Review

Review of carbon capture absorbents

for CO2 utilization
Slyvester Yew Wang Chai, Lock Hei Ngu and Bing Shen How, Faculty of Engineering, Computing
and Science, Swinburne University of Technology Sarawak Campus, Malaysia

Abstract: Carbon capture technologies have been recognized as a potential alternative to alleviate
global warming. Carbon capture and storage (CCS) is preferred over carbon conversion and utilization
(CCU) due to its lower operating costs and higher CO2 reduction capability. Nevertheless, CO2
utilization has the potential to be more economical if value-added products are produced. This
highlights the importance of assessing CO2 utilization routes and alternatives in carbon management.
This review paper aims to evaluate the carbon utilization potential of major CO2 -capturing absorbents
including amine, hydroxide, ionic liquid, amino acids and carbonate absorbents. All absorbents show
potential application for CO2 utilization except for ionic liquids (ILs) due to their unclear CO2 capture
mechanisms. Absorbents that require a desorption process for CO2 utilization include MEA, MDEA,
K2 CO3 and Na2 CO3 due to their high absorption capacity. Industries have utilized the desorbed CO2 as
chemical feedstocks, enhanced oil recovery (EOR) and mineral carbonation. For hydroxide absorbents
and CaCO3 , desorption of CO2 is unnecessary as the absorbed CO2 can be directly utilized to produce
construction materials. Apart from that, the incorporation of advanced technologies and business
models introduced by the fourth industrial revolution are plausible considerations to accelerate the
development of carbon capture technologies. © 2022 Society of Chemical Industry and John Wiley &
Sons, Ltd.

Keywords: carbon capture; CO2 utilization; post-combustion; chemical absorption; global warming

Introduction NASA’s Goddard Institute for Space Studies,5 it has

been found that the land-ocean temperature index (◦ C)
xcessive CO2 emission is regarded

E as the primary contributor to global warming,

which is an inevitable concern that has received
worldwide attention.1,2 The average CO2 concentration
has increased from −0.16 C° in the year 1880 to 1.02
C° in 2020. In an effort to halt the progression of global
warming, developed countries have initiated various
environmental agreements such as the Kyoto Protocol
rose to approximately 414 ppm CO2 (as of October in 1997 and the Paris Agreement in 2015.6,7
2021) which is an increment of approximately 47.86 % CO2 capture and storage (CCS) is recognized by the
as compared to the pre-industrial revolution era (280 United Nations Framework Convention on Climate
ppm).3,4 The drastic increase in CO2 concentration Change (UNFCCC), Intergovernmental Panel on
further contributed to global climate change. Based on Climate Change (IPCC), Kyoto Protocol and Paris

Correspondence to: Lock Hei Ngu, Faculty of Engineering, Computing and Science, Swinburne University of Technology Sarawak Campus,
Malaysia.
Email: lngu@[Link]
Received January 4, 2022; revised April 12, 2022; accepted April 26, 2022
Published online at Wiley Online Library ([Link]). DOI: 10.1002/ghg.2151
This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium,
provided the original work is properly cited.

© 2022 The Authors. Greenhouse Gases: Science and Technology published by Society of Chemical Industry and John Wiley & Sons Ltd.
Greenhouse. Gas. Sci. Technol. 12:394–427 (2022); DOI: 10.1002/ghg.2151 394
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Review of carbon capture absorbents for CO2 utilization

Agreement as one of the potential technologies to commonly associated with low adsorption capacity
combat global warming.8–10 CCS is the preferred mode (i.e., 1.8–4.18 mmol of CO2 /g of absorbent) and low
of CO2 capture compared to CO2 conversion and CO2 selectivity.1,47,48
utilization (CCU), and CO2 capture, utilization and For cryogenic distillation, its application in
storage (CCUS).11–13 This is due to the limited CO2 post-combustion CO2 capture is relatively new as it is
reduction capability and high operating costs of CO2 typically applied in oxy-fuel combustion operations.
utilization as compared to CO2 storage.14–18 Although cryogenic distillation offers excellent CO2
Nevertheless, CCU and CCUS cannot be neglected capture efficiency of up to 95% and is able to capture
since both alternatives possess a high potential to CO2 without the need for chemical reagents, its
convert captured CO2 to a value-added product while intensive energy requirement for refrigeration still
exploiting possible utilization routes for captured withheld its favourability to be commercialized.1,31,43
CO2 .12,16,18 Membrane separation is also an alternative that offers
The capture of CO2 is mainly performed at excellent CO2 capture efficiency (up to 88%),
post-combustion, pre-combustion and oxyfuel eco-friendly and has a much simpler carbon capture
combustion. Post-combustion involves installing unit configuration as compared to other carbon capture
operation after combustion as it aims to separate CO2 technologies.31,43,49 However, its requirement of
from flue gas after converting a carbon source.13,19 It specific conditions to perform effectively remains a
has received the most interest due to its ability to easily hurdle for its commercialization. For example, flue gas
retrofit existing plants.20–22 In pre-combustion, CO2 is applied to membrane separation system need to be free
removed prior to completing a combustion process via of impurities (i.e., SOx and NOx), high CO2 partial
decarbonization.20,23 This process requires additional pressure to ensure high separation efficiency and low
equipment such as a catalytic reactor, absorber or temperature (25◦ C) for a non-metallic or ceramic
separator before the combustion unit, imposing a membrane to avoid membrane degradation.14,41,50
sizable change to an existing plant’s configuration, This review looks into chemical absorbents’
making it less preferable.19,20,24 For oxy-fuel performance and their utilization pathway as it is the
combustion, high purity oxygen (O2 ) is utilized to most preferred alternative and most researched among
combust carbon sources resulting in flue gas the available separation technologies. Under chemical
production that is free from unwanted gases (i.e., NOx) absorption, there are five major absorbent groups:
which ease the CO2 storage.25–27 Similar to amine-based absorbent, carbonate absorbent,
pre-combustion, its ability to be retrofitted into existing hydroxide absorbent, ionic liquid (ILs) and amino acid
plants is not promising due to the requirement of salts. Amine-based absorbents have the most
additional equipment (i.e., air separation unit and publications from 2001 to 2021 with 4960 publications
oxidizer) before a combustion unit.20,28 followed by carbonate absorbents with 704
There are four main CO2 capture technologies, that publications, ILs with 213 publications, hydroxide
is, chemical absorption, adsorption, membrane absorbents with 55 publications and amino acids acid
separation and cryogenic distillation. Chemical salts with 62 publications from the Scopus database.
absorption is the most researched, implemented and Amine-based absorbents are dominantly studied due
commercialized option among the named separation to the early commercialization of monoethanolamine
technologies, especially in post-combustion capture (MEA) for CO2 capture in the 1970s, popularizing it as
due to its distinct advantages.11,14,29–35 These a potential absorbent for research. The remaining four
advantages include excellent CO2 absorption efficiency absorbent groups have also gained increasing interest
of 80–100%, adaptability to low-pressure conditions as potential CO2 absorbents with an increment of
and capability to produce high purity CO2 (up to 150% publications compared to the past 10 years.
99%).2,12–14,31,32,34,36–41 Adsorption is also a highly Past reviews (from 2001–2021) conducted on
regarded CO2 separation technology due to its chemical absorbents are insightful but do not critically
excellent CO2 capture efficiency of up to 90% and review and benchmark the CO2 capture performance
flexibility to be implemented in post- and of all major absorbent groups comprehensively in a
pre-combustion CO2 capture.14,31,42–46 Apart from that, single paper. Amine-based absorbents are discussed in
most adsorbents are widely available, inexpensive and Refs. 1, 2, 31, 32, 41, and 51–56 while carbonate
thermally stable.2 However, adsorbents are also absorbents in Refs. 14, 31, 32, 51, and 56 ILs are

© 2022 The Authors. Greenhouse Gases: Science and Technology published by Society of Chemical Industry and John Wiley & Sons Ltd.
Greenhouse. Gas. Sci. Technol. 12:394–427 (2022); DOI: 10.1002/ghg.2151 395
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Chai et al.

presented in Refs. 2, 51, 54, and 57–59 and amino acid amines include, 2-(2-aminoethoxy) ethanol (DGA),
salts are reviewed in Ref. 51. In this review, all the 1-amino-2-propanol (1A2P) and 2-amino-1-butanol
aforementioned chemical absorbents are deliberately (2A1B) but none have reached the commercialization
discussed. Upon the deliberate discussion of major level of MEA. Primary amines are also known for their
chemical absorbent groups, this review aims to fast kinetics, high water solubility and low price.53,62 It
investigate the suitability of absorbents for CO2 should also be noted that amine absorbents are
utilization with or without desorption which has never typically applied for CO2 capture operation in aqueous
been comprehensively studied. Apart from that, this form instead of their pure state.
review also looks at some of the recently developed The CO2 capture mechanisms of primary amines
hybrid or novel absorbents (i.e., amine/ILs, consist of four steps. First, is the ionization of water
amine/amino acid salts and amine/promoter hybrids) (reaction 1) and then CO2 hydrolysis and ionization
as they possess substantial potential in CO2 absorption. (reaction 2). Next is the protonation of alkanolamine
Therefore, this paper aims not only to perform a (reaction 3). Lastly, the formation of carbamate
deliberate review of all major absorbent groups and (REACTION 4).60 Each of the reactions is as
evaluate their suitability for CO2 utilization based on follows:
their need for a desorption process but also examine
the state-of-the-art synthesized chemical absorbents. H2 O(aq ) → H+aq + OH−aq (1)
( ) ( )
The performance of the CO2 absorbents is evaluated
based on the essential qualities as listed by Davidson.53 CO2(g ) + H2 O(aq ) → HCO−
3 (aq )
+ H+aq (2)
( )
To note, the considered qualities include high CO2
reactivity in terms of CO2 capture efficiency or RNH2(aq ) + H+aq → RNH+ (3)
( ) 3 (aq )
absorption rate, low regeneration temperature, high
absorption capacity and low environmental RNH2(aq ) + CO2(aq ) → RNHCOO−aq + H+aq (4)
( ) ( )
impact.
Although primary amines offer ideal CO2 capture
Chemical absorption absorbent capability, they have their drawbacks. The most
common drawback associated with primary amines is
The following subsections review the unique qualities their proneness to degradation. There are two types of
of each of the five major absorbent groups. The review degradation for alkanolamines (i.e., thermal
begins with organic absorbents (amine-based degradation and oxidative degradation).11,63 These
absorbent, amino acid solution and ionic liquid) degradations can further contribute to more problems
followed by inorganic absorbents (hydroxide and such as solvent loss, fouling, increased viscosity and
carbonate absorbent) and then some of the recently corrosion of downstream equipment.62 Another
developed hybrid or novel absorbents. The discussion unappealing feature of primary amines is their
focused on are the CO2 capture capability (CO2 capture relatively low CO2 absorption capacity of
efficiency, CO2 capture capacity or CO2 absorption approximately 0.35 to 0.56 mol CO2 /mol solvent.64,65
rate) of absorbents, regeneration energy requirement Common pollutants in flue gas such as SOx and NOx
and environmental hazards. Each absorbent’s reaction would also disrupt the primary amines’ CO2 capture
mechanisms are elaborated to grasp the necessary performance.63 Thus, pre-treatment unit operation
knowledge to perform an overview on their ideal needs to be added for flue gas purification. In addition,
absorption condition, interaction with flue gas the regeneration process of primary amines is
composition and end-product of each absorbent. energy-intensive (3.80–4.20 GJ/ton CO2 ) as a high
temperature of approximately 70–200◦ C is
Amine-based absorbent required.13,38,39,66 This has led to a concentrated effort
Primary amines in finding alternatives to minimize solvent regeneration
The primary amine, MEA) is the most well-known and energy consumption.67–70 Despite all these drawbacks,
employed absorbent within the CO2 capture primary amine or specifically the MEA system is still
industry.34,60,61 MEA was popularized due to its the most utilized CO2 capture technology to date.
exceptional CO2 removal capability (87.1–100%) while One of the most recent studies on a pilot-scale CO2
producing a nearly pure CO2 of > 99%. Other primary capture plant with MEA was demonstrated by Akram

