Chem 001

Journal of Environmental Chemical Engineering 11 (2023) 111393
Contents lists available at ScienceDirect
Journal of Environmental Chemical Engineering

journal homepage: www.elsevier.com/locate/jece
A comprehensive review on recent trends in carbon capture, utilization,

and storage techniques
Mohammad Yusuf , Hussameldin Ibrahim *
Clean Energy Technologies Research Institute, Process Systems Engineering, Faculty of Engineering and Applied Science, University of Regina, 3737 Wascana Parkway,
Regina SK S4S 0A2, Canada
A R T I C L E I N F O A B S T R A C T
Editor: Dong-Yeun Koh This review highlights the latest trends in carbon capture, utilization, and storage techniques. The recent ad
vances in the current carbon capture techniques, i.e., post-combustion carbon capture, pre-combustion carbon
Keywords: capture, and oxyfuel combustion systems, have been deliberated. Human exploitation of natural resources is
Greenhouse gas leading to an immense rise in the concentration of greenhouse gas (GHG), i.e., primarily carbon dioxide (CO2) in
Carbon dioxide
the atmosphere. This boosted quantity of CO2 by human intervention leads to increased global temperatures and
Global warming
climate change. Hence there is a crucial need for fixing CO2 to control global climate change and meet the
Carbon capture
CO2 utilization pledges of the Paris Agreement. The global CO2 emission hit an all-time high in 2018, emitting 32.7 billion tons
CO2 storage of CO2 into the atmosphere, whereas the current scenario for global CO2 utilization constitutes a tiny amount, i.
e., 0.2 billion tons/year. Hence various CO2 utilization techniques, such as CO2 deployment in reforming tech
niques and its direct conversion into fuels, have been emphasized. Finally, the CO2 storage methods have been
underlined, and the recent advancements along with the outlook in DAC technique have been discussed at the
end. The DAC technique shows the most promise for future CO2 capture and utilization, pending resolution of
initial investment and techno-economic feasibility challenges. However, it’s important to note that no single
technique is universally applicable, and governments worldwide must address specific ground-level issues for
practical solutions.
1. Introduction by fossil-based fuels, which puts great pressure on the rising global GHG
trajectory emissions [6,7]. This, in turn, is responsible for the
Due to swift industrialization, due to the rising global population and ever-increasing CO2 quantity worldwide [8]. The CO2 concentration, i.
increasing energy demands, the global concentration of greenhouse e., mainly responsible for global warming due to its infrared rays trap
gases (GHGs, i.e., mainly CO2) is intensifying, thus disturbing the ping nature, has escalated from 315 parts/million to 415 parts/million
ecosystem [1–3]. The world population is estimated to be about 7.98 in just the past six decades, as shown in Fig. 1 [9]. This is due to the fact
billion in 2022 and is expected to cross 10 billion by 2050. This will lead that the fossil-based hydrocarbon fuel that has been formed in millions
to the increased demand for energy and water in the near future raising of years under the earth’s crust has been exploited at an enormous rate
their scarcity [4,5]. Still, more than 84% of global energy demand is met by humans after the industrial revolution. Hence to achieve the pledges
Abbreviations: GHG, Greenhouse Gas; DAC, Direct Air Capture; COP26, Climate Change Conference of Parties; COP27, Conference of Parties; UNFCCC, United
Nations Framework Convention on Climate Change; CCS, Carbon capture and sequestration/storage; CCUS, Carbon Capture, Utilization, and Storage; DFT, Density
Functional Theory; NOAA, National Oceanic and Atmospheric Administration; IPCC, Intergovernmental Panel on Climate Change; WGS, Water-Gas-Shift; PPs, Power
Plants; CHPPs, Combined Heat and Power Plants; IGCC, Integrated Gasification Combined Cycle; HRSG, Heat Recovery Steam Generator; AGR, Advanced Gas-cooled
Reactor; MEA, Monoethanolamine; DEA, Diethanolamine; MDEA, Methyl Diethanolamine; MOFs, Metal-Organic Frameworks; PSA, Pressure Swing Adsorption; VSA,
Vacuum Swing Adsorption; TSA, Temperature Swing Adsorption; PTSA, Pressure-Temperature Swing Adsorption; CLC, Chemical Looping Combustion; CLP, Calcium
Looping Process; LNG, Liquified Natural Gas; AMD, Acid Mine Drainage; DRM, Dry Reforming of Methane; BRM, Bi-Reforming of Methane; ORM, Oxy-CO2
Reforming of Methane; THF, Tetrahydrofuran; TBAB, Tetra-n-Butyl Ammonium Bromide; TBAF, Tetrabutylammonium Fluoride; ECBM, Enhanced Coal Bed Methane;
EOR, Enhanced Oil Recovery; MMP, Minimum Miscibility Pressure; NET, Negative Emission Technique; HER, Hydrogen Evolution Reaction; CO2RR, Carbon Dioxide
Reduction Reaction; OER, Oxygen Evolution Reaction.
* Corresponding author.
E-mail address: [email protected] (H. Ibrahim).
https://doi.org/10.1016/j.jece.2023.111393
Received 19 August 2023; Received in revised form 10 October 2023; Accepted 30 October 2023
Available online 3 November 2023
2213-3437/© 2023 Elsevier Ltd. All rights reserved.
M. Yusuf and H. Ibrahim Journal of Environmental Chemical Engineering 11 (2023) 111393
commercial pre-combustion capture techniques; however, the pre-

