Unexpected high performance of ZIF-8 membranes for 1,3-butadiene purification

Abstract

The purification of 1,3-butadiene from C₄ hydrocarbon mixtures currently relies on energy-intensive extractive distillation. In this study, we employed ZIF membranes for this challenging separation for the first time, unveiling their superior capability in isolating 1,3-butadiene from other C₄ hydrocarbons with similar sizes, including 1-butene, isobutene, and n-butane. This strong sieving effect was evident from two types of ZIF-8 membranes: one with low crystallinity fabricated via the all-vapor-phase ligand-induced permselectivation (LIPS) method and another with high crystallinity synthesized through the seeded growth method. The gas permeances decreased with increasing kinetic diameters, following the order of 1,3-butadiene (4.31 Å) > 1-butene (4.46 Å) > n-butane (4.687 Å) > isobutene (4.84 Å). The LIPS-ZIF-8 membrane exhibited a high 1,3-butadiene permeance of approximately 1.43 × 10⁻⁷ mol/m² s Pa (∼430 GPU) and ideal separation factors of 18, 56, and 134 for 1,3-butadiene over 1-butene, n-butane, and isobutene, respectively. In separating four-component C₄ mixtures, these membranes could enrich 1,3-butadiene content from 50% in the feed to 96–98% in the permeate through a single separation step. This unprecedented performance is attributed to differences in C₄ diffusivities that span several orders of magnitude.