Continuous kinetics of 2-hydroxyisobutryic acid esterification using solid acid granular and monolithic activated carbon catalysts

Abstract

Kinetics of 2-hydroxyisobutyric acid (2-HIBA) esterification with ethanol was studied using sulfonated carbon catalysts in granular (sGAC) and monolith (sACM) forms in a continuous flow packed bed reactor. 2-HIBA is a potential biobased carboxylic acid and its ester a sustainably produced industrial solvent. The catalyst monolith form, made from renewable carbon, offers significantly higher space time yields and conversions, yet little kinetic data or models are available for its use, especially under non-ideal conditions. The effect of ethanol/2-HIBA molar ratio (44, 10, 3.6 and 1.5) at different liquid residence times (3–9 min) was investigated using sGAC. Kinetics of sACM esterifications were investigated at a molar ratio of 3.6 by varying the residence time (2–7 min) and compared with the sGAC. The sACM displayed higher ester yields, acid conversions, and significantly higher reaction rates and space–time-yields (2.1–2.8 ×) compared to the sGAC due to higher surface area to volume ratio. The sACM reaction rates and turnover frequency were comparable to solid acid resins and sulfated silica and zirconia. Pseudo-homogeneous, Eley-Rideal and Langmuir-Hinshelwood models were applied to fit the kinetic data, and the reaction system parameters were obtained through regression analysis. The LH dual active site model resulted in the lowest mean relative error for both 2-HIBA and ester concentration residuals. Adsorption/desorption equilibrium constants for 2-HIBA, ethanol, and ester, were higher compared to water suggesting hydrophobic regions in the sGAC/sACM. Estimation of the external and internal mass transfer criteria indicated negligible effects of mass transfer. With further development sACM and the kinetic model can be used for reactor design of continuous esterification processes using solid acid monolith catalysts.