combustion capture approach is immature and in the early develop
ment stage for power plants. The gasification of fuel and CO2 separation
is done by this method. It can be a, economic alternative compared to
other options, but its scope includes installation in the new facilities
only. Whereas modifying a prevailing setup for precombustion could be
excessively pricey. In the oxyfuel combustion method, the fuel is burned
in sheer O2 producing highly concentrated CO2 release i.e., compara
tively easy to capture. After the capture stage, the CO2 is turned into
liquid form via compression and transported to the storage sites through
pipelines, ships, or trains accordingly. In the final step, the CO2 is
introduced into the deep geological formations, which are generally
abandoned oil/gas wells, saline aquifers, and coal beds for long-term
storage.
CO2 mitigation can be done by several means; however, the techno-
economic feasibility of the process is the primary concern for the
commercialization of the technique on a global scale. However, as per
Fig. 1. Atmospheric CO2 concentration (ppm) trend in the last six decades the different investigations carried out, it has been affirmed that a mixed
((Data courtesy NOAA, Global Monitoring Division, Mauna Loa Laboratory,
type of approach, depending upon the availability of resources and
2022[6]).
budget, the CCS solutions may be implemented. As per the recent
analysis by the IPCC, the easiest, most economical, and the most effec
made during the Paris agreement in 2015 by 196 countries of the world tive way is the restoration of the forests by afforestation. This will
and sustainable development, the necessary steps for carbon capture, enhance the air and O2 quality while absorbing the CO2 from the at
storage, and utilization need to be done on an urgent basis [10]. This will mosphere. Afforestation will also help in maintaining the ecosystem by
aid in limiting the global temperature increase to the limit of 2 ◦ C by maintaining the soil quality, rain, and water cycles, and that too in the
2050. The Climate Change Conference of Parties (COP26) held at cheapest means. The afforestation technique has been estimated to have
Glasgow UK brought the different parties of the world together again in the potential to remove about 0.5–3.6 gigatons of CO2 annually. Other
October-November 2021. The COP26 focused on the breakthrough and innovative techniques include biochar and soil sequestration, which
fast-track the goals of Paris Agreement and the and the UN Framework may act as the sink for CO2 utilization. Biochar and soil sequestration
Convention on Climate Change. Currently, this year (i.e., 2022) the 27th technique also has the potential to remove about 2.3–5.3 gigatons of CO2
Conference of Parties (COP27), with “parties” referring to the 197 annually. Other promising techniques include the enhanced weathering,
countries of the world that sanctioned the United Nations Framework DAC, CCS, and biomass energy and CCS techniques. However, the
Convention on Climate Change (UNFCCC) is being held at Sharm application cost of these techniques is higher than the first two mitiga
El-Sheikh, Egypt. The COP27 is expected to aid as an annual break for tion techniques, as discussed above. .
the different countries of the world to consult and collaborate in the This comprehensive review highlights the latest carbon capture,
agreements for better action towards climate change. The agenda of storage, and utilization trends. The overview of CO2 in the present
COP27 is to deliberate the risk of "overshooting” the world’s tempera scenario has been discussed, and corresponding advancements in CO2
ture above the pledges and goals of Paris Agreement. Further it is mitigation techniques are deliberated. Further, their merits and limita
anticipated to track and review the national policies of the various tions have been highlighted, taking into view the latest literature, i.e.,
countries if they are heading toward those collective temperature goals. from the last decade. This study also goes ahead to present outlooks in
Carbon capture and sequestration/storage (CCS) is the process of the way of discussing how these existing technologies can be improved
capturing CO2, i.e., produced during industrial processes and power and new technologies that be integrated into CCUS. Among the different
generation, followed by its storage. This is done to avoid its emission CO2 capture and utilization techniques, the DAC and afforestation routes
into the atmosphere. CCS technologies are expected to have substantial have also been highlighted, and the outlook has been conferred at the
potential to relegate CO2 emissions to energy systems [11]. The plants end.
comprising CCS facilities are quite efficient and can capture most of the
CO2 they produce (i.e., around 90%). According to the status report of
the global CCS Institute 2019, around 40 million metric tons of CO2 from
Table 1
different operating plants are currently captured and stored each year.
CO2 mitigation techniques (removal in gigatons and its associated costs on an
To realize the situation and scale of the present technology, it has been annual basis) as per the analysis reported by IPCC [13].
found that in the United States alone, more than 5 billion metric tons of
CO2 mitigation Category Price (Cost (US Capacity
CO2 were emitted in 2018. Whereas, if we consider the global scenario,
technique $/ton of CO2 (GtCO2
around 37.1 billion tons of CO2 was released into the atmosphere in removed) removed/year)
2018, which put us in an alarming situation to capture and utilize the
Afforestation Natural CO2 5–50 0.5–3.6
CO2 from the atmosphere [12]. Currently, around fifty-one hefty CCS utilization sink
exist globally, whereas, in the US alone, there are about ten large Biochar and soil Advanced natural 30–120 2.3–5.3
operational facilities. sequestration CO2 utilization
Adopting the CCS technique at any plant or facility usually involves sink
Augmented Advanced natural 50–200 2–4
three main steps: i.e., capture, transportation, and storage. Several
weathering CO2 utilization
technologies can capture CO2 at the source (i.e., from the supply emit sink
ting CO2). They generally are of 3 types: post-combustion carbon cap DAC with storage Artificial CO2 100–300 0.5–5
ture (i.e., the primary method employed in the existing power plants), storage
CCS Artificial CO2 100–300 0.5–5
precombustion carbon capture (i.e., highly used in industrial processes),
storage
and oxyfuel combustion systems. Biomass energy Advanced natural 100–200 0.5–5
In the post-combustion carbon capture technique, CO2 is removed + CCS CO2 utilization
from the exhaust of a combustion process. The industries still use several sink
2
2. Overview of CO2 in present scenario effective chemical processing of CO2 is fostered by careful design and the
use of catalysts to provide high selectivity and reaction efficiencies [23,
The continuous rise in CO2 emissions has necessitated the develop 24]. The accessibility of the critical point of CO2 facilitates the design of
ment of carbon capture, utilization, and storage (CCUS) technologies to transcritical cycles at relatively mild working conditions. Even though
mitigate the pollution effects of excessive CO2 in the environment [14]. CO2 does not have a monopoly on this property, it is possibly the most
The colossal negative effects of this major greenhouse gas (GHG) cannot abundant material having a critical point very close to standard tem
be overemphasized, as evidenced by the drastic impact already being perature and pressure [25]. It is important to state the solubility of CO2
experienced globally, including global warming, rapid climate changes, in water, a condition in which it attains equilibrium with carbonic acid.
and poor air quality a few. The extreme climatic change is visible in the Being an acid gas, CO2 is readily reduced by bond reception from water
melting of glaciers and polar ice caps, rise in ocean levels, warmer and leading to the formation of carbonic acid. Thus, CO2 can be employed as
drier climates, wildfires, floods, loss of diversity in plant and animal an inexpensive weak acid in some processes requiring pH control.
species, and serious negative impacts on the production of food and Another potent computational tool utilized in carbon capture and stor
supply of drinking water [15]. CO2 is the most important member of the age (CCS) methods is density functional theory (DFT). DFT is used to
GHG family (carbon dioxide (CO2), methane (CH4), nitrous oxide (N2O), examine how CO2 molecules interact with different sorbent materials in
water vapor (H2O), and ozone (O3)) as it has the most enduring effect in the context of CCS, giving important insights into the viability and
the long term with its warming power exceeded by only that of methane effectiveness of carbon capture operations [26,27]. Scientists may
by over 80 times in the first two decades post emission into the atmo design and improve materials for improved CO2 adsorption and storage
sphere (short term) [16]. It is no news that the bulk of CO2 released to by modelling these interactions, which eventually helps to build more
the environment emanates from anthropogenic sources, with the over efficient CCS devices in the battle against climate change.
dependence on fossil fuels being the most significant factor. Current Power generation, natural gas processing, chemical production,
estimates show that CO2 emission must be reduced to a value lower than hydrogen production, ethanol production, fertilizer production, and
5 GtonCO2/year by 2050 if the Paris Agreement of global temperature cement production are the sectors that can be specifically identified if
rise is made less than 2 ◦ C by 2100 is to be achieved [17]. CO2 capture CCUS facilities are divided based on the industry sector’s maximum CO2
technologies aim at isolating CO2 and mitigating further emissions to the capture capacity on a global scale. Other sectors of the industry are
environment. To attain the goal of net negative CO2 emissions, the expanding their applications and fields of use, including but not limited
capture of CO2 must be followed by utilization endeavors to put the to the production of synthetic natural gas, power generation and
captured CO2 to good use, thereby creating economic opportunities from refining, DAC, methanol, waste incineration, the production of iron and
CO2 capture. In direct utilization, CO2 is used as-is without conversion to steel, bioenergy, power generation, and hydrogen. Table 2 details the
other products, unlike indirect utilization, which entails using the comparison of CCUS facilities and their operational state as of late 2021.
captured CO2 as a feedstock to synthesize more economically useful
products. CCUS offers a cost-competitive approach to fill the gap be 3. CO2 capture techniques
tween the continuous increase in energy demand and the campaign
against CO2 emission. The utilization of CO2 from waste streams is faced The different techniques for the capture of CO2 at the source fall into
with the major challenge of capturing cost as opposed to the acquisition one of the three broad technologies of Pre-combustion, post-combus
of CO2 from natural sources [18]. However, several research efforts have tion, and oxyfuel combustion carbon capture [29]. Carbon capture,
been dedicated to making CCUS cost-effective by exploring different utilization, and storage (CCUS) is a group of methods adopted to achieve
technologies to make CO2 a commodity rather than a liability. Carbon the mitigation of CO2 emissions from fossil-fueled power plants. CCUS
capture using IoT is a promising technique. It combines the power of can be integrated into Power Plants (PPs) and Combined Heat and Power
real-time monitoring, data analysis, and automation to enhance the ef Plants (CHPPs) to curtail the CO2 emission in the flue gas [30]. Lower
ficiency of carbon capture processes. By providing insights and control carbon capture efficiency and difficulty coupling to power plants were
