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

[email protected]

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


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


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



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


Mechanical properties


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!

[email protected]

valorization of natural polymers from waste into biocomposites...global plastics market source:...

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