Guaiacol produced by O-methylation of catechol with methanol over solid catalysts is a green environmental synthesis route. In order to achieve high catalytic efficiency, it is quite necessary to employ low-cost catalysts with high activity and stability. Herein, series of aluminophosphate catalysts were synthesized by a simple precipitation route modified by Zr. The characterization results indicated that the prepared Al-P-Zr catalysts possessed appropriate weak acid and weak base sites, which were beneficial for the O-methylation of catechol with methanol. Different Zr amount and calcined temperature exerted a significant influence on physicochemical properties of the catalysts and catalytic performance. The Al-P-Zr catalysts containing Zr/Al molar ratio of 0.012 calcined under 400 °C showed the optimal catalytic activity and long-term stability for vapor-phase selective O-methylation of catechol with methanol.

The O-methylation of catechol is an effective method for the industrial production of guaiacol used as an important chemical. However, the low catechol conversion and poor catalyst stability are the most critical issues that need to be addressed. Herein, the O-methylation of catechol with dimethyl carbonate was investigated over aluminophosphate (APO) catalysts, using a continuous-flow system to produce guaiacol. APO catalysts were synthesized with varying P/Al molar ratios and calcination temperatures to study their effects on catalytic performance for the reaction. The physico-chemical properties of the APO catalysts were thoroughly investigated using XRD, NH3-TPD, CO2-TPD, FTIR, and Py-FTIR. The P/Al molar ratio and catalyst calcination temperature significantly influenced the structure and texture, as well as the surface acid-base properties of APO. Both the medium acid and medium base sites were observed over APO catalysts, and the Lewis acid sites acted as the main active sites. The APO (P/Al = 0.7) exhibited the highest catalytic activity and excellent stability, due to the suitable medium acid-base pairs.