Two types of SO42–/ZrO2 solid acid catalysts with various calcination times were prepared via incipient wetness impregnation of (NH4)2SO4 to hydrothermally synthesized ZrO2 and subsequently employed to catalyze the esterification of palmitic acid with methanol. The resulting catalysts were characterized by X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, and temperature-programmed oxidation (TPO) to elucidate their physicochemical properties, morphology, and deactivation mechanism. A calcination procedure is required to transform the amorphous ZrO2 into the crystal form. Both chelating and bridged bidentate SO42– coordinate with the ZrO2 surface. The calcination at 600 °C could well eliminate the water in the catalyst and a further higher temperature would accelerate the loss of SO42–. Long-time calcination also decreases the catalytic activity due to the transformation of monoclinic ZrO2 into tetragonal one and the slow leaching of SO42–. The catalytic activity increases with increasing catalyst loading amount, reaction temperature, and molar ratio of palmitic acid to methanol, while the heating temperature over 65 °C and excess methanol amount are unfavorable to the esterification reaction due to the low-boiling-point methanol and attenuation of the palmitic acid concentration. It appears that the reaction conditions of 65 °C, 6 wt % catalyst, 25:1 of methanol to palmitic acid, and 4 h reaction time are economically optimal under atmospheric pressure. The catalyst could not be well regenerated by the ultrasonic methanol washing method because of refractory organic residues. The catalyst activity could be well recovered without major activity loss by the calcination at 600 °C for 1 h. The catalyst deactivation is due to contamination by the refractory organic residues in the catalyst as well as by the leaching of SO42–, and thus both the calcination temperature and time should be strictly controlled to achieve a better catalyst lifetime.
The roles of catalyst acidity and basicity playing in catalytic conversion of oleic acid were studied in a fixed-bed micro-reactor at atmospheric pressure. The chemical compositions of the petroleum-like products were obtained and the reaction pathways of different catalysts are discussed. The metal oxides are suitable for upgrading oleic acid into organic liquid products (OLPs). Over 98% oxygen was removed when CaO, MgO, and TiO2 were implemented, whereas a minimum oxygen removal lower than 20% was obtained by using quartz. The oxygen removal was 73% by alumina; however, the light oil yield (to feed) and the valuable product yield received were the highest in all investigated catalysts. The hydrocarbons in OLPs, overwhelmingly presenting in the product, were found to be alkenes and cycloalkenes, followed by saturated hydrocarbons, and then aromatics lower than 4%. For Lewis acidic catalysts, higher acidity of the catalyst is beneficial to deoxygenation but also secondary cracking. CaO has higher dehydrogenation capability than MgO does.
In this study, the degradation of sulfonamide antibiotics was investigated through persulfate-enhanced UV advanced oxidation process. Factors that may affect the degradation efficiency were analyzed. Results showed that the persulfate imposed a significant enhancement on the UV oxidation process during the sulfathiazole degradation. The combined process of UV/persulfate can effectively remove about 96% of sulfathiazole within 60 min. With the increase in the dosage of persulfate, the removal efficiency increased as well. Different water matrix almost had no effect on the removal efficiency. Two intermediates were found during the sulfathiazole degradation. It can be predicted that the combined process of UV/persulfate has a broad application prospect for removing sulfonamide antibiotics in water treatment.
Waste cooking oil (WCO) hydrotreating to produce green diesel is good for both the environmental protection and energy recovery problems. The roles of catalyst support and reaction temperature on reactions during WCO hydrotreating process were evaluated over an unsupported and a commercial sulfided cobalt and molybdenum (CoMoS) catalyst supported by a mixture of Al2O3, TiO2, and SiO2. The presence of catalyst support helped to improve the dispersion and enlarge the surface area of CoMoS, and was found to be a key factor in reducing reaction temperature, in enhancing the hydrodeoxygenation (HDO) and hydrogenation capabilities, and in decreasing polymerization capability. The increase of reaction temperature strongly improved the deoxygenation, hydrogenation, and cracking reaction activities. Compared to the unsupported CoMoS, the supported one exhibited good deoxygenation and hydrogenation capabilities at 340 °C in WCO hydrotreating to produce diesel fraction; however, high temperature operation needs to be carefully controlled because it may cause overcracking and dehydrogenation.