BIOMASS-BASED FUNCTIONAL MATERIALS Pedro Fardim Lab. of Fibre and - - PowerPoint PPT Presentation

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BIOMASS-BASED FUNCTIONAL MATERIALS Pedro Fardim Lab. of Fibre and - - PowerPoint PPT Presentation

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NEW PERSPECTIVES FOR BIOMASS-BASED FUNCTIONAL MATERIALS Pedro Fardim Lab. of Fibre and Cellulose Technology* bo Akademi University, Turku/bo, Finland pfardim@abo.fi Laboratory of Fibre and Cellulose Technology www.abo.fi BO AKADEMI

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Laboratory of Fibre and Cellulose Technology

www.abo.fi

NEW PERSPECTIVES FOR BIOMASS-BASED FUNCTIONAL MATERIALS

Pedro Fardim

  • Lab. of Fibre and Cellulose Technology*

Åbo Akademi University, Turku/Åbo, Finland pfardim@abo.fi

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Laboratory of Fibre and Cellulose Technology

www.abo.fi

ÅBO AKADEMI UNIVERSITY

 Founded 1918  Swedish-language university  Multi-faculty university, seven faculties  Today 7.000 students, over 600 international students  Two campuses: Åbo and Vasa  Small and personal university  www.abo.fi  www.abo.fi/fa/ie/indexeng.htm

V asa Å bo

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Laboratory of Fibre and Cellulose Technology

www.abo.fi

Faculty of Technology

  • Two departments:
  • chemical engineering
  • information technologies
  • Founded in 1920 as Faculty of

Chemical Engineering, named changed in 2006

  • Main specialisation areas: computer

science, information systems, process chemistry, process system engineering and pulp and paper technology

  • The faculty has two centres of

excellence in scientific research appointed by the Academy of Finland: Process Chemistry Centre (PCC) and Center for Functional Materials (FUNMAT).

  • The faculty offers master’s of science

degrees in Technology, Science and Economics and Business Administration.

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Laboratory of Fibre and Cellulose Technology

www.abo.fi

Our Research and Education Areas

Fibre Technology Cellulose Technology Nano-analysis

New concepts For Fiberlines High-added value fibres

Biomass Pre-treatment & Fractionation

SIMS XPS AFM EM Fluorescence Topochemistry Nanoparticles Beads Films

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Laboratory of Fibre and Cellulose Technology

www.abo.fi

NEW PERSPECTIVES FOR BIOMASS-BASED FUNCTIONAL MATERIALS

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Laboratory of Fibre and Cellulose Technology

www.abo.fi

  • Natural polymers such as starch, cellulose, chitin,

carrageenan

  • Produced by plants and animals

Polysaccharides

Cellulose Chitin cotton coconut hemp wheat bacteries tree alga Starch crab corn

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Laboratory of Fibre and Cellulose Technology

www.abo.fi

From biomass to functional materials

Functionalisa tion Fractionation and isolation Advanced characterisation and nano-analysis Incorporation into products Re- assembly Biomass disassembly Biomass collection Multifunctionalisa tion

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Laboratory of Fibre and Cellulose Technology

www.abo.fi

From wood to polysaccharides

Cellulose Wood Hemicelluloses Lignin Extractives

Disassembly

pulp nanocellulose cellulose solution hemicellulose solution

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Laboratory of Fibre and Cellulose Technology

www.abo.fi

Pulp fibres: Functional Material?

  • Pulp: 350 million ton

worldwide

  • Used in paper,

packaging, tissue, composites

  • Available value chain

(collection - recycling)

  • Tailored optical and

mechanical properties

  • Other functionalities

unexplored

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Laboratory of Fibre and Cellulose Technology

www.abo.fi

Fibre Technology at FCT

Wood Chemical Mechanical Chemimechanical Bleaching LC-refining Papermaking P a

p e r

Fibre separation Fibre functionalisation

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Laboratory of Fibre and Cellulose Technology

www.abo.fi

SMART FIBRE CONCEPT

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Laboratory of Fibre and Cellulose Technology

www.abo.fi

Challenges and opportunities for functional pulps

  • Conditions of functionalisation compatible

with current processes/technology

  • Functionality is transferred to final product
  • Sustainable, low energy intensive,

recyclable

  • Availability of value chains
  • Opportunity to replace oil-based materials
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Laboratory of Fibre and Cellulose Technology

www.abo.fi

Cellulose

  • 50 % of biomass on earth
  • 100-150 billion-ton per year
  • One tree: ~ 14 g of cellulose per day
  • Vegetal (plants)
  • Seaweed (valonia, microdycon)
  • Biosynthesised by bacteria (acetobacter

xylonium)