over emissions, it contributes to mitigating climate change and reducing major drawbacks associated with First-generation carbon capture tech
greenhouse gas levels in the atmosphere. This technology holds great nology, which led to further research efforts culminating in the devel
potential for achieving sustainability goals and combating environ opment of second second-and third-generation carbon capture
mental challenges [19,20]. Currently, the focus is on capturing CO2 technologies characterized to have improved efficiency and relatively
emitted from power generation plants and other industrial production lower cost [31]. The above-mentioned carbon capture technologies are
plants as the technology to directly capture emissions from the transport under development, with the oxyfuel combustion method being
sector, which is also a heavy contributor to environmental pollution, is considered a promising solution from an energy-efficiency power-
still not practical. generation perspective. Authors have inferred that the energy penalty
To adequately design CO2 capture and utilization processes, it is for the oxy-combustion technology is approximately 4%, in comparison
imperative to have a better understanding of the physical and chemical to 8–12% for post-combustion methods [32]. Each of these three ap
properties of CO2. CO2 is a colorless and odorless gas under ambient proaches has its pros, cons, and scenario for best applicability, as dis
temperature and pressure conditions. Its greenhouse gas potential stems cussed in the ensuing sections. Fig. 1 shows the methods under these
from its ability to absorb infrared light at approximately 15 µm wave three broad CO2 capture technologies.
length; a significant overlap with Earth’s surface radiative emissions
exists at this wavelength. Triple and critical points of CO2 are 3.1. Pre-combustion carbon capture technology
(− 56.35 ◦ C and 5.1 bar) and (31.1 ◦ C and 73.8 bar) respectively. The
triple point refers to the temperature and pressure at which a substance’s This carbon capture technology is largely used in industrial processes
gas, liquid, and solid phases coexist in thermodynamic equilibrium. and involves the extraction of CO2 from fossil fuel or biomass fuel prior
In contrast, the critical point is a term used to describe the temper to combustion processes to generate energy [33]. Generally, this tech
ature and pressure at which a substance’s liquid and vapor phase be nology is adopted in coal, biomass, and natural gas gasification pro
comes identical [21]. Under temperature and pressure conditions above cesses to generate syngas [33]. Syngas, a combination of H2, CO, and a
the critical point, CO2 exists as a supercritical gas. It becomes useful in small amount of CO2, is used as a precursor to synthesize green fuels like
power generation (as a working fluid) and as a solvent in many indus methanol and produce electricity as it is employed in powering a tur
trial processes [22]. CO2 is highly stable chemically, making all re bine. So, this technology extracts CO2 out of the syngas for utilization in
actions involving CO2 to be essentially reductive, and can only proceed other processes before the syngas is subjected to combustion in a tur
when the highly negative enthalpy of CO2 formation is subdued. Hence, bine. To achieve this, the water-gas-shift (WGS) reaction creates extra
3
Table 2
CCUS facilities compared to their operational state in late 2021 [28].
Name of the CCS facilities Country Operation Industry CO2 capture CO2 storage method
date capacity
[Mtpa]
Min Max
Alberta Carbon Trunk Line (ACTL) with North West Redwater Canada 2020 Hydrogen 1.3 1.6 CO2-EOR
Partnership’s Sturgeon Refinery CO2 Stream Production
Alberta Carbon Trunk Line (ACTL) with Nutrien CO2 Stream Canada 2020 Fertilizer 0.2 0.3 CO2-EOR
Production
Gorgon Carbon Dioxide Injection Australia 2019 Natural Gas 3.4 4 Saline formations
Processing
Qatar LNG CCS Qatar 2019 Natural Gas 2.2 2.2 CO2-EOR
Processing
CNPC Jilin Oil Field CO2 EOR China 2018 Natural Gas 0.35 0.6 CO2-EOR
Processing
Illinois Industrial Carbon Capture and Storage United States 2017 Ethanol Production 0.55 1 Saline formations
Abu Dhabi CCS (Phase 1 being Emirates Steel Industries) United Arab 2016 Iron And Steel 0.8 0.8 CO2-EOR
Emirates Production
Quest Carbon Capture And Storage Canada 2015 Hydrogen 1.2 1.2 Saline formations/
Production depleted oil fields
Uthmaniyah CO2-EOR Demonstration Saudi Arabia 2015 Natural Gas 0.8 0.8 CO2-EOR
Processing
Karamay Dunhua Oil Technology CCUS EOR Project China 2015 Methanol 0.1 0.1 CO2-EOR
Production
Boundary Dam 3 Carbon Capture and Storage Facility Canada 2014 Power Generation 0.8 1 CO2-EOR
Coffeyville Gasification Plant United States 2013 Fertiliser 0.9 0.9 CO2-EOR
Production
Air Products Steam Methane Reformer United States 2013 Hydrogen 1 1 CO2-EOR
Production
PCS Nitrogen United States 2013 Fertiliser 0.2 0.3 CO2-EOR
Production
Bonanza BioEnergy CCUS EOR United States 2012 Ethanol Production 0.1 0.1 CO2-EOR
Petrobras Santos Basin Pre-Salt Oil Field CCS Brazil 2011 Natural Gas 4.6 4.6 CO2-EOR
Processing
Century Plant United States 2010 Natural Gas 5 5 CO2-EOR
Processing
Arkalon CO2 Compression Facility United States 2009 Ethanol Production 0.23 0.29 CO2-EOR
Snøhvit CO2 Storage Norway 2008 Natural Gas 0.7 0.7 Saline formations
Processing
Sinopec Zhongyuan Carbon Capture Utilization and Storage China 2006 Chemical 0.12 0.12 CO2-EOR
Production
Core Energy CO2-EOR United States 2003 Natural Gas 0.35 0.35 CO2-EOR
Processing
Great Plains Synfuels and Weyburn-Midale Plant United States 2000 Synthetic Natural 1 3 CO2-EOR
Gas
Sleipner CO2 Storage Norway 1996 Natural Gas 1 1 Saline formations
Processing
MOL Szank field CO2 EOR Hungary 1992 Natural Gas 0.059 0.157 CO2-EOR
Processing
H2 and converts the CO in the syngas to extra CO2. The carbon-capturing steam generator (HRSG). A good part of the residual chemical energy in
process is made effective by the increasing density of CO2 after the WGS the coal-fired syngas is changed to H2. The CO2 is removed before
reaction [34] (Fig. 2) illustrates this procedure. combustion, and the gas turbines are then supplied with hydrogen-rich
Contrary to what is obtainable in post-combustion CCUS, pre- syngas for combustion. This promotes the effective separation of the CO2
combustion carbon capture technology can be used at high pressures stream from the syngas. Otherwise, the CO will get burnt by the gas
without combustion pollutants like NOx and SOx. Integrated Gasification turbine, thus necessitating a post-combustion system to eliminate it
Combined Cycle (IGCC) is the most established power cycle that can put [37]. Generally, the water-gas shift process is performed before or after
pre-combustion capture technologies to efficient use. Among the tech the Advanced Gas-cooled Reactor (AGR), and the process in these two
nologies adapting a pre-combustion capture scheme, physical absorp locations are termed sour-shift and sweet-shift, respectively. For sour
tion, membrane capture, and pressure-swing adsorption processes are shift, COS hydrolysis takes place simultaneously with the WGS reaction
the most suited [35]. In an IGCC plant not equipped with a CO2 capture in the same reactor, and the process of carbon capture occurs alongside
system, the produced syngas is stripped of impurities by passage through H2S removal [38]. This is not the case in sweet shift, as carbon capture
a gas clean-up facility before being sent to gas turbines. In plants takes place afterward. The sour-shift process is the favored process as it
equipped with a pre-combustion capture system, CO is converted to CO2 is comparatively cheaper due to the fact that the shift and capture stages
and H2 via the water-gas shift reaction shown in Eq. 1. [36]. can be fully integrated into the existing clean-up system infrastructure.
Also, its ability to achieve the shifting process utilizing water vapor in
CO + H2 O ↔ H2 + CO2 (1)
the syngas further makes it attractive as this means a lower requirement
The shift results from the injection of water vapor (H2O) into the for water injection. However, with regard to complexity and ease of
syngas in the shift reactor, where the catalyzed water-gas shift reaction installation, the sweet shift is better and is best adopted in dry-fed
takes place. Most often, the energy released from this exothermic pro gasifiers [39]. Considering the fact that the sweet-shift reaction takes
cess is recovered by partially heating the steam from the heat recovery place post the low-temperature AGR process, there is no need to cool the
4
Fig. 2. Process diagram carbon capture and compression for an IGCC power plant [40].
syngas afterward as done in the sour-shift process. The implication is Purisol process, which uses N-methyl-2-pyrrolidone solvent (iii) Rectisol
that the syngas can be fed directly to the gas turbine with little tem process, which makes use of cold methanol as a solvent, and (iv) Mor
perature adjustment. physorb process, a comparative process which uses N-Formylmorpho
On the other hand, the performance of the sour shift before the AGR line and other morpholine derivatives. During the absorption stage, CO2
process allows for the simultaneous occurrence of the AGR and carbon is captured by these solvents from the shifted syngas and released during
capture processes with the use of the same solvent post the shifting regeneration by pressure reduction [19]. These solvent-based CO2 cap
process. Sulfur contamination of the stream of captured CO2 is a high ture processes have the advantage of low energy requirements. A major
possibility during this concurring process. Hence, if little or no sulfur is challenge associated with solvent-based CO2 capture is the need for
required in the downstream use of the captured CO2, the sweet-shift syngas cooling prior to CO2 capture and gas reheating before combus
method is the best choice [38]. tion, thereby reducing the plant’s thermal efficiency and increasing
Typical pre-combustion capture processes adopted for the separation operation costs [41]. Recently, research efforts have been directed to
of CO2 from pressurized syngas streams include (i) the Selexol process, wards solving this problem, with the aim being to synthesize solvents
which uses a mixture of dimethyl ethers of polyethylene glycol, (ii) the tolerant to high temperatures use and high-pressure regeneration to
Fig. 3. Process flow chart for the Selexol process [44].
5
lower the energy required for CO2 compression. Aside from the use of stage of the absorber, methanol comes in contact with the feed gas and is
physical solvents, pre-combustion capture based on the utilization of stripped in two stages of flashing through pressure reduction. The re
solid sorbents or membranes has also been studied extensively in recent generated solvent contains a small amount of CO2 but is essentially free
times. These can be operated at relatively much higher temperatures, of sulfur compounds. The acid gas exiting the first stage solvent regen
thereby avoiding the need to cool and reheat the syngas [42]. erator is appropriate for a Claus process (a process used for the treatment
of gas streams containing high (above 5%) H2S concentrations. The
3.1.1. Selexol process design of the second stage is such that the removal of CO2 and sulfur
This physical acid gas removal process employs a solvent mixture of compounds is achieved. The solvent exiting the bottom of the second
dimethyl ether and propylene glycol to selectively capture CO2 and H2S stage is deeply stripped in a steam-heated regenerator and is sent after
from syngas. This process occurs in two stages, with H2S removal first, cooling and refrigeration to the top of the absorption column [46]. This
followed by CO2 removal. Fig. 3 illustrates the overall procedure in this entire process is described in Fig. 4.
process. Here, the high-pressure syngas enters the H2S absorber at 40 ◦ C,
with almost 20% of the total solvent in this absorber coming from the 3.1.4. Morphysorb process
