Clinoptilolites for nitrogen/methane separation

Clinoptilolites, naturally occurring zeolites, currently used by nuclear industry for ion exchange and drying, were evaluated for the nitrogen/methane separation. Ion exchange of purified clinoptilolite was carried out individually with the cations Na⁺, Mg²⁺, Ca²⁺, K⁺ and H⁺, and the adsorption isotherms and diffusion rates were measured. Purified and Mg-clinoptilolite show potential for nitrogen/methane separation and high-pressure adsorption isotherms were measured in a differential absorption bed. Pressure swing adsorption simulations were performed for purified clinoptilolite, Mg-clinoptilolite and the commercial sorbent ETS-4. Purified clinoptilolite shows slightly higher recovery and lower productivity than ETS-4 for similar product purity (∼95%). Mixed ion-exchanged clinoptilolites of Mg/Ca cations, K/Na cations and Mg/Na cations were also prepared and studied for the nitrogen/methane separation. Mg/Na (50/50) mixed ion-exchanged clinoptilolite exhibits very good equilibrium and kinetic selectivity in the low-pressure range, better than purified clinoptilolite. Mixed-exchange clinoptilolites were also found to show a wide range of adsorption characteristics with varying ratios of cation exchange, thereby making them suitable for further improvements in nitrogen/methane separation.