to CO [193]
Copper CO Copper electrode for CO2 reduction to CO [194]
Metallic electrodes in aqueous solution
Copper Hydrocarbons, CO, formate, alcohols • Heterogeneous catalysis [195]
Electrolyzer mode [196]
Platinum CO, methanol Voltammetric study of carbon monoxide and carbon dioxide adsorption on
smooth and platinized platinum electrodes [197]
Palladium CO, formic acid • Hydrogenated palladium electrodes [198]
• Addition of copper to the palladium electrode [199]
• Effect of different crystal structure on the arte of CO2 reduction [200]
The effect of the absorption of hydrogen on the palladium electrodes modified
with copper [201]
Others (Pb, Oxide-derived Au) CO, formate, formic acid • Oxide-derived Au electrodes [202]
• Lead granules in fixed bed reactor at high pressure and temperature [203]
• Electrodeposited tin on carbon paper (gas diffusion electrode [204]
• Molybdenum electrode [205]
Metal-functionalised porphyrin-like graphene [206]
Molecular electrocatalysts
Copper complexes Oxalate • Effect of pH and copper centre [207]
• Effect of electrode potential vs SHE [208]
Dinuclear copper complex electrode [209]
Palladium complexes CO, formic acid • Monodentate Pd complex under anhydrous conditions [210]
• Effect of pyridine and pyrazole ligand presentationin the complex [211]
• Mono- and bi-palaldium phosphine complexes [212]
Effect of acid concentration in the electrolyte [213]
Nickel complexes CO, oxalate, formic acid, • Reduction selectivity of Nickel cyclam in water [214]
formaldehyde • water
Efficiency of CO reduction using dimetallic cyclams in water and low
2
dimethylformamide solution [215]
• Effect of mercury electrodes and electrode potentials [216]
• CO reduction using macrocyclic nickel complexes [217]
• CO
2
reduction using dinickel microcyclic complex [218]
• Activity
2
of mononuclear nickel macrocyclic complex [219]
• Reduction of CO using nickel complex of carbinepyridine in water [220]
2
Electroreduction using Ni-tetra-phthalocyanine for formic acid and
formaldehyde production [221]
Cobalt complexes CO, formic acid, alcohols (methanol,
ethanol), acetone
• Reduction potentials of CO2 based on type of ligands of terdentate cobalt
complexes in DMF [222]
• Immobilisation of the cobalt complexes to dual –film electrode at low
potential under ambient aqueous [223]
Macrocyclic cobalt complexes in aqueous solution [224]
Pyridinium Methanol, formaldehyde, fromic acid A new homogeneous electrocatalyst for the reduction of carbon dioxide to
methanol at low overpotential [225]
Photochemical Transition metal complex CH2OH, CO, CH2O, CH3OH, CH4 Transition metal complex photochemical study [226]
Cascade metal Methanol Novel conversion of carbon dioxide to methanol catalysed by sol-gel
immobilized dehydrogenases [227]
Semiconductor CO, formate, formadehyde, methanol Photoelectrochemical reduction of carbon dioxide using polyaniline-coated
silicon [228]
Metallic molecular catalyst CO, formate, formadehyde, methanol Electrochemistry of tetraaeomacrocyclic metal complexes at illuminated p-
type silicon semiconducting electrodes [229]
Non-metallic molecular catalyst CO, formate, formadehyde, methanol Photoelectrochemical pumping of enzymatic CO2 reduction [230]
Bioelectrochemical Microbial fuel cell with microbial Formic acid Electrochemical reduction of carbon dioxide in an MFC–MEC system [231]
electrolysis cell
Stainless steel electrode with Glycerol Electrochemical reduction of CO2 catalysed by Geobacter sulphur reducens
bacteria grown on polarized stainless steel cathodes [232]
12
33.31% and accelerate crop growth [239]. Similar findings have been on this topic [250] gives an overview of the production costs of elec-
reported by the National Assessment Report of Carbon Utilization trofuels ranging from 160 to 210 €2015/MWh fuel in 2030. An increasing
Technologies (CUTs) [240]. Other findings have also shown that, CO2 number of studies have presented different pathways to produce elec-