recirculation line connected to the CO2 absorber [43]. The major func This process typically uses N-Formylmorpholine and other morpho
tion of the H2S concentrator is to accumulate H2S from the H2S absorber line derivatives to achieve the bulk removal of CO2 and H2S from natural
after the latter is heated to 100 ◦ C. The injection of N2 into the gas and other gas streams in industries. The first commercial application
concentrator leads to the separation of CO2 absorbed in the solvent and of this process was in DEGT Gas Transmission Plant, Canada, and the
subsequent flow back of H2S into the H2S absorber. The H2S in reserve is plant has a CO2 and H2S removal capacity of 50 MMscfd. The plant
sent to the concentrator and removed from there. Syngas containing CO2 generates 1050 long tons/day of Sulphur element at a recovery rate of
travels to the CO2 absorber and produces clean syngas [44]. 99%. In this process, the gas containing CO2 and H2S is absorbed in two
absorbers. In the first and second Recycle Flash Drums, the Morphysorb
3.1.2. Purisol process solvent is consecutively flashed, after which the flash gas is compressed
N-Methyl-2-Pyrrolidone is the solvent used in IGCC power genera and recycled to absorber feed to avert methane gas loss. In the third and
tion plants for the high-pressure separation of CO2 and carbonyl sulfide fourth Recycle Flash Drums, the acid gas to be compressed and liquefied
impurities from syngas. Initially, some H2S and CO2 are removed from to the downhole is generated. Finally, the Morphysorb solution flows
the H2S absorber by injecting raw gas. The solvents are adjusted to low back to the absorbers [47].
pressure and then passed through the absorber (selectively absorbs H2S)
before being recycled to the main syngas stream. CO2 and H2S are
separated by reboiling stripping operation. The hot flash gas, purified 3.2. Post-combustion carbon capture technology
and recycled, is sent to an O2-blown Claus unit where tail gas containing
H2, CO, H2O, CO2, untreated H2S, and SO2 is generated before being sent This is the primary technology used in existing power plants and is
to a hydrogenation column where the remaining sulfur compounds are useful for CO2 separation from exhaust gases generated by the com
converted to H2S. Finally, the tail gas is cooled to remove H2O and the bustion of fossil fuels. The capture unit is positioned after the purifica
remaining CO2 [45]. tion systems, such as denitrogenation, desulphurization, and dedusting
installations [48]. Fig. 5. shows the schematic of a power plant with
3.1.3. Rectisol process post-combustion CO2 capture.
This is the most widely adopted physical solvent gas-treating method A major barrier to using methods under this technology is the low
for acid gas removal at low temperatures with an organic solvent. driving force for CO2, which stems from the fact that the partial pressure
Methanol is conventionally used as the solvent for the bulk removal of of CO2 in the flue gas is low (flue gas is under atmospheric pressure and
CO2, and nearly all the removal of H2S, carbonyl sulfide, inorganic and CO2 concentration is within 13–15) [50]. Carbon capturing methods
organic impurities occur in the absorber’s bottom section. In the first under this technology includes (a) Absorption solvent-based methods,
(b) Adsorption–physical separation, (c) Membrane separation, (d)
Fig. 4. The Rectisol process [45].
6
Fig. 5. Schematic of a power plant with post-combustion CO2 capture [49].
Chemical looping combustion (CLC) and calcium looping process (CLP), adsorption (TSA), and pressure-temperature swing adsorption (PTSA).
and (e) Cryogenic methods.
3.2.3. Membrane separation
3.2.1. Absorption solvent-based methods The membrane separation process, which typically uses a flat sheet,
Chemical absorption is the most adopted method for CO2 capture. It spiral wound, or hollow fiber module, has been depicted in Fig. 6. Here,
relies on the reaction between CO2 and a chemical solvent like alka flue gas is initially cooled to the operating temperature of the membrane
nolamines (monoethanolamine (MEA), diethanolamine (DEA)) or in an absorber before being transported to the membrane.
methyl diethanolamine (MDEA) in aqueous solution. In the first stage of Two types of membrane capture technology exist: gas separation
this two-stage method, the solvent contacts the flue gas in the absorber membranes and gas absorption membranes. In the former, CO2-con
to capture CO2, after which the rich-loading solution is stripped to taining gas is introduced to the high-pressure side of the membrane, and
regenerate CO2 at high temperatures. The solution devoid of CO2 (lean the CO2 is recovered at the low-pressure side. A solid microporous
loading) is recycled back to the absorber, and the pure CO2 stream from membrane is employed for the gas absorption membrane type to enable
the desorber is compressed prior to storage and utilization. The gas flow and absorption in the gas absorption system. A high CO2
conventionally used 30% MEA and MDEA solutions achieve excellent removal rate is attained on the grounds of foaming, flooding, chan
process efficiency and high purity of CO2 [51]. This method is charac neling, and entrainment minimization [55].
terized to be energy intensive owing to a large amount of heat needed to
be supplied to the desorber. 3.2.4. Chemical looping combustion (CLC) and calcium looping process
(CLP)
3.2.2. Adsorption–physical separation Chemical looping technology adopts two reactors, an air reactor and
Adsorption uses a solid surface to remove CO2 from a mixture. a fuel reactor. These reactors usually circulate fluidized beds that are
Physical separation depends on adsorption, cryogenic separation, and integrated for carrier transport. In the air reactor, an oxygen carrier
absorption methods. It can be of physical nature (Van der Waals forces (typically a metal particle like Mn, Fe, and Cu) is oxidized using oxygen
for CO2 adhesion—physisorption) or chemical (covalent bonding be from the air. This process leads to the formation of metal oxides which
tween compounds—chemisorption). Physical adsorption utilizes porous are sent to the second reactor for further reaction with fuels leading to
materials (such as activated carbon, metallic oxides, alumina, or zeolites the reduction of the metal oxides, energy generation, and production of
to capture CO2 [52]. Activated carbons which offer the advantages of flue gas stream of CO2 and H2O. Pure CO2 is then achieved by conden
high surface area and tunable pore structure, contain amorphous carbon sation [56].
and are usually not expensive. However, the weak binding energy with The calcium looping process is a type of chemical looping based on
CO2 necessitates the design of the material to be highly microporous if the reversible carbonation reaction between CO2 and CaO in a carbo
it’s going to be useful as a carbon capture material. Zeolites (crystalline nator (first reactor) followed by transportation of the formed CaCO3 to a
aluminosilicates) possess good adsorption properties for CO2 capture, calciner (second reactor), where pure CO2 stream (>95%) is obtained
but their hydrophilic nature (presence of water) weakens these prop via a reversible reaction. The calcination heat is generated by the
erties by reducing the degree of interactions between coupled com combustion of fuel in atmospheric oxygen. The reactors (circulating
pounds [53]. The use of metal-organic frameworks (MOFs) is a relatively fluidized bed (CFB)) are coupled to transport solids with the gaseous and
new approach and involves the use of metal ions or ion clusters linked by solid mass streams separated in cyclones. Advantages associated with
organic ligands and bridges (creating strong coordination bonds). MOFs calcium looping technology include the use of cheap sorbent and partial
have been characterized to be of simple design, high porosity, and pore desulphurization of flue gas. Also, the process makes use of fluidized
properties that can be easily tailored to the need [54]. Silica which is beds, and this mature elevated-temperature technology can produce
non-carbonaceous is another common adsorption material and is known power [57].
to possess adequate pore size, large surface area, and good thermal
stability. Adsorption methods traditionally used are pressure swing 3.2.5. Cryogenic method
adsorption (PSA), vacuum swing adsorption (VSA), temperature swing Cryogenic CO2 capture is used in post-combustion carbon capture
7
Fig. 6. Scheme of the post-combustion CO2 capture method using a membrane separation process [55].
technology as well as in oxyfuel combustion technology to separate CO2 capture technology, the possibility of incorporation into existing tech
from flue gas. This method adopts liquefied natural gas (LNG) to supply nologies, and reduced mass flow rate of exhaust gases (75% less
cold energy to capture CO2. This method, which involves unit processes compared to combustion in the air). The cons include high material
of compression, expansion, separation, and cooling, promotes the re requirements due to the high temperatures, a decrease in efficiency
covery of highly pure CO2 (99.17%). The use of the cryogenic method in (energy-consuming nature of the oxygen production process), and a high
carbon capture is, however, still very limited due to its high operational capital cost [60].
cost [58]. Some of the distinct characteristics of the pre, post, and oxyfuel
combustion capture technologies as regards their suitability for process
application are highlighted in Table 3 below.
3.3. Oxyfuel combustion carbon capture technology
The exhaust gas from combustion in an oxygen-enriched atmosphere 3.4. Direct air capture (DAC) technique
(oxy-combustion) consists majorly of CO2 and H2O (N2 content is
minimized). The separation of CO2 from H2O is made possible by The novel advancements in CO2 mitigation techniques include the
condensation at a temperature higher than ambient conditions (with the removal of CO2 by direct air capture (DAC) technology proposed by US
exception of very low partial pressure processes) [59]. Highly pure ox research in 2021 [61]. Geological sequestration must be the primary
ygen (about 95%) produced from the air separation process is used for preference for the CO2 mitigation stratagems since the stable time scale
combustion. The general scheme for processes adopting the for geological sequestration is for thousands of years. However, the CO2
oxy-combustion method is shown in Fig. 7. This technology mainly captured from the atmosphere can be utilized directly as a raw material
concerns solid fuel-fired boilers such as CFBs and pulverized coal boilers to produce valuable goods, i.e., fuels and chemicals [62]. The net costs
(PCs). Still, increasing consideration is being given to the possibility of of the DAC techniques can be reduced by the usage and recycling of CO2,
applying oxy-combustion in energy systems with gas turbines. In i.e., via the wealth from the waste concept.
oxy-combustion technologies, low and high-temperature boilers can be The DAC system typically represents a mechanical system that en
distinguished. The process of combustion in low-temperature boilers traps CO2 from the air. A liquid solvent is mostly employed in the system
involves a mixture of oxygen with recirculated exhaust gases, and the to scrub away CO2 from the mixture of gases. The DAC process sche
flame temperatures are identical to those of air-powered units. For matic is represented in Fig. 8. The Swiss firm named Climeworks
high-temperature boilers, the temperature can rise above 2400 ◦ C [59]. installed about 15 commercial-scale plants in Europe that are currently
The pros of oxy-combustion technology are NOx reduction, reduced cost in operation [63].
due to boiler dimension reductions, a relatively simplified carbon The DAC plants can be operated via power produced from energy
Fig. 7. Block diagram of oxyfuel combustion capture system [60].
8
Table 3 Table 3 (continued )

