International Journal of Greenhouse Gas Control 120 (2022) 103771

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International Journal of Greenhouse Gas Control

journal homepage: www.elsevier.com/locate/ijggc

A century of re-exploring CO2 capture solvents

Patrick Brandl a, b, Mai Bui a, b, Jason P. Hallett c, Niall Mac Dowell a, b, *
a
Centre for Process Systems Engineering, Imperial College London, London SW7 2AZ, UK
b
Centre for Environmental Policy, Imperial College London, London SW7 1NE, UK
c
Department of Chemical Engineering, Imperial College London, London SW7 2AZ, UK

A R T I C L E I N F O A B S T R A C T

Keywords: Absorption-based separation processes date back over 120 years, and are recognized as being integral to the
Post-combustion capture delivery of deep decarbonisation. Thousands of new solvents have been proposed but have not yet delivered the
CO2 capture level of cost reduction which has been widely anticipated. For much of the past 50 years, the scientific com­
Carbon capture and storage
munity has focused on developing novel aqueous blends of amines. Whilst they outperform benchmark tech­
CCS
CO2 absorption
nologies, they ultimately fail to address the fundamental performance limiting issue; the solvents
solvent development overwhelmingly consist of water. In this contribution, we present a thought-experiment that uses a hypothetical
solvent to identify the limit of available cost reductions to 65% over current performance benchmarks, reaching a
cost limit of $26/tonCO2 for gas-power.

1. Introduction absorption capacity and reaction rate compared to the single-amine

CO2 capture and storage (CCS) (Bui et al., 2018) is integral to the
affordable and reliable mitigation of climate change in line with the
target set out by the 2015 Paris Agreement. The most mature technology
is amine-based flue gas scrubbing, in which CO2 is absorbed into a sol­
vent and subsequently stripped from it by re-heating (Rochelle, 2009).
Significant cost reductions are expected to be delivered by solvent and
process improvements, e.g., DOE’s target of $30/tCO2 by 2035 (US
Department of Energy, 2020), yet it is not clear if these targets are
actually achievable.
Solvent development has historically focused on reducing the
enthalpy of absorption, increasing the absorption capacity, and
enhancing the reaction kinetics by blending and synthesizing new
amines. However, this approach has not yielded any major break­
throughs, because, as illustrated in Fig. 1, the same physical property
space has been repeatedly explored for over a century. Methanol- and
hot potassium carbonate-based separation processes were deployed in
the late 19th century for acid gas separation in order to produce carbonic
acid (Henry, 1904). By the 1930s, this process was adopted for natural
gas sweeting (Bottoms, 1930; Allen and Arthur, 1933) using aqueous
alkanolamines, including monoethanolamine (MEA) and diethanol­
amine (DEA). The development of solvent technologies continued, with
sterically hindered amines and activated blends introduced in the 1970s
(Appl et al., 1982; Sartori and Savage, 1983) and aimed at increasing the
solvents, e.g., blending sterically hindered 2-amino-2-methyl-1-propa­
nol (AMP) with rate-promoter piperazine (PZ). A common character­
istic of the solvent classes enumerated here is their relatively dilute
nature – they are overwhelmingly composed of water, introducing an
inherent inefficiency to this technology.
It is therefore crucial to clarify if further solvent development is
capable of achieving anticipated cost reduction targets (US Department
of Energy, 2020), or if setting unachievable targets is essentially a po­
tential distraction from the urgent need to deploy CCS technology. In
this contribution, we present a thought-experiment which identifies the
limits of solvent development via a hypothetical ideal solvent. To un­
derstand how physical properties of solvents can translate to cost re­
ductions, we evaluated MEA, (primary), DEA (secondary), MDEA
(tertiary), AMP (sterically hindered), PZ (heterocyclic (di)amines), and
CESAR1 (performance benchmark) as representative solvents, as they
cover a wide range in kinetics, vapour–liquid equilibrium (VLE), and
enthalpy of absorption. This study focuses on the application of
amine-based absorption systems for post-combustion capture of CO2
from a range of flue gases with CO2 concentration ranging between 1
mol% and 30 mol%.
2. Methodology
The underlying process topology from the 1930s has undergone

