Valorization of natural polymers from waste into biocomposites...Global Plastics Market Source:...
Transcript of Valorization of natural polymers from waste into biocomposites...Global Plastics Market Source:...
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Valorization of natural polymers from waste into biocomposites
Giovanni Perotto
19 Nov 2019
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In 2016 in Europe
55 Millions tons of vegetable waste
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• Composting– cheap processing
– low added value
• Animal feed– low income
• Biorefinery– biogas
– chemicals
– biopolymers (PHAs, PLA)
Food biomass valorization
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Global Plastics Market
Source: Nòva-Sole24Ore
GLOBAL PLASTICS DEMAND 2015 by type EUROPE PLASTICS DEMAND 2017 by type
Source: PlasticsEurope Market Research Group (PEMRG) and Conversio Market & Strategy GmbH
PET 7.4%
PUR 7.5%
Other Thermopl
astics 19.3%
LDPE LLDPE17.5%
HDPE12.3%
PVC10.0%
PS, EPS6.7%
2017
60Million tons
PA 1% PC 1%PET 7%
PUR 6% Other Thermoplastics
4%
LDPE LLDPE17%
HDPE 15%
PP 23%
PVC 16%
PS, EPS 7%
ABS, ASA, SAN 3%
2017
350Million tons
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Global Plastic Waste production
Geyer, Jambeck, Law, Production, use, and fate of all plastics ever made, Science Advances, 2017
Packaging represents 40% of the plastic consumption
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Lifetime of plastic productslo
g-n
orm
al p
rob
abili
ty d
istr
ibu
tio
n f
un
ctio
ns
Geyer, Jambeck, Law, Production, use, and fate of all plastics ever made, Science Advances, 2017
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•Natural polymers–Thermoplastic starch
–Cellulose (acetate, nitrocellulose)
•Polymers from renewable resources–PolyLacticAcid
–PHAs
•Synthetic biodegradable–Polyadipate
–PCL
Bioplastics
Use of “noble” resourcesReduced biodegradability
Require complicated processingExpensive
Fossil fuel raw materials
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• Use of waste instead of the edible portion
• Minimal processing
• No harsh chemicals
• High waste to bioplastic conversion efficiency
• Useful final properties
Desiderata
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100 % VEGETABLE-BIOCOMPOSITE FILMS
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Trust The Process
Acidic pH
40 °C, 12 hours
Neutralization- dialysis- NaOH- CO3
2-
- evaporation
Casting& overnight drying
Perotto et al, Bioplastics from vegetable waste via an eco-friendly water-based process; Green Chemistry, 2018
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We made it!
2 cm
2 cm
2 cm
2 cmPerotto et al, Green Chemistry, 2018
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Bioplastic film structure
Carrot waste powderCarrot bioplastic
Perotto et al, Bioplastics from vegetable waste via an eco-friendly water-based process; Green Chemistry, 2018
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13C CP-MAS NMR
Comparing carrot powder and carrot bioplastic• Bioplastic film has the C-peaks related to
cellulose more pronounced and sharp• Cellulose is “more crystalline”
• The C-peaks related to pectin are in their de-esterified form• Production of low methoxyl pectin
• Partial hydrolysis of the non-crystalline part of cellulose and de-methoxylation of pectin
• Amorphous polysaccharides will become the soft matrix, isolated crystalline cellulose will be the hard filler
Carrot bioplastic
Carrot waste
Perotto et al, Bioplastics from vegetable waste via an eco-friendly water-based process; Green Chemistry, 2018
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RESULTS
Is it good for something?
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Mechanical properties of bioplastics
0.00 0.02 0.04 0.06 0.08 0.10
0
5
10
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20
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30
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40
45
Tensile
Str
ess (
MP
a)
Tensile Strain (mm/mm)
Carrot
Parsley
Radicchio
Cauliflower SampleYoung Modulus
(MPa)Elongation at
break (mm/mm)UTS (MPa)
Carrot 1300 ± 200 0.058 ± 0.008 38 ± 5Parsley 180 ± 50 0.10 ±0.02 8.0 ± 0.4
Radicchio 230 ± 40 0.05 ±0.01 4.4 ± 0.4Cauliflower 470 ± 80 0.04 ± 0.01 10.0 ± 0.9
Perotto et al, Bioplastics from vegetable waste via an eco-friendly water-based process; Green Chemistry, 2018
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Perotto et al, Bioplastics from vegetable waste via an eco-friendly water-based process; Green Chemistry, 2018
Mechanical properties of bioplastics
0.00 0.02 0.04 0.06 0.08 0.10
0
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10
15
20
25
30
35
40
45
Tensile
Str
ess (
MP
a)
Tensile Strain (mm/mm)
Carrot
Parsley
Radicchio
Cauliflower SampleYoung Modulus
(MPa)Elongation at
break (mm/mm)UTS (MPa)
Carrot 1300 ± 200 0.058 ± 0.008 38 ± 5Parsley 180 ± 50 0.10 ±0.02 8.0 ± 0.4
Radicchio 230 ± 40 0.05 ±0.01 4.4 ± 0.4Cauliflower 470 ± 80 0.04 ± 0.01 10.0 ± 0.9
Cellulose% (mol)
Pectin% (mol)
Hemicellulose% (mol)
Aliphatic polyesters
% (mol)Carrot 61 28 8 3Parsley 48 31 15 6
Radicchio 44 34 4 18Cauliflower 46 24 9 21
Bioplastic composition
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Perotto et al, Bioplastics from vegetable waste via an eco-friendly water-based process; Green Chemistry, 2018
Mechanical properties
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Perotto et al, Bioplastics from vegetable waste via an eco-friendly water-based process; Green Chemistry, 2018
Packaging
Overall Migration (mg/dm2)
Carrot 3.5 ± 0.7Parsley 2.8 ± 0.7
Radicchio 1.7 ± 0.5Cauliflower 1.8 ± 0.4
Oxygen Permeability
Blending with PVA greatly helps!
Migration in food
Tenax® used as dry food simulant2 hours @ 70 °C
EU limit: 10 mg/dm2Carrot PVA Carrot PVA0.0
20.0
40.0
60.0
80.0
75.0k
80.0k
85.0k
90.0k
95.0k
100.0k
Oxygen p
erm
eabili
ty
ml m
/(m
2 d
ay K
Pa)
Blend 30:70
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Biodegradability
0 5 10 15 20 25 30
-20
0
20
40
60
80
100
120
140
160
BO
D (
mg/L
)
Time (days)
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• Simple processing
• Non vegetable-specific
• Mechanical properties similar to other biosource-derived plastics
• Structure is homocomposite of pectin-hemicellulose-cellulose
• Can be easily combined with other polymers to produce blends
• Safe for dry food contact
• Interesting for packaging applications
• Biodegradability is preserved
Conclusion
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Aknowledgements
Athanassia Athanassiou
Giovanni [email protected]
Ilker Bayer
Roberto Simonutti Luca Ceseracciu Thi Nga Tran Uttam Paul Susana Puyol-Guzman