Distinct characteristics of the pre, post, and oxyfuel combustion capture S. Characteristics Pre- Post- Oxy-Combustion
technologies. No. Combustion Combustion Carbon Capture
S. Characteristics Pre- Post- Oxy-Combustion Carbon Carbon
No. Combustion Combustion Carbon Capture Capture Capture
Carbon Carbon existing it does not obtain high-purity
Capture Capture industrial involve re- oxygen; also
1 Method of Production of Capture of Reaction of high systems and designing the entails re-
carbon capture syngas (CO CO2 from the carbon content fuel installation of pristine modification of the
and H2), flue gas stream with oxygen of a fuel industrial pristine industrial
conversion to after high purity of conversion for system; hence, system.
CO2 and H2 combustion of ≥ 95% so as to the production it is less costly
through WGS carbon- produce in the of syngas and than other
reaction, and intensive fuels combustion its conversion options of CCS
the capture of with high chamber for to CO2 and H2 technology.
CO2 from carbon complete
mixture before element. combustion; flue
combustion of CO2 gas contains low sources obtained from renewable, geothermal, and burning waste ma
the fuel. concentration CO2 content. terials. In the DAC operation framework, a fan is typically employed to
is 10 – 15% Concentration of pull the air into a collection unit, where the selective filter retains CO2
and separation CO2 is as high as
potential is ~95%.
capture. The CO2 is subsequently sent underground, chemically bonded
low. with KOH via treating it from the solution, resulting in its separation
2 Conditions of High pressure Low pressure Low pressure from air. Finally, the collected CO2 from the solvent stripping is purified
operation of (20–30 bar) (0.15 – 1 bar) (~1 bar) and high and compressed before being used in different industrial applications.
carbon capture and low/high and low/high temperatures as
However, for the commercialization of DAC globally, an enormous
chamber temperature temperature. carbon removal
depending on process occurs in amount of capital investment is entailed. The investment for DAC may
the industrial the combustion transcend around US$ 100bn by 2030 on a worldwide scale [63] [64].
systems. chamber.
3 Concentration ~ 30% CO2 ~15% CO2 - 4. CO2 utilization techniques
of CO2 in flue concentration concentration
gas stream
4 Compatibility Usage involves Ease of Entails re- To put the captured CO2 stream to good use, several techniques have
with industrial re-designing of retrofitting to designing of been adopted over the years to convert CO2 to green fuels and high-value
systems industrial existing industrial systems chemicals. The term green in this context indicates that the use of such
systems to systems for incorporation
fuels and high-value products does not contribute to the emission of CO2
accommodate without of air separation
fuel modification. system; are less back to the environment. If they do, the amount is usually far negligible
conversion compatible. in comparison to conventional fossil fuels. In broad terms, CO2 utiliza
processes; less tion can be classified into direct utilization and indirect utilization [65].
compatible.
5 Maintenance Complex Maintenance The maintenance
maintenance of CCS is less procedure is
4.1. Direct Utilization of CO2
procedure as complicated as complicated the air
maintenance an industrial separation, Several direct utilization techniques of CO2 are still in existence,
procedure system to combustion including fire extinguishers, soft drinks, foaming agents, and propellants
involves a which it is chamber, and the
[66]. Some direct utilization methods, such as mineral carbonation and
total shutdown attached need entire industrial
of the not be shut system need to be CO2-enhanced oil recovery, inherently offer CO2 storage hence
industrial down during shut down. contributing significantly to the mission of net negative emissions.
system. maintenance Direct CO2 utilization entails the use of CO2 in its raw form in industrial
operations. processes without conversion to other products. Here, CO2 is a direct
6 Potential for Production of Strong Process high-purity
global carbon carbon-free potential for CO2 stream for
raw material in a process rather than a precursor to an intermediate
reduction fuel for global carbon improved CO2 product which is finally utilized. The direct use of CO2 is discussed
combustion footprint separation from below.
shows its reduction due flue gas; however,
capacity to to its ease of the need to modify
4.1.1. Utilization of CO2 in Iron and steel making
reduce CO2 retrofitting to existing industrial
emission from existing to accommodate The production of steel starts with the mining of iron ore, after which
the utilization commercial this CCS option the ore is upgraded by magnetic separation or floatation, pelletized for
of fossil fuel; and industrial reduces its ease of feeding into the blast furnace, converted to pig iron via reduc
nonetheless, systems. versatility of tion, and then processed into steel with the use of an electric arc furnace
modification operationalization.
of existing
or a basic oxygen furnace. The presence and behavior of CO2 play an
industrial important role in each of these processes. The emitted CO2 from iron ore
systems to reduction and the combustion of substances like coke together with CO2
accommodate introduced from storage plays a crucial role by regulating the molten
this
steel’s temperature and preventing excess oxidation, thereby controlling
technology
limits its the production of dust from the basic oxygen furnace [67]. Recirculated
applicability. CO2 in the blast furnace controls the tuyere’s region temperature,
7 Cost of Expensive Investment Capital investment generating a stirring effect and increasing the CO ratio by coke oxida
investment technology entails the cost due to the high cost tion. Also, CO2 is utilized in the carbonation of steel slag, and the
due to the re- of installing of installation and
resulting carbonated steel slag is a relevant construction material [68].
design of the CCS plant; air separation to
9
Fig. 8. Process schematics of the DAC process.

