화학공학소재연구정보센터
Industrial & Engineering Chemistry Research, Vol.42, No.16, 3680-3689, 2003
Staged O-2 introduction and selective H-2 combustion during catalytic reactions of alkanes on cation-exchanged H-ZSM5
Stoichiometric reactions can be used to remove H-2 and the associated kinetic and thermodynamic barriers that lead to low dehydrocyclodimerization selectivity during alkane reactions on cation-modified H-ZSM5. O-2 co-reactants can form H2O in exothermic reactions that balance the enthalpy of endothermic dehydrogenation steps. O-2 reacts preferentially with H-2 via homogeneous and heterogeneous pathways, but also with hydrocarbons as H-2 is depleted; thus, it must be gradually introduced as H-2 forms in dehydrogenation reactions. Staged O-2 protocols significantly increased aromatics yields during C3H8 reactions on unexchanged and on Ga- and Zn-exchanged H-ZSM5. On Ga/H-ZSM5, the maximum aromatic yields increased from 54% to 68% and aromatization/cracking selectivity ratios increased from 2.1 to 3.9 when O-2 was introduced gradually into a gradientless batch reactor as H-2 formed. O-2 introduced was converted to H2O with >95% selectivity; an equivalent amount of O-2 initially added with C3H8 led to low H2O selectivities (<60%). Similar effects Of O-2 addition and of staging protocols were observed for alkane reactions on H-ZSM5 and Zn/H-ZSM5. Staging strategies led to selective use of O-2 to remove thermodynamic and kinetic bottlenecks and to unprecedented aromatics yields during alkane reactions on cation-exchanged H-ZSM5.