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Laboratory of Fibre and Cellulose Technology

www.abo.fi

Cellulose Wood (86%) Other (14%) softwood (51%)hardwood (35%) Pulp&paper (80%) Dissolving pulp (20%) Regenerated cellulose Cellulose derivatives

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Laboratory of Fibre and Cellulose Technology

www.abo.fi

Chemical modification of cellulose

  • Homogeneous reaction medium (HM)

– one phase, requires dissolution

  • Heterogeneous reaction medium (HT)

– two phase

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Laboratory of Fibre and Cellulose Technology

www.abo.fi

Cellulose dissolution

  • Raw material (availability, costs,

pretreatment)

  • Choice of solvent system

– Viscose (xanthate) – NMMO (N-methylmorpholine N-oxide) – NaOH-water (urea, ZnO) – Ionic Liquids (ILs) – Others (several derivative and non-derivative)

  • Environmental aspects
  • Is the solvent inert?
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Laboratory of Fibre and Cellulose Technology

www.abo.fi

Cellulose based materials

  • Microfibrillar or nanocellulose (HT)
  • Cellulose nanorods or crystals (HT)
  • Regenerated cellulose from solution

(HM) (fibres, particles, films, aerocellulose)

  • Cellulose derivatives (HT or HM)
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Laboratory of Fibre and Cellulose Technology

www.abo.fi

Nanocellulose and nanocrystals

Microfibrils Nanocrystals + Acid Microfibrils Nanocrystals + Acid

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Laboratory of Fibre and Cellulose Technology

www.abo.fi

Cellulose Technology at FCT

Cellulose Beads Particles Aerocellulose Composites Functional chemicals Functional coating Drug release Chemical sorbents Biomaterials Medical applications Rheology modifiers in coating, food, cosmetics Bioplastics

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Laboratory of Fibre and Cellulose Technology

www.abo.fi

  • Lab. of Fibre and Cellulose Technology

Bead-making process

Frozen viscose Defrosting Deaeration Drop formation Regeneration Washing Drying Cellulosic beads Bead reactor 2 Cellulose-OCS2Na + H2SO4  2 Cellulose-OH + Na2SO4 + 2 CS2 Cell I  Cell II (irreversible)

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Laboratory of Fibre and Cellulose Technology

www.abo.fi

  • Lab. of Fibre and Cellulose Technology

Form factor

0,6 0,65 0,7 0,75 0,8 0,85 0,9 0,95 1 3 3,5 4 4,5 5 5,5 6 Selluloosapitoisuus, % Form Factor

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Laboratory of Fibre and Cellulose Technology

www.abo.fi

Beads of regenerated cellulose

x100 x1000 x5000 x10000 x100 x500 x5000 x10000 100 m 10 m 5 m 1 m

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Laboratory of Fibre and Cellulose Technology

www.abo.fi

Cellulose chemistry: opportunity to tailor functionality of materials

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Laboratory of Fibre and Cellulose Technology

www.abo.fi

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Laboratory of Fibre and Cellulose Technology

www.abo.fi

Aerocellulose (with tailored porosity)

100 µm 100 µm 100 µm 100 µm 100 µm 100 µm 100 µm 100 µm 100 µm 100 µm 100 µm

1250 μm 600 μm 250 μm

4x

100 µm 100 µm 100 µm 100 µm 100 µm 100 µm 100 µm 100 µm 100 µm 100 µm 100 µm

1250 μm 600 μm 250 μm

4x 1x

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Laboratory of Fibre and Cellulose Technology

www.abo.fi

Challenges and opportunities for functional cellulose

  • Challenges:

– Dissolution in inert solvents and purity of

raw materials

– Evenness of functionalisation, stabilization

  • f suspension in heterogeneous conditions
  • Opportunities

– Renewable resource with high availability – Excellent possibilities for chemical and

physical functionalisation. New functional materials

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Laboratory of Fibre and Cellulose Technology

www.abo.fi

What are hemicelluloses?