* Corresponding author at: Centre for Process Systems Engineering, Imperial College London, London SW7 2AZ, UK.
E-mail address: niall@imperial.ac.uk (N. Mac Dowell).

https://doi.org/10.1016/j.ijggc.2022.103771
Received 2 November 2021; Received in revised form 18 July 2022; Accepted 9 September 2022
Available online 13 September 2022
1750-5836/© 2022 The Author(s). Published by Elsevier Ltd. This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/4.0/).
P. Brandl et al.
process intensification over time with absorber intercooling, flash
drums, multi-pressure stripping, vapour compression, or split configu­
rations (Kohl and Nielsen, 1997), but the essential features of an
absorber and stripper column have persisted. The overall specific
reboiler duty has reduced from more than 4 MJ/kgCO2 to approximately
2.33 MJ/kgCO2, which includes improvements from solvent develop­
ment as well as process intensification (Singh and Stéphenne, 2014). The
thermodynamic minimum work required to recover CO2 from an
exhaust gas varies with concentration, increasing from 5 to 7 kJ/molCO2
(coal power), 7 – 10 kJ/molCO2 (gas power), and greater than 21
kJ/molCO2 (air capture). On this basis, the second law efficiency for
current state-of-the-art post-combustion capture is approximately 12%
(gas-power) and 27% (coal-power) (Wilcox et al., 2017), implying that
there remains substantial room for improvement.
We estimate capture cost of solvents being utilized in a process to­
pology resembling the archetypal absorber-stripper configuration
known since the 1930s (Fig. 2). The reported specific capture cost
($/tonCO2) is based on the discounted capital and operating expenditure
but excludes CO2 transport and storage contributions. All solvents are
utilized at their individual optimal operating conditions in equipment
that is optimally sized, leading to minimal capture cost at the specific gas
CO2 composition. The representative amine solvents considered in this
study include MEA, (primary), DEA (secondary), MDEA (tertiary), AMP
(sterically hindered amine), PZ (heterocyclic (di)amines), and CESAR1
(performance benchmark).
The modelling approach aims to compare the techno-economic
performance of different solvents based only on their thermo-physical
properties, independent of process-related improvements, by
comparing all solvent in the same archetypal process configuration at
the same amine concentration on a mass basis of 30 wt%. This eliminates
the impact of the process topology on the screening. Process intensifi­
cation is not considered in this study in order to focus specifically on the
effects of thermo-physical properties. However, different flue gas CO2
concentration between 1 and 30 mol% was evaluated. A detailed
description of the model and methodology is provided in the Supple­
mentary Material.
Fig. 1. Timeline of solvent development including total heat of absorption, kinetics (colour scale; red = fast, blue = slow), and VLE (size; high capacity = large, low
capacity = small). Comparison at pCO2=10 kPa and 40 ◦ C. List of abbreviations and data sources are described in Supplementary Material. The text labels with
rectangular borders correspond to the amine solvents evaluated in this study in terms of capture costs (Fig. 5).
2
International Journal of Greenhouse Gas Control 120 (2022) 103771
3. Results and discussion
On reviewing the literature, it is interesting to observe that there has
been near-exclusive focus on a limited set of thermo-physical properties
(Oexmann and Kather, 2010), in which new solvents might outperform
benchmarks, yet these do not equate to significant cost reductions.
Transport properties, in particular, are often neglected in favour of heat
of absorption, kinetics, and VLE, which is especially unfortunate as they
are key to heat and mass transfer processes, which in turn dictate process
size, and thus capital cost (Nematollahi and Carvalho, 2019).
Fig. 3 illustrates the difference in thermo-physical properties relative
to MEA, highlighting cost reductions over MEA (green, outermost re­
gions) and cost increases (red, centre). The relative difference compared
to MEA in density, heat capacity, and thermal conductivity is small,
potentially allowing less focus on those properties. The impact of surface
tension and viscosity on cost reduction is of the same order as the VLE
and heat of absorption, thus making it necessary to include them in any
assessment.
Solvent development is inherently constrained by physical bounds in
each thermo-physical property. The best solvent would consistently
outperform in each and every property. We derive a limiting solvent, a
hypothetical construct, embodying the concept of being able to indi­
vidually optimize the solvent’s thermo-physical properties without any
association to a molecular structure, i.e., creating an artificial solvent
agnostic of any reaction chemistry. It is the result of simultaneously
optimizing all solvent properties within realistic physical bounds (see
Table S8 of Supplementary Material). Each bound is derived from an
experimentally measured pure liquid, e.g., viscosity of water, or the re­
action rate of OH− ions with CO2.
The limiting solvent quantifies a more practical limit than the ther­
modynamic minimum work of separation by including the inefficiencies
of heat and mass transfer. However, it is important to emphasise that
actually synthesizing this material is likely impossible, as this limiting
solvent modelling result does not consider the relationships between
individual thermophysical properties, e.g., equilibrium loading and heat
of absorption, as described by the van’t Hoff equation. Further im­
provements may be possible through additional process engineering
modifications. A comparison of the limiting solvent with a representa­
tive selection of solvents is illustrated in Fig. 3. It can be observed here
P. Brandl et al. International Journal of Greenhouse Gas Control 120 (2022) 103771