© 2022 The Authors. Greenhouse Gases: Science and Technology published by Society of Chemical Industry and John Wiley & Sons Ltd.
396 Greenhouse. Gas. Sci. Technol. 12:394–427 (2022); DOI: 10.1002/ghg.2151
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Review of carbon capture absorbents for CO2 utilization

et al.68 in 2021. In this study, a typical 30 wt.% MEA it was reported that at a fixed absorber stage, the
system with a CO2 capture efficiency and capacity of temperature required for DGA to achieve a 90% CO2
90% and 1 ton CO2 /d, respectively, was used as a removal efficiency is lower compared to a MEA system.
benchmark against a 40 wt.% MEA system. The aim of For example, it was shown that in a two-stage absorber,
increasing the wt.% of MEA is to improve the CO2 the temperature required for an MEA system to achieve
capture performance while reducing the solvent 90% CO2 removal efficiency is approximately 67.5◦ C
regeneration energy requirement. From their findings, whereas DGA only requires a temperature of 63◦ C to
the 40 wt.% MEA system applied to a 6.6 vol.% CO2 achieve a similar efficiency. It was also shown that the
gas stream was able to maintain a plausible CO2 regeneration efficiency of DGA is superior compared
capture efficiency of 89.6% while reducing the to MEA. From the result, it was shown that at a reboiler
regeneration energy consumption by 25.1%. It was also temperature of 110◦ C, the regeneration efficiency of
presented that if the temperature of the regeneration DGA is approximately 90 % while MEA is only 66 %.
unit increases from 125.7 to126.8◦ C, the CO2 capture Therefore, depending on the application conditions,
efficiency and capacity can be increased to 91% and both DGA and MEA can offer different advantages to a
74.6 g CO2 /kg MEA, respectively. However, the main system. All in all, this shows that primary amines
drawbacks of increasing the regeneration temperature application is still relevant in the current CO2 capture
are the increase in overall energy consumption by sector and gaps are still available for further research.
12.3% and the thermal degradation degree of solvent.
Another recent application of 30 wt.% MEA in a
post-combustion capture pilot plant was demonstrated Secondary amines
at Niederaussem from August 2017 to February 2019.71 Some examples of secondary amines are
The capture capacity of this facility is approximately 2-(methylamino) ethanol (MMEA),
0.25 tons CO2 /d with a capture efficiency of 90%. This N-ethylmonoethanolamine (EMEA),
study focuses on the degradation of MEA which is 2-(tertbutylamino) ethanol (TBMEA) and
defined by the formation of oxidative degradation diethanolamine (DEA) the most applied secondary
products (acetate, formate and oxalate) and the amine in CO2 capture.52,64,72,73 The majority of the
accumulation of trace elements (chloride, sulphur, secondary amines characteristics are similar to primary
sulphate, nitrate and iron) in the solvent. From the amines as they also have high reaction rates and high
result, it was shown that the degradation of MEA after mass transfer toward CO2 . Based on Al-Baghli et al.,52
100 h was 0.47 wt.%. or in terms of solvent the difference between the CO2 loading of MEA and
consumption rate is approximately 0.21–0.35 kg MEA DEA (only DEA for comparison as the CO2 loading of
per ton of CO2 . To reduce the degradation of solvent, most secondary amines is not available) is only 0.0076
Moser et al.71 proposed a solvent management strategy, mol CO2 /mol solvent. Secondary amines also offer an
namely an ion exchange-based reclaiming process to exceptionally high absorption efficiency that ranges
control the concentration of anionic degradation from 56.3 to 90%.52,72,74
products and trace elements in MEA. In this process, a Similar to primary amines, secondary amines also
proprietary anion exchange resin was used to remove require a tremendous amount of energy for their
anionic trace elements from the solvent reducing the regeneration process due to carbamate formation.
degradation degree of MEA. However, further analysis Carbamate possess a relatively high heat of CO2
is required to optimize this process as this application desorption, thus requiring a high temperature (70 to
is still relatively new in CO2 capture operation. 200◦ C) to regenerate the utilized amine.13,38,66,72 The
Apart from MEA, Pellegrini et al.39 also investigated CO2 capture mechanisms of secondary amines are also
the CO2 absorption capability of DGA. In this similar to primary amines.38 Thus, Reaction (1) to (4)
comparative study, a 13–27 wt.% MEA and 8–27 wt.% can be referred to as the CO2 capture mechanisms of
DGA system was used to absorb CO2 from flue gas secondary amines by changing the RNH2 (primary
with 7 wt.% CO2 . From the CO2 removal efficiency amines) to R2 NH (secondary amines).38,60 Next, it has
result, it was shown that a 27 wt.% MEA system was a low CO2 absorption capacity of approximately
able to achieve high efficiency (∼ 95%) compared to a 0.45–0.50 mol CO2 /mol solvent.64 Also, secondary
27 wt.% DGA system (∼ 88%) if absorber is operated at amines can cause adverse environmental and health
20◦ C. However, from the temperature profile analysis, hazards due to their volatile nature.11 Thitakamol75

© 2022 The Authors. Greenhouse Gases: Science and Technology published by Society of Chemical Industry and John Wiley & Sons Ltd.
Greenhouse. Gas. Sci. Technol. 12:394–427 (2022); DOI: 10.1002/ghg.2151 397
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Chai et al.

reported the loss of a significant amount of amine not effectively mineralize the DFS unlike the
absorbent due to its volatility, leading to additional bicarbonate ions produced by AMP. Nevertheless, this
operating costs. regeneration configuration which no longer requires
One of the most recent studies on unblended the operation of a compressor and reboiler was able to
secondary amine for CO2 capture was conducted by reduce the regeneration energy consumption of a
Barzagli et al.74 in 2020. In this lab-scale analysis, conventional amine desorption process by 93.7% from
primary amine (MEA, DGA, 1A2P, 2A1B), secondary 3.65 to 0.23 GJ/ton CO2 .
amine (MMEA, EMEA, TBMEA, DEA) and tertiary
amine (DMMEA and MDEA) are analyzed for direct Tertiary amines
air capture (DAC). From the reported result, secondary Tertiary amines (i.e., 2-(dimethylamino)ethanol
amine MMEA is shown to possess the highest CO2 [DMAE], N-methyldiethanolamine [MDEA] and
capture efficiency at 88.9 % among all the analyzed 2-diethylaminoethanol [DEAE]) have been receiving
amines. Other than MMEA, EMEA, BUMEA and DEA increasing attention as a CO2 capture absorbent due to
also show plausible CO2 capture efficiency ranging their higher CO2 absorption capacity of 1 mol
from 74.5 to 85.9%. However, most of the captured CO2 CO2 /mol solvent compared to the absorption capacity
by these secondary amines is in the form of carbamate of primary and secondary amines, which is
which is typically associated with high solvent approximately 0.5 mol CO2 /mol solvent.60,77 Other
regeneration requirements. Among the secondary than that, due to the absence of α − H atom, tertiary
amines, only TBMEA does not produce carbamate as it amines are not able to react directly with CO2 to form
is a sterically hindered amine like AMP, DMMEA and carbamates.60 This would result in the formation of
MDEA that only tends to produce bicarbonate and bicarbonate ions which require a much lower
carbonate ions. However, within the sterically hindered regeneration energy of approximately 58.8 kJ/mol CO2
amines shown here, TBMEA possesses a relatively low for tertiary amines to be regenerated compared to
CO2 capture efficiency of 56.3% as compared to AMP primary and secondary amine, which are 86.9 and 68.9
having an efficiency of 72.3%. From this study, it is kJ/mol CO2 , respectively.11,66,72,77
shown that none of the secondary amines possess a The common drawback of tertiary amines is their low
good balance between an excellent CO2 capture CO2 absorption rate (∼ 2.13 mol CO2 /h) compared to
efficiency with a low solvent regeneration energy primary and secondary amines.77 To make up for this
requirement. Thus, secondary amines are typically deficiency, promoters such as piperazine (PZ) or
blended with other solvents for better performance. carbonic anhydrase (CA) are typically blended with
In 2021, Wang et al.76 also conducted another tertiary amines to increase their CO2 absorption
lab-scale experiment on amines CO2 capture which rate.62,64,65 Based on Lawal et al.,78 MDEA is prone to
includes DEA. In this study, an integrated absorption oxidative degradation, leading to the diminishing of
and mineralization process was proposed to absorb CO2 absorption capacity.
CO2 with amine-based solvents then CO2 -rich solvents The CO2 capture reaction via a tertiary
are regenerated via a mineralization process with amines-CO2 -H2 O system is as follows66,77,79 :
semidry desulfurization slag (DFS). In this process, a
gas mixture of 15 vol.% CO2 and 85 vol.% N2 was R3 N(aq ) + CO2(g ) + H2 O(aq )
introduced into a 500 ml flask filled with amine
solvents to undergo CO2 absorption. After the ↔ R3 NH+ (aq ) + HCO−
3 (aq )
(5)
absorption process, CO2 -rich solvent is then mixed
with DFS (Ca-rich compound) to undergo In 2021, Antonini et al.80 demonstrated the
mineralization to form calcium carbonate while application of an MDEA CO2 capture facility for the
regenerating the utilized solvent using a reflux system. generation of low-carbon hydrogen. In this application,
The reported CO2 loading of rich and lean DEA was a CO2 capture configuration (as shown in Figure 1)
approximately 0.73 and 0.18 mol CO2 /mol DEA that utilizes a dual flash, semi-lean recycle and split
respectively. For its desorption process, it was shown flow to desorber was implemented to capture CO2
that the maximum achievable efficiency is 85% which from syngas that contains 16.27 mol.% CO2 . The
is 13% lower as compared to that of AMP. The reason optimal CO2 to MDEA molar ratio and MDEA weight
for this is that carbamate formed post-absorption could fraction CO2 -free solution obtained via simulation

© 2022 The Authors. Greenhouse Gases: Science and Technology published by Society of Chemical Industry and John Wiley & Sons Ltd.
398 Greenhouse. Gas. Sci. Technol. 12:394–427 (2022); DOI: 10.1002/ghg.2151
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Review of carbon capture absorbents for CO2 utilization

Figure 1. Flowsheet of dual flash, semi-lean recycle and semi-lean splitter CO2 capture
process. Modified with permission from Antonini et al.80 Copyright 2021 Elsevier B.V.

work are 0.3 and 40 % respectively. Based on the result of the system.82 Among the polyamines, only the
obtained, it was shown that a regeneration energy incorporation of PZ was able to increase the CO2 and
requirement of 0.61 MJ/kg CO2 was obtainable at a desorption rate performance without having an
CO2 capture efficiency of 90%. This results in a 54.5% adverse effect on the viscosity of the solvent. It was
reduction of regeneration energy regeneration. Apart observed that the 0.3 M PZ/3 M MDEA blended
from that, such configuration has the potential to be a solvent has a CO2 loading and specific desorption rate
sustainable operation due to the production of clean of 0.67 mol CO2 / solvent and 0.0352 mol CO2 /mol
hydrogen and the high CO2 recovery percentage of > [Link] while only having a slight increase in
97% which is suitable for further utilization. viscosity (0.2418 mPa.s). The main difference between
Jaffary et al.81 have also conducted a study on MDEA the enhancement performance of PEI-B and PZ was in
CO2 capture back in 2021. In this study, polyamines the available primary amino groups present in the
(polyethylenimine [PEI-B], tetraethylenepentamine respective polyamines. In short, PEI-B contains up to
[TEPA] and PZ) are used as activators for MDEA to six primary amino groups while PZ has none.
absorb a 100% CO2 gas in a 100 ml three-necked
round-bottom flask. From the result obtained, it was Ionic liquid
shown that an unblended 3 M MDEA system possesses
ILs are salts that exist in a liquid phase at room
the lowest CO2 loading capacity and specific
temperature. ILs can sometimes be referred to as
desorption rate at 0.63 mol CO2 /mol solvent and
non-volatile liquids and as its name implied, are made
0.0313 mol CO2 /mol solvent·min, respectively. Among
up of cations and anions. Factors that have attracted
the three polyamines mentioned, PEI-B was shown to
researchers’ interest are the remarkable solubility of
have the best enhancement ability as it was able to
CO2 in ILs and the unique characteristics that it
increase the CO2 loading and specific desorption rate
possesses, such as negligible vapor pressure, flexible
of MDEA to 1.08 mol CO2 /mol solvent (i.e., 71.4 %)
designability, high thermal stability and
and 0.0385 mol CO2 /mol amine·min (i.e., 23 %)
eco-friendliness.58,83 As stated by several studies,57,84,85
respectively. However, an increment in viscosity had
ILs can be easily regenerated due to their low or
occurred at the same time (from 2.122 mPa.s
negligible vapor pressure but data on the regeneration
(unblended MDEA) to 15.945 mPa.s (0.3 M PEI-B/3 M
of ILs are limited.
MDEA)). This is unfavourable as the increase in
Currently, ILs are still not preferred commercially due
viscosity can negatively affect the CO2 absorption rate
to their low absorption capacity and high viscosity.77,86

© 2022 The Authors. Greenhouse Gases: Science and Technology published by Society of Chemical Industry and John Wiley & Sons Ltd.
Greenhouse. Gas. Sci. Technol. 12:394–427 (2022); DOI: 10.1002/ghg.2151 399
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Chai et al.

