The Evolution of A New Class of CO Absorbents: Aromatic Amines

The evolution of a new class of CO2 absorbents: aromatic amines
Graeme Puxty1, Will Conway1, Qi Yang2, Robert Bennett1, Debra Fernandes1, Pauline Pearson3,
Dan Maher1, and Paul Feron1
1
CSIRO Energy, Newcastle NSW, Australia
2
CSIRO Manufacturing, Clayton VIC, Australia
3
CSIRO Energy, Clayton VIC, Australia
Abstract
Over the past few decades a great deal of research effort has been brought to bear on developing
amine based CO2 absorbents with improved performance characteristics relative to aqueous
monoethanolamine (MEA). The important performance characteristics are the energy required for
CO2 desorption, rates of mass transfer, long term stability in the presence of O2 and high temperatures,
corrosion, volatility, toxicity and biodegradability. To-date the focus has been on aliphatic molecules
and absorbent formulation. For example aqueous blends of 2-amino-2-methyl-1-propanol (AMP) and
piperazine (PZ) are probably the best known absorbent formulations that yield benefits relative to
MEA across most of these characteristics [1-2].
Aromatic compounds have received little attention as potential CO2 absorbents, most likely due to
their assumed low aqueous solubility and toxicity (think polyaromatic hydrocarbons). They are also
inherently stable and often associated with persistent organic pollutants. However, the addition of
heteroatom functionality such as amino groups alters many of these properties in a favourable way,
while retaining greater stability than aliphatic compounds.
Our research has found that aromatic amines uniquely combine a number of properties favourable for
CO2 capture applications. Of particular note is a low energy requirement for CO2 desorption. This is
a consequence of the highly rigid aromatic structure resulting in a small or even negative entropy
change upon protonation of associated amino groups, which translates to a more negative enthalpy of
protonation (as most amines have a similar free energy of protonation). This is in contrast to aliphatic
amines which tend to have a less negative protonation enthalpy and a larger and positive entropy of
protonation. This is illustrated with experimentally determined values in Figure 1, with aromatic
amines shown as red squares [3-4]. The consequence of this is that at desorption temperatures
aromatic amines become increasingly weak bases enhancing CO2 release. The contribution of this
change in basicity to CO2 cyclic capacity is shown in Figure 2 for MEA and two aromatic amines.
1
Figure 1: Experimentally determined enthalpy and entropy of protonation values for a range of
amines.
Figure 2: Contributions to the measured CO2 cyclic loading (αrich – αlean, mol CO2 / mol amine) from
the change in protonated amine pKa with temperature due to the protonation enthalpy in contrast to
the contribution from other reactions. BZA = benzylamine and CAL007 = codename for a second
aromatic amine.
2
In addition to the low energy requirement these aromatic amines have good reaction kinetics and rates
of mass transfer with CO2, are of low to moderate viscosity, relatively non-corrosive and are highly
stable. They are also of low toxicity and readily biodegradable through the action of naturally
occurring enzymes. In small scale pilot plant testing (20 kg/hr CO2) two different formulations based
on aromatic amines have demonstrated excellent process performance. Figure 3 shows the
experimentally measured reboiler duty of CAL005 and CAL007, 2 absorbents based on aromatic
amines, in comparison to 30 wt% MEA.
Figure 3: Experimentally determined reboiler duties as a function of liquid to gas ration (L/G) for 3
different absorbents. CAL005 and CAL007 are both based on aromatic amines.
The significant gains in process performance are clear and make a strong case for aromatic amines to
be seriously considered as a new generation of CO2 absorbents.
1. Mangalapally, H. P.; Hasse, H., Pilot plant study of two new solvents for post combustion
carbon dioxide capture by reactive absorption and comparison to monoethanolamine. Chem
Eng Sci 2011, 66 (22), 5512-5522.
2. Rabensteiner, M.; et al., Pilot plant study of aqueous solution of piperazine activated 2-
amino-2-methyl-l-propanol for post combustion carbon dioxide capture. Int J Greenh Gas
Con 2016, 51, 106-117.
3. Fernandes, D.; et al., Protonation constants and thermodynamic properties of amines for
post combustion capture of CO2. J Chem Thermodynamics 2012, 51, 27-102.
4. Richner, G.; et al., Thermokinetic properties and performance evaluation of benzylamine-
based solvents for CO2 capture. Chem. Eng. J. 2015, 264, 230-240.

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