Synthesis of Solketal Catalyzed by Acid-Modified Pyrolytic Carbon Black from Waste Tires

Abstract

Solketal, a widely used glycerol-derived solvent, can be efficiently synthesized through heterogeneous catalysis, thus avoiding the significant product losses typically encountered with aqueous work-up in homogeneous catalysis. This study explores the catalytic synthesis of solketal using solid acid catalysts derived from recovered carbon blacks (rCBs), which are obtained through the pyrolysis of end-of-life tires. This was further converted into solid acid catalysts through the introduction of acidic functional groups using concentrated H2SO4 or 4-benzenediazonium sulfonate (BDS) as sulfonating agents. Additionally, post-pyrolytic rCB treated with glucose and subsequently sulfonated with sulfuric acid was also prepared. Comprehensive characterization of the initial and modified rCBs was performed using techniques such as elemental analysis, powder X-ray diffraction, thermogravimetric analysis, a back titration method, and both scanning and transmission electron microscopy, along with X-ray photoelectron spectroscopy. The catalytic performance of these samples was evaluated through the batch mode glycerol acetalization to produce solketal. The modified rCBs exhibited substantial catalytic activity, achieving high glycerol conversions (approximately 90%) and high solketal selectivity (around 95%) within 30 min at 40 °C. This notable activity was attributed to the presence of -SO3H groups on the surface of the functionalized rCBs. Reusability tests indicated that only rCBs modified with glucose demonstrated acceptable catalytic stability in subsequent acetalization cycles. The findings underscore the potential of utilizing end-of-life tires to produce effective acid catalysts for glycerol valorization processes.