gas fertilizer could increase the water use efficiencies by reducing trofuels and investigated their feasibility and potential [251] indicating
evaporation losses during crop transpiration and photosynthesis [241]. that the costs of renewable energy systems with electrofuels are not
For example, this effect has been observed in high latitude wheat more expensive than business as usual (BAU) fossil fuels systems.
plantations in the United State and Canada, with wheat production Goldmann et al. [72] studied the potential of electrofuels as aviation
increasing by 10% and corresponding reduced water consumption fuels, with emphasis on their compatibility with current aircraft en-
[242]. Increased carbon dioxide in wheat plantation in arid climates gines. Bongartz et al. [252] investigated and compared different
resulted in 8% gain in wheat production and improved crop water transportation fuels produced from renewable hydrogen and green
productivity by up to 50% [243]. Without CO2 boost, 29% of yield carbon dioxide for light-duty vehicles. Blanco et al. [253] made a cost
reduction has been reported due to the lack of rain in unirrigated wheat optimization study for hydrogen and Power-to-Liquid in the EU energy
crop. system. The EU energy transition to a RES based energy system and the
CO2 can be captured in algal systems to produce algal-bio-fertilizer, role of Power-to-Methane has been investigated in Ref. [254]. The role
which can then be used to improve rice quality while simultaneously of Power-to-Liquid and Power-to-Gas in the future German energy
increasing its yield [244]. From a climate standpoint, this alternative is system has been discussed in Ref. [255]. Hansson et al. [256] has
more environmental friendly as compared to synthetic chemical ferti- looked into potential of CCU based electrofuels for Sweden, and found
lizers. Among various CO2 utilization technologies in multiple field that the potential for electrofuels is limited by electricity demand rather
trials, algal fertilizer has shown the highest efficacy and greatest than the required CO2 missions cuts. Other papers looked into feasi-
emissions reduction [245]. On the other hand, Zhao et al. [246] found bility of using electrofuels in Germany [257]. Koytsoumpa et al. [258]
that, increasing CO2 pressure can result in faster conversion of waste investigated the emission-to-liquid concept in steel and power industry.
phosphogypsum into ammonia sulfate, which can in turn be used to Production of electrofuels not only depends on the TRL of CCU, but
produce fertilizers for the agriculture sector. This approach not only also the TRL of water and steam electrolysis. Low temperature alkaline
reduces the environmental impact of the large amount of waste phos- electrolysis is the only commercially available technology, but for
phogypsum every year, but also sequesters captured CO2. purposes of supporting flexible systems, has the disadvantage of slow
The integration of chemicals and energy production in large-scale dynamic response [260]. The use of polymer electrolyte membrane
industrial algal biofarms has led to the “algal biorefinery” concept. The (PEM) electrolysis has been emerging in the last decade [261], with
main advantage of this process is the large intake or consumption of main challenge being the reduction of requirement for scarce noble
CO2 for algal biomass production, since production 1 ton of dry algal metals [262]. Solid Oxide Electrolysis cell (SOEC) is a promising future
biomass production requires about 1.8 tons of CO2 [179]. Potential technology with low costs and high efficiency (up to 80%LHV) [96]. It
products from algal biorefinery include bioenergy, carbohydrate, pro- has been demonstrated on the small scale and has promising response
tein extract and some organic chemical for cosmetic, pharmaceutical rates, but still has issues with cell durability [263]. A recent review of
