An experimental and kinetic modeling study of γ-valerolactone pyrolysis

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• 作者：Ruben De Bruycker^a ; Hans-Heinrich Carstensen^a ; Marie-Franç ; oise Reyniers^a ; Guy B. Marin^a ; John M. Simmie^b ; Kevin M. Van Geem^a ; ^{kevin.vangeem@ugent.be" class="auth_mail" title="E-mail the corresponding author}
• 关键词：γ-valerolactone ; 4-pentenoic acid ; Pyrolysis ; Isodesmic reaction ; Kinetic model
• 刊名：Combustion and Flame
• 出版年：2016
• 出版时间：February 2016
• 年：2016
• 卷：164
• 期：Complete
• 页码：183-200
• 全文大小：3465 K

文摘

The pyrolysis of γ-valerolactone, a cyclic ester readily obtainable from cellulosic biomass and which has potential as a fuel, was investigated from 873 to 1113 K at 0.17 MPa in a tubular continuous flow reactor. Unimolecular decomposition of γ-valerolactone forms 4-pentenoic acid and its selectivity increases upon addition of toluene, a radical scavenger. A kinetic model, consisting of 520 species and 3589 reactions, was developed. Kinetic and thermodynamic data relevant for γ-valerolactone consumption, including hydrogen abstraction, hydrogen addition and fuel radical decomposition, were calculated at the CBS-QB3 level of theory. Experimental and calculated mole fraction profiles are in good agreement. Reaction path analysis shows that γ-valerolactone is mainly consumed by isomerization to 4-pentenoic acid and hydrogen abstraction from the carbon atom α to the carbonyl group and the carbon atom α to the ring oxygen. CC scission of 4-pentenoic acid forming allyl and carboxy methyl is an important source of radicals.