Desalination of seawater ion complexes by MFI-type zeolite membranes: temperature and long term stability, Journal of Membrane Science, http://dx.doi.org/10.1016/j.memsci. 2013.10.071 This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting galley proof before it is published in its final citable form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain. 2 high rejection (>93%) for all major seawater ions including Na + (except for K + , 83%) at an applied pressure of 700 kPa and room temperature (22 °C), but showed a continuous decrease in ion rejection when increasing the temperature from 22 °C and 90 °C. Permeation flux of the zeolite membrane significantly increased with increasing in temperature. Upon closer observation of the major cations, size selective diffusion in the zeolite membrane was observed over the temperatures tested. Larger ions Ca 2+ and Mg 2+ were less responsive to temperature than smaller ions Na + and K + . No changes in membrane structure were observed by X-ray diffraction (XRD) and field emission scanning electron microscopy (FESEM) after 180 days seawater exposure. However, energy-dispersive X-ray spectroscopy (EDS) mapping on the surface of the membrane revealed a small quantity of tightly bound divalent cations present in the structure, which appear to have penetrated the zeolite, accelerated by temperature. They were suspected to have altered the permstructure, explaining why original high rejections at room temperature were not reversed after heat exposure. The work has shown that zeolite membranes can desalinate seawater, but other unusual effects such as ion selective diffusion as a function of temperature indicate a unique property for desalination membrane materials.

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Zeolitic imidazolate framework-8 or ZIF-8 membranes have shown great promise in separating propylene/propane (C3) mixtures; however far fewer works have analyzed ethylene/ethane (C2) transport behavior in ZIF-8 membranes. This work studies C2 permeation behavior, transport properties, and selectivity as a function of temperature and pressure in single and binary gas mixtures. In single and binary separation tests conducted from 25 to 100 °C, the permeances of ethylene and ethane show a negative correlation with temperature attributable to activation energies of diffusion (E d) for ethylene and ethane (11.7 and 13.2 kJ/mol) that are lower than their respective heats of adsorption (16.2 and 17.1 kJ/mol). Low E d values are observed for C2 molecules in ZIF-8 due to pore flexibility. C2 diffusive selectivity is limited in ZIF-8 due to the similar size of C2 molecules which are both smaller than the effective ZIF-8 pore aperture (low energetic selectivity) and sizable entropic selectivity is limited by the zeolitic pore shape. Binary selectivity is 20% lower than ideal selectivity due to cooperative adsorption, which enhances ethane adsorption in the presence of ethylene. The presence of relatively stronger adsorbing C2 molecules in mixture with hydrogen decreases H2 permeability and inverts the H2 temperature dependency of permeation from adsorption controlled to diffusion controlled. In single and binary C2 pressure dependent experiments performed between 1 and 4 atm, starkly contrasting ethylene/ethane separation profiles are observed due to differences in single and binary adsorption isotherms for C2 molecules. The ZIF-8 structure is amenable to adsorption/pressure induced distortions which greatly affect C2 permeation behavior.