and nutraceutical industries. Apart from algae, some microorganisms cost trends from the 1990s to 2017 on electrolysis costs [264] shows a
such as such as Escherichia coli (E. coli) could produce succinic acid from significant drop in costs for future projections as a result of a learning
indirect CO2 transformation with glucose from wheat or unrefined rates. Alkaline electrolysis is still the cheapest technology currently
sugar. Many ventures have been being established around biosuccinic available with costs ranging between 600 and 2600 €2015/kWel while
acid production, as summarized in Table 8. PEM has range between 1900 and 3700 €2015/kWel, for the future
Another agricultural-biological routes of utilizing CO2 is the pho- projections (2030) SOEC has cheapest costs ranging between 400 and
tosynthetic approach to grow palisade layer plant cell culture to pro- 1000 €2015/kWel followed by alkaline 400–900 €2015/kWel and PEM
duce low cost sugars (glucose and sucrose). This process has been pa- 300–1300 €2015/kWel [250].
tented and commercialized by Naturally Scientific, a company that has During the last decade, several demonstration plants have been built
been producing both sugars and oils in their demonstration plant lo- and operated [265]. The implementation of PtX technologies has
cated in Nottingham, UK since 2013 [179]. peaked in 2018, with 18 projects currently running with Germany
having highest share of the projects [261]. However, most of the pro-
5.3. Electrofuels - chemical storage technologies jects are limited to production of hydrogen, and only few demonstra-
tion projects with CCU have been implemented. Two demonstration
Chemical storage of variable electricity is an important part of the projects have been reported on methanol production in Iceland [266]
future energy systems, as it both improves the system flexibility while and Sunfire e-crude production in Dresden [267], both based on use of
producing fuels for transport or chemical industry [36]. Excess elec- CO2. MefCO2 project [268] aims to demonstrate production of me-
tricity can be utilized to produce these commodities as a form of in- thanol from captured CO2 from power plant and electrolytic hydrogen
direct energy storage. Electrofuels are produced by merging carbon produced from surplus renewable electricity. In FReSMe project the aim
source and electrolytic hydrogen in so-called xTE processes [37] (see is to demonstrate capturing the CO2 from steel industry and producing
Fig 5). Carbon sources can be derived by either point source carbon methanol with electrolytic hydrogen [269]. Sunfire is planning to build
capture or DAC, biomass gasification, or biogas. Combustion of the another facility in Norway with capacity of 8000 t/year starting in 2020
resulting electrofuel does emit net CO2 emissions if only renewable [270].
electricity is used as input [247]. These fuels can minimize the use of
biomass if biogenic CO2 is used [248]. If CO2 from DAC is used, these
fuels offer the closed-loop carbon cycling [249]. Carbon capture and
utilization of CO2 emissions for production of low carbon fuels re- Table 8
present the biggest market for CCU technology, as there is a need for Companies involved in biosuccinic production [179].
fossil carbon source substitute [8]. Company's name Location Production
A range of products can be obtained making these processes flexible
and applicable for different purposes from transport fuels to ammonia Bioamber (joint DNP Green and ARD) Pomacle, France 2 kta−1
DSM and Roquette Freres Lestrem, France 2 kta−1
for industrial purposes. The most commonly suggested fuels are me-
Myriant Louisiana, USA 20 kta−1
thane, methanol and DME, but there is an option to produce e-petrol or BASF and CSM Purac, Spain
e-diesel via Fisher-Tropsch synthesis. A recent review of the literature
13
the case of gas-fired power plant; by comparison, the typical energy

