From wine pomace and potato wastes to novel PHA- based - - PowerPoint PPT Presentation

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

. Marchese1, L. Sisti1, A. Celli1, M. Ferri1,2, S. Monari2, A. T assoni2, M. Ehrnell3, L. Eliasson3, E. Xanthakis3, T. Mu4,

• H. Sun4

1 Department of Civil, Chemical, Environmental, and Materials Engineering, University of Bologna,

Italy; 2Department of Biological, Geological, and Environmental Sciences, University of Bologna, Italy;

3Agrifood & Bioscience Unit, RISE – Research Institutes of Sweden, Sweden; 4Laboratory 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

UNIBO ITRI Use of polypheno ls as additives for polymers INRA Depolymerisati

• n

UM Fiber functionalizati

• n

INRA, UM, Supagro Characterization

• f strain

performances IAPPST UNIBO SEE Process set-up with engineered strains

Polyphen

• l

extracts Succini c Acid BPA-free biopolyme rs Biocomposit es Biopolyeste rs Dietary suppleme nts Vine Shoots Mixed fruit & vegetable hydrolysat e Potato processing waste Active packaging Extracti

• n

residues Aromatic acids (vanillic acid)

WP4 T ask 1

Pectins Proteins

UNIBO polymerizati

• n

PHBV matrix

INNOVEN, UniROMA IAPPST INNOVE N UNIBO Enzymatic Chemical Extraction RISE CO2, pressured liquid extraction

Wine Pomaces Lignocellulosi c fjllers

INRA Polymerisati

• n

UNIBO ITRI Use of polypheno ls as additives for polymers INRA Depolymerisati

• n

UM Fiber functionalizati

• n

INRA, UM, Supagro Characterization

• f strain

performances IAPPST UNIBO SEE Process set-up with engineered strains

Polyphen

• l

extracts Succini c Acid BPA-free biopolyme rs Biocomposit es Biopolyeste rs Dietary suppleme nts Vine Shoots Mixed fruit & vegetable hydrolysat e Potato processing waste Active packaging Extracti

• n

residues Aromatic acids (vanillic acid)

WP4 T ask 1

Pectins Proteins

UNIBO polymerizati

• n

PHBV matrix

INNOVEN, UniROMA IAPPST INNOVE N UNIBO Enzymatic Chemical Extraction RISE CO2, pressured liquid extraction

Wine Pomaces Lignocellulosi c fjllers

INRA Polymerisati

• n

Choice of polymeric matrix

Poly(hydroxyalkanoate)s (PHA)s are a family

• f microbial biopolymers.

They have excellent biocompatible and biodegradable properties The PHAs are particularly expensive and lack mechanical properties.

CO2

PHBV: poly(3-HydroxyButirate-co-Valerate)

PHB/PHV: 98/2 (mol/mol)

PHBV thermal properties: Tonset: 288°C TD: 302°C Tm: 172°C, ΔHm: 78 J/g Tc: 114°C, ΔHc: 73 J/g

a b c d a b e a b c, d e

1H

NMR

Composites preparation load: 45−50 g screw speed: 50 rpm temperature: 200 °C mixing time: 5 min For each fjber residue, difgerent blends were prepared containing 5, 10 or 20 wt% of residue. The composites are prepared by melt mixing in a Brabender microcompounder.

Extractions of polyphenols from wine pomaces

T wo methods:

Solvent-based extractions Pressurized liquid extractions (only on

red pomaces)

Merlot Garganeg a

Best conditions: Acetone/Water 75/25 (vol/vol) Best conditions: Ethanol/Water 50/5 (vol/vol)

Characterization of chemically extracted residue (UNIBO)

40 120 200 280 360 440 520 10 20 30 40 50 60 70 80 90 100

white pomaces from Unibo red pomaces from Unibo

T emperature (°C) Weight (%)

Thermogravimetric analyses

50 150 250 350 450 550

• 8
• 6
• 4
• 2

white pomaces from Unibo

T emperature (°C) Derivative Weight (%/min)

hemicellulose cellulos e lignin

Gargane ga (WHITE) residue Merlot (RED) residue

Characterization of chemically extracted residue

10 20 30 40 50 60 70 80 90 100

T emperature (°C) Weight (%)

Thermogravimetric analyses

700 1200 1700 2200 2700 3200 3700 white pomaces red pomaces 50 150 250 350 450 550

• 8
• 6
• 4
• 2

T emperature (°C) Derivative Weight (%/min)

FT-IR spectra

C=O stretch hemicellul

• se

C-O stretch cellulos e hemicellulose cellulos e lignin

Bio-composites with residue from solvent extracted red and white pomaces

Sample code Tm (°C) b ΔHm (J/g) b Tc (°C) c ΔHc (J/g) c Tm (°C) d ΔHm (J/g) d PHBV 172 78 114 73 168 82 PHBV-W- 5CE 171 78 111 72 168 80 PHBV-W- 10CE 170 71 111 67 168 78 PHBV-W- 20CE 169 63 109 57 167 66 PHBV-R- 5CE 170 72 112 68 168 77 PHBV-R- 10CE 169 74 110 65 168 74 PHBV-R- 20CE 170 64 108 57 168 66

1° heating scan cooling scan 2° heating scan

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.

