LE BIOMASSE LIGNOCELLULOSICHE

Qualsiasi materiale organico rinnovabile, di origine vegetale o animale, che non abbia subito alcun processo di fossilizzazione Allinterno di questa categoria rientrano le piante da coltivazione (cereali, frutta, verdura ecc) e i loro residui (paglia, malli, fogliame ecc), le piante acquatiche, il legno (angiosperme e gimnosperme) e i suoi residui (rami, corteccia ecc), gli scarti municipali, i reflui animali, gli scarti cellulosici (carta da giornale) ed altri tipi di scarti Tra le biomasse vegetali è importante fare una distinzione: esistono, infatti, biomasse ricche di polisaccaridi e amido (mais, canna da zucchero) e biomasse definite lignocellulosiche (costituite principalmente da cellulosa, emicellulose e lignina). BIOMASSE

BIOMASSE LIGNOCELLLOSICHE Rappresentano circa il 50% della biomassa mondiale e la loro produzione annua è stimata intorno ai 100 miliardi di tonnellate

Differenti tipi di scarti lignocellulosici ed il loro utilizzo attuale BIOMASSE LIGNOCELLLOSICHE

Categoria A Residui derivanti la crescita e la raccolta di prodotti per uso alimentare (paglia, potature, fogliame ecc.) A1Produzione di cereali, riso, mais e semi (girasoli e legumi) A2Residui legnosi provenienti dalla potatura di vigne, oliveti, frutteti A3 Specie rimanenti (residui di tabacco, verdura, barbabietola da zucchero) Categoria B Residui derivati dalla lavorazione di prodotti agricoli per la vendita B1Residui della produzione di vino B2Residui della produzione di olio doliva B3Malli, gusci e noccioli di nocciole, castagne, frutta B4 Gusci di semi di soia, girasole e colza, semi e bucce di frutta e verdura, lolla del riso BIOMASSE LIGNOCELLLOSICHE

TWO AGRICULTURAL RESIDUES AND TWO HERBACEOUS ENERGY CROPS AS A SOURCE OF LIGNOCELLULOSIC MATERIALS Agroindustrial by-products from crops processing and invasive, fast growing perennial plants are receiving increasing attention for: Annual renewability Large annual biomass stock Widespread availability Ability to grow in different soil types and climatic conditions RICE HUSK (600 mln tons/year) ARUNDO DONAX (550 mln tons/year) WHEAT STRAW MISCANTHUS SINENSIS

WHERE ARE CULTIVATED IN ITALY RICE HUSK AND GIANT CANE

WHAT IS RICE HUSK ? Rice is one of the most cultivated crops in the world with a global production of about 680 million tons/year). Italy produces approximately 1.4 million tons/year of rice, with the 90% of this production concentrated in the Northern Italy; Rice husk, the outer cover of rice grain, is among the principal processing side-products of the rice milling industry and accounts for about 20% by weight of rice; Rice husk does not possess a remarkable commercial interest and its price is very low ( /ton in Italy; Because of the elevated ashes and lignin content, rice husk is not appropriate as animal feed raw material; Rice husk can be burnt under controlled conditions to obtain a large amount of silica.

Arundo donax is a tall perennial cane growing in damp soils, either fresh or moderately saline Arundo donax is strong candidate for use as a renewable biofuel source because of its fast growth rate, ability to grow in different soil types and climatic conditions. What is Arundo donax (Giant Cane)

ANALYTICAL PROTOCOL CARATTERIZZAZIONE DELLE PIANTE ANNUALI Per vedere se possono essere utilizzate nello stesso impiantp di biorefinery HEMICELLULOSE

Lignin: from 19% to 30% Lignin: from 19% to 30% Carbohydrates: from 62% to72% Carbohydrates: from 62% to72% *constituted of around 85-90% amorphous silica Compositional evaluation of RH, GC, WS, and MS expressed as klason lignin, ash, and holocellulose content RICE HUSK GIANT CANE WHEAT STRAW MISCANTHUS SINENSIS Lignin (%) Ash (%) 16.0* Holocellulose (%)

AVERAGE MOLECULAR WEIGHT INDEXES OF EXTRACTED LIGNIN SAMPLES RICE HUSK - Acidolysis L. ARUNDO DONAX - Acidolysis L. WHEAT STRAW - Acidolysis L. MISCANTHUS SINENSIS – Acidolysis L. Mn (g/mol) Mw (g/mol) I4,05,55,63,7 GPC DATA FOR ACIDOLYSIS LIGNIN (AL) SPECIMENS EXTRACTED FROM RICE HUSK, ARUNDO DONAX, WHEAT STRAW, AND MISCANTHUS SINENSIS

QUALITATIVE ASSESSMENT OF INTERMONOMERIC LINKAGES BY 2D-HSQC-NMR RICE HUSK ACIDOLYSIS LIGNINARUNDO DONAX ACIDOLYSIS LIGNIN γ γ OCH 3 P-OH (p-coumarate) G-OH (ferulate)

RICE HUSK L. ARUNDO DONAX L WHEAT STRAW L. MISCANTHUS SINENSIS L. Aliph OH (mmol/g)2,894,353,423,47 β-O-4 (mmol/g)1,271,741,311,69 Cond PhOH + S-OH (mmol/g) 0,210,320,290,27 G-OH (mmol/g)0,61 0,670,58 P-OH (mmol/g)0,660,530,430,77 COOH (mmol/g)0,220,150,290,17 31P-NMR QUANTIFICATION OF LABILE HYDROXYL GROUPS ON EXTRACTED LIGNIN SAMPLES

The amount of ashes in R.H are much more higher than in W.S, M.S and A.D In all these annual plants is present an high molecular weight fraction of polysaccharides free of aromatic compounds In all these annual plants is present a large amount of polysaccharides containing aromatic compounds The molecular weight distribution of fractions in R.H is different than in A.D, M.S and W.S R H is mainly formed by guaiacyl and p-hydroxyphenyl units, and by -O-4 and -5 intermonomeric bonds A.D and W.S. are mainly formed by guaiacyl and p-hydroxyphenyl units, and by -O-4, -5 and - intermonomeric bonds CONCLUSIONS

Can agroindustrial by-products from crops processing and invasive, fast growing perennial plants be the right starting materials for a biorefinery process? Yes Can different agroindustrial by-products and invasive, fast growing perennial plants be treated in the same biorefinery plant ? Yes for A.D W.S and M.S, serious problems for R.H