Il Modello EcoRemed: impiego di biomasse agricole da suoli contaminati per la produzione di biodiesel
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1 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
2 Phytoremediation advantages over traditional technologies (ex situ - in situ) lower costs safeguard of soil properties disadvantages long-term treatment commercial exploitation: biofuels?
3 Bioethanol WORLDWIDE PRODUCTION COMMERCIAL APPLICATIONS alcoholic beverages solvent/reagent for chemical syntheses medical cosmetics automotive fuel (USA: E10, E15 Brazil: E100, blends)
4 Bioethanol Starch enzymatic hydrolysis Mixture of sugars alcoholic fermentation BIOETHANOL seeds, tubers, etc. sugar crops FERMENTATIVE METHOD Ascomycetes: Sacch. cerevisiae Basidiomycetes: Candida utilis
5 Bioethanol and Biodiesel Starch enzymatic hydrolysis Mixture of sugars alcoholic fermentation BIOETHANOL seeds, tubers, etc. sugar crops residual oils plants for unfertile soils Triglycerides alcoholysis BIODIESEL oleaginous crops methanol glycerol
6 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
7 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
8 Second-generation bioethanol Lignocellulosic materials hydrolysis Mixture of sugars alcoholic fermentation BIOETHANOL Triglycerides alcoholysis BIODIESEL methanol glycerol
9 Lignocellulosic materials 40-50% 25-35% cellulases hemicellulases fermentable sugars 15-20%
10 Pre-treatment cellulose encapsulated in the lignin-hemicellulose matrix Steam explosion
11 Industrial application Mossi & Ghisolfi - Crescentino (Vercelli) PROESA technology
12 Second-generation biodiesel Lignocellulosic materials hydrolysis Mixture of sugars alcoholic fermentation BIOETHANOL growth of oleag. yeasts Oleaginous biomass extraction Triglycerides alcoholysis BIODIESEL methanol glycerol
13 Oleaginous microorganisms waste organic matters urban/industrial wastewaters lignocellulosic materials Lipid droplets within the microorganisms MICROALGAE photoautotroph OLEAGINOUS YEAST chemoheterotroph CO 2 + water + light (+ nutrients) Algae + O 2 O 2 + Nutrients Yeasts + CO 2 Possible synergistic application
14 Recycle of glycerol Bioplastics Further improvements Lignocellulosic materials hydrolysis Mixture of sugars alcoholic fermentation BIOETHANOL oleag. yeasts culture BIOPLASTICS Oleaginous biomass extraction Triglycerides alcoholysis BIODIESEL methanol glycerol
15 Distribution of fatty acids Agronomic treatment A B C A A Fatty acid Hydrolysate mixture ADH 50% ADH 50% ADH 50% ADH 100% (sorption with act. carbon) ADH 100% (with adapted L. starkeyi) Myristic acid C14: Palmitic acid C16: Palmitoleic acid C16:1 <1 <1 <1 <1 <1 Stearic acid C18: Oleic acid C18: Linoleic acid C18: Linolenic acid C18: Arachidonic acid C20:4 <1 <1 <1 <1 <1 Reduced tendency to oxidation Satisfactory cold performance
16 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
17 Fate of heavy metals in biodiesel process HEAVY METALS Root Absorption lignocellulosic materials Hydrolysis lignin TRIGLYCERIDE EXTRACTION HM in non-lipidic components? bi- or tri-insaturated fatty acids ROOT ABSORPTION ALCOHOLYSIS reduced uptake FERMENTATION storage HM in glycerol? oxidative-stress Biosorption mechanisms: defense binding, transmembrane transport Fermentation Triglyceride extraction mixture of sugars oleaginous biomass spent medium non-lipidic components HYDROLYSIS HM in the aqueous misture of sugars? chelating groups of lignin BIOPLASTICS triglycerides Alcoholysis BIODIESEL methanol glycerol
18 Fate of heavy metals (bioethanol process) HEAVY METALS Root Absorption lignocellulosic materials Hydrolysis Lignin (chelation?) 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 mixture of sugars Alcoholic fermentation biomass ethanol solution Distillation water DISTILLATION EtOH: logp = -0,58 bioethanol
19 KEY ASPECTS SELECTION OF PLANTS Compartimentalization SELECTION OF MICROORGANISMS Bioaccumulation Resistance to toxic pollutants SELECTION OF THE PROCESS Hydrophilic pollutants: oleaginous fermentation to be preferred Hydrophobic pollutants: alcoholi fermentation to be preferred
20 THE END
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