Macrovoid-free high performance polybenzimidazole hollow fiber membranes for elevated temperature H2/CO2 separations

Thermally robust membranes are required for H2 production and carbon capture from hydrocarbon fuel derived synthesis (syn) gas. Polybenzimidaole (PBI) materials have exceptional thermal, chemical and mechanical characteristics and high H2 perm-selectivity for efficient syngas separations at process relevant conditions. The large gas volumes processed mandate the use of a high-throughput, small footprint hollow fiber membrane (HFM) platform. In this work, an industrially attractive spinning protocol is developed to fabricate PBI HFMs with unprecedented H2/CO2 separation performance. A unique dope composition incorporating an acetonitrile diluent is discovered enabling asymmetric macro-void free PBI HFM fabrication using a water coagulant. The influences of dope viscosity, coagulant chemistry, and air gap on HFM morphology are evaluated. Elevated temperature (up to 350 °C) H2 permeances of 400 GPU with H2/CO2 selectivities > 20 are achieved. This unprecedented separation performance is a ground breaking achievement at temperatures traditionally considered out-of-reach for polymeric membranes. •A novel spinning protocol to fabricate macrovoid free PBI HFMs developed.•A unique dope composition enabling use of a water external coagulant identified.•Asymmetric HFMs having thin dense selective layer and porous support achieved.•PBI HFMs having high H2 permeance and H2/CO2 selectivity at 250 °C demonstrated..