Fig. 2. The process topology considered in this study is an archetypal absorption-based post-combustion CO2 capture plant comprising a conventional absorber-
stripper configuration.

Fig. 3. Comparing thermo-physical

properties of the unloaded solvents at
40 ◦ C and 30 wt% as a factor of MEA.
Cost reduction relative to MEA is
highlighted in green (outermost re­
gion), whereas cost increase relative to
MEA is indicated by the red central
region. Note the inverse scale for heat
of absorption, viscosity and heat ca­
pacity. All properties except density
are alkalinity based. The lower and
upper bounds of the thermo-physical
properties are summarised in
Table S8 of the Supplementary
Material.

that the largest room for improvement lies with viscosity, surface ten­
sion, and the heat of absorption.
Next, we determine the key factors to go beyond the well-explored
thermo-physical property space. The screening discloses the interac­
tion between chemistry, thermo-physical properties, and techno-
economic performance and is highlighted by a sequential step-by-step
optimization of the solvent’s properties starting with MEA and reach­
ing the limiting solvent (see Fig. 4). The biggest cost contributors are
steam and the absorber, with the operating expenditure dominating the
overall capture cost. The first optimization step involves the transport
properties (i.e., viscosity, heat capacity, thermal conductivity, surface
tension, and density), the second step includes kinetics, the third one is
heat of absorption, and the last step, the VLE. The limiting solvent shows
that improved heat and mass transfer rates lead to lower solvent
flowrate and smaller equipment. The specific reboiler duty decreases to
1.55 MJ/kgCO2, which is roughly a third of MEA’s reboiler duty and 34%
lower than CESAR1. We predict a lower limit of $26/tCO2 for capture cost
(34% of MEA’s capture cost) for the limiting solvent utilized in an
archetypal process capturing 90% of the CO2 in a typical gas-power flue
gas. We observe the upper bound of the second law efficiency of an
archetypal post-combustion capture unit to be limited to 32% (gas-
power) and 55% (coal-power).
We find that CESAR1’s capture cost, excluding transport and storage,
is very close to current EU emission trading scheme (ETS) prices for most
relevant flue gas CO2 concentrations, and breaks even with the US §45Q
tax-credit at high gas CO2 concentrations (see Fig. 5). Overall, the dif­
ferences in capture costs between the real solvents are small, which is
unsurprising given the similar chemistry and consistently high contents

3
P. Brandl et al. International Journal of Greenhouse Gas Control 120 (2022) 103771

Fig. 4. Deriving the limiting solvent starting from MEA by optimizing the solvent properties and its impact on capture cost (colour bar, left scale) and specific
reboiler duty (red, right scale) at flue gas CO2 concentration of 4 mol% and 90% capture rate.

solvents, both first-generation amines (e.g., MEA) and second-generation

200
MDEA “advanced” solvents (e.g., CESAR1), contain more water than active
180 DEA amine, which means the majority of the liquid circulated within a cap­
AMP ture plant is not actively contributing to the capture task. Consequently,
160 MEA the reduction in capture costs achieved by CESAR1 relative to MEA
Capture cost in $/tonCO2

