From wine pomace and potato wastes to novel PHA- based bio-composites: examples of sustainable routes for full valorisation of the agro-wastes M. Vannini, 1 , P . Marchese 1 , L. Sisti 1 , A. Celli 1 , M. Ferri 1 , 2 , S. Monari 2 , A. T assoni 2 , M. Ehrnell 3 , L. Eliasson 3 , E. Xanthakis 3 , T. Mu 4 , H. Sun 4 1 Department of Civil, Chemical, Environmental, and Materials Engineering, University of Bologna, Italy; 2 Department of Biological, Geological, and Environmental Sciences, University of Bologna, Italy; 3 Agrifood & Bioscience Unit, RISE – Research Institutes of Sweden, Sweden; 4 Laboratory of Food Chemistry and Nutrition Science, Institute of Food Science and T echnology, Chinese Academy of Agricultural Sciences; Key Laboratory of Agro-Products Processing, Ministry of Agriculture and Rural Afgairs, China
WP4 T ask 1 UNIBO Enzymatic Chemical Mixed fruit Extraction INNOVE RISE CO2, & N Potato pressured vegetable Wine Vine Shoots liquid processing hydrolysat extraction Pomaces waste e SEE INRA, UM, Process set-up INRA Supagro Depolymerisati with Characterization engineered on IAPPST of strain strains performances Aromatic Polyphen Extracti Lignocellulosi acids Succini on ol Proteins Pectins c fjllers (vanillic c Acid residues extracts acid) UM ITRI UNIBO Fiber IAPPST Use of functionalizati UNIBO polypheno on polymerizati ls as UNIBO on additives for polymers Dietary BPA-free Biocomposit Active Biopolyeste suppleme biopolyme es packaging rs nts rs INRA Polymerisati on PHBV INNOVEN, matrix UniROMA
WP4 T ask 1 UNIBO Enzymatic Chemical Mixed fruit Extraction INNOVE RISE CO2, & N Potato pressured vegetable Wine Vine Shoots liquid processing hydrolysat extraction Pomaces waste e SEE INRA, UM, Process set-up INRA Supagro Depolymerisati with Characterization engineered on IAPPST of strain strains performances Aromatic Polyphen Extracti Lignocellulosi acids Succini on ol Proteins Pectins c fjllers (vanillic c Acid residues extracts acid) UM ITRI UNIBO Fiber IAPPST Use of functionalizati UNIBO polypheno on polymerizati ls as UNIBO on additives for polymers Dietary BPA-free Biocomposit Active Biopolyeste suppleme biopolyme es packaging rs nts rs INRA Polymerisati on PHBV INNOVEN, matrix UniROMA
Choice of polymeric matrix Poly(hydroxyalkanoate)s (PHA)s are a family of microbial biopolymers. They have excellent biocompatible and CO 2 biodegradable properties The PHAs are particularly expensive and lack mechanical properties .
PHBV: poly(3-HydroxyButirate- co -Valerate) 1 H e c NMR c, d d PHB/PHV: 98/2 (mol/mol) b b a a PHBV thermal properties: T onset : 288°C T D : 302°C b a T m : 172°C, ΔH m : 78 J/g T c : 114°C, ΔH c : 73 J/g e
Composites preparation The composites are prepared by melt mixing in a Brabender microcompounder . load: 45−50 g For each fjber residue, difgerent blends screw speed: 50 rpm were prepared containing temperature: 200 °C 5, 10 or 20 wt% of residue. mixing time: 5 min
Extractions of polyphenols from wine pomaces T wo methods: Merlot Garganeg a Solvent-based Pressurized liquid extractions (only on extractions red pomaces) Best conditions: Ethanol/Water 50/5 (vol/vol) Best conditions: Acetone/Water 75/25 (vol/vol)
Characterization of chemically extracted residue (UNIBO) Thermogravimetric Gargane Merlot analyses ga (RED) (WHITE) residue 100 0 residue Derivative Weight (%/min) 90 80 white 70 -2 Weight (%) pomaces 60 from Unibo lignin 50 -4 40 white pomaces 30 from cellulos 20 Unibo e -6 red 10 pomaces from 0 hemicellulose Unibo 40 120 200 280 360 440 520 -8 50 150 250 350 450 550 T emperature (°C) T emperature (°C)
Characterization of chemically extracted residue Thermogravimetric FT-IR spectra analyses 100 90 80 70 Weight (%) 60 Derivative Weight (%/min) 0 50 C=O 40 stretch -2 hemicellul 30 ose C-O 20 white pomaces lignin stretch 10 red pomaces -4 cellulos 0 e cellulos e -6 3700 3200 2700 2200 1700 1200 700 T emperature (°C) hemicellulose -8 50 150 250 350 450 550 T emperature (°C)
Bio-composites with residue from solvent extracted red and white pomaces 1° heating cooling scan 2° heating T m ΔH m T c ΔH c T m ΔH m Sample scan scan code (°C) b (J/g) b (°C) c (J/g) c (°C) d (J/g) d PHBV 172 78 114 73 168 82 PHBV-W- 171 78 111 72 168 80 5CE PHBV-W- 170 71 111 67 168 78 10CE PHBV-W- 169 63 109 57 167 66 20CE PHBV-R- 170 72 112 68 168 77 5CE PHBV-R- 169 74 110 65 168 74 10CE PHBV-R- 170 64 108 57 168 66 20CE First scan, from 30 to 210°C at 20°C/min; 1 min at 210°C; cooling scan, from 210°C to 0°C at 20°C/min; 1 min at 0°C; second scan, from 0 to 210°C at 20°C/min.