Adapted from Jeong-Potter and Farrauto [64].
4.1.2. Utilization of CO2 in the alumina industry 4.1.5. CO2 utilization in concrete building materials
The commercial process for the production of alumina is the Bayer Carbonation curing of concrete (a mixture of cement, water, and
process which involves the conversion of bauxite (an ore) to aluminum aggregates) is a developing curing approach relative to conventionally
with alumina as an intermediate product. In this process, bauxite is used water curing. Unlike in water curing, where calcium silicate hy
digested in a concentrated NaOH solution, after which soluble drates are formed, carbonation curing forms carbonate materials (typi
aluminum oxides are separated. The residual solid waste after this cally CaCO3 or MgCO3). Carbonation yields both positive and negative
digestion is termed red mud, characterized to be highly caustic (pH 13 or effects on the strength and durability of concrete-based materials. A
higher), difficult to dispose of, and very toxic, thus creating an envi good example is carbonation’s tendency to increase the corrosion rate in
ronmental issue. The toxicity of red mud is attributed to its caustic na reinforced steel but can also ameliorate compressive and splitting
ture, and CO2 is an effective neutralization agent. Relative to other acids strength for curing durations exceeding 28 days [75]. Carbonation
that can play this neutralization role, CO2 has the major advantage of curing has also been observed to facilitate pore volume reduction within
low cost and high availability [69]. The neutralization product is mostly concrete-based materials as evidenced by SEM characterizations which
still alkaline in nature (very mild) because of deeply rooted alkali spe revealed the occupation of pore spaces by calcite (CaCO3), leading to a
cies, but the bulk of the caustic species is easily converted to carbonates. dense structure with better compressive strength [76].
The formation of carbonates, therefore, provides a permanent capture of
CO2 if left undisturbed. The neutralization also adds utility to red mud 4.2. Indirect utilization of CO2
itself, with a good example being the extraction of rare earth materials
that typically constitute red mud waste [70]. This alternative converts CO2 into something that is more beneficial
overall. The goal here is to create an anthropogenic carbon cycle,
4.1.3. Utilization of CO2 rare earths recovery from acid mine drainage wherein CO2 is transformed into more useful fuels and chemicals, which
Oxygen-mediated weathering of sulfide minerals generates acid in due course tend to become CO2 again in a significantly less concen
mine drainage (AMD), which contains highly useful rare earth elements trated amount (making the fuels and chemicals green in nature). Capture
in addition to leached metals [71]. The recovery of these rare earth el and transformation of this CO2 can be done once more, thereby avoiding
ements poses a challenge, with the current procedure of neutralization the need to introduce new CO2 into the environment. This trans
with NaOH being limited. The addition of CO2 as a carbonate source formation of CO2 to fuels and high-value chemicals sort of stores the
could make this procedure more effective since the more negative Gibbs energy and potential of CO2 until when needed. The thermochemical,
free energy of carbonates relative to oxides and hydroxides will provide electrochemical, photocatalytic, or biological approach can be adopted
the stronger equilibrium reaction equilibrium necessary for the separa to achieve CO2 conversion to green fuels and useful chemicals.
tion of the rare earth [72].
4.2.1. Thermochemical conversion of CO2
4.1.4. CO2 enhanced oil recovery Here, sufficient energy is supplied in the presence of a reducing agent
Enhanced oil recovery applies to methods used for the extraction of to convert CO2 to fuels and chemicals [77]. The thermochemical means
additional oil post primary and secondary recovery stages. More than is associated with the major disadvantage of high temperature and
30% of a reservoir’s total oil recovery is attributed to enhanced oil re pressure requirements in addition to the difficulty of achieving effi
covery, which is typically achieved via three techniques viz: thermal, ciency in catalyst use since the catalyst used needs to be stable under the
chemical and gas injection. The injection of CO2 at high pressure is an conditions involved [78]. Methane reforming processes involving the
example of the gas injection technique. High pressure and injection in a use of CO2 are major CO2 thermochemical conversion processes. These
supercritical state increase the CO2-oil mutual solubility. This CO2 in include dry reforming of methane (DRM), bi-reforming of methane
jection reduces the interfacial tension and viscosity of the oil in addition (BRM), and oxy-CO2 reforming of methane (ORM).
to promoting a volumetric swelling of the oil with all these facilitating
higher oil recovery [73]. CO2-enhanced oil recovery is the most adopted 4.2.1.1. Dry reforming of methane. DRM uses CO2, which is the most
gas injection technique and accounts for over 50% of the use of this copious global greenhouse gas (GHG), to decompose methane and
technique in enhanced oil recovery projects [74]. produce syngas. Hence, the process is also called CO2 reforming of
10
methane (CRM). This process route receives a great deal of attention Numerous research efforts have been geared towards solving the
owing to the fact that it not only produces syngas but also puts to good challenges associated with DRM majorly by investigating various cata
use the two most important greenhouse gases, thereby contributing to lyst combinations. Several catalysts have been studied in the bid to
the continuous quest to mitigate global warming and environmental attain desirable activity, stability, and selectivity. Transition metals
degradation [79]. In this highly endothermic process, syngas is pro have been known for their good catalytic ability due to their partially
duced with a relatively low H2/CO ratio of 1, which is more suitable for empty d-orbital which offers a high surface area for molecules to react,
hydrocarbons synthesis via the Fischer-Tropsch process than the their ability to reduce the activation energy of reactants by forming
hydrogen-rich gas obtained from steam reforming of methane [80]. transition states with the reactants and finally their ability to exhibit
Typically, the DRM process is performed in the temperature range of multiple oxidation states [83]. Noble metals refer to a family of transi
600–1000 ◦ C and at low pressure [81]. The DRM reaction is: tion metals with the best resistance to chemical attacks and oxidation
and include ruthenium (Ru), rhodium (Rh), palladium (Pd), osmium
CH4 + CO2 →2CO + 2H2 ΔH298 = 247KJ/mol (2)
(Os), iridium (Ir), platinum (Pt), gold (Au) and silver (Ag). From liter
The dry reforming process route has the major drawback of high ature, Ru, Rh and Pt noble metals have the best activity and selectivity in
energy requirement as it is a highly endothermic process. This increases reforming reactions under the same temperature, pressure, particle size
the cost of operating the reactor. The high temperature needed for the and dispersion conditions [84]. However, the use of noble metals is not
process feasibility also leads to the sintering of the metal catalyst, which attractive from a commercial perspective due to very high cost and
also contributes to cost by necessitating the need for catalyst regenera limited availability. Relative to the other non-noble metals constituting
tion. Catalyst deactivation caused by carbon deposition is another the transition metal family, Ni exhibits the highest activity and yet a
setback to this process and in the long run not only calls for catalyst low-cost option [85]. Thus, methane reforming with Ni-based catalysts
regeneration but can also lead to reactor clogging. The carbon deposi has been extensively studied and is still being studied considering the
tion leading to catalyst deactivation and reactor clogging is attributed to myriad of experimental conditions yet to be investigated in the ongoing
undesired reactions of methane decomposition and CO disproportion search for greater catalyst activity, stability, and selectivity. In the quest
ation (Boudouard reaction), as shown in Eqs. (3) and (5) respectively. In to make Ni catalysed DRM a commercial process, researchers have
addition to methane decomposition and Boudouard reactions, other side adopted different approaches including the use of catalyst supports that
reactions associated with DRM include hydrogenation of CO2, hydro improve stability and activity, a combination of Ni and other metals with
genation of CO and reverse water-gas-shift reactions as shown in Eqs. promotional effect in bi-metallic and tri-metallic formulations, use of
(5)–(7) respectively. Eqs. (5) and (6) further contribute to the formation different preparation techniques (synthesis routes) and catalyst
of carbon. Due to these side reactions, DRM is still being scrutinized with pre-treatment methods. Table 4 shows the research outcomes.
its implementation at a commercial scale [82].
4.2.1.2. Bi-reforming of methane. BRM is a propitious process for syngas
CH4→ Cs + 2 H2 ΔH298=74⋅9KJ/mol (3)
production, with a hydrogen-to-carbon monoxide ratio of two in the
2CO → Cs + CO2 ΔH298= − 172⋅4KJ/mol (4) reaction products, relevant, for example, when the purpose is methanol
synthesis [91]. This process, although highly endothermic (hence high
CO2 + 2 H2 ↔ Cs + 2 H2O ΔH298=− 90 KJ/mol (5) energy requirement), combines the SRM and DRM processes, with the
stoichiometric H2/CO ratio of 2 being its major advantage over DRM and
CO + H2 ↔ Cs + H2O ΔH298=− 131⋅3KJ/mol (6)
SRM owing to the fact that this is a more favorable syngas composition
CO2 + H2 ↔ CO + H2O ΔH298=41KJ/mol (7) for most downstream operations such as conversion to liquid via
Fischer-Tropsch synthesis [92]. The reaction is:
Table 4
Performance of Ni-based catalysts in DRM.
Catalyst Preparation T TOS CH4 CO2 H2/ Major finding/Conclusions Ref.
method (oC) (h) Conv. Conv. CO
(%) (%)
5%Ni/SBA-15 WI 700 50 71 85 1.0 Catalyst synthesized via β-CMI has smaller Ni particle size with increased [86]
β-CMI 700 50 82.7 95 0.9 dispersion and offered higher resistance to deactivation by coke deposition
relative to the catalyst synthesized by WI.
5%Ni/SBA- TSI 650 30 75 87 1.0 In comparison to the catalysts of lower SBA-15 pore size, the 7 nm SBA-15 [87]
15(pore size = pore size catalyst gave the smallest size of Ni particle. This was attributed to
7 nm) the larger pores being more accessible during the Ni impregnation step. This
Other SBA-15 led to better activity and stability.
pore sizes:
4 and 5 nm
5%Ni-Ce/SBA- WI 973 100 72 77 1.23 Ceria addition facilitated the emergence of Ni particles of consistent size (av. [88]
16 5.7 nm) in the mesopores of the SBA-16. This can be attributed to the
confinement effect of SBA-16 framework and strong Ni-SBA-16 interaction.
On the other hand, Ni-Ce/SBA-16 exhibited higher reducibility, with the
dominant specie being Ce3+ in both fresh and spent catalysts. Ni-Ce/SBA-16
was observed to perform better.
5%Ni-0.5%Sc/ CI 800 7 85 90 0.95 The conversion of reactants and yield of H2 was increased by Low Sc loading. [89]
MCM-41 The Sc promoter facilitated Ni-MCM-41 interaction and increased basicity
leading to higher surface CO2 adsorption and suppression of carbon
formation.
5%Ni-3%Ce/ SD 750 20 93.8 96 1.0 Ce-modified catalyst produced via a sublimation deposition technique [90]
mSiO2 WI 88 94.7 0.96 showed better stability with lower coke deposition. The ameliorated
resistance of this catalyst to sintering and coking was explained to be due to
a stronger confinement effect originating from its relatively superior
mesoporous channel, relatively higher reducibility, and higher dispersion of
Ni nanoparticles (due to the stronger Ni-SiO2 interaction).
11
3CH4+CO2 + 2 H2O ⇋ 4CO +8H2 ΔH298 K = +220 kJ/mol (8) 4.2.3. Photocatalytic reduction of CO2
The conversion of CO2 into fuels using photocatalysis stands out
among the variety of strategies available because it successfully trans
forms CO2 into usable fuels. Light absorption, charge separation, and the
4.2.1.3. Oxy-CO2 reforming of methane. ORM reforming has the appeal activation of CO2 on the photocatalyst surface are crucial components in
of auto-thermal operation, but safety concerns associated with the this process. The latter, the adsorption/activation of CO2, is a very
presence of oxygen have limited its use [93]. It involves reforming complex stage in this procedure, and more research is still needed to
methane with carbon dioxide and oxygen to yield syngas. completely comprehend it. Understanding the underlying mechanism is
difficult since the creation of both products and intermediates is highly
3CH4+CO2 +O2 ⇋ 4CO +6 H2 ΔH298 K = +58 kJ/mol (9) dependent on a variety of variables, and the study circumstances are not
constant. In this technique, photons of equal or greater energy compared
Compared to DRM, ORM is less endothermic and hence saves energy
to the semiconductor’s band gap (Eg) stimulate electrons (e-) and holes
better. However, high-temperature differences within the catalyst bed
(h+) in the semiconductor material, causing them to move to the con
can deactivate the catalyst, especially for the bolstered systems [94].
duction and valence bands, which are initially unoccupied. Distinct
The syngas produced in oxy-reforming also falls short of the desired
redox reactions are initiated by these energetic carriers to generate final
2:1 H2/CO ratio.
products [101]. While the CO2 is adsorbed on a photocatalyst in an SC,
as shown in Fig. 9, its linear structure is transformed to a bent form with
4.2.2. Electrochemical reduction of CO2
lowered activation energy to facilitate further reactivity. The final
The CO2 utilization approach leads to the yield of several products
product’s selectivity and ease of formation can be tuned by altering
aside from CO, including methanol, ethanol, formic acid, oxalic acid,
factors similar to that of electrochemical reduction [102]. For aqueous
formaldehyde, and a few others, depending on the specific pathway
phase photocatalysis with H2O and CO2, the expectation is that meth
promoted by the catalyst and solvent used [95]. The faradaic efficiency
anol (CH3OH) will be formed at a higher rate relative to methane (CH4).
and selectivity of the reaction are dependent on parameters such as
This is a result of the formation of carbonate, bicarbonate, and carbonic
catalyst, pH, electrode potential, electrolyte species, etc. The electro
acid species, leading to the emergence of methanoic acid (HCOOH),
chemical process’s lower temperature and pressure requirement makes
which is subsequently reduced to CH3OH [103].
it attractive, especially when the aim is to selectively form more complex
In a recent study Vu et al. [104] concluded that a feasible method for
chemicals [96]. A major challenge associated with the conversion of CO2
developing photocatalytic systems with customizable light absorption
to valuable chemicals in aqueous electrolytes is the cathode’s reaction
properties, effective separation of electron-hole pairs, lengthened life
with water, which tends to generate hydrogen gas at the expense of a
time of charge carriers, and increased resistance to photocorrosion in
significant amount of energy. To control this, cathodes with minimal
volves using semiconductors within a heterostructure. The Z-scheme
potential for H2 can be chosen, or non-aqueous solvents can be used
configuration among these heterostructures appears to be a more effi
[97]. Also, careful design of the catalyst can help by promoting yields at
cient system since it permits prolonged electron lifetimes and counter
lower low voltages required to avert the formation of hydrogen. The
acts electron energy deficiencies. However, with little variation between