Table 1. Different groups of ILs and their the chemical interaction of a phosphonium-based ionic
respective example.59 liquid with CO2 , respectively.58,88
From a review conducted by Lian et al.89 on ILs, it
Ionic liquids (ILs) Examples of ionic
was shown that the main advantage that an ILs-based
groups liquids (ILs) process has over an MEA-based process is in the
Imidazolium-based r 1-N-Octyl-3-methylimidazolium
economical aspect. It was shown that up to 24.8 to
ionic liquids hexafluorophosphate-C8min 30.01% of energy and 29.99% in primary cost can be
r 1-Ethyl-3-methylimidazolium saved due to the less energy-intensive absorption and
ethyl sulphate-Emim desorption process of an ILs-based process. In the
Ammonium-based r 2-(2-Hydroxyethoxy)-ammonium absorption process, the ILs-based process requires the
ionic liquids lactate feed gas mixture to be at a lower pressure (30 bar) as
r Bis(2-hydroxyethyl)-ammonium
compared to an MEA process (> 30 bar) which
acetate
r requires it to have a multistage compressor to achieve
Phosphonium-based N-Butyl-4-methylpyridinium
this condition. The heat required for an MEA
ionic liquids tetrafluoroborate-MeBuPy
r N-Butyl-4-Methylpyridinium
desorption operation is also much higher at 393.75 kW
thiocyanate-MeBuPy compared to an ILs desorption process which only
Functionalized ionic r AMPim[NTf2] requires 172.26 kW.90 Apart from that, it was also
liquids (TSILs) r AMPim[BF4] presented that there are two proven unblended ILs that
can achieve a high CO2 solubility and low energy
Table 2. Average absorption capacity of different consumption compared to MEA. These ILs are
ILs groups.59 1-butyl-3-methylimidazolium hexafluorophosphate
([Bmim][PF6 ]) and 1-Butyl-3-methylimidazolium
Average absorption
bis(trifuloromethanesulfonyl)imide ([Bmin][Tf2 N])
ILs groups capacity, mol CO2 /mol ILs which have a CO2 capture capacity of 0.513 and 0.681
Imidazolium-based ionic liquids 0.333
mol CO2 /mol solvent respectively while the solubility
of MEA is only 0.5 mol CO2/mol solvent.83,91 The CO2
Ammonium-based ionic liquids 0.147
capture energy consumption of [Bmim][PF6 ] and
Phosphonium-based ionic liquids 0.507
[Bmim][Tf2 N] is also 35.6 (2.70 GJ/ton CO2 ) and 71.5
Functionalized ionic liquids 0.285
% (1.194 GJ/ton CO2 ), respectively lower compared to
(TSILs)
a typical MEA process (4.195 GJ/ton CO2 ).

However, the CO2 absorption performance of ILs can

be enhanced by incorporating an amine function into Amino acid solution
the ILs structure.87 Due to the extremely flexible Common natural amino acids are taurine, proline and
designability of ILs, ILs need to be reviewed in groups arginine while some examples of non-natural amino
rather than individually. Some well-known ILs groups acids include piperazine-2-carboxylic acid,
include imidazolium-based ionic liquids, 2-(pyrimidin-2-ylamino) acetic acid and
ammonium-based ionic liquids, phosphonium-based (1-piperazino)-2-propionic acid.92 Natural amino acids
ionic liquids and task-selective ionic liquids (TSILs). have attracted interest as a CO2 capture absorbent due
Table 1 presents some examples of the respective group. to their eco-friendly characteristics. The fact that they
The absorption condition for different ILs varies exist naturally in the environment helps strengthen this
considerably. Taking ammonium-based ionic liquids as prospect.93 Also, they are less volatile due to their ionic
an example, the ideal absorption condition for nature.37 Amino acid also possess similar functional
2-(2-hydroxyethoxy)-ammonium lactate is 303 K and groups as alkanolamines resulting in their reactivity
65.7 bar while bis(2-hydroxyethyl)-ammonium acetate and CO2 absorption capacity to be comparable to
is 298.15 K and 15.15 bar.59 Table 2 shows the average amine-based absorbents.2,37,64,92 In addition, amino
absorption capacity of the fore mentioned ILs groups. acid solution have found great success in CO2 capture
Also, the reaction mechanisms vary according to the implementation in various applications (i.e., biogas
type of ILs group. Figures 2(A and B) show the CO2 upgrading, flue gas decarbonization and natural gas
capture mechanisms in amine-functionalized ILs and purification).93

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Review of carbon capture absorbents for CO2 utilization

Figure 2. (A) CO2 capture mechanisms in amine-functionalized ILs.58 ; (B) Chemical

interaction of a phosphonium-based ionic liquid with CO2 .88

Although amino acids offer several advantageous to capture CO2 from a simulated flue gas (12.8% CO2 )
features, the intensive regeneration energy requirement with an approximate capacity of 0.70 mol CO2 /mol
has been a concern in its application for CO2 capture. glycine.92 This process also incorporated
Based on the experimental data presented by Knuutila glyoxal-bis(iminoguanidine) (GBIGs) for
et al.,37 the regeneration energy requirement for crystallization of the bicarbonate anions form after
CO2 -rich amino acid solvent ranges from 7.5 to 11.4 CO2 absorption by glycine. This precipitation process
MJ/kg CO2 . Other than that, the absorption capacity of generates GBIGH2 2+ (HCO3 – )2 (H2 O)2 while
amino acids after the regeneration process drops regenerating glycine without any high-temperature
drastically. As presented in the work by Munoz et al.,37 heating as compared to a typical desorption process.
the absorption capacity of most regenerated amino Based on Munoz et al.,92 the absorption capacity of
acid solvents dropped by half of their initial capacity. regenerated glycine may tend to drop from 0.70 to 0.50
The CO2 capture interaction between amino acid and mol CO2 /mol glycine after one cycle. After the
CO2 produces carbamate, as depicted in Figure 3. regeneration of glycine, GBIGs can then be regenerated
Apart from that, Zhang et al.93 stated that the CO2 via heating of GBIGH2 2+ (HCO3 – )2 (H2 O) and
capture performance of amino acids solution is greatly separated CO2 can be stored or utilized. This two-stage
dependent on three factors, namely amino acid regeneration process with an enthalpy of reaction of
concentration, pressure and temperature. For example, −28.69 kJ/mol has shown to be favourable compared
the CO2 loading of sodium β-alaninate (SA) shows a to a direct regeneration of glycine pathway which
tremendous variation from 0.353 to 1.864 mol requires a reaction enthalpy of 69 kJ/mol.
CO2 /mol amino acid, with a concentration, pressure
and temperature range of 10 to 30 wt.%, 2–25 bar and Hydroxide absorbent
303–333 K, respectively.
From the experimental work by Knuutila et al.37 and Calcium hydroxide
Munoz et al.,92 the absorption capacity and Ca(OH)2 aqueous solution has the potential to be an
regeneration energy requirement of amino acids vary effective absorbent for CO2 capture due to the
greatly depending on the amino acid utilized. In advantageous features it offers. First, Ca(OH)2 is
general, the absorption capacity of amino acid solution relatively low in cost due to the abundance of both raw
can range from as low as 0.22 to as high as 2.23 mol materials required for its production which are CaO
CO2 /mol amino acid.37,92 and H2 O.95 These materials are inexpensive and
More recently, Kasturi et al.94 demonstrated the non-hazardous to the environment. Next, Ca(OH)2
application of aqueous amino acids salt namely glycine and CO2 reaction mechanism, namely carbonation
process, is a typical and well-researched reaction.96,97

© 2022 The Authors. Greenhouse Gases: Science and Technology published by Society of Chemical Industry and John Wiley & Sons Ltd.
Greenhouse. Gas. Sci. Technol. 12:394–427 (2022); DOI: 10.1002/ghg.2151 401
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Chai et al.

Figure 3. CO2 capture mechanisms of amino acid salt.92

Third, CaCO3 produced via the carbonation process Ca(OH)2 . Thus, achieving the required RH would be
can be easily handled with reclamation and an additional problem to be taken into consideration.
regeneration processes readily available. The Shih et al.101 prove that the reaction of Ca(OH)2 and
reclamation process in CO2 sequestration offers CO2 to form CaCO3 as shown in Reaction 6, only
various advantages such as low environmental risk, occur above a critical RH value of 8%.
long-term storage and inexpensive.95
However, the Ca(OH)2 absorbent application has not Ca(OH)2(s) + CO2(g ) ↔ CaCO3(s) + H2 O(l) (6)
received much interest due to three main limitations. Within the temperature range of 25–750°C, this
First is the energy-intensive extraction process reaction will be thermodynamically favored.95
required to extract CaO from natural limestone. Apart Reaction 6 shown above is a combination of many
from that, the extraction process also emits a sub-reactions. Initially, solid Ca(OH)2 will undergo
tremendous amount of CO2 .95 Second, is the disposal dissolution in water as shown in Reaction 7:
of a large amount of CaCO3 and H2 O produced from
the carbonation process. As mentioned, reclamation Ca(OH)2(s) ↔ Ca2+ + 2OH−aq (7)
(aq ) ( )
and regeneration processes are available to handle the
disposal of CaCO3 . However, handling it in a large The solubility of Ca(OH)2 in water is highly
amount is problematic as it would impose a high dependent on temperature. Based on Han et al.,95 the
disposal cost.95 Third, the regeneration process of correlation between the Ca(OH)2 solubility in water
Ca(OH)2 is energy-intensive.98 To regenerate Ca(OH)2 , and temperature can be denoted as:
CaCO3 needs to undergo a calcination process at a  
solubility of Ca OH2 g/kg of solution
high temperate of approximately 650 to 765◦ C to
obtain CaO, which is a direct source of Ca(OH)2 .98,99 = −0.0108T (◦ C) + 1.7465 (8)
Based on Moreno et al.,100 relative humidity (RH)
plays a vital role in the CO2 capture performance of This reaction is followed by a series of reactions on
the hydration of CO2 to form carbonate ions. These

© 2022 The Authors. Greenhouse Gases: Science and Technology published by Society of Chemical Industry and John Wiley & Sons Ltd.
402 Greenhouse. Gas. Sci. Technol. 12:394–427 (2022); DOI: 10.1002/ghg.2151
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Review of carbon capture absorbents for CO2 utilization

reactions are presented from Reactions 9–12: The overall CO2 absorption reaction with NaOH is as
follows:
CO2(g ) ↔ CO2(aq ) (9) NaOH(aq ) + CO2(g ) → NaHCO3(aq ) (14)
CO2(g ) + H2 O(l) ↔ H2 CO3(aq ) (10) The absorption reaction is initiated by the ionization
of Na+ and OH− in pure water. This is followed by the
H2 CO3(aq ) ↔ H+aq + HCO− (11) physical absorption of gaseous CO2 to aqueous CO2 in
( ) 3 (aq )
the NaOH solution as shown in Reaction 15. Next,
HCO−
3 (aq )
↔ H+aq + CO2− (12) aqueous CO2 reacts with OH− to generate HCO3 −
( ) 3 (aq )
and CO3 2– as expressed in Reaction 16 and 17:
The predominant level of bicarbonate ion and CO2(g ) ↔ CO2(aq ) (15)
carbonate ion is dependent on the pH of the solution.
Formation of CO3 2− and HCO3 – are favourable at pH CO2(aq ) + OH−aq ↔ HCO− (16)
> 10.5 and 6.5 < pH < 10.5, respectively.95 Lastly, Ca ( ) 3 (aq )

ions from the dissolution of Ca(OH)2 will react with HCO−

3 (aq )
+ OH−aq ↔ H2 O(l) + CO2− (17)
CO3 2– to form CaCO3 . This reaction is as follows: ( ) 3 (aq )

