A promising alternative to chemical absorption usingsolvents such as MEA is the use of physical solvents in whichthe solvent selectively binds CO2 at high partial pressures andlow temperatures (in accordance with Henrys Law). Physicalabsorbents such as Selexol (a mix of dimethylethers ofpolyethylene glycol) and Rectisol (methanol chilled to40 8C), for example, have been used industrially for40 years for natural gas sweetening and the treatment ofsynthesis gas. The advantage in this case is the lower heatconsumption in the solvent regeneration step, as the strippingprocess can be driven by heat or a pressure reduction (i.e.,“flash distillation”).[36] Physical solvents are suitable for CO2capture from high pressure streams such as those relevant forprecombustion capture in IGCC plants.Ionic liquids constitute another class of physical solventswhich are also known to be selective for CO2 absorption.[20, 37]These comprise combinations of large organic cations andsmaller inorganic anions and are typically viscous liquids nearroom temperature. In addition to their extremely low vaporpressures, they are non-flammable, environmentally benign,and can exhibit exceptional thermalstability. The mechanism for capture isoften based on physisorption, andinvolves weak association between theionic liquid and CO2 molecules (ratherthan chemical bonds), with heats ofadsorption of around11 kJmol1.
[38, 39] In view of this low
heat of reaction, the obvious benefit for
CO2 capture is the minimal energy
required for solvent regeneration. The
capacity is directly proportional to the
partial pressure of CO2 and improves at
pressures above 1–2 bar. For this
reason, ionic liquids were initially proposed
for precombustion applications.
It should be noted that some ionic
liquids react with CO2 in a chemisorption
mechanism. An additional benefit
is that ionic liquids can simultaneously
serve to remove CO2 and SO2 (“SO2
polishing”), since the SO2 solubility is
8–25 times greater than that of CO2 at
the same partial pressure.[40] This may
not necessarily be advantageous, however,
as an additional step to separate
CO2 from SO2 will be required.
While the viscosity of ionic liquids minimizes solvent loss
from the gas stream, this attribute also limits mass transfers,
and they often suffer from low rates of absorption. To
surmount these shortcomings and increase the capacity of
simple ionic liquids, “task specific ionic liquids”[41] have been
developed. The introduction of functional groups such as
amines into TSILs, have allowed higher rates of adsorption to
be achieved at pressures relevant to flue streams (ca. 1 bar). A
number of reports have also demonstrated extremely high
CO2/N2 selectivities in polymerized ionic liquids, which
exhibit enhanced CO2 solubilities relative to the monomeric
ionic liquid itself.[42] These solid materials also show exceptional
promise as facilitated transport ionic liquid membranes.[43]
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