Biodiesel production from agroforestal residues using oleaginous yeasts Domenico Pirozzi, Giuseppe Toscano, Gerardo Caputo, Giuseppe Travaglini, Abu Yousuf, Gaetano Zuccaro Dipartimento di Ingegneria Chimica, dei Materiali e della Produzione (DICMAPI) Università “Federico II", Napoli, Italia La ricerca e l’innovazione nelle bioraffinerie integrate - ECOMONDO 6/11/2014 Second-generation biodiesel Organic wastes oleaginous fermentation Oleaginous biomass extraction Triglycerides alcoholysis methanol BIODIESEL glycerol La ricerca e l’innovazione nelle bioraffinerie integrate - ECOMONDO 6/11/2014 Oleaginous microorganisms • lipid accumulation under N-depletion • mostly triglycerides oil bodies within a microorganism MICROALGAE photoautotroph OLEAGINOUS YEASTS • promising results • • affected by light,requirements CO2 simpler cultural • higher C/N chemoheterotroph O2 + Nutrients Yeasts + CO2 La ricerca e l’innovazione nelle bioraffinerie integrate - ECOMONDO 6/11/2014 Second-generation biodiesel renewable • abundantly available • ubiquitous • Lignocellulosic materials hydrolysis Organic Mixture ofwastes sugars oleaginous microorganisms Oleaginous biomass extraction Triglycerides alcoholysis methanol BIODIESEL glycerol La ricerca e l’innovazione nelle bioraffinerie integrate - ECOMONDO 6/11/2014 Lignocellulosic materials 40-50% cellulases fermentable sugars 25-35% hemicellulases 15-20% La ricerca e l’innovazione nelle bioraffinerie integrate - ECOMONDO 6/11/2014 Pre-treatment cellulose encapsulated in the lignin-hemicellulose matrix Steam explosion La ricerca e l’innovazione nelle bioraffinerie integrate - ECOMONDO 6/11/2014 Alternative products Lignocellulosic materials hydrolysis Mixture of sugars alcoholic fermentation BIOETHANOL oleaginous microorganisms Oleaginous biomass extraction BIOPLASTICS Triglycerides alcoholysis methanol BIODIESEL glycerol La ricerca e l’innovazione nelle bioraffinerie integrate - ECOMONDO 6/11/2014 CROP: Arundo donax (Giant reed) • high biomass productivity • adaptability to different climatic and soil conditions – • marginal lands: polluted soils, salinized soils protection of hilly soils subjected to erosion La ricerca e l’innovazione nelle bioraffinerie integrate - ECOMONDO 6/11/2014 donax: cultivation under different agronomic conditions A. site water temp. A Torre Lama irrigated high B Torre Lama rainfed high C Centro Rotary rainfed low Biomass% Lipid % Lipid Cellulose, Hemicell., Lignin, % Plant biomass yield, t/haconc. conc. g/L fraction, % g/L 46,2 23,2 16,2 48,7 9.99 19.7 197 43,8 23,5 18,9 50,8 7.81 19.5 152 42,6 7.50 22,8 42,7 16.7 18,7 125 good adaptability to the drought and to the low temperature La ricerca e l’innovazione nelle bioraffinerie integrate - ECOMONDO 6/11/2014 Inhibitors in the hydrolysates of A. donax site water temp. A Torre Lama irrigated high B Torre Lama rainfed high C Centro Rotary rainfed low Acetic acid Levulinic acid Formic acid Furfural 5-HMF vanillin hydroxybenzaldeyde 6.22 1,44 1,67 0,1 0,73 0,035 0,056 7,22 1,21 1,80 0,38 1,06 0,041 0,101 7.10 1,23 1,88 0,35 1,13 0,055 0,088 La ricerca e l’innovazione nelle bioraffinerie integrate - ECOMONDO 6/11/2014 cell biomass, g/L Pretreatments to remove inhibitors 4 • no treatment • overliming with concentrated Ca(OH)2 • neutralization with NaOH + active carbons • overliming + neutralization + active carbons 2 100 200 300 The L. starkeyi were able to grow in the presence of the pre-treated hydrolysate time, h La ricerca e l’innovazione nelle bioraffinerie integrate - ECOMONDO 6/11/2014 Adaptation of L. starkeyi Lipomyces 50% ADH 75% ADH 100% ADH cell biomass, g/L ADH = hydrolysate of Arundo donax • • • 4 ADAPTATION OF L. STARKEYI I cycle II cycle III cycle 2 50 100 The adapted L. starkeyi were able to grow in the presence of the raw hydrolysate time, h La ricerca e l’innovazione nelle bioraffinerie integrate - ECOMONDO 6/11/2014 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 La ricerca e l’innovazione nelle bioraffinerie integrate - ECOMONDO 6/11/2014 Optimization of the process HYDROLYSIS + OLEAGINOUS FERMENT. EXTRACTION + TRANSESTERIFICATION • cellulases from psychrophilic bacteria microwaves • thermophilic yeasts Lignocellulosic materials hydrolysis Mixture of sugars oleaginous yeasts Oleaginous biomass extraction Triglycerides alcoholysis methanol BIODIESEL glycerol Recycle of glycerol La ricerca