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.

中文翻译：

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由 PTSA 和 UiO-66(Zr) 合成的高效固体酸催化酯化生产生物柴油

p-甲苯磺酸 (PTSA) 是用于生物柴油生产的典型均相酸。由于具有高潮解性和不可回收性的缺点，因此需要合成可回收的固体酸。为此，使用UiO-66(Zr)通过缺陷协调来支持PTSA，并比较了四种不同的制备路线。用热重分析（TG）、X射线粉末衍射（XRD）、傅里叶变换红外光谱（FTIR）、吡啶红外光谱（py-FTIR）、氮吸附-脱附和碱对所得催化剂（UiO-G）进行了表征。滴定。此外，研究了酯化参数对转化率的影响，以获得最佳条件。为了进一步验证UiO-G的高催化活性，建立了固-液-液酯化动力学模型，其中计算了活化能、反应级数和指数因子的动力学参数。结果表明 PTSA 成功插入 UiO-66(Zr) 中而不会破坏其原始结构。这样，在甲醇/油酸的摩尔比为 12 和催化剂量为 8 wt% 的情况下，在 70 °C 下 2 小时，油酸向生物柴油的最大转化率为 91.3%。此外，UiO-G 可以显着降低活化能，活化能为 28.61 kJ mol 甲醇/油酸的摩尔比为 12 和催化剂量为 8 wt%，在 70 °C 下 2 小时可达到 3%。此外，UiO-G 可以显着降低活化能，活化能为 28.61 kJ mol 甲醇/油酸的摩尔比为 12 和催化剂量为 8 wt%，在 70 °C 下 2 小时可达到 3%。此外，UiO-G 可以显着降低活化能，活化能为 28.61 kJ mol^-1，平均反应阶数为1.51，指数前因子为29.11 min ^-1。