New High-Value Chemicals, Polymers and Materials from renewable resources: a contribution to the development of the Biorefinery concept

Size: px
Start display at page:

Download "New High-Value Chemicals, Polymers and Materials from renewable resources: a contribution to the development of the Biorefinery concept"

Transcription

1 New High-Value Chemicals, Polymers and Materials from renewable resources: a contribution to the development of the Biorefinery concept Armando J. D. Silvestre, CICECO, Aveiro Institute of Materials and Department of Chemistry, University of Aveiro, Portugal

2 Outlook Bioeconomy Examples of Biorefinery driven research High value extractives from agro-forest residues New materials from cork oak (suberin) New biobased polyesters New composite materials from (nano)cellulose fibers

3 Bioeconomy Bio-Economy A new concept of sustainable development: The goal of a biorefinery: to replace oil refineries Using biomass to produce: Fuels and energy, Chemicals and materials Circular economy: No waste, no pollution

4 Bioeconomy Is it technologically feasible? in a global scale? Technology is quickly going beyond our short term perspective Yet, even big things take time to grow The Biorefinery

5 Biorefinery Feedstock's used Whole-crop biorefinery (WCB) Lignocellulosic feedstock (LCF) biorefinery HV fractions e.g. grains Carbohyd Biomass Frac LCF Frac Lignin Products Fuels&Energy Green juice Extract

6 Biorefinery LCF-Biorefineries can be developed based on existing pulp mills Reduced investment Valorisation of waste streams Black liquor HO Hemicelluloses By-products CH 2 OH Primary treatment Conversion Chemicals Fuels/energy Phenolics Hydroxyacids Tall oil

7 Outlook Bioeconomy and circular economy: Examples of Biorefinery driven research High value extractives from agro-forest residues New materials from cork oak (suberin) New biobased polyesters New composite materials from (nano)cellulose fibers

8 CICECO: Biorefineries, Biobased Materials and Recycling Group

9 High value extractives from agro-forest residues High value triterpenic acids and phenolic compounds from E. globulus bark Triterpenic compounds are particularly abundant (up to 20 g/kg) in barks and high biological activity Working on: anticancer antibacterial anti-inflamatory - Supercritical CO 2 extraction - scale-up and demonstration of the process at industrial scale (P, T, EtOH) - Purifications process patented - Process close to industrialization

10 High value extractives from agro-forest residues Other by-products studied Cork fruits and vegetables Olive trees and oil production New extraction processes Ionic liquids ILs (aq) natural deep eutectic solvents (NADES)

11 CICECO: Biorefineries, Biobased Materials and Recycling Group

12 New Biobased polyesters Polyesters from 2,5-Furanedicarboxylic acid (FDCA) The sleeping giant has waken PET PEF

13 New Biobased polyesters Polyesters from 2,5-Furanedicarboxylic acid (FDCA) A wide number of linear FDCA polyesters have been described in recent years Two exemples:

14 New Biobased polyesters Biodegradable FDCA based copolyesters BHEFDC PLA hydrolytic degradation F/LA 26/74 F/LA 26/74 F/LA 92/8 F/LA 92/8

15 New Biobased polyesters Unsaturated polyester resins (UPRs) from FDCA

16 CICECO: Biorefineries, Biobased Materials and Recycling Group

17 New materials from cork (suberin) Cork is the thick outer bark of Quercus suber L. Cork can be sustainably harvasted every 9-12 years Portugal is the world leader in cork production and processing (> ton/year)

18 New materials from cork (suberin) Around 25% ( ton/year) of the total cork processed ends up as a low granulometry residue which is generally burned to produce energy. Can this residue be further valorised? What is cork chemical composition? Suberin due to its abundance and unique properties is the most promising candidate for cork residues valorisation

19 New materials from cork (suberin) New isolation and processing method using ionic liquids Amorphous material Barely elastic and brittle Moderately hydrophobic Water contact angle: θ 90 Waterproof Bactericidal effect Smooth or sliding surface Anti-biofouling effect

