Il Modello EcoRemed: impiego di biomasse agricole da suoli contaminati per la produzione di biodiesel Domenico Pirozzi Dipartimento di Ingegneria Chimica, dei Materiali e della Produzione (DICMAPI) Università “Federico II", Napoli, Italia IRISpecchi 4 - RIFIUTI E SVILUPPO ECONOMICO ECOLOGICO, 11/7/2014 Phytoremediation • advantages over traditional technologies (ex situ - in situ) – – • disadvantages – • lower costs safeguard of soil properties long-term treatment commercial exploitation: biofuels? IRISpecchi 4 - RIFIUTI E SVILUPPO ECONOMICO ECOLOGICO, 11/7/2014 Bioethanol WORLDWIDE PRODUCTION • • • • • COMMERCIAL APPLICATIONS alcoholic beverages solvent/reagent for chemical syntheses medical cosmetics automotive fuel (USA: E10, E15 – Brazil: E100, blends) IRISpecchi 4 - RIFIUTI E SVILUPPO ECONOMICO ECOLOGICO, 11/7/2014 Bioethanol Starch seeds, tubers, etc. enzymatic hydrolysis sugar crops Mixture of sugars alcoholic fermentation BIOETHANOL FERMENTATIVE METHOD Ascomycetes: Sacch. cerevisiae Basidiomycetes: Candida utilis IRISpecchi 4 - RIFIUTI E SVILUPPO ECONOMICO ECOLOGICO, 11/7/2014 Bioethanol and Biodiesel Starch seeds, tubers, etc. enzymatic hydrolysis Mixture of sugars alcoholic fermentation BIOETHANOL sugar crops residual oils plants for unfertile soils oleaginous crops Triglycerides alcoholysis methanol IRISpecchi 4 - RIFIUTI E SVILUPPO ECONOMICO ECOLOGICO, 11/7/2014 BIODIESEL glycerol Classification of Biofuels First Generation (from sugars, grains, or seeds) • Bioethanol – – • from sugar crops: sugar beets, sugarcane from grains or seeds: corn, wheat, potato Biodiesel – from rapeseed, soybeans, sunflowers, jatropha, coconut, palm, recycled cooking oil Bottlenecks of the first generation biodiesel • fertile soils not available • social problems • deforestation IRISpecchi 4 - RIFIUTI E SVILUPPO ECONOMICO ECOLOGICO, 11/7/2014 Classification of Biofuels First Generation (from sugars, grains, or seeds) • Biodiesel – • rapeseed, soybeans, sunflowers, jatropha, coconut, palm, recycled cooking oil Ethanol – – From grains or seeds: corn, wheat, potato From sugar crops: sugar beets, sugarcane Second Generation (from lignocellulose: crop residues, grasses, woody crops) • Biological fuels – • Hydrolysis Fermentation Thermochemical fuels (most made via “gasification”) – – – – – Fischer-Tropsch liquids (FTL) Methanol, MTBE, gasoline Dimethyl ether (DME) Mixed alcohols Green diesel IRISpecchi 4 - RIFIUTI E SVILUPPO ECONOMICO ECOLOGICO, 11/7/2014 Second-generation bioethanol Lignocellulosic materials hydrolysis Mixture of sugars alcoholic fermentation BIOETHANOL Triglycerides alcoholysis methanol IRISpecchi 4 - RIFIUTI E SVILUPPO ECONOMICO ECOLOGICO, 11/7/2014 BIODIESEL glycerol Lignocellulosic materials 40-50% cellulases fermentable sugars 25-35% hemicellulases 15-20% IRISpecchi 4 - RIFIUTI E SVILUPPO ECONOMICO ECOLOGICO, 11/7/2014 Pre-treatment cellulose encapsulated in the lignin-hemicellulose matrix Steam explosion IRISpecchi 4 - RIFIUTI E SVILUPPO ECONOMICO ECOLOGICO, 11/7/2014 Industrial application Mossi & Ghisolfi - Crescentino (Vercelli) PROESA technology IRISpecchi 4 - RIFIUTI E SVILUPPO ECONOMICO ECOLOGICO, 11/7/2014 Second-generation biodiesel Lignocellulosic materials hydrolysis Mixture of sugars alcoholic fermentation BIOETHANOL growth of oleag . yeasts Oleaginous biomass extraction Triglycerides alcoholysis methanol IRISpecchi 4 - RIFIUTI E SVILUPPO ECONOMICO ECOLOGICO, 11/7/2014 