Thus, giving the net reaction during the initial stage

Ca2+ + CO2− ↔ CaCO3(s) (13) of overall CO2 absorption can be expressed as:
(aq ) 3 (aq )
2NaOH(aq ) + CO2(g ) → Na2 CO3(aq ) + H2 O(l) (18)
The experiment conducted by Han et al.95 on CO2
Given that Na2 CO3 is produced, it exists as Na+ and
capture capability of Ca(OH)2 shows the absorption
CO3 2– ions in the system. As CO2 is continuously fed
capacity of Ca(OH)2 ranges from 1 to 3.05 g CO2 /g
into the system, CO2 is continuously absorbed and
Ca(OH)2 .L, the average absorption efficiency ranges
reacts with Na2 CO3 to form NaHCO3 as shown:
from 11.83 to 19% and has an approximate absorption
rate of 0.69 to 1.07 g CO2 /min. These data are highly Na2 CO3(aq ) + CO2(g ) + H2 O(l) → 2NaHCO3(aq )
dependent on the pH of the system and the amount of
Ca(OH)2 added. (19)
Yoo et al.104 experimented to investigate the CO2
Sodium hydroxide (NaOH) capture efficiency of NaOH at varying wt.%. In this
The usage of NaOH for CO2 absorption has been study, an NaOH system with a concentration of 1 to 5
studied intensively for the past 80 years. However, the wt.% was used to capture a gas mixture with 31.5 vol.%
majority of the studies conducted were focused on CO2 in a Pyrex reactor set-up. The obtained results
academic endeavours such as absorption mechanisms show that as NaOH wt.% increases from 1 to 5%, the
and system performance rather than on CO2 CO2 capture efficiency also increases from 35.73 to
capture.102,103 NaOH has an excellent CO2 absorption 57.99%. It was deduced by the investigator that the
capacity which is higher than that of MEA absorbent. CO2 capture efficiency in a NaOH system is highly
Yoo et al.104 stated that the theoretical absorption dependent on the concentration of the solvent.
capacity of NaOH is 1.11 tons CO2 /ton NaOH while In another study conducted by Kordylewski et al.,106
MEA is approximately 0.72 tons CO2 /ton MEA. In an NaOH system with a concentration of 0–50% was
addition, NaOH is also more abundant and implemented to capture a gas mixture with a 15 vol.%
inexpensive as compared to MEA.104 CO2 in a Dreschel washer set-up. The results obtained
However, NaOH cannot be easily regenerated due to from their experimental work show that the CO2
the formation of NaHCO3 when reacted with CO2 . removal efficiency increases from approximately 2% in
Due to its high solubility in an aqueous solution and its a 0 % NaOH system up to 92% in a 50% NaOH system.
decomposed product, Na2 CO3 . Na2 CO3 is a thermally The results agree with the deduction and the result
stable compound that can be decomposed to Na2 O, at a obtained by Yoo et al.104 . Apart from that, the effect of
temperature of over 800◦ C.105 Na2 O as a direct source temperature on the CO2 capture efficiency of the
of NaOH can be mixed with water to obtain the latter NaOH system was also investigated. From the result, it
compound.104 was shown that by increasing the absorption

© 2022 The Authors. Greenhouse Gases: Science and Technology published by Society of Chemical Industry and John Wiley & Sons Ltd.
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Chai et al.

temperature from 25 to 61.5◦ C, the overall CO2 capture form aqueous CO2 , hydration of CO2 to form carbonic
efficiency can be improved by approximately 5–20%. It acid (H2 CO3 ) and absorption of H2 CO3 by limestone
was also stated that after the formation of Na2 CO3 post to produce calcium bicarbonate. These reactions are as
absorption by NaOH, the carbonate can still capture shown:
CO2 to form NaHCO3 but with relatively low CO2
CO2(g ) → CO2(aq ) (20)
capture efficiency of 4–5%.
Additional hydroxide absorbent includes potassium CO2(aq ) + H2 O(l) → H2 CO3(aq ) (21)
hydroxide (KOH). However, the research on KOH is
limited to its CO2 performance data as a detailed H2 CO3(aq ) + CaCO3(s) → Ca2+ + 2HCO− (22)
(aq ) 3 (aq )
description of its CO2 capture mechanisms is not
available like Ca(OH)2 and NaOH.107,108 The overall net reaction is as presented:
CO2(g ) + CaCO3(s) + H2 O(l) (23)
Carbonate absorbent
→ Ca2+ + 2HCO− (23)
Calcium carbonate (aq ) 3 (aq )

The utilization of CaCO3 absorbent is typically Currently, the largest operating AWL reactor can be
incorporated in a process called accelerated weathering found at a coal-fired power plant in Wilhelmshaven,
of limestone (AWL). AWL process is the enhanced Germany.112 In this industrial-scale study led by
version of the naturally occurring carbonate Kirchner et al.112 , a multi-column absorption set-up
weathering process, which is an extremely slow was applied for CO2 capture from flue gas with 10–12
process. AWL can accelerate the speed of the process vol.% CO2 . The reported CO2 capture efficiency of this
due to the higher CO2 concentration of flue gas post-combustion AWL application is 55% and it was
compared to atmospheric air.109 This process is reported that the effluent produced has a fivefold
well-known for its economically and environmentally increase in alkalinity (10 mM total alkalinity)
friendly characteristics. Rau et al.110 stated that the compared to a precombustion AWL application (2 mM
CO2 mitigation cost offered by AWL could be as low as total alkalinity). This indicated that limestone is
$3 to $4/ tonne CO2 as the cost for both its main successfully weathered and long-term storage of
material, namely limestone and seawater are either capture CO2 is achievable. Apart from that, no harmful
extremely low or negligible. For its environmental substances (NOx, SOx and heavy metals) were detected
perk, the discharge of calcium bicarbonate effluent in the effluents. Thus, the disposal of effluent into the
produced via AWL can help combat the ocean’s ocean is considered safe.
acidification problem.109,111 However, it was reported
by Kircher109 that about 50% of the captured CO2 in Sodium carbonate
the effluent disposed into the ocean can re-enter the Na2 CO3 is an ideal absorbent for CO2 capture in terms
atmosphere which thus reduces the overall CO2 of environmental consideration as it is non-hazardous,
capture efficiency of this system. To overcome this, it non-volatile and can act as a multi-pollutant capture
was recommended that a suitable discharge site and system. Also, it poses a low equipment corrosion rate
optimal size of waste stream need to be determined and will not cause fouling to the piping system. It was
prior to disposal of effluent into the ocean. also reported by Barzagli et al.114 that aqueous Na2 CO3
Apart from that, the large commercialization of AWL possesses a relatively high CO2 absorption efficiency of
system for CO2 capture is limited by its requirement to 80%.
be built near coastlines. The purpose of setting AWL However, Na2 CO3 is not feasible due to its economic
system near the coastline is for easier access to seawater drawback. Sprigarelli et al.31 and Valluri et al.115 state
and disposal of calcium bicarbonate effluent into the that Na2 CO3 has a low CO2 absorption rate due to its
ocean.12 The CO2 capture efficiency of this system was low physical mass transfer rate leading to a higher
reported to be as high as 97% in a lab-scale operation absorption tower requirement. To overcome this
but will be significantly reduced to < 20% for problem, several studies focused on improving
application in small industrial processes.112,113 The Na2 CO3 CO2 absorption rate by adding additives such
AWL process CO2 capture mechanisms can be divided as sucrose, PZ, DEA, MEA and hypochloride. These
into three steps: dissolving of gaseous CO2 in water to additives were proven to be able to improve the

© 2022 The Authors. Greenhouse Gases: Science and Technology published by Society of Chemical Industry and John Wiley & Sons Ltd.
404 Greenhouse. Gas. Sci. Technol. 12:394–427 (2022); DOI: 10.1002/ghg.2151
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Review of carbon capture absorbents for CO2 utilization

absorption rate. However, the blended additives will bubbles to be produced. This, can in turn, help to
further increase the already high regeneration energy increase the contact area of the gas and liquid leading
of Na2 CO3 which is approximately 3.2 MJ/kg CO2 . to a better mass transfer. For the regeneration
Thus, increasing the overall operating cost and performance of the Na2 CO3 -DF200 system, it was
resulting in a negligible effort on the economic determined that heat of 3.18 MJ/kg CO2 is required to
saving.31 regenerate the absorbent. It was deduced that the
The CO2 capture mechanisms and precipitation of addition of frothers has a negligible impact on the
NaHCO3 via aqueous Na2 CO3 is as follows: regeneration energy requirement due to its extremely
low concentration. All in all, the regeneration energy
CO2−
3 (aq )
+ H2 O(l) + CO2(g ) → 2HCO−
3 (aq )
(24) required for this system is approximately 24.2% lower
compared to a typical MEA system.
Na+aq + HCO− ↔ NaHCO3(s) (25)
( ) 3 (aq )
Potassium carbonate
From a reaction simulation conducted by Sprigarelli Aqueous K2 CO3 has gained interest as an absorbent
et al.,31 the theoretical CO2 absorption capacity of due to its various advantageous features such as low
Na2 CO3 is approximately 0.73 kg CO2 /kg CO3 2– which cost, low toxicity, high degradation resistance and low
is higher than that of a typical MEA system of 0.40 kg enthalpy requirements. However, two disadvantages
CO2 /kg MEA. This CO2 absorption capacity is that limit its applications for CO2 capture are its
expected to decrease in the presence of impurities such intensive regeneration energy and low mass transfer
as SOx and NOx but Na2 CO3 acts as a multi-pollutant rate. It was reported that the energy required for
control system. K2 CO3 regeneration ranges from 87.1 to 143
In 2021, Valluri and Kawatra115 presented a study on kJ/mol.116,117 Apart from that, the application of
post-combustion CO2 capture with dilute sodium K2 CO3 in CO2 capture is typically coupled with a
carbonate slurry. In this study, the absorption and promoter to make up for its low mass transfer rate.32
desorption performance of the Na2 CO3 slurry system Based on the experiment conducted by Sreedhar
was investigated. In this mini-pilot scale study, an et al.32 and Plaza et al.,118 up to 9 promoters comprised
absorber packed with polypropylene pall rings is used of MDEA, MEA, DEA, glycine, carbonic anhydrase
to capture CO2 (16 vol.% CO2 ) using Na2 CO3 slurry at CA, PZ, arginine, sarcosine and proline were tested
a temperature and pressure of 31 to 38.5◦ C and 1 bar, with K2 CO3 . With these promoters, the absorption rate
respectively. The resulting NaHCO3 solution was sent of K2 CO3 can be enhanced 45-fold as compared to
to a flash drum to undergo regeneration (at 98◦ C and 2 unpromoted K2 CO3 while exhibiting excellent
bar) of Na2 CO3 for further CO2 capture and separation absorption efficiency of 80 to 99.4%. However, the
of pure CO2 for storage. Based on the results, it was addition of these promoters has its drawbacks such as
shown that the CO2 capture efficiency of Na2 CO3 possible losses through evaporation, which can cause
(40%) is far inferior to the efficiency of an MEA and degradation and corrosion to downstream
NaOH system of approximately 95%. It was observed equipment.32 The CO2 capture mechanisms in a
that as the solvent concentration of the respective PZ-promoted K2 CO3 system focus on the reaction
systems increases from 0.1 to 0.2 M, the CO2 capture interaction of PZ rather than K2 CO3 .118 The CO2
efficiency of Na2 CO3 increases to 55.6% while the MEA capture mechanisms are as follows:
and NaOH only have a 2% increase in their efficiency.
However, the CO2 capture efficiency of Na2 CO3 is still
inferior. Therefore, to overcome this, Valluri and PZ + CO2
Kawatra115 added a frother namely DF200 into the ⎧ k
Na2 CO3 system to enhance its CO2 capture efficiency. ⎪
⎪ − PZ−OH−
↔ PZCOO− + H2 O
⎪OH
⎪
With the addition of as little as 10 ppm of DF200, the ⎪
⎪ k
⎪ PZ−H2 O
−
CO2 capture efficiency of Na2 CO3 was enhanced to ⎨H2 O ↔ PZCOO + H3 O
⎪
k
99.90% which is approximately 2.9% higher compared ↔ PZCOO− + PZH+
+ PZ PZ−PZ (26)
⎪
⎪
to the 0.2 M MEA and NaOH systems. The added ⎪
⎪
kPZ−CO2−
⎪
⎪CO2− ↔ PZCOO− + HCO−
3

frothers helps to modify the bubble surface of the ⎪

⎪ 3 3
⎩ k
− PZ−PZCOO−
absorbent which allows smaller and more uniform PZCOO ↔ PZCOO + H+ PZCOO−
−

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Chai et al.

