Functionalization of pyrolyzed hydrochar with nitrogen containing deep eutectic solvent for carbon capture at low and high pressure

Abstract

The purpose of this research is to evaluate the effectiveness of pyrolyzed hydrochar functionalized with nitrogen containing deep eutectic solvent (DES) in the absorption of CO₂ under low- and high-pressure conditions. Pyrolyzed hydrochars were synthesized by hydrothermally carbonizing pine at the temperature of 200°C and 260°C, followed by pyrolysis at 600°C. These pyrolyzed hydrochars were impregnated with 3 different nitrogen containing DES namely choline chloride: urea, choline chloride: glycerol, and tetrabutylammonium bromide: glycerol all in 1:2 molar ratio. It was found that the functionalized pyrolyzed hydrochars were enhanced with nitrogen and oxygen functionalities (N-H, C-N, and CO). The results also show a substantial reduction in surface area for the functionalized pyrolyzed hydrochars, ranging from 10.19 to 227.74 m²g⁻¹, compared to the surface areas of pyrolyzed hydrochars of 306–337 m²g⁻¹. On the other hand, an increase in N content up to 38 % was identified after functionalization of pyrolyzed hydrochars. Upon conducting CO₂ uptake at low (0.1–1 bar) and high (2.5–3.5 bar) pressure, the functionalized pyrolyzed hydrochars exhibited an CO₂ uptake of up to 9.5 mmol/g at high pressure, which was attributed to the increased total nitrogen content, enhanced surface functionalities, and available micropore volume. The low-pressure isotherm for functionalized pyrolyzed hydrochars showed Langmuir-type isotherm, suggesting a monolayer adsorption. In contrast, the high-pressure isotherms were better fitted to the Freundlich isotherm, suggesting a multilayer adsorption behavior. It was concluded that the enhanced CO₂ uptake is the result of the combined impact of increased surface functionalities and porosity, which results in improved physical and chemical adsorption mechanisms at the high pressure.