Catalysis Today, Vol.345, 88-96, 2020
The elastic behavior of zeolitic frameworks: The case of MFI type zeolite under high-pressure methanol intrusion
The high-pressure behavior of six synthetic zeolites with the MFI topology, characterized by different chemical composition (framework-Si partially replaced by Al or B and counterbalanced by Na or H as extra-framework cations), has been investigated by in-situ powder synchrotron X-ray diffraction using silicone-oil and methanol as hydrostatic pressure-transmitting fluids. For each sample, the compressibility in silicone-oil has been found to be considerably higher than that in methanol. This difference in terms of bulk elasticity is due to the adsorption of methanol already at P < 0.1 GPa, with different magnitudes as a function of the sample crystal-chemistry. The high number of experimental pressure points allowed an accurate determination of the monoclinic-to-orthorhombic phase transition (MOPT), detected between 0.3 and 0.7 GPa in the samples compressed in silicone-oil, whereas the orthorhombic Pnma polymorph has been found to be stable already at similar to 0.1 GPa in four samples compressed in methanol. This suggests that the adsorption of methanol may increase the P-stability range of the orthorhombic Pnma phase. A comparative analysis of the effect of pressure on the methanol adsorption by MFI-zeolites with different chemical composition is provided, which offers potentially useful information on their application as catalysts in the methanol-to-olefins conversion processes and in industrial high-pressure processes.