Hydrogen production employing Cu(BDC) metal–organic framework support in methanol steam reforming process within monolithic micro-reactors

Cu(BDC) metal–organic framework (MOF) was used as a support for the copper (Cu) catalyst applied in the methanol steam reforming (MSR) process at low temperatures (130–250 °C) with a feed WHSV = 9.2 h^?1 within the monolithic reactor. Also, the effects of diverse promoters were examined on the catalytic activities of the Cu/X–Cu(BDC) (X = Ce, Zn, Gd, Sm, La, Y, Pr) catalysts. Results showed that the Ce/Sm–Cu(BDC) supports exhibited highest activities, lowest reduction temperatures and largest specific surface areas, which caused highest distributions of the active copper metal nanoparticles on the supports. The reactor tests displayed that the activities of Cu/X–Cu(BDC) (X = Ce, Zn, Gd, Sm, La, Y, Pr) catalysts followed the order X = Ce > Sm > Y > La > Pr > Cu(BDC) > Zn > Gd. The highest activities of Ce and Sm containing catalysts were attributed to the presence of CeO₂ and Sm₂O₃ caused the oxygen vacancies on the catalyst surface which had positive effects on the methanol reforming process. The time-on-stream stability tests showed the highest resistance of the Cu/Ce–Cu(BDC) catalyst to the carbon formation during 32 h. Consequently, the Cu/Ce–Cu(BDC) with the highest stability, methanol conversion and carbon monoxide selectivity could be used in practical industrial applications.