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 flow temperature (FT) of the coal ash from the Liuqiao no. 2 mine in North Anhui Province (C00) is too high (∼1520 °C) to fit the Shell gasifier due to its relatively high content of SiO2 and Al2O3. To solve this problem, a series of coals were blended with C00 with different ratios, and the relations between FT and the ash composition were investigated. The coal ash was analyzed by X-ray diffraction, Fourier transform infrared (FTIR) spectroscopy, and scanning electron microscopy–EDX to elucidate the mechanism of the improved ash fusion performance and the slag formation in the waste heat boiler of the gasifier. It is shown that FT is relevant to the coal ash compositions as well as the structures formed at high temperatures. The existence of alkaline oxides (CaO, MgO, and Fe2O3) decreases the coal ash FT to a low level. The FT can decrease to <1350 °C to cater to the Shell gasifier by blending C00 and C03 with a mass ratio of 4:6 owing to the plentiful alkaline oxides in C03. The FTIR results indicate that the high flow temperature of C00 is attributed to the formation of mullite at high temperatures. The coal blending with various ratios changes the compositions of CaO, MgO, and Fe2O3, which can form some low-melting-point eutectic compounds with SiO2 and Al2O3 under high temperatures, inhibit the formation of mullite, and thus decrease the ash FT. The coal ash FT was found to have a good linear relation with the ash compositions, which can sever as a reference to the coal blending. According to the model parameters, it is shown that Mg has the most significant promoting effect on the decrease in FT of the coal ash. The caking tendency of fly ash increases with the rising Ca content and an excessive Ca-based fluxing agent used in the coal blending will lead to the aggregation of the Ca-rich clasts around the fly ash particle, resulting in the plugging of the waste heat boiler in the gasifier. Therefore, the Mg-based fluxing agent is more promising to improve the ash fusion performance and reduce the caking tendency of the coal fly ash.
The performance of the bimetallic 2Ru15Ni/La 2 O 3 –MgO–Al 2 O 3 catalyst in the steam reforming of xylene greatly depends on the metal loading sequence and support calcination temperature.