Influence of the Catalyst Particle Size on the Aqueous Phase Reforming of n-Butanol Over Rh/ZrO2

Heikki Harju, Giuseppe Pipitone, Leon Lefferts*

*Corresponding author for this work

Research output: Contribution to journalArticleScientificpeer-review

17 Citations (Scopus)
112 Downloads (Pure)


Butanol is a by-product obtained from biomass that can be valorized through aqueous phase reforming. Rh/ZrO2 catalysts were prepared and characterized, varying the size of the support particles. The results showed a relatively mild effect of internal mass transport on butanol conversion. However, the influence of internal transport limitations on the product distribution was much stronger, promoting consecutive reactions, i.e., dehydrogenation, hydrogenolysis, and reforming of propane and ethane. Hydrogen consuming reactions, i.e., hydrogenolysis, were more strongly enhanced than hydrogen producing reactions due to internal concentration gradients. Large support particles deactivated faster, attributed to high concentrations of butyraldehyde inside the catalyst particles, enhancing deposit formation via aldol condensation reactions. Consequently, also the local butyric acid concentration was high, decreasing the local pH, enhancing Rh leaching. The influence of internal transfer limitation on product distribution and stability is discussed based on a reaction scheme with three main stages, i.e., (1) formation of liquid intermediates via dehydrogenation, (2) formation of gas via decarbonylation/decarboxylation reactions, and (3) hydrocarbon hydrogenolysis/reforming/dehydrogenation.

Original languageEnglish
Article number17
Number of pages13
JournalFrontiers in Chemistry
Publication statusPublished - 28 Jan 2020
MoE publication typeA1 Journal article-refereed


  • aqueous phase reforming
  • hydrogen
  • mass transfer
  • reaction pathway
  • rhodium


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