penalty for post-combustion capture is 21% in the case of coal-fired
power plant, and 14.7% in the case of gas-fired plant for post-com-
bustion CC [275]. Another paper reports that the energy penalty in the
case of coal plant post-combustion removal has a theoretic minimum of
11%, energy penalty of 40% is easily achievable, while 29% of energy
penalty is a reasonable target [276]. A recent literature review on the
efficiency penalty for different types of plants with CC found that most
of the power plants have efficiency penalty of around 10% points, in-
dependent on the fuel type [277]. This energy penalty can provide the
basis for modulating power plant output to help balance supply and
demand in the grid.
Nord and Bolland [278] simulated plant flexibility of pre-combus-
tion capture and showed good operation and wide load range in their
results. According to Abdilahi et al. [279], carbon capture can increase
the flexibility of the existing power plants due to the controllability of
its operations related to the transport and storage of the CO2. Flexible
carbon capture can improve the investment value by allowing for a
temporary increase in electrical output that can help in relation to grid
reliability [280]. Power plants with CC can be operated as load fol-
lowing plants in systems with high penetration of renewables, and
analysis shows that bidding into intraday electricity market has the
highest potential [281]. Tait et al. [153] reported no significant barriers
for flexible operation of post-combustion capture pilot plant. Never-
theless, while the plant is operating at part load, the CO2 content of the
flue gases decreases. CCS plant operators would prefer to run it as a
base load in order to save on operating costs [282].
Fig. 5. Electrofuel production concepts and technology readiness levels, Some authors have dealt with the integration of CCS into energy
adapted from Ref. [259]. planning. One of the papers integrated CCS into EFOM model, a linear
optimization energy model [283]. Their model showed that for the case
of South Korea traditional fossil fuel plants would start investing in CCS
6. Integration of energy systems and carbon capture
at an emission price of 40 USD/tonne of CO2 [283]. However, wind
energy would be cheaper than the combination of traditional fossil fuel
Future energy demands can potentially be met with 100% renew-
plant combined with CCS storage [283]. Another paper focused on
ables provided that they are conceptualized and planned using a
operational optimization of an energy system [284]. The authors
system-level integrated approach [36]. Use of CCU technologies in the
claimed that integration of fossil power plants with CO2 capture with
future energy system could play an important role as it can help to
renewable energy in the system, increased the flexibility of the energy
increase the flexibility of renewable energy systems by indirectly
system and reduced operating costs for 20% compared to the base case
storing variable electricity into a wide range of fuels and chemicals. In a
[268]. Another possibility is to use an on-site CCU technology that
recent report, the European Commission acknowledged that the CCS's
would avoid the need for CO2 transport and storage and their associated
role could only be in the short/medium term for industrial processes,
energy demand. One example is the utilization of carbon from post-
and to generate net-negative emissions from biomass combustion
combustion treatment in a Brazilian sugarcane factory [285]. Using co-
[271]. Krey et al. [272] looked into different pathways with and
electrolysis of CO2 and water, and methane synthesis, additional me-
without CCS and concluded that the combination of bioenergy coupled
thane can be produced on-site. With this scheme, the Brazilian su-
with CCS makes the most sense in terms of emission reductions. In-
garcane factory managed to convert 54% of the total sugarcane carbon
tegrated value chains of CCU can help the integration of technology
to useful end-use products, compared with the initial carbon efficiency
with energy system [10] and support better the integration of renew-
of 17% [285].
able energy with different end-use products. Carbon capture from more
Much work on the potential of CCS and CCU has been carried out,
distributed generation systems in the future will not necessarily prove
yet there is still a lack of holistic energy modelling papers that explicitly
infeasible, especially in the case that the transportation and storage
compared zero-carbon energy systems that included CCS with zero-
demand is minimized [273].
carbon energy systems that do not include CCS. It is not clear whether
Two carbon capture (CC) technologies are particularly interesting
the total energy system costs would be favourable in either of those two
for integration with energy systems; post-combustion and pre-com-
cases in the future energy systems. While life cycle analysis framework
bustion CC technology. As pre-combustion CC technology includes ga-
for CCS systems exists [286], it is still not available for CCU systems
sification process of the fuel, there is a demand for electricity for the
[287]. In their article [288], authors reviewed different LCA studies of
