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Pyrolysis is a thermochemical route for converting waste plastics into hydrocarbons that might be further upgraded to fine chemicals via the process such as hydrotreatment. In this study, the pyrolysis of five typical plastics (PE, PP, PVC, PS and PET) and steam reforming of their derived volatiles were coupled in one process, named as pyro-reforming. The reaction behaviors, especially the property of their derived cokes, in the pyro-reforming were investigated. The results indicated that the volatiles from the pyrolysis of PE had the highest reactivity with steam to produce H 2 of the highest yield, followed by that of PP, PVC, PET and PS. The Cl in PVC promoted nickel sintering, enhanced formation of heavy aromatics through aromatization. Moreover, the existence of Cl interrupted formation of carbon nanotube, forming the highest amount of coke with hemp rope-like fiber form of very coarse surface. This was very different from the carbon nanotube form of coke with smooth surface and uniform outer/inner diameters from the pyro-reforming of PE or PP. The pyro-reforming of PET or PS generated mainly the aromatic intermediates that were chemically more inert in steam reforming, forming polymeric type of coke with no carbon nanotube morphology and very low crystallinity. The light organics in pyrolytic products could be reformed to provide hydrogen for hydrotreatment of the heavier ones. [Display omitted] • H2 yield in pyro-reforming follows the order: PE > CEL > PP > PVC > PET > PS. • Cl in PVC promotes Ni sintering, aromatization and formed coke of highest amount. • PET/PS pyrolysis forms chemically inert aromatics that are difficult to be reformed. • PE/PP/PVC coke contains carbon crystal and aliphatic ones in nanotube/twine form. • Coke of PET/PS is polymeric type with amorphous morphology and low crystallinity. [ABSTRACT FROM AUTHOR]

[Display omitted] • Much more coke forms in upper-layer Ni/KIT-6 in steam reforming of acetic acid. • Used Ni/KIT-6 is more effective to inhibit coking than fresh counterpart Ni/KIT-6. • More O-containing species form over used catalyst via influence from original coke. • O-containing species pass down to lower layer and promote polymeric coke formation. • Used catalyst in upper layer reduces the stability and crystallinity of coke. Deactivated or coked catalyst from steam reforming may not always be treated as a solid waste, which might be potentially used as a sacrificial or protective layer of catalyst for reducing coke formation of catalyst in the lower bed in the same steam reforming process. In this study, steam reforming of acetic acid over Ni/KIT-6 at 600 °C was conducted with used Ni/KIT-6 in upper layer and freshly reduced Ni/KIT-6 in lower layer (dual-bed system). The results suggested that significantly more coke (3 to 4 times) formed on upper-layer catalyst (used or fresh catalyst) than on lower-layer fresh catalyst. The upper-layer used catalyst was more effectively than counterpart of fresh catalyst for mitigating coking in lower-layer catalysts. The in-situ IR technique suggested that carbonaceous species on the used catalyst impacted or reacted with the intermediates newly formed, generating more oxygen-containing species with functionalities like C O C and C O of anhydride or ketones/aldehyde form. These oxygen-containing species could polymerize/condense and pass down to the lower bed, forming more polymeric coke of lower thermal stability. Differently, more unsaturated hydrocarbon species formed on the upper-layer fresh catalyst, making the coke of highly aromatic nature with a higher thermal stability and crystallinity. Additionally, modification of reaction intermediates with the used catalyst in upper layer also formed carbon nanotubes of irregular structures with coarse surface. [ABSTRACT FROM AUTHOR]

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]