Separation of C4 olefins and paraffins on vanadotungstates-based zeolitic octahedral metal oxides at high temperature

[Display omitted] •ZOMOs based on V and W with different crystal structure and cations were synthesized.•The materials showed selective adsorption properties for C4H6, nC4H8, and nC4H10.•The adsorption properties of the materials were dependent on the structure and cation.•The C4 hydrocarbons were separated by the materials even at high temperatures. C4 olefins and paraffins separation is one of the great challenges of hydrocarbon separation because of the extremely similar physical properties. Herein we report two zeolitic materials based on vanadotungstates, vanadotungstates with cubic symmetry (VT-1) and vanadotungstates with trigonal symmetry (VT-5), with various cations, which effectively separate 1,3-butadiene/1-butene and 1,3-butadiene/n-butane. The structures and the cations of the materials both have influence on the static adsorption capacity, Henry selectivity, ideal adsorbed solution theory (IAST) selectivity, and dynamic separation performance. The separation efficiency is confirmed by the breakthrough measurements and the results show that high separation performances of 1,3-butadiene/1-butene and 1,3-butadiene/n-butane are achieved by VT-5 with trimethylamine cation (TMA-VT-5) simultaneously even at high temperatures. The robust material can be regenerated and reused without loss of the separation performance.