activity of the electrocatalyst is majorly at the surface of the electrode.
these structures, the improvement in photocatalytic efficiency in het
As the CO2 molecules undergo reduction to the active anion radical
erostructures is mostly perceptible in contrast to individual semi
form, they adsorb to the cathode. Chandrasekaran and Bockris [97]
conductors. This could be explained by the difficulties in controlling the
showed this using polarization modulation Fourier transform infrared
interfacial connection between semiconductors because of their unique
spectroscopy. In a recent study, Xie et al. [98] found that for now,
characteristics and integrated semiconductor structures. Also, in the
maintaining the structure of Cu-based nanocatalysts and achieving the
current scenario most of the research on CO2 photoconversion has been
desired cooperative effects between the catalyst and support, ultimately
on the reduction half-reaction, with the oxidation half-reaction, such as
improving catalytic selectivity, can still be accomplished by securely
H2O oxidation, receiving less attention. To speed up this oxidation
attaching the catalysts to designated substrates. To be useful in elec
half-reaction and enhance the photocatalytic reduction of CO2, it is
trochemically decreasing CO2, these Cu-catalysts must be stabilized
imperative to develop new and effective techniques. It is also crucial to
using brand-new methods, which must be developed. In another recent
learn more about photocatalytic CO2 reduction’s reverse processes
study, Jiang et al. [99] investigated the effect of surface roughness on
[105]. For metal-free materials to have a wide range of practical ap
the Cu-based CO2 reduction process. They contrasted the efficiency and
plications, photoactivation recycling is a critical capability. However,
selectivity of Cu samples that had been electrochemically polished with
many stability tests that have been discussed in the literature have only
those of Cu surfaces that had been rendered rough through plasma
been conducted for a few hours, which is far shorter than the timeframe
treatment in various gases (Ar, O2, or N2). The electrochemically active
required by the industry. In addition, a greater comprehension of the
surface controlled the variations in total current densities, as well as the
causes of catalyst deactivation is required.
ratios of current densities for the hydrogen evolution reaction (HER) to
CO2RR and to produce C2 + compounds compared to C1 products, and
they showed little dependence on the plasma’s chemical composition.
These findings provide an explanation for the observed rise in the for
mation of oxygenates and hydrocarbons relative to carbon monoxide
(CO) and the ratio of oxygenates to hydrocarbons as surface roughness
increases. Further, Jin et al. [100] concluded that, replacing the
energy-intensive oxygen evolution reaction (OER) with a more effective
procedure like the electrooxidation of glycerol, a byproduct of the pro
duction of industrial biodiesel and soap, could result in a significant
reduction in electricity costs of up to 53% and help reduce carbon
emissions. In conclusion, the electrochemical conversion of CO2 to CO is
crucial for creating a carbon cycle that takes into account environmental
and energy considerations.
Fig. 9. Photocatalytic reduction of CO2 [104].
12
4.2.4. Biological conversion of CO2 gas separation, gas transportation, refrigeration, and storage. [115]CO2
CO2 can be photosynthetically processed by living species, such as sequestration in the form of clathrate hydrates under seabed is another
plants, microalgae, and cyanobacteria. These organisms use CO2 as a proposal (the last CCS step) is considered another promising proposal for
source of carbon to create lipids, sugars, proteins, and other materials long-term bulk storage of CO2. However, the study of thermodynamic
they need. Photosynthetic routes can differ for different organisms but characters, the phase equilibrium conditions related to the development
generally involve the formation of carbohydrates via a reaction between of CO2 hydrate in seabed conditions, the wave motion, depth analysis,
CO2 and H2O [106,107]. By providing CO2 to these organisms, the and the particle/seabed sand analysis for hydrates stability are the
capture and conversion of CO2 into various products is achieved. Factors crucial parameters that need to be studied extensively [116].
limiting this process include temperature, the growth rate of the or According to the process thermodynamics, the smallest pressure
ganisms, light, the organism’s tolerance for the presence or absence of required to form the gas hydrate at a temperature of around 1 ◦ C is about
required nutrients (contaminants), and biomass collection and utiliza 55.6 bars. Hence, elevated pressure, i.e., appropriate depth, is required
tion once it has been grown [108]. Reaction vessels used for the culti to enhance the rate of hydrate formation and for the longer stability
vation of microbes and inside which CO2 conversion takes place include purpose for long-term storage [117].
raceway ponds (open pond with continual mild circulation) and closed Fig. 10 demonstrates the alteration in the density of seawater and
photobioreactors (requires adequate control of temperature and oxygen) CO2 for different ocean conditions with depth. The liquid CO2 is
[109]. comparatively more compressible, and at depths of around 2.5–3.0 km,
it turns out to be neutrally buoyant. The discharged liquid droplets of
5. CO2 storage techniques CO2 sinks to the seabed beneath this range.
Several gas hydrate promoters have been tested to reduce the equi
CO2 storage has been in the limelight for the past two decades. After librium condition for the formation of gas clathrates. Tetrahydrofuran
the signing of the Paris agreement treaty in 2015, the CO2 storage ap (THF) is the most extensively analyzed promoter, i.e., studied by re
proaches were extensively examined to overcome the issue and figure searchers [119]. The equilibrium of hydrate formation reduces with the
out a promising solution for CO2 storage. Generally, CO2 storage is addition of THF at any temperature. It has also been found that the
classified into two main categories, i.e., natural and man-made storage. equilibrium pressure can get reduced by 50% if 3.2 mol% propane is
Terrestrial CO2 sequestration comes under the natural mode, whereas added to a mixture of carbon dioxide and oxygen for hydrate formation
the storage of CO2 in geological formations lies under man-made CO2 [120]. However, boosting the concentration of THF after a threshold
storage. The different potential and currently used CO2 storage tech value may cause a decrease in the hydrate formation. Further, several
niques are discussed below. research is also been carried out by other promoters such as tetra-n-butyl
ammonium bromide (TBAB), Tetrabutylammonium Fluoride (TBAF),
5.1. Terrestrial sequestration and other quaternary ammonium salts [121,122].
Recent investigations also focused on the reactor type and configu
The method of capturing CO2 from the atmosphere and storing it in ration in the formation of clathrate hydrates. Zheng et al. [79] investi
the vegetation and soil is described as terrestrial sequestration. The chief gated the effect of bed volume and the impact of the orientation of the
procedure for terrestrial storage comprises CO2 removal from the at reactor’s bed during the clathrate hydrate formation for carbon capture.
mosphere via photosynthesis and deterrence of CO2 emission from They summarized that low water saturation, and the horizontal
telluric sources[110]. configuration are comparatively preferable to form more hydrates.
5.2. Ocean sequestration 5.4. Geological sequestration
Ocean sequestration is a promising and mass approach for CO2 It is the most extensively used seizure technique, i.e., employed for
storage as it can become the greatest container with the expected po CO2 sequestration. In this practice, CO2 is stored in geological forma
tential storage of 40,000 Giga tons of CO2. Ocean sequestration is also tions underground, like abandoned oil and gas reservoirs, saline aqui
estimated to store about 90% of present CO2 emissions [111]. fers, and abandoned coal beds [123]. The sequestration techniques are
In this technique, CO2 is injected into the water bodies at a depth of deliberated below:
1 km via ships, pipelines, or the offshore platform. The water has a lesser
density than the CO2 injected at this deepness and is therefore estimated
to dissolve and spread into the water [112]. On the other hand, there are
massive concerns about the environmental effect of this technique on
marine life since high CO2 concentrations in water bodies may vary their
pH by increasing the acidity.
Further, experimental studies in ocean sequestration are very
expensive and complex [113].
5.3. CO2 capture via gas hydrates
Gas hydrate or clathrate hydrates are ice-like crystals that are formed
by water molecules and various other constituents like carbon dioxide,
nitrogen, hydrogen, and oxygen. These small gas molecules get impris
oned inside the cavities of crystal lattices formed by water molecules
[114]. The oceans are assessed to have around 39,000 Gt-C (143,
000Gt-CO2), i.e., 50 times larger than the CO2 content in the atmo
sphere. About 38% of anthropogenic CO2 emissions (1300 Gt) have been
estimated to be absorbed by the oceans during the past two centuries.
Separating CO2 via clathrates hydrates is a promising technique for
its capture and has been in the limelight for the last decade [88]. This
new process of CO2 capture is being employed in different industries for Fig. 10. Change in the density of CO2 and seawater with depth [118].
13
5.4.1. Storage in the saline aquifers Juan Basin. Other projects were reported for deep coal seam CO2 storage
Due to their immense capacity, the saline aquifer formations act as in Alberta, Canada, and in the Sydney basin in Australia [133].
the finest salted sink for CO2 storage when compared to other geological The laboratory and field-testing feasibility of commercial CO2 in
sequestration techniques [124]. It has been estimated that about 103 Gt jection into coal beds and seams has been reported in the San Juan Basin,
of CO2 can be stored in the Alberta deep saline basin due to its solubility which is the world’s first ECBM project [134]. Other enhanced coal bed
trapping mechanism [125]. On the other hand, there is the Utsira methane recovery projects reported in the world for laboratory and field
aquifer, where the produced CO2 is injected into the North Sea region testing include the Sydney Basin in Australia and deep coalbed methane
[126]. The saline aquifers are the preferred option for CO2 storage since in Alberta, Canada [135].
it is useless for agricultural, industrial, and other human purposes [127].
Besides the storage in saline aquifers, the CO2 is also stored in the basalts 5.4.4. CO2 storage during EOR
and mineral carbonation [128]. The pictorial representation of the CO2 EOR by utilizing CO2 in the mature oilfields in the miscible and
storage concept in the saline aquifers can be seen in Fig. 11 below. immiscible states is a well-known industrial practice. When CO2 is
introduced into the reservoir, it swells the oil present in it, thus reducing
5.4.2. Abandoned oil and gas reservoirs its viscosity and decreasing its interfacial tension. This results in the
The oil and gas reservoirs age with time since, during the production miscibility of CO2 with the oil permitting for the single-phase flow. The
phase, the pressure inside them reduces gradually. Once the lifespan of miscibility of CO2 in the oil results in elevated recovery of the hydro
the reservoir is complete, and the extraction of hydrocarbons from it is carbons from the reservoir. The miscibility of CO2 in oil is estimated by
no more profitable, the reservoir is then declared abandoned. These the minimum miscibility pressure (MMP). At pressures higher than
depleted reservoirs can act as excellent CO2 containers for geological MMP, CO2 is miscible in oil, whereas, at pressures lower than MMP, it is
sequestration. Due to their property for enhanced hydrocarbon recov immiscible. Although the CO2 injection technique is mainly used for the
ery, reservoir characterization knowledge, existing leakproof infra recovery of hydrocarbons in mature oil reservoirs, it is a promising so
structure, and demonstrated seal, and storage capacity, depleted gas lution for storing CO2 to reduce its atmospheric concentrations. In the
reservoirs are highly favorable spaces for CO2 storage. These kinds of past 15 years, EOR operations using CO2 have been conducted in more
reservoirs are estimated to have a volume of storing about 390 Gt of CO2 than 70 locations. These include the operations in the West Texas field,
[129]. However, the storage capacity available in depleted reservoirs is Weyburn Field in Canada, Shengli Oilfield in China, and several other
significantly lower because of the need to dodge the exceeding pressures fields of the world [136]. These fields are well known for their parallel
since it can ravage the cap rock and cause substantial significant seepage enhanced hydrocarbon recovery and storage processes [137].
hazards posed by the abandoned wells [130].
6. Effect of tree plantation on world CO2 levels
5.4.3. Storage in coal seams
CO2 is also used to recover the coal seam gas (i.e., methane) during Afforestation is the natural CO2 sink that can reduce global warming
the enhanced coal bed methane (ECBM) recovery process [131]. The by absorbing CO2 from the atmosphere. Forests are seldom known as the
Coal beds comprise a huge network of fractures via which the gas lungs of nature due to their plausible contribution towards CO2 capture
molecules diffuse into the medium resulting in the desorption of tightly (i.e., above and below the ground in leaves, branches, and roots) and
adsorbed CH4. This CH4 produced from coal seams can be easily used as maintaining the ecological balance. It is one of the most studied
an energy source. It has been proven that methane recovery is enhanced (negative emission technique) NET for CO2 mitigation. It is estimated to
from around 50% to about 90% when CO2 is injected into the coal seams remove 0.5–3.6 Giga tons of CO2 per year at a minimal cost ranging from
when compared to conventional techniques. This infused CO2 is stock US$ 5–50 per ton of CO2 removed [138]. Afforestation plays an
piled in the coal seam formations after the recovery of methane [132]. In important role in the global carbon cycle, as portrayed in Fig. 12 below.
the process of CO2 storage in the coal seams, the storage occurs at su However, according to recent studies, CO2 captured by the affores
perficial depths when compared to types of formation since, here, CO2 tation technique is comparatively lower and utilizes more land, which
gets adsorbed on the surface of coal. Nonetheless, the technical feasi may otherwise be used for food crop cultivation [140]. Further, the
bility of this storage process strongly relies on the porosity and perme residence time for the afforestation CO2 sequestration technique on the
ability characteristics of coal. This is due to the effect of stress which time scale is comparatively low when compared to the geological
varies with the depth of coal seams during the process of its formation sequestration techniques. The time scale varies for around some cen
for millions of years. turies for the afforestation techniques, which is much lower than the
Few of the sites have been explored and tested for laboratory and stable geological sequestration techniques, i.e., several thousands of
commercial CO2 injection and storage space. For example, the world’s years or more [141].
first coal bed methane project (ECBM) has been carried out in the San
7. Conclusions and outlook
The increasing trend of GHG concentration in the earth’s atmosphere