PZCOO− + CO2 this subsection only highlights some of the recent

⎧ development of different hybrid absorbents.
⎪
⎪
kPZCOO− −H2 O
One popular absorbent system developed is the
⎪
⎪H 2 O ↔ PZ(COO− )2 + H3 O
⎪
⎪ hybrid of alkanolamines and ILs.125,126,128–131 In 2021,
⎨PZ PZCOO
k − −PZ
↔ PZ(COO− )2 + PZH+
+ (27) Damanafshan et al.129 analyzed the carbon capture
⎪
⎪
kPZCOO− −CO2−
− − performance of an aqueous MDEA and [Omin][BF4 ]
⎪
⎪CO3
2−
↔
3
PZ(COO )2 + HCO3
⎪
⎪ IL blend. It was reported that the blended absorbent
⎩ kPZCOO− −PZOO−
PZCOO− ↔ PZ(COO− )2 + H+ PZCOO− can enhance CO2 absorption capacity of approximately
0.05 to 2 mol CO2 /mol amine compared to a typical
Bohloul et al.119 have also conducted a study that MDEA solution. In this system, the sole chemical
aims to investigate the effect of temperature (313.15 to reaction that occurred is MDEA with CO2 to form
333.15 K), pressure (0 to 1.2 MPa) and concentration of bicarbonate while the IL ([Omin][BF4 ]) only interacts
K2 CO3 (15 to 30 wt.%) have on the CO2 absorbability physically with CO2 . Although no data were presented
of K2 CO3 . The CO2 absorption setup is an absorption on the handling of the post-absorption product,
cell filled with K2 CO3 solutions to absorb a gas stream bicarbonates can be potentially utilized to produce
with pure CO2 . It was observed from the experimental construction material following the chemical reaction
result that as temperature increases there is a sharp shown by Reaction 28 instead of proceeding with the
drop in CO2 loading of K2 CO3 as much as 0.46 mol typical regeneration pathway for an amine absorbent.
CO2 /mol K2 CO3 whereas as pressure increases, CO2
loading can be increased by as much as 0.57 mol CaO + Ca(HCO3 )2 → 2CaCO3 + H2 O (28)
CO2 /mol K2 CO3 . Other than that, it was also shown
that the 20 wt.% K2 CO3 system has shown the highest Other than that, the development of non-aqueous
CO2 loading among the proposed concentration. The amine solvents is also a promising alternative to be
optimized conditions deduced from this study were investigated. The application of non-aqueous amines is
313.15 K, 1 MPa and 20 wt.% K2 CO3 gives a peaked incredibly limited in the carbon capture industry.
CO2 loading of 1.25 mol CO2 /mol K2 CO3 , which is However, their reported properties are promising for
approximately 2.5 times higher than the CO2 loading CO2 capture application.132,133 The non-aqueous amine
of a conventional MEA system. is used as a replacement of water with organic
compounds (i.e., ethylene glycol [MEG] and
Hybrid/novel absorbent triethylene glycol [TEG]) during the preparation of
From subsections Amine based absorbent–Carbonate amines solvent. This replacement leads to lower water
absorbent, several absorbents have been identified for content in a non-aqueous amine system compared to a
the CO2 capture and utilization system. Although all typical aqueous amine system. The CO2 capture
the absorbents present plausible CO2 capture and reaction can be redirected towards a less stable
utilization capabilities, some of their applications are carbonate species with the reduced water content,
restricted by severe limitations. These include toxicity resulting in a lower regeneration temperature.133 This
of amine absorbents group and ILs, low CO2 capture would not only reduce the regeneration energy
absorption rate for MDEA, limited application data of requirement but can also curb the degradation and
carbonate absorbents in CO2 capture, limited direct evaporation of solvent while lowering the corrosion
utilization option of hydroxide absorbents and CaCO3, rate imposed on operational infrastructure.133 From a
and uncertainty on the post-absorption product by study conducted by Tan et al.,134 a non-aqueous amine
amino acid salts.65,107,120–123 To resolve these (MEA + TEG) solvent was employed for CO2 capture.
limitations, researchers have ventured into synthesizing This study shows that the replacement of water with
novel absorbents via hybrid mixing and incorporating TEG in the preparation of the amine solvent reduces
promoters or enhancers into CO2 capture the regeneration energy consumption of a typical MEA
systems.32,38,65,66,83,118,124–126 The purpose of these system from 4.20 to 1.99 MJ/kg CO2 . Apart from that,
initiatives is to combine the advantages of the different the non-aqueous amine system with 0.5 M MEA
absorbents to enhance their CO2 capture performance retained a similar CO2 loading of approximately 0.50
and overcome their limitations.89,127 As numerous mol CO2 /mol MEA compared to an aqueous 0.5 M
hybrid absorbents are being proposed over the years, MEA system.

© 2022 The Authors. Greenhouse Gases: Science and Technology published by Society of Chemical Industry and John Wiley & Sons Ltd.
406 Greenhouse. Gas. Sci. Technol. 12:394–427 (2022); DOI: 10.1002/ghg.2151
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Review of carbon capture absorbents for CO2 utilization

Table 3. CO2 capture performance of consumption is only at 3.83 GJ/ton CO2 which is
NaADS/PZ/DETA and typical MEA system.127 approximately 0.37 GJ/ton CO2 lower than a typical
MEA system. This is mainly due to the lower vapor
CO2 capture NaADS/PZ/ 30 wt.% Surplus
pressure and specific heat capacity of NaADS. All in all,
performance DETA MEA it is proven by these researchers that the synthesis of
CO2 loading, mol 0.48 to 0.74 0.31 to 0.48 0.34 to 0.41
novel absorbents is an essential initiative to foster a
CO2 /mol sovent more sustainable absorption process. However, as
CO2 capture 57.10 70.20 13.1 highlighted by Budzianowski et al.,135 the utilization
efficiency, % potential of these novel absorbents has not been
CO2 capture rate, 3.79 4.66 0.87 evaluated which can withhold its potential to develop a
CO2 /min sustainable carbon capture process.

In another study conducted by Xiao et al.,130 the Comparison of CO2 chemical absorption
performance of hybrid absorbents which incorporate absorbents
MEA and IL; and MDEA and IL were analyzed. The Based on the chemical absorbents for CO2 capture
incorporation of MEA into a [Bmim]BF4 system presented from subsections Amine based absorbents to
enhanced its CO2 loading from approximately 0.02 to Hybrids/novel absorbent a summary and comparison
0.12 g CO2 /g absorbent (about a fivefold increment). are provided in this subsection. Table 4 indicates that
For MDEA and [Bmim]BF4 system, an increment of most aqueous amine absorbents possess relatively
2.5 times in CO2 loading was observed. Apart from higher CO2 removal efficiency (80–90%). In addition, a
that, the regeneration of such hybrid absorbent was descending trend in the CO2 absorption rate and
more energy-efficient than a conventional MEA regeneration energy requirement of amines can be
system. Generally, the desorption temperature required observed starting from primary amines followed by
for the hybrid system is lower at 353 K compared to the secondary and tertiary amines. As shown in Table 4,
369 K required by a conventional MEA system. Herein, primary amines are typically associated with the
it is shown that the post-absorption product will highest CO2 absorption rate and regeneration energy
undergo desorption to regenerate the absorbent and followed by secondary and tertiary amines. The
separate the captured CO2 . Therefore, it is deduced unfavourable properties of amines are their inferior
that the separated CO2 can be used as a potential CO2 capture capacity as compared to some hydroxide
feedstock for industrial applications. absorbents (i.e., Ca(OH)2 ) and amino acid solutions
Besides the typical IL and amine hybrid, Chen et (i.e., Arginine, 4-(2-Aminoethyl)piperazine-1-yl acetic
al.127 have also proposed mixing amino acid salt with acid and 3-(2,5-Dimethylpiperazine-1-yl) propanoic
amines. Sodium aliphatic diamine sulphonate acid).
(NaADS) was used as a suitable amino acid salt for For ionic liquid absorbents, their CO2 capture
hybrid mixing with PZ and diethyenetriamine (DETA). capabilities are inferior compared to other chemical
The mixing ratio of PZ/DETA/NaADS of 15/15/10 absorbents. However, the standout point of ionic
wt.% was used and the CO2 capture performance of liquids is their high designability, ease of regeneration
this hybrid solvent was evaluated using a two rotating and eco-friendliness. The flexible designability of ionic
packed bed set-up. From the reported results, a 30 wt.% liquids allows them to alter their physical and chemical
unblended NaADS only shows a CO2 loading and CO2 properties to cater to a specific application. This opens
capture efficiency of approximately 0.74 mol CO2 /mol up a wide range of applications of ionic liquids for CO2
NaADS and 37.5 %, respectively. With the addition of capture purposes. For the regeneration of ionic liquids,
PZ and DETA, these values were enhanced to 0.89 mol it was reported that the energy required is only 172.26
CO2 /mol solvent (i.e., 20.3%) and 70.2% (i.e., 87.2 %), kW which is significantly lower than that of MEA
respectively. As a comparison, Table 3 shows the CO2 (393.75 kW) regeneration process. They are also
capture performance of the hybrid solvent as compared inflammable and non-volatile making them
to a typical MEA system. Apart from that, the proposed environmentally friendly.
solvent also has an upper hand on the regeneration On the other hand, amino acid solutions have a high
performance as the reported regeneration energy average CO2 capture capacity (> 1 mol CO2 /mol

© 2022 The Authors. Greenhouse Gases: Science and Technology published by Society of Chemical Industry and John Wiley & Sons Ltd.
Greenhouse. Gas. Sci. Technol. 12:394–427 (2022); DOI: 10.1002/ghg.2151 407
408
Table 4. Summary of CO2 capture absorbents.

Absorption performance Regeneration performance

Capacity, mol Removal Rate, Post- Regeneration energy CO2 Post-

Absorbents CO2 /mol Efficiency, mol absorption requirement, MJ/kg purity, regeneration
(Concentration) absorbent % CO2 /hr product CO2 % product Handling modes Sources
Amine-based absorbent
MEA (30–40 wt.%) 0.35–0.56 80 – 100 7.35 r RNHCOO– 3.80–4.20 99 r After r Regeneration at 2, 31, 32, 36,
regeneration will 70–200◦ C to 39, 41, 52,
obtain its regenerate 64–66
respective amine respective
absorbents and absorbents
CO2 r Utilization of
separated CO2 in
food and beverage
industry, and urea
production
DGA (8–27 wt.%) − 88–90 − • − − • • 39
1A2P (0.15 mol) − 88.4 − • − − • • 74

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2A1B (0.15 mol) − 87.1 − • − − • •
DEA (30 wt.%) 0.50 82–90 4.15 1.57 − • 52, 64, 72
MMEA (0.15 mol) − 88.9 − − − • 74
EMEA (0.15 mol) − 85.9 − − − •
TBMEA (0.15 mol) − 56.3 − − − •
MDEA (30 wt.%) 1 80 – 99 2.13 r R1 R2 R3 N+ -H 0.61–1.34 − • 2, 32, 64, 65, 72, 80
r HCO3 –
DMMEA (0.15 mol) − 40.8 − • − − • 74
DEAE (30 wt.%) 0.46–0.61 − − • 1.42 − • 66
Ionic liquid (ILs) absorbent
[Bmin][BF4 ] 0.44 − − r CH3 NO2 2.63–2.80 − − − 2, 57, 59, 83,
r CH2 NO2 – 91, 153
r HCO3 –
r Carbonate

© 2022 The Authors. Greenhouse Gases: Science and Technology published by Society of Chemical Industry and John Wiley & Sons Ltd.
salts
[Bmim][PF6 ] 0.51 − − • 2.70 − − −
[Bmim][Tf2 N] 0.68 − − • 1.19 − − −

(Continued)
Chai et al.

