Screening of Alkali Metal-Exchanged Zeolites for Nitrogen/Methane Separation.

Methane (CH 4 ) is the primary component of natural gas and must be purified to a certain level before it can be used as pipeline gas or liquified natural gas (LNG). In particular, nitrogen (N 2 ), a common contaminant in natural gas needs to be rejected to increase the heating value of the gas and meet the LNG product specifications. The development of energy-efficient N 2 removal technologies is hampered by N 2 's inertness and its resemblance to CH 4 in terms of kinetic size and polarizability. N 2 -selective materials are so rare. Here, for the first time, we screened 1425 alkali metal cation exchange zeolites to identify the candidates with the best potential for the separation of N 2 from CH 4 . We discovered a few extraordinary zeolite frameworks capable of achieving equilibrium selectivity toward N 2 . Particularly, Li + -RRO-3 zeolite with a specific two-dimensional structure demonstrated a selective N 2 adsorption capacity of 2.94 mmol/g at 283 K and 1 bar, outperforming the capacity of all known zeolites. Through an ab initio density functional theory study, we found that the five-membered ring of the RRO framework is the most stable cationic site for Li + , and this Li + can interact with multiple N 2 molecules but only one CH 4 , revealing the mechanism for the high capacity and selectivity of N 2 . This work suggests promising adsorbents to enable N 2 rejection from CH 4 in the gas industry without going for energy-intensive cryogenic distillations.