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The small molecular organics in bio-oil could not be effectively transformed into hydrocarbons with long aliphatic chains or aromatic rings via hydrotreatment, but they could be reformed with steam to generate hydrogen for the hydrotreatment. In this study, the pyrolysis of cellulose coupled with steam reforming of volatiles of small molecular size were performed at 400–600 °C over Ni/Al 2 O 3 catalyst, which is termed as a pyro-reforming process for simultaneous production of hydrogen and heavy organics for further production of biofuels. The results indicated that the effective reforming of small volatiles became dominant at 600 °C. The coke formed at the low temperatures was mainly polymeric coke of aliphatic nature with low thermal stability, low carbon crystallinity, high reactivity towards oxidation and high hydrophilicity. Increase of temperature to 600 °C reduced the formation of coke (from maximum of 15.0%–12.8%) and suppressed the formation of polymeric coke by promoting gasification of precursors of coke. This enhanced formation of catalytic coke with amorphous morphology as well as defective ring structures. However, homogeneous polymerization of volatiles also took place, forming amorphous coke between catalyst particles. Formation of polymeric coke should be tackled for the successful implementation of pyro-reforming process. [Display omitted] • Pyro-reforming of cellulose to H 2 and heavy organics occurs effectively at 600 °C. • Coke formed at 400 °C is polymeric, originating from polymerization of volatiles. • More thermally stable catalytic coke while less polymeric coke forms at 600 °C. • Ratio of aliphatic coke decreases at higher temperature, but it is not negligible. • Homogeneous polymerization of volatile occurs and fills gap of catalyst particles. [ABSTRACT FROM AUTHOR]

[Display omitted] • Pyro-reforming of sawdust co-produces H 2 and heavy organics effectively above 550℃. • Small acids and ketones are reformed while furans, anhydrate sugars, phenols retain. • Coking from cracking/polymerization of volatiles reached the maximum at 500℃. • Dominant reforming at 650℃ aids coke elimination and forms nanotube coke. • Coke at lower temperature is amorphous and more aliphatic with low crystallinity. In hydrotreatment of bio-oil, it is difficult to convert the aliphatic compounds with the carbon number less than four into liquid fuel via hydrodeoxygenation. Thus, ideally, the very light organics of bio-oil could be reformed to generate hydrogen for further upgrading the heavier organics in bio-oil to biofuel or fine chemicals. In this study, the pyrolysis of poplar sawdust coupled with the simultaneously steam reforming of the bio-oil (pyro-reforming) were studied over Ni/SBA-15 catalyst at the medium temperature range from 450 to 650 °C for transforming mainly the light aliphatic compounds into H 2. The results showed that the effective steam reforming of the aliphatic compounds like carboxylic acid and small aldehydes/ketones took place to remarkable extent from 550 °C, while the furans, anhydrate sugars, light phenols and heavy phenolics of fused ring structures could be largely retained in the resulting bio-oil. Coking reached the maximum with increasing temperature to 500 °C from cracking/polymerization of the volatiles. Further increase of temperature to 650 °C accelerated steam reforming and gasification of precursors of coke, shifting the morphology of coke from amorphous form to unregular carbon nanotube structures (stringed beads-like) and making the coke more aromatic and more resistant to oxidation. Nevertheless, in overall, the coke produced from 450 to 650 °C was aliphatic with low C/H ratio, low thermal stability and low crystallinity, originating from the significant contribution from the aliphatic compounds in the bio-oil for coking. [ABSTRACT FROM AUTHOR]