Separation of Argon and Oxygen by Adsorption on a Titanosilicate Molecular Sieve

A titanosilicate molecular sieve adsorbent, Ba-RPZ-3, was synthesized and tested for its use in the separation of O2+Ar mixtures at room temperature. A clean resolution of both gases was achieved in pulse chromatographic experiments using a standard column (0.25″ OD, 3.5 grams of adsorbent). In another experiment, using a column containing 30 grams of adsorbent and a continuous O2+Ar feed at 10 cm3/min, argon breakthrough was detected more than 5 minutes before the oxygen breakthrough, and the separation was sufficiently sensitive to achieve quantitative separation of mixtures with low argon content (5% Ar). Equilibrium adsorption isotherms and isosteric heats of adsorption for oxygen and argon were found to be almost identical at room temperature. The thermodynamic selectivity was found to be mildly in favor of oxygen (∼1.1–1.2). However, the adsorption of oxygen was observed to be much faster than argon, indicating that the separation of the O2+Ar mixtures was based on the sieving properties of the adsorbent and the difference in sizes of O2 molecules and Ar atoms. This indicates that a suitably-oriented oxygen is physically smaller than argon, despite the fact that many references assume that oxygen is larger than argon.