is causing rising global warming. The thick polar ice caps of the Ant
arctic continent and the Arctic glaciers are melting rapidly because of
the greenhouse effect. This is an eye-opening situation for the govern
ments of the world to understand the importance of checking and con
trolling CO2 emissions worldwide. CO2 capture and utilization are
encouraging approaches to fixing global CO2 levels. However, the type
of technique utilized depends on the availability of resources, techno-
economic feasibility, practically viable rate, and scale at which the
technique is applied for a particular location. Among the different CO2
storage techniques, geological sequestration seems to be more encour
aging due to the large time scale of safe storage space. In contrast, the
storage in the ocean or as gas hydrates is comparatively unstable due to a
very less range of temperature stability and specific pressure needed at
Fig. 11. Concept of storing CO2 in a deep saline aquifer [118]. the seabed. The CO2 utilization technique can be employed accordingly
14
Fig. 12. Global carbon cycle and the role of the tree.
Adapted from Green and Byrne [139].
to economize the overall process and exercise the circular economy of industrial demonstration zones in high-carbon industries like steel,
concept. Direct CO2 utilization techniques can be adopted depending on cement, and chemicals while also hastening the development of infra
the economic feasibility of the location. Although among the indirect structural clusters for CCUS.
CO2 utilization techniques, the thermochemical, electrochemical, and
photochemical methods are still emerging and not practiced at the in CRediT authorship contribution statement
dustrial level. However, the gas reforming techniques are favorable for
CO2 utilization in value-added products like syngas production. None Conceptualization: H.I.; Methodology: M.Y., H.I.; Formal analysis:
theless, the catalyst development to make the process energy efficient is M.Y.; Resources: H.I. Writing-original draft: M.Y.; Review and editing:
still a domain of continuous research. The tree plantation is considered H.I.; Visualization: M.Y.; Supervision, Project administration, and
to significantly affect global CO2 control and climate change, and it is Funding acquisition: H.I.
the cheapest way for CCUS. However, as per recent studies, it has been
concluded that the availability of land for afforestation due to the Declaration of Competing Interest
growing population is challenging. Further, the CO2 storage time scale is
comparatively less than the geological sequestration timescale. Among The authors declare that they have no known competing financial
the recent CO2 capture and utilization advancements, the DAC tech interests or personal relationships that could have appeared to influence
nique is the most promising and viable for the future, provided the initial the work reported in this paper.
investment and techno-economic feasibility issues are addressed. It can
also be summarized that any one CO2 capture and utilization technique Data Availability
is not feasible universally. The different world governments need to
focus and address the issues on different ground levels to come up with Data will be made available on request.
practicable solutions accordingly. In order to promote and build CCUS
initiatives for widespread commercial application, governments must Acknowledgements
intervene proactively. This entails improving process machinery and
investigating cutting-edge capture technologies, including sophisticated The financial support provided by the Natural Sciences and Engi
techniques like negative emission technology combined with CCS/CCU, neering Research Council of Canada (NSERC DG: RGPIN-2018-03955),
along with improvements in energy systems and hydrogen technology. Canada Foundation for Innovation (CFI JELF: 37758), the Vice-Presi
Clear legislative instructions and strong industrial policies are essential dent (Research) Discretionary Fund at the University of Regina are
for the CO2 utilization business. The government should create a na gratefully acknowledged. The authors also extend their gratitude to the
tional demonstration platform for technology demonstrations with in Clean Energy Technologies Research Institute (CETRI) for allowing ac
dustry, academia, and research, enhance financing for scientific and cess to their research infrastructure. The views expressed herein are
technological research in CO2 utilizations, and improve CO2 utilizations those of the writers and not necessarily those of our research and
efficiency. In addition, an essential component of accomplishing large- funding partners.
scale development is driving the integration and demonstration of
CCUS initiatives. The government should encourage the establishment
15
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Journal of Environmental Chemical Engineering 11 (2023) 111393

Contents lists available at ScienceDirect

Journal of Environmental Chemical Engineering

A comprehensive review on recent trends in carbon capture, utilization,

commercial pre-combustion capture techniques; however, the pre-

Fig. 3. Process flow chart for the Selexol process [44].

Fig. 4. The Rectisol process [45].

Fig. 5. Schematic of a power plant with post-combustion CO2 capture [49].

Fig. 7. Block diagram of oxyfuel combustion capture system [60].

Table 3 Table 3 (continued )

Fig. 8. Process schematics of the DAC process.

Fig. 9. Photocatalytic reduction of CO2 [104].

5.2. Ocean sequestration 5.4. Geological sequestration

5.3. CO2 capture via gas hydrates

The increasing trend of GHG concentration in the earth’s atmosphere

References adsorbents, Chin. Chem. Lett. 33 (2022) 2595–2599, https://doi.org/10.1016/j.

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