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Catalytic effect of metal nitrate salts during pyrolysis of impregnated biomass

Eibner S., Broust F., Blin J., Julbe A.. 2015. Journal of Analytical and Applied Pyrolysis, 113 : p. 143-152.

DOI: 10.1016/j.jaap.2014.11.024

Catalytic pyrolysis is a promising way to improve bio-oil product quality. In this study, metal salts were directly impregnated in biomass to generate in situ catalysts and investigate their impact on pyrolysis products. Seven metals ¿ Ce, Mn, Fe, Co, Ni, Cu and Zn ¿ were selected and impregnated in eucalyptus using nitrate salts. A fixed-bed reactor, pre-heated at 500 °C and inerted with N2 flow, was used for pyrolysis. Both gas and bio-oil compositions were analysed, paying particular attention to the production of anhydrosugars. The anhydrosugar yields were found to be strongly influenced by the presence of metal salt catalysts. In particular, both Zn and Co salts yielded more anhydrosugars in comparison with catalyst-free sample. Moreover, LAC (1-hydroxy-(1R)-3,6-dioxabicyclo[3.2.1]octan-2-one) was produced in higher amounts than levoglucosan which is commonly produced without any catalyst. Metals were found to remain in all chars and tended to form metal-based nanoparticles (e.g. Cu0, Ni0, ZnO) able to act as in situ catalysts during the pyrolysis process. It seems that those metal nanoparticles are closely related to LAC production. In parallel to metal cations, nitrates were also suspected to play a significant role during pyrolysis. The suspected impact of anions on levoglucosenone production is discussed. Concerning gas yields, the impregnated nitrate salts were found to strongly affect CO2 production.

Mots-clés : eucalyptus; biomasse; cellulose; pyrolyse; nitrate; catalyse; particule de bois; température; nanoparticule

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