Controlling kinetic and diffusive length-scales during absorptive hydrogen removal in methane dehydroaromatization on MoCx/H-ZSM-5 catalysts

Neil K. Razdan, Anurag Kumar, Aditya Bhan

Research output: Contribution to journalArticlepeer-review

12 Scopus citations

Abstract

Addition of Zr metal absorbent to MoCx/H-ZSM-5 in the form of staged-bed, stratified-bed, and interpellet physical mixtures effectively scavenges H2 from catalyst proximity, enhancing maximum single-pass benzene + naphthalene yield during methane dehydroaromatization (DHA) reactions to 14–16% compared to 8% in formulations without zirconium. The coupling of spatially-distinct catalytic and absorptive functions is achieved by dispersive/diffusive transport which conveys H2 to staged Zr both co- and counter-current to bulk advection, thereby suppressing axial H2 partial pressure profiles along the catalyst bed and enhancing net aromatization rates. We evince hitherto unreported significance of dispersive hydrogen transport during methane DHA by measurement of Péclet number, Pe = 1.32, in H2 tracer studies with step-change or impulse input to inert catalyst proxies. Kinetic limits to methane pyrolysis are quantified by Damköhler number, Da, for synthesis of benzene, DaB = 0.15, and naphthalene, DaN = 0.03, determined from kinetic studies which rigorously account for reversibility of DHA reactions. Detailed reaction-transport models synthesize interplay of kinetic, diffusive, and convective length-scales captured by Péclet and Damköhler number to predict influence of catalyst-absorbent proximity and process flow-conditions on aromatization rates. Systematic control of catalyst bed-length, L, or linear flow velocity, u, predictably alters Pe and Da to effect improvements in methane conversion with and without Zr metal, corroborating results from simulation of the reaction-transport model.

Original languageEnglish (US)
Pages (from-to)370-381
Number of pages12
JournalJournal of Catalysis
Volume372
DOIs
StatePublished - Apr 2019

Bibliographical note

Funding Information:
The authors thank Dr. Andrew Hwang for and Mr. Brandon Foley for helpful technical discussions. This work was funded by the US Department of Energy, Office of Basic Energy Science, Catalysis Science Program (Award DE-SC00019028).

Publisher Copyright:
© 2019 Elsevier Inc.

Keywords

  • Methane conversion
  • Molybdenum carbide
  • Non-oxidative
  • Polyfunctional catalysis
  • Reversibility

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