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 journalArticle

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 1 2019

Fingerprint

Methane
Hydrogen
methane
beds
catalysts
Catalysts
Kinetics
kinetics
hydrogen
Aromatization
absorbents
Naphthalene
Benzene
naphthalene
proximity
Metals
benzene
Advection
advection
Zirconium

Keywords

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

Cite this

Controlling kinetic and diffusive length-scales during absorptive hydrogen removal in methane dehydroaromatization on MoCx/H-ZSM-5 catalysts. / Razdan, Neil K; Kumar, Anurag; Bhan, Aditya.

In: Journal of Catalysis, Vol. 372, 01.04.2019, p. 370-381.

Research output: Contribution to journalArticle

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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 P{\'e}clet 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 Damk{\"o}hler 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 P{\'e}clet and Damk{\"o}hler 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.",
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