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 Table 4. (Continued).

Absorption performance Regeneration performance

Capacity, mol Removal Rate, Post- Regeneration energy CO2 Post-

Absorbents CO2 /mol Efficiency, mol absorption requirement, MJ/kg purity, regeneration
(Concentration) absorbent % CO2 /hr product CO2 % product Handling modes Sources
Bis(2-hydroxyethyl)- 0.04–0.11 − − • − − − −
ammonium
acetate
N-Butyl-4- 0.01–0.11 − − • − − − −
methylpyridinium
tetrafluoroborate-
MeBuPy
Review of carbon capture absorbents for CO2 utilization

N-Butyl-4- 0.06–0.1 − − • − − − −
Methylpyridinium
thiocyanate-

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MeBuPy
AMPim[NTf2] 0.18–0.27 − − • − − − −
APMim[BF4] 0.32–0.36 − − • − − − −
Amino acid absorbent
Natural amino acid 92, 122,
159–161
Taurine (1 M) 0.52–1.1 − − r Protonated − − r If undergo r Precipitates depend
amino acid regeneration will on the type of amino
r Bicarbonate obtain the acid salt utilized, if
salt of amino respective precipitates are
acid absorbent and desired product, a
r Carbamate CO2 desorption process
is not required
r If precipitates are
not desired, can opt
for regeneration to

© 2022 The Authors. Greenhouse Gases: Science and Technology published by Society of Chemical Industry and John Wiley & Sons Ltd.
regenerate
absorbents
Proline (1 M) 0.45–0.89 − − • − −
Arginine (1 M) 0.80–1.7 − − • − −
Glycine (1 M) 0.50–0.70 − − • − −

(Continued)

409
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410
Table 4. (Continued).

Absorption performance Regeneration performance

Capacity, mol Removal Rate, Post- Regeneration energy CO2 Post-

Absorbents CO2 /mol Efficiency, mol absorption requirement, MJ/kg purity, regeneration
(Concentration) absorbent % CO2 /hr product CO2 % product Handling modes Sources
Non-natural amino acid
Potassium 0.40–0.55 − − r Protonated 7–12 − r If undergo r Precipitates depend
sarcosine (4 M) amino acid regeneration will on the type of amino
r Bicarbonate obtain the acid salt utilized, if
salt of amino respective precipitates are
acid absorbent and desired product, a
CO2 desorption process
is not required
r If precipitates are
not desired, can opt
for regeneration to
regenerate
absorbents

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2-(Pyrimidin-2- 0.26–1.08 − − • − −
ylamino) acetic
acid (1 M)
[4-(2-Aminoethyl) 1.11–1.86 − − • − −
piperazin-1-yl]
acetic acid (1 M)
3-(2,5- 1.13–2.23 − − • − −
Dimethylpiperazin-
1-yl) propanoic
acid (1 M)
Sodium β-alaninate 0.353–1.864 − − • − − 93
(10–30 wt.%)
Trisodium 0.027–0.05 − − • − −
phosphate (1–2.5
M)
Potassium taurinate 0.057–1.097 − − • − −

© 2022 The Authors. Greenhouse Gases: Science and Technology published by Society of Chemical Industry and John Wiley & Sons Ltd.
(2 –6 M)
Potassium 0.092–0.753 − − • − −
threonate (1 M)

(Continued)
Chai et al.

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 Table 4. (Continued).

Absorption performance Regeneration performance

Capacity, mol Removal Rate, Post- Regeneration energy CO2 Post-

Absorbents CO2 /mol Efficiency, mol absorption requirement, MJ/kg purity, regeneration
(Concentration) absorbent % CO2 /hr product CO2 % product Handling modes Sources
Hydroxide absorbent
Ca(OH)2 (1–5 wt.%) 2.02–5.13 3–32.17 0.94–1.46 r CaCO3 4.07 − r If opt for r Direct utilization to 95, 98, 99,
regeneration will produce 180
obtain CaO and construction
CO2 materials
r If opt for
regeneration,
Review of carbon capture absorbents for CO2 utilization

CaCO3 will be
decomposed at
approximately 650

Greenhouse. Gas. Sci. Technol. 12:394–427 (2022); DOI: 10.1002/ghg.2151

to 765◦ C to obtain
CaO, a direct
source of Ca(OH)2
NaOH (1–5 wt.%) Experimental: 46.57–66 − r NaHCO3 Decomposition of − r If opt for r Stored as NaHCO3 2, 104, 181,
0.0019– NaHCO3 to Na2 CO3 : regeneration will and not preferable 182
0.0020Theoretical: 1.95 obtain Na2 CO3 , to undergo
0.5–1 Decomposition of Na2 O, CO2 and regeneration
Na2 CO3 to Na2 O: H2 O process due to
4.09 – 5.07 formation of
Na2 CO3
r If opt for
regeneration,
NaHCO3 will be
decomposed at
160◦ C to obtain
Na2 CO3 and a
second

© 2022 The Authors. Greenhouse Gases: Science and Technology published by Society of Chemical Industry and John Wiley & Sons Ltd.
decomposition at
800◦ C to
edcompose
Na2 CO3 to obtain
Na2 O, a direct
source of NaOH

(Continued)

411
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412
Table 4. (Continued).

Absorption performance Regeneration performance

Capacity, mol Removal Rate, Post- Regeneration energy CO2 Post-

Absorbents CO2 /mol Efficiency, mol absorption requirement, MJ/kg purity, regeneration
(Concentration) absorbent % CO2 /hr product CO2 % product Handling modes Sources
KOH (0.5 M) − 56 − r K2 CO3 6.82 − r If opt for r Direct utilization to 107, 158,
regeneration will produce 183, 184
obtain K2 O and construction
CO2 materials
r If opt for
regeneration,
K2 CO3 will be
decomposed at >
899◦ C to obtain
K2 O, a direct source
of KOH
Carbonate absorbent

Greenhouse. Gas. Sci. Technol. 12:394–427 (2022); DOI: 10.1002/ghg.2151

K2 CO3 (20–40 0.7–1.05 60–99.4 − r KHCO3 1.98–3.25 − r K2 CO3 r Regeneration at 32, 118, 145,
wt.%) r H2 O 100–200◦ C to 146, 185,
r CO2 decompose KHCO3 186
back to K2 CO3
r Utilization of
separated CO2 for
dry ice production
CaCO3 (11.5 wt.%) 0.91–1 49.64–97 − r Ca(HCO3 )2 − − r Do not undergo r Disposed to ocean 109, 113,
regeneration to combat ocean 123
process acidification
Na2 CO3 (30 wt.%) 1 90 − r NaHCO3 3.2 − r Na2 CO3 r Regeneration at 31, 145, 146
r H2 O 120–160◦ C to
r CO2 decompose
NaHCO3 back to
Na2 CO3
r Utilization of
separated CO2 for

© 2022 The Authors. Greenhouse Gases: Science and Technology published by Society of Chemical Industry and John Wiley & Sons Ltd.
dry ice production

(Continued)
Chai et al.

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 Table 4. (Continued).

Absorption performance Regeneration performance

Capacity, mol Removal Rate, Post- Regeneration energy CO2 Post-

Review of carbon capture absorbents for CO2 utilization

Absorbents CO2 /mol Efficiency, mol absorption requirement, MJ/kg purity, regeneration
(Concentration) absorbent % CO2 /hr product CO2 % product Handling modes Sources
Hybrid/Novel Absorbent

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MDEA/[Omin][BF4] 0.91–1.32 − − r R1 R2 R3 N+ -H − − − − 129
(30–50 r HCO3 –
wt.%/5–20 wt.%)
MEA/TEG (0.1–2 0.20–0.80 − − r RNHCOO– Only the regeneration − r After r Regeneration at
M/-) energy requirement regeneration will 80◦ C to regenerate
for the 0.5 M obtain its respective
MEA/TEG system respective amine absorbents
was reported to be absorbents and
1.99 MJ/kg CO2 CO2
MEA/[Bmim]BF4] 0.12 − − r RNHCOO– − − − − 130
(30/70 wt.%)
MDEA/[Bmim][BF4] 0.05 − − r R1 R2 R3 N+ -H − − − −
(30/70 wt.%) r HCO3 –
NaADS/PZ/DETA 0.89 70.2 − − 3.83 − − − 127
(15/15/10 wt.%)

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413
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Chai et al.

amino acid) compared to the other absorbent groups. Absorbents evaluation

Nevertheless, the desorption process harms the CO2
absorption capacity of regenerated amino acids. As This section evaluates absorbents based on their
discussed under amino acid solution subsection, the handling method after CO2 capture. This evaluation
absorption capacity of most amino acids is halved after aims to separate chemical absorbents into two groups
regeneration. In addition, the regeneration energy based on their suitability for CO2 utilization after a
requirement for amino acid solutions varies greatly desorption process (conversion of separated CO2 ) or
depending on the amino acid utilized. For example, for straight after CO2 absorption (direct utilization of
non-natural amino acids such as potassium sarcosine, CO2 ). After the absorption of CO2 , the CO2 -rich
its regeneration energy requirement can be as high as absorbents will typically undergo a desorption process
12 MJ/kg CO2 while Zhang et al.93 reported that to regenerate their absorbent and separate the absorbed
sterically hindered amino acids such as N-cyclohexyl CO2 for further utilization. These include the
1,3-propanediamine possess a lower regeneration utilization of CO2 as chemical feedstocks, enhanced oil
energy consumption.136 recovery (EOR), water treatment, production of fire
Based on Table 3, Ca(OH)2 exhibits superior CO2 retardants and mineral carbonation.137–140 In some
capture capacity (up to 5.13 mol CO2 /mol Ca(OH)2 ) studies, CO2 has been directly utilized to form CaCO3 ,
not only among hydroxide absorbents but also K2 CO3 and concrete for value-added re-purposing
including the other major absorbent groups as well. As without desorption.104,107,138,141 Apart from that, novel
a whole, hydroxide absorbents possess relatively low CO2 utilization pathways are also presented in this
CO2 capture efficiency (32.17–66%) and have a section. It is worth noting that the utilization of the
reasonably high regeneration energy requirement of aforementioned hybrid absorbents is not highlighted in
4.07 to 6.82 MJ/kg CO2 . Similar to hydroxide the following sections. This is because the maturity of
absorbents, carbonate absorbents also require high these absorbents is still in its infancy where their actual
energy (approximately 3.2 MJ/kg CO2 ) for their suitability and practicability for large-scale CO2
regeneration process. However, the CO2 capture capture application are yet to be tested.135 The
capacity (> 1 mol CO2 /mol carbonate) and efficiency utilization pathway is highlighted because
(> 90 %) of these absorbents are comparable to those incorporating CO2 utilization in a CO2 capture system
of typical aqueous amine absorbents. should be fundamental for carbon management. This
Although the CO2 capture capabilities of recently can allow the CO2 capture industry to overcome cost
developed novel or hybrid absorbents are not as feasible limitations and develop a sustainable process by
as the major absorbents, their capacity to enhance the producing value-added products via the utilization
standalone absorbent’s weakness is the main highlight pathway.139 Apart from that, a CCU system can also
of these absorbents. For example, in the hybrid/novel promote CO2 capture for large industrial CO2 emitters
absorbent subsection, the low absorption capacity of an that are not accessible to a proper geological CO2
ionic liquid namely [Bmim]BF4 was drastically storage which is a must for typical CCS systems.142 As
enhanced with the blending of MEA and MDEA. In the possible leakage of CO2 from geological storage is
this case, the CO2 loading of the blended absorbent of also a concern within the carbon capture industry,143
MEA + [Bmim]BF4 (0.12 g CO2 /g absorbent) is higher the application of CCU can also subside this concern.
than that of a standalone [Bmim]BF4 absorbent (0.02 g
CO2 /g absorbent). However, the CO2 loading of the Potential CO2 capture absorbents for CO2
blended absorbent is lower as compared to a utilization after desorption
standalone aqueous MEA solution (0.25 to 0.40 kg This subsection discusses suitable absorbents for CO2
CO2 /kg MEA). The advantageous trade-off for the utilization after undergoing desorption. Typically, CO2
amine side is the eco-friendly features of ionic liquid. absorbed via carbon capture and utilization (CCU)
Therefore, the blending of different chemical technologies will undergo a desorption process to
absorbents is not only to achieve superior CO2 capture regenerate the utilized absorbent and separate the CO2
capabilities (i.e., CO2 capture efficiency, rate, and for utilization as a chemical feedstock to produce
capacity) but is to achieve a well-rounded quality value-added products, supercritical extraction solvent
of an ideal absorbent as stated in the Intorduction. for separation purposes, in EOR or replacement of