gasification process. For example, a 300 MW integrated combined cycle
CCS and CCU technologies, and investigated their environmental im-
gasification plant requires between 36.5 and 38 MW of power for the
pacts, pointing that CCU is more profitable, but has a bigger environ-
gasification process [274]. Gasification process can be run flexibly, and
mental impact as the products produced can emit emissions.
does not need to match the exact timing of the power plant electricity
One important advantage of CCU is that if appropriate electrolysis
generation, which could be beneficial for balancing the supply and
technology is used, the flexibility of the whole energy system can be
demand on the power grid. On the other hand, the post-combustion
increased. Hydrogen produced via electrolysis could be used directly in
capture removes CO2 from flue gases, after combustion occurred, and is
the future, or the syngas (a mixture of hydrogen, carbon monoxide and
more mature and established technology.
other gases) produced by combining carbon with electrolytic hydrogen
The total energy penalty is more significant in the case of pre-
could be transformed to different hydrocarbons using different synth-
combustion capture than in the case of post-combustion capture, as it
eses processes [248]. The most beneficial electrolysis technology from
amounts to 28.4% in the case of a typical coal-fired plant and 25.3% in
the energy system point of view is solid-oxide electrolysis cell (SOEC),
14
mainly due to its fast ramp-up and ramp-down possibilities. SOEC can need to be studied in more detail. Nowadays, researchers are focused on
be ramped-up from 0% to 100% capacity in a few seconds. However, issues of carbon capture, storage and utilization separately, while sy-
during the cold start, ramping up the cell can take several hours [289]. nergies and process integration are unexplored. Integration of CCUS
Low-temperature proton exchange membrane electrolysis cell (LT PEM technologies with existing systems, interaction with the energy pro-
EC) has also a fast response within a part load range of 5–100% [289]. duction and CO2 utilization pathways is to be investigated. It should be
It has also a relatively short cold start time of only 5 min. Schmidt et al. noted that due to a number of different CCUS technologies and their
[290] report that the PEM electrolysis has a fastest cold start under different TRL level, it will be complicated to integrate them with the
20 min, while SOEC and alkaline are under 60 min, while system re- energy system. There have been number of laboratory studies on dif-
sponse rates are in milliseconds for PEM and on the seconds level for ferent CCUS technologies and their operating conditions. However,
SOEC and alkaline. Some manufacturers claimed that alkaline cells there is a lack of demo-scale and commercial CCUS technology appli-
could be developed to include flexible running possibility, if the de- cations in industrial environment. These are required to investigate
mand for that kind of cells would increase 289]. technical problems of such technologies, their operating conditions and
reliability, especially under flexible operating conditions. In the CCUS
7. Limitations, challenges and future research perspectives research area, due to the challenges named above, future research
should be directed to these topics.
The great challenge of integrating carbon capture in the energy
systems is the high and long-term investments and finding the most
suitable end-utilization of the collected carbon. Integrating different 8. Conclusions
industrial actors to invest and to use CCU or CCS technologies is re-
maining challenging. The low carbon pricing and carbon policy is not This review paper surveys and discusses the latest findings related to
supporting implementation of these technologies. the integration of VRES based energy systems and CCU technologies.
Carbon capture has also a technical challenge of collection and The importance of such integration and resulting synergistic effects are
purification of CO2 from different sources and intermittent operation of highlighted. It is stressed that flexible CCU technologies will be needed
the capture itself is not yet fully investigated nor demonstrated on the to meet future energy demands using 100% RES energy system. These
large scale. It is also possible that the capability to sequester carbon technologies can help stabilize volatile RES energy system by virtual
permanently may serve as an adverse incentive which further perpe- storage of excess energy in a wide range of fuels and chemicals. The
tuates the use of fossil energy, in contradiction of the ultimate purpose benefits from using the CCU technologies in this manner are the im-
of the system. Or it can be seen as a supplement for renewable energy provement of security of energy supply by reducing fossil fuel depen-
transition by using BECCS. Potentially unresolved issues such as storage dence, and the reduction of GHG emissions for mitigation of climate
safety and leakage of stored carbon are still debated, though according change.
to Ref. [291] these issues can be avoided by careful selection of storage Pre- and post-combustion CC technologies are especially promising