PZ
140 across most gas CO2 concentrations (e.g., >3 mol%) is marginal (Fig. 5).
CESAR1
Limiting Solvent This is an inherent ineffectiveness that is not being addressed by the
120
EU ETS continued development of other aqueous mixtures of amines. Further­
100 45Q more, the effect of corrosion and degradation may outweigh the impact
of the solvent thermodynamics. This questions the rationale behind the
80 solvent development approach that dominated the past 50 years (see
60 Fig. 1). New chemistries such as amino acids (ProK and LysK), phase-
change solvents (DEEA + MAPA), amine-free carboxylic acid salts
40 (PhOK), or water-free CO2BOLs (Heldebrant et al., 2017), e.g., DBU in
20 hexanol, potentially offer alternative pathways to reduce the cost asso­
Gas-power Hydrogen
Coal-power Ammonia
Iron/Steel ciated with regeneration.
0 In order to circumvent the intrinsic inefficiencies of the conventional
absorber-stripper process, i.e., heating, boiling, condensing, and cooling
0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30
CO2 concentration in flue gas in mol-% a liquid, it is vital to exploit potential synergies between solvent and
process. That includes utilizing anti-solvent regeneration, e.g., polarity
Fig. 5. Capture cost of the solvents representing different amine classes, swing, reducing solvent circulation rates by removing non-binding
CESAR1 (performance benchmark), and the limiting solvent for flue gas CO2
carriers, and minimizing corrosion and degradation by avoiding
compositions between 1 mol% and 30 mol%. Tax credit US §45Q and EU ETS
aqueous amine environments. Equipment intensification, e.g., rotating
are added for reference. The available potential for cost reductions through
solvent improvement is highlighted in grey (based on the current performance packed beds or 3D printed packings, and process integration, e.g.,
benchmark CESAR1). intercooling, split-configurations, or mechanical vapour-compression,
can compensate disadvantages of individual solvent systems, e.g., high
viscosity of CO2BOLs.
of ~90 mol% water. The capture cost of advanced solvents like CESAR1
Even our hypothetical limiting solvent cannot completely overcome
is still similar to the capture cost of MEA, and far from the limiting
the intrinsic process inefficiency, and whilst it appears possible to ach­
solvent. Evidently, only a small cost improvement has been achieved
ieve the aforementioned cost targets, they appear exceedingly testing for
over >100 years of solvent R&D.
the current technology paradigm. Scientists and engineers must there­
fore build upon previous successes in this space (Rochelle et al., 2019;
4. Conclusions
Jiang et al., 2021), and further exploit synergistic effects between sol­
vent and process design, optimizing performance in conjunction with
We presented a thought-experiment that used a hypothetical solvent
process intensification.
to identify the limit of available cost reductions. This “limiting solvent”
Whilst R&D activity will obviously continue, with ambitious clean
achieved a 65% cost reduction over current performance benchmarks,
energy standards and enhanced CO2 sequestration being discussed in the
reaching a cost limit of $26/tonCO2 for gas-power. The majority of

4
P. Brandl et al.
US and legislated “net zero” targets in the UK, EU, and China, allied with
an EU ETS price in excess of $65/tCO2, the immediate priority is to focus
on deployment.
Data and materials availability
All data is available in the main text or the supplementary materials.
CRediT authorship contribution statement
Patrick Brandl: Methodology, Software, Investigation, Formal
analysis, Writing – original draft. Mai Bui: Methodology, Formal anal­
ysis, Writing – review & editing. Jason P. Hallett: Conceptualization,
Supervision, Writing – review & editing. Niall Mac Dowell: Concep­
tualization, Methodology, Supervision, Writing – review & editing.
Declaration of Competing Interest
Authors declare no competing interests.
Data availability
No data was used for the research described in the article.
Acknowledgments
PB thanks the Imperial College Library. The authors gratefully
acknowledge the financial support from UKCCSRC under EPSRC grant
EP/P026214/1, Canadas Oil Sands Innovation Alliance (COSIA), CO2
Capture Project (CCP), Petroleum Institute, Research Councils UK
(RCUK) under grants EP/M001369/1 (MESMERISE-CCS), EP/
M015351/1 (Opening New Fuels for UK Generation), EP/N024567/1
(CCSInSupply), and NE/P019900/1 (GGR Opt).
Supplementary materials
Supplementary material associated with this article can be found, in
the online version, at doi:10.1016/j.ijggc.2022.103771.
International Journal of Greenhouse Gas Control 120 (2022) 103771
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