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414 Greenhouse. Gas. Sci. Technol. 12:394–427 (2022); DOI: 10.1002/ghg.2151
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Review of carbon capture absorbents for CO2 utilization

hazardous substance as an alternative Next, is the ILs absorbent group. Based on Table 4,
medium.138,139,144 Thus, making absorbents with high the CO2 absorption capacity of ILs is highly dependent
absorption capacity and low regeneration energy on their preparation process. The flexible designability
requirement plausible candidates for this criterion.32 of ILs plays an important role in their CO2 utilization
The most practical absorbents for industrial ability. As mentioned under the Comparison of CO2
application are amine absorbents. After CO2 chemical absorption absorbents section, ILs can alter
absorption, CO2 -rich amine absorbents will undergo their chemical and physical properties to fit a specific
desorption to regenerate back the absorbent while application. This is the same for the case of CO2
separating CO2 into a CO2 -rich stream.2,31 Separated utilization, where specific ILs with high CO2 capture
CO2 from amine-based absorbents has been utilized in capacity and low regeneration energy can be developed
the food and beverage industry, urea production and to fit this purpose. However, the development of novel
EOR operations.31,60 MEA is the prime candidate in ILs with desired properties can be extremely complex
terms of commercialization potential as it is backed up and expensive which thus, hinders large-scale
by proven technologies and has been commercialized, application.83,89,120 In addition, even though certain ILs
unlike the other amine absorbents. Based on Table 4, can achieve high absorption capacity such as amino
MEA is also shown to be able to produce a nearly pure acid-based ILs, their preparation process is considered
CO2 (99%) stream after its desorption process which is to be unfriendly to the environment.89 It should also be
suitable as a chemical feedstock. However, MDEA also noted that data on the CO2 capture efficiency and CO2
possesses substantial potential as it has a relatively high absorption rate of ILs are relatively limited and the
CO2 absorption efficiency (99%) and requires the mechanisms of ILs with carbon capture are still
lowest energy (1.34 MJ/kg CO2 ) to be regenerated unclear.89,153 Nevertheless, ILs still present high
compared to the other amine absorbents.1 Other potential in the CCU sector but for ILs to fit into this
potential amines such as DEA and DEAE can also fit criterion, continuous research is required to develop
into this criterion due to their substantial CO2 capture novel ILs that can overcome the above-mentioned
capacity (0.46 to 0.61 mol CO2 /mol absorbent) and low limitations.58,89,120,154
regeneration energy requirement (1.42 to 1.57 MJ/kg Apart from the aforementioned past utilization of
CO2 ). Thus, MEA, MDEA, DEA and DEAE are desorbed CO2 , there are still numerous
plausible candidates for CO2 utilization after uncommercialized pathways that can be potentially
desorption. incorporated into future chemical absorption CCU
For the carbonate absorbents, CO2 absorbed by plants. Based on Alpher and Orhan,155 there are two
K2 CO3 and Na2 CO3 has been separated for dry ice groups of such pathways, namely emerging and applied
production in the early 1900s.145,146 Both K2 CO3 and R&D CO2 conversion technology. The emerging
Na2 CO3 are suitable candidates for this mode of CO2 technology refers to technologies that have been
utilization as they are easily regenerated at 100–200◦ C demonstrated at the plant level. Some of the modes of
and 120–160◦ C, respectively.31,147,148 For dry ice utilization include the production of CO2 -based
production, the separated CO2 stream will undergo a polymers, formic acid and fuels. For the applied R&D
two-stage cooling. First, the gas stream will be cooled technology, these are CO2 utilization methods that
down to remove water via condensation. The dried gas have been tested at a lab-scale level. The value-added
stream will then be further cooled down to −110◦ C for products that can be obtained from the offered
dry ice generation.149 The production of dry ice is an technologies are isocyanates, organic carbonates,
attractive CO2 utilization alternative due to its wide lactone and carboxylic acid. In addition, the utilization
range of usage in the modern era. Aside from its of CO2 for the cultivation of microalgae has attracted
application in dry ice blasting for cleaning purposes, increasing attention due to the economic and
dry ice has also been applied in creating entertainment environmental advantages it offers.156 In this
effects and even as insect anesthetics.150–152 Apart from cultivation process, separated CO2 can be directly fed
that, K2 CO3 and Na2 CO3 also possess applaudable into a biological media containing microalgae as a
CO2 absorption capacity compared to MEA as shown growth nutrient without chemical additives. The
in Table 4. Similar results can be seen comparing the microalgae would consume incoming CO2 and grow
CO2 absorption and regeneration energy requirement into a matured state. Once matured, the microalgae are
of both carbonate absorbents to MEA. converted into valuable products ranging from syngas,

© 2022 The Authors. Greenhouse Gases: Science and Technology published by Society of Chemical Industry and John Wiley & Sons Ltd.
Greenhouse. Gas. Sci. Technol. 12:394–427 (2022); DOI: 10.1002/ghg.2151 415
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Chai et al.

Figure 4. Process flow on CO2 utilization for microalgae cultivation.156

methane, hydrogen to bio-products (bio char, bio-oil, One of the well-known direct utilizations of waste
bio-crude, bio ethanol, etc.). The flow diagram for this CO2 is to produce construction materials. This mode
process is illustrated in Figure 4. of utilization has been an attention catcher due to its
All in all, MEA, MDEA, K2 CO3 and Na2 CO3 are various advantages, including its flexible usability of
some of the potential absorbents for this mode of produced solid carbonates, ability to permanently
utilization due to their high absorption capacity. Even sequestrate large quantities of CO2 via its carbonation
though, MEA requires high regeneration energy, its process, well-known carbonation mechanisms, and it is
application in the CO2 capture sector has been proven a thermodynamically favoured reaction.
in numerous industries. For K2 CO3 and Na2 CO3 , their Table 4 shows that the applicable absorbent for this
CO2 capture capabilities are comparable to MEA. utilization is the hydroxide absorbent group. The
However, MDEA might be the best choice for hydroxide absorbents include Ca(OH)2 , NaOH and
utilization after desorption as it not only possesses high KOH which can react with CO2 to form CaCO3 ,
CO2 absorption but also requires less energy for its NaHCO3 and K2 CO3, respectively. Although these
regeneration compared to MEA, K2 CO3 and Na2 CO3 . absorbents can be regenerated, it is still an unpreferred
For ILs to be a viable option, the stated limitations need alternative as the thermal decomposition of the
to be overcome. Apart from that, there is still produced carbonates requires high temperature,
tremendous potential for developing the utilization of ranging from 650 to > 899◦ C.99,104,158 This results in a
separated CO2 . high requirement of energy for the regeneration
process. Thus, highlighting that direct utilization after
Potential CO2 capture absorbents for absorption is the preferred pathway for hydroxide
direct CO2 utilization after absorption absorbent. CaCO3 has a wide span of utilization,
This subsection discusses absorbents that can directly ranging not only in the construction industries but also
utilize CO2 after their absorption. Direct utilization of in the pharmaceutical and cosmetics industries.141
CO2 after absorption is not a well-known pathway due Whereas the utilization of NaHCO3 is limited to
to its limited application. Nevertheless, it presents a replacing oxalic acid for rare earth precipitation. Based
distinctive advantage, where a desorption process is no on Ngu et al.,107 K2 CO3 was utilized to produce
longer required (lower energy consumption). It is construction material in a mixture of sand and
stated by Vega et al.157 that 50–80% of energy Ca(OH)2 . In this process, K2 CO3 reacts with Ca(OH)2
consumption for typical carbon capture operations to precipitate CaCO3 while regenerating KOH without
stems from the regeneration process. Therefore, any energy requirement. This utilization process is
removing a regeneration process can help converse a illustrated in Figure 5. It was suggested that the
large amount of energy thus saving cost.107 produced construction material can be applied to road

© 2022 The Authors. Greenhouse Gases: Science and Technology published by Society of Chemical Industry and John Wiley & Sons Ltd.
416 Greenhouse. Gas. Sci. Technol. 12:394–427 (2022); DOI: 10.1002/ghg.2151
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Review of carbon capture absorbents for CO2 utilization

Figure 5. Direct CO2 utilization process of KOH absorbent.107

construction and slab construction. Among the undergoing a desorption process due to their post-CO2
presented hydroxide absorbents, Ca(OH)2 is the most absorption products.159,160 However, opting for a
ideal candidate for direct utilization among the desorption process might not be preferable for amino
hydroxide absorbents due to its various mode of acid salts as its energy-intensive desorption process is a
utilization and excellent CO2 capture capacity of 1.68 concern for large-scale applications.160,161 Therefore,
to 5.13 mol CO2 /mol absorbent. direct utilization of CO2 is more feasible for amino acid
For carbonate absorbents, CaCO3 is the only salts. As shown in Table 4, amino acids can form a
applicable absorbent for direct CO2 utilization. This variety of products ranging from protonated amino
unconventional CO2 direct utilization was proposed by acids and bicarbonate salt of amino acids.160,161 The
Rau et al.123 via a process known as AWL that utilizes formation of these products depends on the type of
waste limestone (CaCO3 ) and seawater to absorb CO2 amino acid salts used and tailoring it to an application
to produce calcium bicarbonate solution. As presented where the product formed is desired, to promote direct
in Table 4, the theoretical CO2 capture efficiency can be utilization. Hence a preliminary analysis is required to
up to 97% and can be done at a reasonably low cost. select the exact amino acid salts for desired product
The suggested handling of calcium bicarbonate production when absorbing CO2 .122 To summarize, all
solution was disposing it into the ocean to combat stated hydroxide absorbents and CaCO3 can be
ocean acidification. However, this is only viable if the considered as potential absorbents for this mode of
forementioned process is carried out near coastal areas. utilization. All the mentioned absorbents show
To resolve this location restriction, calcium comparable results to MEA, proving their substantial
bicarbonate can be used to precipitate CaO to form CO2 capture capabilities. Although the direct
CaCO3 to produce construction materials as shown by utilization option mainly focuses on construction
Reaction 28. The process flow for this process is shown materials production, it does not directly result in a
in Figure 6. This boosts the potential of CaCO3 limited market for the produced products. This is
absorbent to be applied for direct CO2 because of the increasing growth rate of the
utilization. construction industry globally.162–165 As the
The amino acid solution group has been closely construction industry remains at a high growth rate,
compared to amine absorbents as both absorbent the marketability of construction materials will also
groups possess similar reaction mechanisms with CO2 increase over time. Thus, this utilization option can be
due to the identical amino-functional groups’ presence a potential pathway to develop a sustainable carbon
in their molecules.88 Amino acid solutions have the capture process especially in the construction
flexibility to opt for both utilization with or without industry.

© 2022 The Authors. Greenhouse Gases: Science and Technology published by Society of Chemical Industry and John Wiley & Sons Ltd.
Greenhouse. Gas. Sci. Technol. 12:394–427 (2022); DOI: 10.1002/ghg.2151 417
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Chai et al.