50 100 150 200 250 300 350 400 450 500 550 10 20 30 40 50 60 70 80 90 100

T emperature (°C) Weight (%)

50 100 150 200 250 300 350 400 450 500 550 10 20 30 40 50 60 70 80 90 100

T emperature (°C) Weight (%)

Thermal stability

PHBV PHBV-W-5CE PHBV-W-10CE PHBV-W-20CE White residue

All the composites are stable over 230°C. The thermal stability slightly decreases with the fjller content.

PHBV PHBV-R-5CE PHBV-R-10CE PHBV-R-20CE Red residue

150 200 250 300 350 400 PHBV PHBV 5% fjbers PHBV 10% fjbers

T emperature (°C) D e r iv a tiv e W e ig h t (% /m

Tensile tests

P H B V P H B V

• W
• 5

C E P H B V

• W
• 1

C E P H B V

• W
• 2

C E P H B V

• R
• 5

C E P H B V

• R
• 1

C E P H B V

• R
• 2

C E 1450 1500 1550 1600 1650 1700 1750

Young Modulus

P H B V P H B V

• W
• 5

C E P H B V

• W
• 1

C E P H B V

• W
• 2

C E P H B V

• R
• 5

C E P H B V

• R
• 1

C E P H B V

• R
• 2

C E 5 10 15 20 25 30 35

strain at break

P H B V P H B V

• W
• 5

C E P H B V

• W
• 1

C E P H B V

• W
• 2

C E P H B V

• R
• 5

C E P H B V

• R
• 1

C E P H B V

• R
• 2

C E 0,0 0,5 1,0 1,5 2,0 2,5 3,0 3,5

elongation at break

(MPa) (MPa) (%)

Characterization of pressurized extracted residue-comparison between the methods

40 100 160 220 280 340 400 460 520 580 10 20 30 40 50 60 70 80 90 100 residue from Rise

T emperature (°C) Weight (%)

50 100 150 200 250 300 350 400 450 500 550 600

• 8
• 3

residue from Rise red pomaces from Unibo

T emperature (°C) Derivative Weight (%/min)

hemicellulose cellulos e lignin

Bio-composites with red-pressurized extracts

Thermal Properties

Sample code Tm (°C) b ΔHm (J/g) b Tc (°C) c ΔHc (J/g) c Tm (°C) d ΔHm (J/g) d PHBV 172 78 114 73 168 82 PHBV-5PE 171 77 112 71 169 82 PHBV-10PE 171 73 110 66 169 76

50 100 150 200 250 300 350 400 450 500 550 10 20 30 40 50 60 70 80 90 100 PHBV PHBV + 5% residue PHBV + 10% residue residue from RISE

T emperature (°C) Weight (%)

The thermal stability of PHBV and the composite containing 5 wt% of RISE extracts are comparable. 1° heating scan cooling scan 2° heating scan

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. 200 220 240 260 280 300 320 60 70 80 90 100 PHBV PHBV + 5% residue PHBV + 10% residue residue from RISE

T emperature (°C) Weight (%)

Tensile tests on bio-composites based on red pomaces residues

PHBV PHBV-R-5CE PHBV-R-10CE PHBV-R-5PE PHBV-R-10PE 200 400 600 800 1000 1200 1400 1600 1800 2000

Young Modulus

PHBV PHBV-R-5CE PHBV-R-10CE PHBV-R-5PE PHBV-R-10PE 5 10 15 20 25 30 35

strain at break

PHBV PHBV-R-5CE PHBV-R-10CE PHBV-R-5PE PHBV-R-10PE 2,8 2,9 3,0 3,1 3,2 3,3 3,4 3,5 3,6 3,7

elongation at break (MPa) (MPa) (%)

Characterization of potato’s residue

FT-IR spectrum

50 100 150 200 250 300 350 400 450 500 550 600

20 40 60 80 100 120

• 12
• 10
• 8
• 6
• 4
• 2

2

T (°C) weight % Deriv weight %

700 1200 1700 2200 2700 3200 3700

Pectin ester groups Pectin and cellulose C-O stretch and C-C stretch Pectin glycosi dic bonds Pectin ring vibratio n