D e r iv a tiv e W e ig h t (% /m Thermal stability 100 100 PHBV 90 90 PHBV-R-5CE PHBV-R-10CE 80 80 PHBV-R-20CE 70 70 PHBV Red residue Weight (%) Weight (%) PHBV-W-5CE 60 60 PHBV-W-10CE 50 50 PHBV-W-20CE PHBV 40 40 PHBV White residue 5% 30 fjbers 30 PHBV 20 10% 20 fjbers 10 10 0 0 50 100 150 200 250 300 350 400 450 500 550 50 100 150 200 250 300 350 400 450 500 550 150 200 250 300 350 400 T emperature (°C) T emperature (°C) T emperature (°C) All the composites are stable over 230°C. The thermal stability slightly decreases with the fjller content.
(MPa) strain at break 35 Tensile tests 30 25 (MPa) Young Modulus 20 1750 15 10 1700 5 1650 0 V E E E E E E B C C C C C C H 5 0 0 5 0 0 P - 1 2 - 1 2 W R - - - - 1600 W W - R R - V V - - B - - V V B V V H B B H B B P H H H H P P P P P 1550 (%) elongation at break 1500 3,5 1450 3,0 V E E E E E E B C C C C C C H 5 0 0 5 0 0 P - - 1 2 1 2 W R 2,5 - - - - W - R R W - V V - - - - B V V B V V H B B H B B H H P P H H 2,0 P P P P 1,5 1,0 0,5 0,0 V E E E E E E B C C C C C C H 5 0 0 5 0 0 P - 1 2 - 1 2 W R - - - - W W - R R - V V - - B - - V V B V V H B B H B B P H H H P H P P P P
Characterization of pressurized extracted residue-comparison between the methods 100 Derivative Weight (%/min) 90 80 70 lignin -3 Weight (%) residue from Rise 60 red pomaces from Unibo 50 40 30 cellulos e 20 residue hemicellulose from Rise 10 -8 0 50 100 150 200 250 300 350 400 450 500 550 600 40 100 160 220 280 340 400 460 520 580 T emperature (°C) T emperature (°C)
Bio-composites with red-pressurized extracts 100 PHBV PHBV + 5% Thermal Properties 90 residue PHBV + 10% 80 residue 100 1° heating cooling scan 2° heating residue from 70 scan scan T m ΔH m T c ΔH c T m ΔH m Sample RISE Weight (%) code 60 (°C) b (J/g) b (°C) c (J/g) c (°C) d (J/g) d 90 PHBV 172 78 114 73 168 82 50 Weight (%) PHBV-5PE 171 77 112 71 169 82 40 PHBV-10PE 171 73 110 66 169 76 30 80 PHBV First scan, from 30 to 210°C at 20°C/min; 1 min at 210°C; cooling scan, from 20 PHBV + 5% 210°C to 0°C at 20°C/min; 1 min at 0°C; second scan, from 0 to 210°C at residue 10 20°C/min. PHBV + 10% 70 residue 0 residue from 50 100 150 200 250 300 350 400 450 500 550 RISE T emperature (°C) 60 The thermal stability of 200 220 240 260 280 300 320 PHBV and the composite T emperature (°C) containing 5 wt% of RISE extracts are comparable.
Tensile tests on bio-composites based on red pomaces residues (MPa) strain at break 35 30 25 20 Young Modulus (MPa) 15 2000 10 1800 5 1600 1400 0 PHBV PHBV-R-5CE PHBV-R-10CE PHBV-R-5PE PHBV-R-10PE 1200 (%) elongation at break 1000 800 3,7 600 3,6 400 3,5 200 3,4 0 3,3 PHBV PHBV-R-5CE PHBV-R-10CE PHBV-R-5PE PHBV-R-10PE 3,2 3,1 3,0 2,9 2,8 PHBV PHBV-R-5CE PHBV-R-10CE PHBV-R-5PE PHBV-R-10PE
FT-IR spectrum Characterization of potato’s residue Pectin ester groups Pectin glycosi Pectin Thermogravimetric analysis dic ring bonds vibratio 120 2 n 0 100 3700 3200 2700 2200 1700 1200 700 -2 Deriv weight % hemicellulose 80 Pectin C-O stretch weight % -4 and and C-C 60 cellulose stretch -6 C-O 40 stretch -8 and C-C 20 -10 stretch 0 -12 50 100 150 200 250 300 350 400 450 500 550 600 T (°C)
Bio-composites with potato’s residue 100 Thermal properties PHBV PHBV+5% 90 residue 80 PHBV+10% residue 70 PHBV+20% 100 Weight (%) residue 60 50 Weight (%) PHBV 40 90 1° heating cooling scan 2° heating PHBV+5% residue scan scan 30 T m ΔH m T c ΔH c T m ΔH m Sample PHBV+10% code (°C) b (J/g) b (°C) c (J/g) c (°C) d (J/g) d 20 residue PHBV 172 78 114 73 168 82 80 PHBV+20% 10 residue PHBV-5Pot 170 75 114 71 169 81 0 potato's PHBV- 40 100 160 220 280 340 400 460 520 580 residue 172 73 114 66 169 76 10Pot T emperature (°C) 70 PHBV- 150 200 250 300 171 63 113 59 169 68 20Pot T emperature (°C) First scan, from 30 to 210°C at 20°C/min; 1 min at 210°C; cooling scan, from 210°C to 0°C at 20°C/min; 1 min at 0°C; second scan, from 0 to 210°C at 20°C/min.
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