Esterification catalyzed by an efficient solid acid synthesized from PTSA and UiO-66(Zr) for biodiesel production.

p-Toluenesulfonic acid (PTSA) is a typical homogeneous acid for biodiesel production. Due to the shortcomings of high deliquescence and non-recyclability, it is necessary to synthesize a recyclable solid acid. For the sake of this, UiO-66(Zr) is used to support PTSA through defect coordination, and four different preparation routes are compared. The obtained catalyst (UiO-G) is characterized with thermogravimetry analysis (TG), X-ray powder diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), pyridine FTIR spectroscopy (py-FTIR), nitrogen adsorption-desorption, and base titration. In addition, the effects of esterification parameters on conversion are investigated to obtain the optimal conditions. To further verify the high catalytic activity of UiO-G, the kinetic model of solid-liquid-liquid esterification is established, in which the kinetic parameters of activation energy, reaction order, and exponential factor are calculated. Results indicate the PTSA is successfully inserted in UiO-66(Zr) without destroying its original structure. With that, the maximum conversion of oleic acid to biodiesel of 91.3% is achieved with a molar ratio of methanol/oleic acid of 12 and a catalyst amount of 8 wt% at 70 °C for 2 h. Moreover, UiO-G could remarkably reduce the activation energy, where the activation energy is 28.61 kJ mol-1, the average reaction order is 1.51, and the pre-exponential factor is 29.11 min-1.