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Silicalite-1 was hydrothermally synthesized in the presence of different concentrations of Na + using tetrapropylammonium hydroxide (TPAOH) as a template. The synthesis was followed by a base treatment. The silicalite-1samples were characterized using X-ray diffraction, scanning electron microscopy, N 2 adsorption, X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy and NH 3 temperature-programmed desorption. The samples were used as catalysts for the vapor phase Beckmann rearrangement of cyclohexanone oxime. During the synthesis, the sodium ions were incorporated onto the silicalite-1 crystals, but were then removed by the base treatment. All the catalysts exhibited nearly complete conversion of cyclohexanone oxime to ε-caprolactam with selectivities grater than 95%. Addition of less than 2.5 mol-% Na + (relative to TPAOH) did not influence the catalytic properties. However, for Na + concentrations≥5 mol-%, the particle sizes of silicalite-1 increased and the catalytic activities decreased, which can be attributed to carbon deposition. The results in this work are of great importance for the polymer industry.

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