e l’innovazione nelle bioraffinerie integrate - ECOMONDO 6/11/2014 Phytoremediation • advantages over traditional technologies (ex situ - in situ) – – • disadvantages – • lower costs safeguard of soil properties long-term treatment commercial exploitation: biofuels? La ricerca e l’innovazione nelle bioraffinerie integrate - ECOMONDO 6/11/2014 Effect of soil pollutants • Contamination of biofuels? • Performance of enzyme/microorganisms? – Oxidative stress – Enzyme inhibition – Disruption of regulatory proteins – Reduced repair of DNA Impairment La ricerca e l’innovazione nelle bioraffinerie integrate - ECOMONDO 6/11/2014 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 • compartimentation HM in glycerol? •FERMENTATION detoxification • 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 hydrophobicity of the contaminant selection of the biofuel BIODIESEL Alcoholysis methanol glycerol La ricerca e l’innovazione nelle bioraffinerie integrate - ECOMONDO 6/11/2014 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? • chelating groups of lignin FERMENTATION • Biosorption mechanisms: binding, transmembrane transport Alcoholic fermentation biomass ethanol solution bioethanol Distillation water DISTILLATION • EtOH: logP = -0,58 La ricerca e l’innovazione nelle bioraffinerie integrate - ECOMONDO 6/11/2014 Conclusions • L. starkeyi can be cultured under N-limiting conditions in the presence of hydrolysates of A.donax biomass, to obtain significant lipid yields. • Raw hydrolysates could be used as growth medium upon suitable pre-treatment, or with adapted yeasts • The performance of biodiesel obtained from the microbial oils is satisfactory • A suitable II-generation biofuel can be produced on the basis of the contaminants present in the soil La ricerca e l’innovazione nelle bioraffinerie integrate - ECOMONDO 6/11/2014 THANK YOU FOR YOUR ATTENTION La ricerca e l’innovazione nelle bioraffinerie integrate - ECOMONDO 6/11/2014 Exploitation of lignocellulosic biomasses • large amounts of waste biomasses available – non-food parts of crops (stems, leaves and husks) – forest products – industry wastes (woodchips, skin and pulp from fruit pressing, etc.); • higher yield of triglycerides per unit area • non-food crops for partially-fertile soils – switchgrass, jatropha, miscantus, etc. La ricerca e l’innovazione nelle bioraffinerie integrate - ECOMONDO 6/11/2014 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 La ricerca e l’innovazione nelle bioraffinerie integrate - ECOMONDO 6/11/2014 Bioethanol WORLDWIDE PRODUCTION COMMERCIAL APPLICATIONS • alcoholic beverages • solvent/reagent for chemical syntheses • medical • cosmetics • automotive fuel (USA: E10, E15 – Brazil: E100, blends) La ricerca e l’innovazione nelle bioraffinerie integrate - ECOMONDO 6/11/2014 Bioethanol Starch seeds, tubers, etc. enzymatic hydrolysis sugar crops Mixture of sugars alcoholic fermentation BIOETHANOL FERMENTATIVE METHOD Ascomycetes: Sacch. cerevisiae Basidiomycetes: Candida utilis La ricerca e l’innovazione nelle bioraffinerie integrate - ECOMONDO 6/11/2014 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 BIODIESEL glycerol La ricerca e l’innovazione nelle bioraffinerie integrate - ECOMONDO 6/11/2014 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 La ricerca e l’innovazione nelle bioraffinerie integrate - ECOMONDO 6/11/2014 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 La ricerca e l’innovazione nelle bioraffinerie integrate - ECOMONDO 6/11/2014 Second-generation bioethanol Lignocellulosic materials hydrolysis Mixture of sugars alcoholic fermentation BIOETHANOL Triglycerides alcoholysis methanol BIODIESEL glycerol La ricerca e l’innovazione nelle bioraffinerie integrate - ECOMONDO 6/11/2014 Industrial application Mossi & Ghisolfi - Crescentino (Vercelli) PROESA technology La ricerca e l’innovazione nelle bioraffinerie integrate - ECOMONDO 6/11/2014 Oleaginous microorganisms MICROALGAE OLEAGINOUS YEAST photoautotroph chemoheterotroph CO2 + water + light (+ nutrients) O2 + Nutrients Algae + O2 Yeasts + CO2 Possible synergistic application La ricerca e l’innovazione nelle bioraffinerie integrate - ECOMONDO 6/11/2014 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 BIODIESEL glycerol La ricerca e l’innovazione nelle bioraffinerie integrate - ECOMONDO 6/11/2014
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