Kinetic model describing self-limiting CO2 diffusion in supported amine adsorbents

Abstract

A reaction–diffusion shrinking core model describing the decay in diffusivity of supported amine sorbents upon CO2 sorption under both simulated direct air capture and point source capture conditions is described. The decay in CO2 diffusivity is associated with crosslinking in the aminopolymer samples and general pore blockage in the amino-silane derived samples, which occurs as CO2 is adsorbed. The model is used to extract four kinetic parameters that govern the CO2 uptake kinetics and working capacity: an apparent reaction rate constant, an initial effective diffusivity, and two dimensionless decay parameters. Ideally, an initially reaction limited system would allow for direct determination of the intrinsic reaction rate constant; however, sorption experiments suggest mass transfer resistances related to gas mixing, external boundary layers and intraparticle diffusion are present. Reaction rate constants are determined and agree well with theoretical values predicted with the Eyring equation parameterized using density functional theory energies from literature sources. The kinetic performance is expressed as the average effective diffusivity as a function of average conversion, which can be correlated to the dispersion of sorption sites on the support and the morphology of the active sorbent phase. Four supports are impregnated or grafted with amines, SBA-15, single-walled zeolite nanotubes (ZNT), Syloid SiO2, and γ-Al2O3. Due to its pore structure, γ-Al2O3 supported amines can be modeled at the μm scale or at the nm scale, where the shell balance is on the μm-sized macroporous particle aggregate or on the nm-sized amine film on the surface of the Al2O3 nanoparticles, which comprise the spherical particle aggregates. Faster diffusion rates are maintained under 400 ppm rather than 10% CO2 due to a slower reaction rate giving a slower decay in diffusivity. This work provides a first principles kinetic analysis of CO2 sorption where previous models are semi-empirical and use arbitrary kinetic parameters.