Abstract: Silicoaluminophosphate molecular sieves (SAPO-5) were synthesized by hydrothermal crystallization using both a conventional aqueous medium and a HF medium. The SAPO-5 samples were characterized by X-ray diffraction, scanning electron microscopy, solid state NMR, Fourier transform infrared reflectance spectroscopy, and temperature-programmed desorption of adsorbed NH3. The effect of Si content and presence of HF in the initial gel on the structure of the SAPO-5 synthesized and the manner of Si incorporation into the framework were investigated. Their acidity and catalytic activity for phenylhydroxylamine (PHA) rearrangement in the synthesis of p-aminophenol (PAP) from nitrobenzene were studied. The incorporation of Si in the samples prepared in the presence of HF was mainly by the SM3 mechanism and patches of Si(4Si) were predominant. This resulted in a decrease in the acid amount and increase in acid strength. The presence of HF during synthesis increased the integrity of the SAPO-5 crystal and helped incorporate more Si in the SAPO-5 structure by inhibiting the polymerization of Si species to a reticulated silica gel. The samples prepared in the HF medium exhibited better catalytic performance for PHA rearrangement in the synthesis of PAP, and a PAP yield of 53.2% could be obtained.

Key words: silicoaluminophosphate molecular sieve, hydrogen fluoride, p-aminophenol, nitrobenzene, hydrogenation