High-Throughput Screening of Experimental Metal–organic Frameworks for High Water Content Syngas Hydrogen Purification under Pressure Swing Adsorption Conditions

Metal–organic frameworks (MOFs) are promising
sorbents for
adsorption-based hydrogen (H2) purification in blue hydrogen
process, but existing large-scale computational screenings rarely
examine adsorption performances of MOFs under elevated pressure, temperature
and high water content, which is typical of industrial hydrogen-rich
syngas. In this work, we perform a high-throughput virtual screening
of 11,334 porous experimental MOFs to identify candidates for pressure
swing adsorption (PSA)-based H2 purification from syngas
under a range of realistic dry and wet conditions. Grand canonical
Monte Carlo simulations are carried out for five-component dry syngas
(H2/CO2/CO/CH4/N2) at
three temperatures (30–70 °C) and five pressures (1–30
bar); 1080 Pareto-optimal MOFs are selected based on nondominated
sorting of CO2, CO, and CH4 working capacities
under all 15 conditions from the dry simulations, without imposing
arbitrary performance thresholds. Under targeted dry operating conditions
(70 °C, adsorption at 30 bar and desorption at 1 bar), top materials
exhibit CO2 working capacities above 15 mmol/g and CO2/H2 selectivities exceeding 1000, while maintaining
appreciable adsorption for CO and CH4. Adsorption capabilities
of the three carbon impurities for most MOFs are severely suppressed
when 35 vol % H2O is introduced to the guest mixture in
the wet simulations for the 1080 Pareto-optimal candidates; only seven
MOFs retain measurable uptakes for all three carbon species, of which
only four are considered thermal and water stable in the literature.
Additional screening at 1 vol % H2O identifies 16 more
MOFs with appreciable uptakes and literature validated thermal and
water stability, yielding a set of 20 final candidates recommended
for further investigations. Moreover, comparison to performance threshold
selection methods highlights the versatility of Pareto-based candidate
selection for discovering balanced MOF materials for hydrogen purification
from syngas under realistic PSA conditions.