Krystyna Nowinska

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.

V-containing silica SBA-3 mesoporous catalysts were prepared by means of one-pot hydrothermal procedure with NH₄VO₃ or VOSO₄ as vanadium precursors under various acidic medium of the reaction mixture (pH < 1, 2.2 or 3.1). The combined spectral techniques (DR UV-vis, FTIR, EPR) as well H₂-TPR allowed to determine the nature of vanadium species in the studied samples. A successful incorporation of vanadium into the structure of silica SBA-3 was attained for the samples with low V content (5 wt%) exhibited the presence of isolated vanadium and also of polynuclear surface species. The resulting V-bearing samples contain the Brønsted and Lewis acidic centres evidenced by FTIR spectra of adsorbed pyridine and by catalytic activity for 2-propanol decomposition and cumene cracking. Ammonia TPD allowed to estimate the number and strength of acid sites in regards to the vanadium content. Propene oxidation with N₂O revealed noticeable activity of the synthesised V-SBA-3 samples in epoxidation reaction. On the basis of TOF analysis indicating the activity of particular vanadium ions it seems that not all of the introduced V atoms take part in the formation of mild electrophilic oxygen species responsible for propene oxide formation.

Fe-ZSM-5 zeolites with a Si/Al ratio equal to 25 and 50, comprising 0.4 wt% of Fe and calcined at different temperatures, were used for oxidative dehydrogenation (ODH) of C₂–C₄ hydrocarbons. The calcination temperature (873 or 1173 K) slightly influenced hydrocarbon conversion, while it distinctly affected the selectivity towards respective olefins. It stems from the modification of acidic centers present in Fe-ZSM-5 samples. Calcination at 1173 K resulted in the decrease of total acidity, especially of strong Brønsted sites. UV-vis spectra evidenced the presence of very different iron(III) species, while the existence of Fe(II) ions was inferred from IR spectra of the adsorbed NO molecule. IR bands located at about 1840 and 1750 cm⁻¹ indicate the presence of isolated iron(II) species, particularly in Fe-ZSM-5(1173) samples.