Thermogravimetric analysis

hemicellulose C-O stretch and C-C stretch

Sample code Tm (°C) b ΔHm (J/g) b Tc (°C) c ΔHc (J/g) c Tm (°C) d ΔHm (J/g) d PHBV 172 78 114 73 168 82 PHBV-5Pot 170 75 114 71 169 81 PHBV- 10Pot 172 73 114 66 169 76 PHBV- 20Pot 171 63 113 59 169 68

40 100 160 220 280 340 400 460 520 580 10 20 30 40 50 60 70 80 90 100 PHBV PHBV+5% residue PHBV+10% residue PHBV+20% residue

T emperature (°C) Weight (%)

Bio-composites with potato’s residue

Thermal properties

1° heating scan cooling scan 2° heating scan

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. 150 200 250 300 70 80 90 100 PHBV PHBV+5% residue PHBV+10% residue PHBV+20% residue potato's residue

T emperature (°C) Weight (%)

PHBV PHBV-5Pot PHBV-10Pot PHBV-20Pot 200 400 600 800 1000 1200 1400 1600 1800 2000

Young Modulus

PHBV PHBV-5Pot PHBV-10Pot PHBV-20Pot 5 10 15 20 25 30 35

strain at break

PHBV PHBV-5Pot PHBV-10Pot PHBV-20Pot 0,0 0,5 1,0 1,5 2,0 2,5 3,0 3,5 4,0 4,5

elongation at break

Tensile tests on bio-composites based on potato residues

(MPa) (MPa) (%)

Conclusions

• New bio-composites based on PHBV have been prepared by

melt compounding.

• The content of fjller has been 5, 10 or 20 wt%.
• The fjller is deriving from potatoes and pomaces. In particular, the fjller is the

residue after further valorization of wastes of potato and pomaces processing.

• The bio-composites are thermally stable and easily processable.
• The Young Modulus remains fairly constant whereas the strenghth and

the elongation slightly decrease meanwhile the material cost decreases.

• In some cases, the elongation has been maintained (red UNIBO

pomaces) or improved (red RISE pomaces and potatoes).

• The fjller-matrix interface compatibility will be studied by SEM.
• The use of a compatibilizer will be evaluated and tested in the future.

Thank you for your attention!

Bologna: le 2 T

• rri

and la fontana del Nettuno.

www.unibo.it

Micaela Vannini

micaela.vannini@unibo.it

Department of Civil, Chemical, Environmental, and Materials Engineering

NoAW’s partners: NoAW is coordinated by INRA (France) and the consortium involves 32 partners from universities, public research

• rganizations

and

• ther

institutions from a dozen countries (16 academics + 16 privates

• r

associations).

1) Solvent-based extraction Optimised chemical extraction with 75% (v/v)

acetone was selected as the best process for the recovery of bioactive molecules from both red and white grape pomace.

Gargane ga (WHITE) residue Merlot (RED) residue

Total flow: 8 g/min

2) Pressurized extraction

Grape pomace Pre- treatment Supercritica l extraction

350 bar, 80°C, 1h

Defatted grape waste Pressurized extraction

100 bar, 80°C, 50min

Fibrous extraction residue Extract rich in oil and lipophilic compounds

EtOH:H2O separation

Extract rich in polyphen

• ls

CO2 Co-solvent fmow 6 g/min (EtOH:H2O 50:50) CO2 fmow 2 g/min

Pre- milling Drying Milling

CO2 CO2 fmow 30 g/min

Total flow: 8 g/min

Grape pomace Pre- treatment Supercritica l extraction

350 bar, 80°C, 1h

Defatted grape waste Pressurized extraction

100 bar, 80°C, 50min

Fibrous extraction residue Extract rich in oil and lipophilic compounds

EtOH:H2O separation

Extract rich in polyphen

• ls

CO2 Co-solvent fmow 6 g/min (EtOH:H2O 50:50) CO2 fmow 2 g/min

Pre- milling Drying Milling

CO2 CO2 fmow 30 g/min

2) Pressurized extraction

Starch processing Starch Potatoes Waste water Residues isoelectric or ammonium sulfate precipitation method Protein Ethanol precipitation

Potato residues from IAPPST (Institute of Agro-Products Processing Science &

Technology, Chinese Academy of Agricultural Sciences)

Starch processing Starch Potatoes Waste water Residues isoelectric or ammonium sulfate precipitation method Protein Ethanol precipitation

About 2 million tonnes (dry basis) of sweet potato residues are produced during starch processing every year.

Potato residues from IAPPST (Institute of Agro-Products Processing Science &

Technology, Chinese Academy of Agricultural Sciences)