20 CICECO: Biorefineries, Biobased Materials and Recycling Group

21 New composites based on (nano)celluloses Vegetable fibers and nanofibers Vegetable cellulose VC Nanofibrilated cellulose NFC Bacterial cellulose NFC NFC and BC: nanometric diameter, high aspect ratios, High water holding capacity enhanced mechanical properties enable the production of transparent composites

22 New composites based on (nano)celluloses Preparation of composites with thermoplastic matrices Controlled heterogeneous modification of cellulose fibers in situ biosynthesis of BC Preparation of composites with other polysaccharides Transparent materials/films Composites by in situ polymerization Biomedical applications Membranes for fuel cells Bacterial cellulose membranes in transdermal drug release

23 Controlled heterogeneous modification of cellulose fibers The Objective - to limit it to the outmost regions of the fibers - Preserving their bulk physical properties, - While controlling the change of surface properties Polymeric matrices Modification examples: fatty acids perfluorinated acids

24 Controlled heterogeneous modification of cellulose fibers Surface hydrophobization of bacterial and vegetable cellulose fibers using ILs as solvent media and catalysts

25 Controlled heterogeneous modification of cellulose fibers Transparent Nanocomposites based on bacterial cellulose and polylactic acid Melting mixing PLA Injection molding Acetylate BC (DS = 0.02) - Higher homogeneity - Thermal stability and - Mechanical performance - Low water up-take

26 Controlled heterogeneous modification of cellulose fibers Alternatively fibers will be naturally compatible with filmogenic polysaccharides starch chitosan pullulan Other fibers

27 New composites based on (nano)celluloses Production of Bacterial cellulose (BC) Preparation of composites with thermoplastic matrices Controlled heterogeneous modification of cellulose fibers in situ biosynthesis of BC Preparation of composites with other polysaccharides Transparent materials/films Composites by in situ polymerization Biomedical applications Membranes for fuel cells Bacterial cellulose membranes in transdermal drug release

28 Preparation of composites with other polysaccharides Transparent Nanocomposites based on BC or NFC and pullulan P PBC5 PBC40 PG PGBC10 PGBC E (MPa) PG PGBC5 PGBC10 PGBC20 PGBC40 PGBC60

29 New composites based on (nano)celluloses Production of Bacterial cellulose (BC) Preparation of composites with thermoplastic matrices Controlled heterogeneous modification of cellulose fibers in situ biosynthesis of BC Preparation of composites with other polysaccharides Transparent materials/films Composites by in situ polymerization Biomedical applications Membranes for fuel cells Bacterial cellulose membranes in transdermal drug release

30 Composites by in situ polymerization Poly(hydroxyethylmethacrylate) based nanocomposites

31 Composites by in situ polymerization Poly(hydroxyethylmethacrylate) based nanocomposites BC/PHEMA/PEGDA are not cytotoxic for ADSCs and seem to be ideal for harboring cell growth

32 Composites by in situ polymerization Poly(styrene sulfonic acid) based nanocomposites

33 New composites based on (nano)celluloses Production of Bacterial cellulose (BC) Preparation of composites with thermoplastic matrices Controlled heterogeneous modification of cellulose fibers in situ biosynthesis of BC Preparation of composites with other polysaccharides Transparent materials/films Composites by in situ polymerization Biomedical applications Membranes for fuel cells Bacterial cellulose membranes in transdermal drug release

34 Application of BC in membranes for dermal drug release Wet BC membrane Oven dried (30ºC) BC BC-Ldc-Glyc Lidocaine Ibuprofen Caffeine Drug Glycerol Solution, 1h No lidocaine agglomerates SEM Good dispersion

35 Acknowledgements All co-authors colleagues, PostDoc PhD and MSc students University of Aveiro and CICECO Funding Agencies and projects

36 And thank you all!

37