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:...
Valorization of natural polymers from waste into biocomposites
Giovanni Perotto
19 Nov 2019
In 2016 in Europe
55 Millions tons of vegetable waste
• Composting– cheap processing
– low added value
• Animal feed– low income
• Biorefinery– biogas
– chemicals
– biopolymers (PHAs, PLA)
Food biomass valorization
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
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
Lifetime of plastic productslo
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Geyer, Jambeck, Law, Production, use, and fate of all plastics ever made, Science Advances, 2017
•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
• Use of waste instead of the edible portion
• Minimal processing
• No harsh chemicals
• High waste to bioplastic conversion efficiency
• Useful final properties
Desiderata
100 % VEGETABLE-BIOCOMPOSITE FILMS
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
We made it!
2 cm
2 cm
2 cm
2 cmPerotto et al, Green Chemistry, 2018
Bioplastic film structure
Carrot waste powderCarrot bioplastic
Perotto et al, Bioplastics from vegetable waste via an eco-friendly water-based process; Green Chemistry, 2018
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
RESULTS
Is it good for something?
Mechanical properties of bioplastics
0.00 0.02 0.04 0.06 0.08 0.10
0
5
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
Perotto et al, Bioplastics from vegetable waste via an eco-friendly water-based process; Green Chemistry, 2018
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
5
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
Perotto et al, Bioplastics from vegetable waste via an eco-friendly water-based process; Green Chemistry, 2018
Mechanical properties
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
Biodegradability
0 5 10 15 20 25 30
-20
0
20
40
60
80
100
120
140
160
BO
D (
mg/L
)
Time (days)
• 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
Aknowledgements
Athanassia Athanassiou
Giovanni [email protected]
Ilker Bayer
Roberto Simonutti Luca Ceseracciu Thi Nga Tran Uttam Paul Susana Puyol-Guzman
THANK YOU!