Journal of Analytical and Applied Pyrolysis 94 (2012) 223–229 Contents lists available at SciVerse ScienceDirect Journal of Analytical and Applied Pyrolysis journa l h o me page: www.elsevier.com/locate/jaap Py-GC/MS characterization of a wild and a selected clone of Arundo donax, and of its residues after catalytic hydrothermal conversion to high added-value products Erika Ribechini a,∗ , Marco Zanaboni a , Anna Maria Raspolli Galletti a , Claudia Antonetti a , Nicoletta Nassi o Di Nasso b , Enrico Bonari b , Maria Perla Colombini a a Dipartimento di Chimica e Chimica Industriale, University of Pisa, Via Risorgimento 35, 56126 Pisa, Italy b Land Lab Scuola Superiore Sant’Anna, via Santa Cecilia 3, 56127 Pisa, Italy a r t i c l e i n f o Article history: Received 4 October 2011 Accepted 17 December 2011 Available online 27 December 2011 Keywords: Py(HMDS)-GC/MS GC/MS Giant reed (Arundo donax) Catalytic hydrolysis Lignin Polysaccharides a b s t r a c t Two analytical procedures based on gas chromatography and mass spectrometry were used to study the compositions of a wild population and a selected clone (Torviscosa) of giant reed (Arundo donax L.), one of the most promising biomass both in terms of energy and fine chemicals production. Gas chromatography/mass spectrometry (GC/MS) was used to characterize and quantitatively determine the monosaccharide composition. Pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS), using hex- amethyldisilazane (HMDS) as a derivatising agent, was used to characterize the lignocellulosic polymers. Analytical pyrolysis was also used to study the composition of residues left after the catalytic hydrolysis used to convert cellulose to levulinic acid and hemicellulose to furfural. GC/MS allowed us to determine the monosaccharide composition and polysaccharide content of the giant reed samples, highlighting that there was no significant difference between the wild population and the selected clone. GC/MS also highlighted that the giant reed leaves have a higher percentage (roughly 60%) of polysaccharide material than the stalks, which contain approximately 50%. Py-GC/MS, following the disappearance of the pyrolysis products of polysaccharides, showed that 150 ◦ C and 190 ◦ C are the best temperatures to obtain the complete catalytic conversion of hemicellulose and cellulose, respectively. Analytical pyrolysis also highlighted that in the course of catalytic hydrother- mal conversion a partial depolymerisation of lignin was obtained. In particular, the formation of lignin units containing free phenol groups via the cleavage of the -aryl ether bonds was demonstrated. The presence of these free phenols in the lignin network suggests the possible exploitation of lignin residues as antioxidant components or in high value biopolymer industries rather than the traditional use as low-value fuel for energy production. © 2011 Elsevier B.V. All rights reserved. 1. Introduction Lignocellulosic biomass is an abundant and sustainable source for the production of fuels and high added-value products, the so- called “fine chemicals”. The successful subtraction of simple and defined chemical building blocks from the natural complexity of the biomass represents a very important step for biomass exploitation. Thus selective production of furfural and levulinic acid by biomass has gained increasing attention: acid hydrothermal conversion of C 5 -sugars of hemicellulose produces furfural, while the decom- position of C 6 -sugar fragments leads to levulinic acid as a final product [1]. Furfural and levulinic acid are versatile intermediates for organic chemical synthesis. Levulinic acid is one of the United ∗ Corresponding author. Tel.: +39 0502219312; fax: +39 0502219260. E-mail address: erika@dcci.unipi.it (E. Ribechini). States Department of Energy’s (DOE) top 12 bio-derived feedstocks [2]: it can be used as a solvent, antifreeze, food flavouring agent, and as an intermediary in the synthesis of biofuels, pharmaceuticals and plasticizers. To develop conversion processes for the efficient use of biomass resources, it is important to understand their carbohydrate and lignin chemistry. This is extremely important in order to predict the formation of target compounds, to relate the conversion yields to the biomass characteristics, and to compare the potentialities of various types of biomass. In addition, in order to increase the profitability of the entire conversion process, the possible valoriza- tion pathways for solid lignin residues must be assessed, which also entails a careful chemical characterization. For these purposes, a variety of characterization methods have normally been used which are commonly employed in paper and pulp industries and which are mainly based on wet chemistry, such as TAPPI stan- dard methods. These include the determination of water content, 0165-2370/$ – see front matter © 2011 Elsevier B.V. All rights reserved. doi:10.1016/j.jaap.2011.12.013