Hydrothermally Stable Sulfonated Carbons as Solid Acid Catalysts for the Hydrolysis of Lignocellulose

The recycling of homogeneous acids imposes great challenges to the feasibility of lignocellulose hydrolysis processes. Although heterogeneous catalysts would offer a perspective to circumvent these challenges, conventional solid acids are instable under the hydrothermal conditions typical of hydrolysis processes. In this regard, acid functionalized carbons appear as auspicious alternatives due to the higher perseverance of carbon frameworks. The strong Brønsted acid sites in sulfonated carbons would be particularly well suited to catalyze the hydrolysis of cellulosic biomass. The utilization of these materials has so far been impeded by the controversy regarding the stability of sulfonic acid groups in carbons. Furthermore, it remains uncertain how the constraints imposed on the reaction system by the insolubility of lignocellulose influence the ability of solid acids to function as hydrolysis catalysts. This thesis shows that hydrothermally stable sulfonated carbons can be prepared by utilizing the structure-stability dependence of sulfonic acid groups in carbonaceous materials. The sulfonation of materials featuring a low degree of graphitization resulted in active solid Brønsted acid catalysts that however deactivated through the leaching of sulfonic acid groups. An in-depth physicochemical characterization of the catalysts paired with a systematic study of the stability of model sulfonic acids, revealed that the leaching-tendency is defined by substituent effects. Activating/deactivating substituents control the hydrothermal stability of aryl sulfonic acids by decreasing/increasing the tendency of the carbon-sulfur bond to undergo solvolysis. The presence of stabilizing and destabilizing substituents was found to be tunable by the temperature dependent decomposition of oxygen containing surface groups. Sulfonation of cellulose carbonized at 350°C resulted in a catalyst with 850 µmol g-1 hydrothermally (180 °C) stable sulfonic acid groups. Additionally, a hitherto unknown mode of deactivation was identified that proceeds by the ion-exchange of cationic impurities with protons of the active sites. This mode of deactivation can be fully overcome by implementing countermeasures to reverse or suppress ion-exchange processes. To tackle the limitations of homogeneous acids, the stable sulfonated carbons were used as catalysts in a semi-batch based lignocellulose hydrolysis process. It was found that the chemical recalcitrance and the insolubility of the substrate imposed strong limitations on the reaction with the catalyst and that soluble product formation occurred predominantly via auto-hydrolysis. The propensity of cellulose to undergo auto-hydrolysis could be enhanced by amorphizing its crystal structure through mechanical pretreatment in ball-mill. A heterogeneously catalyzed hydrolysis was achieved through mechanocatalytic processes facilitated by the concerted ball-milling (CBM) of the sulfonated carbon with the substrate. Sulfonic acid groups were pinpointed as active sites during the mechanocatalytic formation of soluble oligosaccharides. The secondary hydrolysis to monosaccharides in the semi-batch reactor was no longer constrained by the insolubility of the substrate. The combination of CBM pretreatment and hydrolysis in the semi-batch reactor was successfully extrapolated to the conversion of spruce fir wood to achieve yields in C5 and C6 derived products that are competitive with state-of-the-art diluted acid processes.