Hydrothermal stability of pelletized zeolite 13X for energy storage applications

Three samples of pelletized zeolite Na-13X from different industrial suppliers were hydrothermally treated in an open system for up to 3500 adsorption/desorption cycles. Before and after this aging procedure, the samples have been characterized by water uptake measurements, X-ray powder diffraction (XRD), Hg-porosimetry, N₂- and CO₂-adsorption and small-angle X-ray scattering (SAXS). Large differences in the degree of degradation were found between the different materials: The adsorbent with the best performance maintains 79% of its original water uptake capacity after 3500 cycles, whereas this value is reduced to 65% after only 1600 cycles in case of the most unstable sample. For all materials, the residual water adsorption capacity was found to be higher than it was to expect from XRD data. In addition to structural changes of the zeolite cages, Hg-porosimetry and SAXS reveal a modification of the sample morphology in the meso- and macropore range. CO₂ adsorption experiments evidence that as a result of the aging process mass transfer kinetics are slowed down significantly. These findings indicate that the influence of hydrothermal treatment on the water adsorption performance not only depends on the crystal structure of the actual adsorbent, but is indeed a result of a complex interplay with the system of larger pores. The crucial role of the binder material is underlined by the fact that the most stable sample was produced by a so-called binder-free method.