(730e) Hydrothermal Stability of Chloromethyl Polystyrene Based Solid Acid Catalysts and Mechanism of Cellulose Hydrolysis

Cellulose is one of the major components of lignocellulosic biomass and the most abundant renewable polymer on earth. As such it could serve as a sustainable feedstock for the production of commercially important fuels and chemicals. However, cellulose conversion to smaller platform molecule is the major bottleneck for economically competitive utilization of lignocellulosic biomass.

The most common processes to depolymerize cellulose employ liquid acid or enzyme catalyzed hydrolysis to produce glucose. However, issues such as reactor corrosion, slow reaction rates, and inability to recycle limits the cost-effective conversion of cellulose. Alternatively, solid acids have been proposed as reusable catalysts for cellulose hydrolysis. Introduction of binding groups in the catalyst structure is hypothesized to increase the affinity between the solid acid and cellulose, brining the glycosidic bonds within contact with catalytic sites resulting in a higher hydrolysis rate. This hypothesis finds support in adsorption studies of small cellulosic molecules such as cellobiose and glucose. However, the mechanism of such catalytic activity has not been elucidated.

Chloromethyl polystyrene based bifunctional catalysts have showed high activity towards cellulose depolymerization. It is hypothesized the chlorine participates in hydrogen bonding with the hydroxyl groups in cellulose chains. However, the chloromethyl groups is rather label and could hydrolyze in hydrothermal conditions generating hydrochloric acid. Hydrochloric acid could also catalyze cellulose depolymerization, but its effect on the overall catalytic mechanism has not be evaluated.

In this work we studied partially sulfonated chloromethyl polystyrene catalyst for cellulose hydrolysis. Structural analysis of catalyst revealed that synthesis procedure results in little to no chlorine available on the external surface, but presence of hydroxyl groups, which can also participate in hydrogen bonding with cellulose. The catalyst showed high activity towards hydrolyzing cellulose resulting in levulinic acid and formic acid as major products. However, analysis of the solid and the liquid media revealed chloromethyl group hydrolysis and hydrochloric acid generation. This observation raised the question if the catalyst is indeed acting as a solid acid.

In order to elucidate the mechanism of hydrolysis we subjected the catalyst to hydrothermal reaction conditions in the absence of cellulose. Monitoring pH and chloride ion concentration, we developed a kinetic profile of hydrochloric acid generation. Cellulose hydrolysis kinetic models involve ion concentration as a preexponential factor on the expression for the reaction rate constant. We hypothesized that incorporating the time dependence of the acid concentration in the kinetic model of cellulose hydrolysis to glucose and subsequent dehydration to HMF, levulinic acid, and formic acid would be able to accurately predict experimental results. An acceptable agreement between model and experimental product yields pointed to the liquid acid acting as the primary catalyst, obscuring any catalytic activity, if any, of the solid catalyst. Further support was obtained by carrying out hydrolysis by a titrated solid acid catalyst, in which the sulfonic acid groups have been ion exchanged and, thus, rendered inactive; similar yields were obtained as the non-titrated catalyst. The results in this investigation highlight the need for systematic study of proposed solid acids for cellulose hydrolysis and consideration of potential release of homogeneous acids in the reaction media.