Figure 6. Direct CO2 utilization process by CaCO3 absorbent to produce building

block.

Challenges and future prospect of are important directions for future research to ensure
CO2 capture technology that it remains a relevant alternative to achieve climate
protection.
As developed nations have widely commercialized Apart from that, the numerous absorbents as
renewable energy technologies, the necessity for rapid discussed under Chemical absorption absorbent
growth by the CCS sector between 2020 to 2050 is section have shown substantial CO2 capture and
required to advance to the same progress level as in utilization capabilities; they are not ready yet for
renewable energies.166,167 Without being at an large-scale applications due to the lack of validation
equivalent level with renewable energy technologies, data in pilot plants.122 To note, lab-scale results may
they may obtain a more vigorous political course of vary once applied to a pilot plant or industrial plant.
promotion and development over the coming years. For example, Rau113 stated that CO2 capture efficiency
Their energy-saving potentials and gradual expansion via CaCO3 absorbent at lab scale can be as high as 97%.
would contribute to climate protection quicker than Still, this efficiency was significantly reduced to 21%
carbon capture technologies.168 Also, renewables might when applied to pilot plants or industrial plants.112,169
be a preferable option for investors due to the lower Thus, before large-scale applications, absorbents must
levelized electricity generation costs compared to CCS undergo pilot plant validation. Other than that,
power plant.167 These facts are especially important as research on the synthesis of novel absorbents via
continuous fundings play a crucial role in developing hybrid mixing has been one of the main focuses for the
and commercializing carbon capture technologies. future development of carbon capture technologies.
However, carbon capture technologies possess the However, most of the novel absorbents are still in their
upper hand to reduce existing greenhouse gases (GHG) infancy as most related research has only started in the
significantly. As stated by Viebahn et al.,168 if CCS can last 11 years.32,65,130,170,171 The majority of the current
be employed successfully, it would significantly reduce studies only focus on the absorption (i.e., CO2 loading
CO2 emission and present an opportunity to reach capacity and reaction rate) and desorption
climate protection. Nevertheless, initiatives or ideas to (regeneration energy) capabilities of these novel
nudge the development of carbon capture technologies absorbents and have yet to be coupled with a utilization

© 2022 The Authors. Greenhouse Gases: Science and Technology published by Society of Chemical Industry and John Wiley & Sons Ltd.
418 Greenhouse. Gas. Sci. Technol. 12:394–427 (2022); DOI: 10.1002/ghg.2151
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Review of carbon capture absorbents for CO2 utilization

potential.125,126,129,130 Therefore, Damanafshan et al.,129 automatized and sustainable industry.174 This is

in a more recent work, pointed out that ongoing achievable in the CO2 capture industry via the
investigations on additional criteria (i.e., degradation implementation of applicable business models
rate, vapor pressure, corrosiveness and solvent cost) set suggested by experts and the development of
by Budzianowski et al.135 and the respective utilization production systems by incorporation of new advanced
potential needs to be established to nudge the technologies. Four of the five business models,
development of these novel absorbents for industrial including circular supplies, restoration of resources,
scale-up.139 extension of product’s life cycle, and product as service,
On the other hand, CO2 utilization pathway are applicable for a CO2 capture system to develop a
consideration is crucial for developing a sustainable sustainable process.174 For developing a fully
carbon capture process. Nevertheless, there are still automated and more efficient process system, the
some challenges that limit their application. Although incorporation of advanced digital technologies
CO2 can be utilized to produce various value-added (artificial intelligence [AI] and big data analysis) and
products (as discussed under Absorptions evaluation physical technology (3D printing) are crucial.174,175 By
section), product marketability is an issue for incorporating AI into a CO2 capture system,
consideration. Huang and Tan172 mentioned that the optimization possibilities are higher, operation risks
market scales for products developed via CO2 can be significantly reduced and human errors can be
utilization are generally small. Thus, it is important to eliminated.174 This would optimize the process and the
establish a good market to ensure the relevance and managerial processes in a socioeconomic system. The
profitability of a CO2 utilization application. Apart implementation of big data analysis focuses on process
from that, the necessity to include additional optimization, which improves the efficiency of a
infrastructures or equipment to cater to CO2 utilization process.174–176 Big data analytics can also effectively
processes would impose an increment in the required analyze an extensive set of data and uncover hidden
operation energy. To conduct a comprehensive market patterns or correlations from a study. This helps
and economic analysis, techno-economic analysis enhance the performance of decision making and
(TEA) is a crucial tool for evaluating the technical create products to meet the aim of certain purposes.177
performance and economic feasibility of a For example, big data analytics can help screen through
technology.173 In addition to the increase of the different mixing ratios of hybrid absorbents and help
required energy input, the carbon emission level of the researchers determine the optimal ratio for a particular
system would also be affected negatively. Therefore, to blend. For 3D printing, it would enable old materials to
evaluate the carbon emission state for operating a CCU be replaced with renewable resources, provide rapid
system, life cycle assessment (LCA) needs to analyse its development for products, allow the production of
environmental impact. Suppose TEA and LCA of a complex parts to be simplified and ecologically
particular system indicate negative results. In that case, favoured due to the reduction of materials or product
the necessity to explore or develop more transportation.174,176
energy-efficient and eco-friendly alternatives (i.e., CO2 For example, Wu et al.178 have utilized an artificial
utilization for microalgae cultivation, energy recovery, neural network (ANN) and particle swarm
heat integration or process integration.) is crucial to optimization (PSO) model to develop an intelligent
overturning the undesirable outcome. It should also be predictive controller (IPC) for large-scale
noted that these alternatives can also be employed in solvent-based post-combustion CO2 capture (PCC)
accomplished systems to enhance their performance processes. It was shown that in this study, the proposed
further. The purpose of developing an optimal CO2 IPC system was able to determine the best control
utilization (CCU or CCUS) system is as mentioned sequence for a PCC process. For example, in a
under the Absorptions evaluation section. Thus, it is simulation scenario when flue gas flow rate drops
believed that efforts in developing an optimal CCU which causes the CO2 capture efficiency of a PCC
alternative are an important direction for future process to slightly increase, the IPC would detect this
research. anomaly and make the required adjustment (decrease
The arrival of the fourth industrial revolution (IR 4.0) lean solvent flow rate) to allow the system to achieve its
may open opportunities for CO2 capture technologies intended set-point of 70% CO2 capture efficiency. The
development. IR 4.0 aims to develop a fully rapid adjustment can be crucial as even a slight

© 2022 The Authors. Greenhouse Gases: Science and Technology published by Society of Chemical Industry and John Wiley & Sons Ltd.
Greenhouse. Gas. Sci. Technol. 12:394–427 (2022); DOI: 10.1002/ghg.2151 419
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Chai et al.

increase from the intended CO2 capture level can Table 5. Challenges of chemical absorbents
increase the operating temperature of a re-boiler to technologies for CO2 capture operation and their
accommodate for the regeneration process of the respective key enablers.
increased CO2 -rich solvent, resulting in higher energy
consumption. Apart from that, this can also reduce the Challenges Enablers
need for manual labour to control operations. This Majority of existing r Incorporate IR 4.0’ technologies
process can help push the commercialization of PCC chemical absorbents (big data analysis and artificial
operations as it can help PCC processes to adapt to possesses poor intelligent (AI)) into studies of
unpredictive industrial conditions while significantly carbon capture hybrid absorbents to enable
reducing any fluctuations in the process. Apart from capabilities faster and more efficient
screening of potential absorbents.
that, Sarma et al.179 have also demonstrated the r
Lack of data on the Conduct TEA and LCA for future
potential of 3D printing in aiding the development of
economic and CCU operation.
CO2 capture operations. Their study deduced that the environmental
three 3D printed polymers, namely high-density performance of CCU
polystyrene (HDPS), acrylonitrile butadiene styrene operations
(ABS) and nylon, were found to be potential candidates Research on newly r Prioritize analysis on economic,
to replace conventional steel packing for a CO2 synthesized environmental and utilization
absorption process. This would reduce the high capital chemical absorbents prospect of newly synthesized
cost associated with a typical amine system. Apart from not well rounded as instead of just the typical
majority of crucial absorption and desorption
that, these polymers also show plausible stability even criteria for analysis.
after 5000 h of amine exposure at a temperature of commercialization
60◦ C. Sarma et al.179 stated that 3D printing has helped have not been
to open up opportunities for CO2 capture development investigate
as more studies (i.e., novel packing design) can be Majority of carbon r Venture into the utilization of 3D
conducted on the identified polymers for further CO2 capture technologies printing to reduce cost required
are unsustainable for material purchases.
capture performance improvement. Although all these
due to high r Prioritize on the development of
new technologies offer tremendous potential for the
operational cost and CO2 utilization potential of
development of carbon capture technologies, they are lack of economic existing chemical absorbent
still not widely incorporated with one another. Thus, revenue systems.
incorporating IR 4.0 technologies into CCU r Implement IR 4.0’ principal
development is a considerable direction. Table 5 (business models and process
optimization) into existing CO2
presents an abridged version of all the present
capture facilities to optimize
challenges and potential enablers for carbon capture economic prospect of systems.
technologies.

utilization after desorption and (ii) direct CO2

Conclusion utilization after absorption. For the first pathway,
Due to the adverse damage that excessive emission of chemical absorbents such as MEA, MDEA, K2 CO3 and
CO2 has caused to the environment, carbon Na2 CO3 are suitable candidates for this utilization
management alternatives such as CCS and CCU have pathway. Excluding MEA, the absorbents as mentioned
been actively employed and studied. However, due to earlier, possess plausible CO2 capture capacity (0.7 to
the unsustainable nature of typical CCS technologies, 1.05 mol CO2 /mol absorbent) and relatively low
the need to develop a sustainable carbon management regeneration energy requirement (0.61 to 3.25 MJ/kg
pathway via CCU is crucial. In the hope of identifying CO2 ). Under this utilization pathway, value-added
plausible chemical absorbents for CCU processes, this applications include EOR operations, urea, dry ice,
review has deliberately reviewed all major absorbent food and beverage production. On the other hand,
groups as presented under the Chemical absorption hydroxide absorbents (i.e., Ca(OH)2 , NaOH and KOH)
absorbent section. For evaluating the chemical and CaCO3 are deduced to be suitable for direct CO2
absorbents for CO2 utilization, the utilization pathways utilization based on their past utilization. It was shown
were divided into two groups, that is, (i) CO2 that the products produced via the direct CO2

© 2022 The Authors. Greenhouse Gases: Science and Technology published by Society of Chemical Industry and John Wiley & Sons Ltd.
420 Greenhouse. Gas. Sci. Technol. 12:394–427 (2022); DOI: 10.1002/ghg.2151
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Review of carbon capture absorbents for CO2 utilization

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Slyvester Yew Wang Chai Lock Hei Ngu

Slyvester Yew Wang Chai is a PhD Ir. Dr. Lock-Hei Ngu is a senior
researcher from Swinburne University lecturer in chemical engineering at the
of Technology Sarawak (SUTS) Swinburne University of Technology
Campus, Malaysia. He is specialized Sarawak (SUTS) Campus, Malaysia.
in CO2 capture related studies and Her current fields of research include
is currently investigating the potential CO2 absorption and adsorption,
of chemical absorption alternatives to carbon utilization and biomass
curb CO2 from the cement industry. adsorbents for wastewater treatment.

© 2022 The Authors. Greenhouse Gases: Science and Technology published by Society of Chemical Industry and John Wiley & Sons Ltd.
426 Greenhouse. Gas. Sci. Technol. 12:394–427 (2022); DOI: 10.1002/ghg.2151
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Review of carbon capture absorbents for CO2 utilization

Bing Shen How

Bing Shen How as a senior
lecturer in Swinburne University of
Technology Sarawak (SUTS) Campus,
Ir. Dr. How Bing Shen is diligent
in higher education and committed to
his profession. He has published about
70 articles with an h-index of 20 in the
field of process system engineering.

© 2022 The Authors. Greenhouse Gases: Science and Technology published by Society of Chemical Industry and John Wiley & Sons Ltd.
Greenhouse. Gas. Sci. Technol. 12:394–427 (2022); DOI: 10.1002/ghg.2151 427