Hypersonic aircrafts suffer from heat management problems caused by the air friction produced at high speeds. The supercritical catalytic cracking of fuel is endothermic and can be exploited to remove heat from the aircraft surfaces using specially designed heat management systems. Here, we report that an acid/base-treated activated carbon (AC) catalyst shows superior performance to the conventional ZSM-5 catalyst at 4 MPa and 450 °C. Further, under these conditions, coke formation is thermodynamically avoided. Of the prepared catalysts, the AC catalyst treated with NaOH and subsequently with HNO3 (denoted AC-3Na-N) was the most active catalyst, showing the highest selectivity toward light olefins and best heat sink capacity. The acid/base-treated ACs and ZSM-5 catalysts were characterized by scanning transmission electron microscopy, X-ray photoelectron spectroscopy, NH3 temperature-programmed desorption, and Fourier-transform infrared spectroscopy measurements. Characterization reveals the importance of acid strength and density in promoting the cracking reaction pathway to light olefins observed over the acid/base-treated AC catalysts, which show comparable activity at 450 °C to that of the ZSM-5 catalyst operated above 550 °C. The low-temperature activity suppressed coke and aromatic compound (coke precursors) formation. The stability of the acid/base-treated activated carbon catalysts was confirmed over a time-on-stream of 30 min.
Supercritical methylcyclohexane cracking of NiAl2O4 spinel-based catalysts with varying Ni/Al deficiencies was investigated. Thus, catalysts with Ni content of 10–50 wt.% were prepared by typical co-precipitation methods. The calcined, reduced, and spent catalysts were characterized by X-ray diffraction, O2 temperature-programmed oxidation, NH3 temperature-programmed desorption, N2 physisorption, O2 chemisorption, scanning and transmission electron microscopy, and X-ray fluorescence. The performance and physicochemical properties of the reference stoichiometric Ni3Al7 catalyst differed significantly from those of the other catalysts. Indeed, the Ni-deficient Ni1Al9 catalyst led to the formation of large Ni particles (diameter: 20 nm) and abundant strong acid sites, without spinel structure formation, owing to the excess Al. These acted with sufficient environment and structure to form the coke precursor nickel carbide, resulting in a pressure drop within 17 min. On the other hand, the additional NiO linked to the NiAl2O4 spinel structure of the Al-deficient Ni5Al5 catalyst formed small crystals (10 nm), owing to the excess Ni, and displayed improved Ni dispersion. Thus, dehydrogenation proceeded effectively, thereby improving the resistance to coke formation. This catalytic behavior further demonstrated the remarkable activity and stability of this catalyst under mild conditions (450 °C and 4 Mpa).