BIODIESEL glycerol Oleaginous microorganisms • waste organic matters • urban/industrial wastewaters • lignocellulosic materials Lipid droplets within the microorganisms MICROALGAE OLEAGINOUS YEAST photoautotroph chemoheterotroph CO2 + water + light (+ nutrients) O2 + Nutrients Algae + O2 Yeasts + CO2 Possible synergistic application IRISpecchi 4 - RIFIUTI E SVILUPPO ECONOMICO ECOLOGICO, 11/7/2014 Further improvements Recycle of glycerol Bioplastics Lignocellulosic materials hydrolysis Mixture of sugars alcoholic fermentation BIOETHANOL oleag . yeasts culture Oleaginous biomass extraction BIOPLASTICS Triglycerides alcoholysis methanol IRISpecchi 4 - RIFIUTI E SVILUPPO ECONOMICO ECOLOGICO, 11/7/2014 BIODIESEL glycerol Distribution of fatty acids Agronomic treatment A B C A A Hydrolysate mixture ADH 50% ADH 50% ADH 50% ADH 100% (sorption with act. carbon) ADH 100% (with adapted L. starkeyi) 2 23.7 <1 16.3 46.5 6.5 1.6 <1 1.8 24.1 <1 16.2 45.8 6.7 1.8 <1 1.9 23.8 <1 16.3 46 6.6 1.8 <1 1.7 22.3 <1 15.8 49.5 6.3 1.5 <1 1.9 22.7 <1 16 48.7 6.4 1.5 <1 Fatty acid Myristic acid C14:0 Palmitic acid C16:0 Palmitoleic acid C16:1 Stearic acid C18:0 Oleic acid C18:1 Linoleic acid C18:2 Linolenic acid C18:3 Arachidonic acid C20:4 • Reduced tendency to oxidation • Satisfactory cold performance IRISpecchi 4 - RIFIUTI E SVILUPPO ECONOMICO ECOLOGICO, 11/7/2014 Effect of soil pollutants • Contamination of biofuels/wastes • Poor performance of microorganisms (reduced biofuel yield) – – – – Oxidative stress Enzyme inhibition Disruption of regulatory proteins Reduced repair of DNA Impairment A suitable choice of plants, microorganism, process is required IRISpecchi 4 - RIFIUTI E SVILUPPO ECONOMICO ECOLOGICO, 11/7/2014 Fate of heavy metals in biodiesel process HEAVY METALS Root Absorption lignocellulosic materials lignin Hydrolysis mixture of sugars TRIGLYCERIDE EXTRACTION • HM in non-lipidic components? • bi- or tri-insaturated fatty acids ROOT ABSORPTION ALCOHOLYSIS • reduced uptake •FERMENTATION HM in glycerol? storage •• oxidative-stress defense Biosorption mechanisms: binding, transmembrane transport Fermentation spent medium HYDROLYSIS • HM in the aqueous misture of sugars? • chelating groups of lignin oleaginous biomass Triglyceride extraction non-lipidic components triglycerides BIOPLASTICS BIODIESEL Alcoholysis methanol IRISpecchi 4 - RIFIUTI E SVILUPPO ECONOMICO ECOLOGICO, 11/7/2014 glycerol Fate of heavy metals (bioethanol process) HEAVY METALS Root Absorption lignocellulosic materials Hydrolysis Lignin (chelation?) mixture of sugars ROOT ABSORPTION • reduced uptake • storage HYDROLYSIS • oxidative-stress defense • HM in the aqueous misture of sugars? •FERMENTATION chelating groups of lignin • Biosorption mechanisms: binding, transmembrane transport Alcoholic fermentation ethanol solution bioethanol Distillation water biomass DISTILLATION • EtOH: logP = -0,58 IRISpecchi 4 - RIFIUTI E SVILUPPO ECONOMICO ECOLOGICO, 11/7/2014 KEY ASPECTS • SELECTION OF PLANTS – • SELECTION OF MICROORGANISMS – – • Compartimentalization Bioaccumulation Resistance to toxic pollutants SELECTION OF THE PROCESS – – Hydrophilic pollutants: oleaginous fermentation to be preferred Hydrophobic pollutants: alcoholi fermentation to be preferred IRISpecchi 4 - RIFIUTI E SVILUPPO ECONOMICO ECOLOGICO, 11/7/2014 THE END IRISpecchi 4 - RIFIUTI E SVILUPPO ECONOMICO ECOLOGICO, 11/7/2014
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