sites and CO2 monitoring. One of the critical obstacles for implementing for integration with energy systems. Their inherent flexibility can allow
CCU in the energy systems is a lack of clear system boundaries for the these two CC technologies to be used for balancing the electricity
emission assessment and in some cases system analysis, coupled with supply and demand in the power grid. In such systems, techno-eco-
lacking policy incentives. nomic penalties relative to steady-state capture systems can be offset by
Another limitation is connected with the lack of established decision variations in electricity price in a renewable-intensive power grid. This
support schemes for planning CCUS infrastructure, as well as matching is significant since, in future energy systems, there will be a need for
carbon sources and sinks [292]. It is yet unclear how should the deci- fast dynamic response technologies.
sions be made, e.g. whether the closest sink should be matched to the Lastly, the paper summarizes the options for utilization of captured
closest carbon sources or if priority should be given on some other CO2. The CO2 can either be used directly, or as raw material for man-
method [292]. ufacturing chemical products; a significant number of potential CO2
Literature also reveals that there is a lack of energy planning tools utilization pathways were surveyed and discussed. However, it needs to
that would integrate CCUS planning, including matching of carbon be emphasized that there is a large difference in scale (by orders of
sources and sinks, pipeline planning, as well as integrating CCUS to the magnitude) between the potential market for CO2 as feedstock, and the
energy system [293]. amount that needs to be removed to be significant for climate stabili-
Integrated CCUS concept may have limitations and potential dis- zation purposes. For the latter issue, NETs like BECCS and DAC-CCS will
advantages. For example, tightly integrated systems that achieve high be essential. However, further research in this area is needed to ac-
levels of efficiency and sustainability are vulnerable to cascading fail- celerate the development of technologies for climate stabilization.
ures from internal (e.g., failure of equipment) or external disruptions
(e.g., loss of supply of vital feedstocks) [294]. Integrated energy sys-
tems need to be built as resilient systems, however, the complexity of Acknowledgements
system operation of integrated system needs to be considered. Such
systems must be planned with provisions for flexibility, redundancy or The co-authors Mikulčić and Wang greatly acknowledge the
abnormal operating modes. In depth discussion of these issues is be- National Key Research and Development Program of China (No.
yond the scope of this paper, but may be the topic of future research. 2017YFB0603902), the financial support of the National Natural
Finally, the literature reveals that CCUS is still relatively immature Science Foundation of China (Nos. 51761125012 and 51676157), and
technology compared to the other existing low-carbon technologies, the Post-doctoral international exchange program by the China
missing large demonstration sites in different environments [293]. Postdoctoral Foundation. The co-author Ridjan Skov greatly acknowl-
There are also possible limitations that are yet unknown as they are edges the funding contribution from EP2Gas project EUDP no.64017-
many uncertainties in regard to this technology, such as lack of de- 0011. The co-author Dominković was financed by the CITIES project nr.
veloped carbon markets, lack of long-term assessment of the CCUS DSF1305-00027B funded by the Danish Innovationsfonden. Its con-
operation, and data uncertainty [295]. tribution is greatly acknowledged. The authors would like to thank the
As reported by Child et al. [296] flexible electricity generation, grid financial support from Universiti Teknologi Malaysia Research
exchange and storage, both short and long term energy storages, sup- University Fund under Vote Numbers Q.J130000.3509.05G96 and
port the energy transition. CCU products and related technologies as the Q.J130000.21A2.04E44.
final step of the energy transition, a fully 100% RES energy system, still
15
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Renewable and Sustainable Energy Reviews 114 (2019) 109338

Contents lists available at ScienceDirect

Renewable and Sustainable Energy Reviews

Flexible Carbon Capture and Utilization technologies in future energy T

1. Introduction Storage (CCS) are envisioned to play complementary roles within an

Nomenclature HRSG Heat recovery steam generator

Fig. 1. Integrated VRES based energy system and CCUS system.

coupled GDP growth from CO2 emissions. However, four emerging

Fig. 3. Smart energy system concept, adapted from Ref. [37].

in that market [47]. 3.2. Transport

Chemical Looping Combustion (CLC) systems make use a solid

Storage of CO2 capture solvent Yes No No

Solvent • Solvent for chemical reactions and process [165]

5.1.2. Chemical conversion of CO2 Table 6

Group Inorganic CO2 HC HC HCFC HFC HFC HFC HFC HFC

the case of gas-ﬁred power plant; by comparison, the typical energy

References comprehensive review of the feasibility of 100% renewable-electricity systems.

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