  • Biopolymers present in different biomass

materials (wood, plants, cereals)

  • A moderate low DP in comparison with

cellulose (50-300 vs 3000-10000)

  • A multitude of combinations of sugar units

as backbone and side groups

  • Interesting properties: bioactive,

biodegradable, water soluble

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Laboratory of Fibre and Cellulose Technology

www.abo.fi

Number of patents containing term hemicellulose during 1980-2008 searched (19.1.2009) by SciFinder Scholar.

1985 1990 1995 2000 2005 50 100 150 200

Number of patents Year

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Laboratory of Fibre and Cellulose Technology

www.abo.fi

POLYSMART consortium

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Laboratory of Fibre and Cellulose Technology

www.abo.fi

Polysmart overview

(E) Fibre and sheet properties Wood Pulping (A) Disassembly of wood matrix (D) Bioactive paper Paper making / Converting Hemicelluloses (B) Bio- conversion (C) Chemical modification Biofuel Biomaterials Reassembly

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Laboratory of Fibre and Cellulose Technology

www.abo.fi

Disassembly of hemicelluloses by hydrothermal treatment

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Laboratory of Fibre and Cellulose Technology

www.abo.fi

Extraction of hemicelluloses

wood pre-hydrolysis (acid or alkaline) auto-hydrolysis (water) Hemicelluloses delignification cellulose lignin

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Laboratory of Fibre and Cellulose Technology

www.abo.fi

Extraction equipment (PHWE)

Liquor in Steam in Steam out Pump Digester Cooler Liquor collection Water in Water out Heat exchanger

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Laboratory of Fibre and Cellulose Technology

www.abo.fi

Extraction equipment (LiqCir)

200 g of wood/biomass 4000 g of wood/biomass

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Laboratory of Fibre and Cellulose Technology

www.abo.fi

Summary of exploratory experiments

  • Time and temperature are main variables

in extraction of xylan

  • Xylan can be disassembled from wood at

different levels up to 95% w/w

  • Higher xylan disassembly leads to

disassembly of lignin up to 30% w/w

  • About 29% of xylan in wood (11% on

wood basis) can be disassembled without removal of lignin

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Laboratory of Fibre and Cellulose Technology

www.abo.fi

Effects of hemicellulose extraction on fibre properties

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Laboratory of Fibre and Cellulose Technology

www.abo.fi

Refining - SR

10 15 20 25 30 35 10 20 30 40 50 60 70 Valley beating time (min) SR (°)

Ref 170 °C 10 min 170 °C 40 min

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Laboratory of Fibre and Cellulose Technology

www.abo.fi

Tensile vs Tear

2 4 6 8 10 20 30 40 50 60 70 80 90 100 110 120 Tensile index (Nmg-1) Tear index (mNm2g-1)

Ref Pre.10 Pre.40

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Laboratory of Fibre and Cellulose Technology

www.abo.fi

Effect of Hemicellulose extraction on Kraft Pulping and Fibre Chemistry

  • Extraction of xylan reduces the yield in

kraft cooking (about 10% lower)

  • Lower dosages of alkali are needed in

cooking (33 % reduction in active alkali)

  • Only 3% of residual hemicelluloses in

birch after water extraction and pulping

  • Dissolving pulp grade possilbe after 40

min pre-treatment + kraft pulping + bleaching

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Laboratory of Fibre and Cellulose Technology

www.abo.fi

Effects of hemicellulose extraction on fibre properties

  • Refining (higher energy consumption)
  • Decrease the fibre length
  • Slightly increase in bulk of handsheets
  • Reduction in tensile index
  • Benefitial for tear index after refining
  • Positive for light scattering of

handsheets

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Laboratory of Fibre and Cellulose Technology

www.abo.fi

Utilization of hemicelluloses

  • Fibre modification
  • Paper coatings/converting
  • Bioactive packaging
  • Bioactive films in tissue healing
  • Food and cosmetic additives
  • Biofuels
  • Pharmaceuticals
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Laboratory of Fibre and Cellulose Technology

www.abo.fi

Challenges and opportunities for functional hemicelluloses

  • Challenges:

– Disassembly from wood – Negative impact on fibre properties using

current technology

– Purity/evenness of biopolymer

  • Opportunities

– Large availability – Incorporation into products – Few commercial exploitation

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Laboratory of Fibre and Cellulose Technology

www.abo.fi

Complementary research activities between Finland and Japan

  • Fractionation technology
  • Cellulose chemistry and technology
  • Lignin chemistry and utilization
  • Fibre based functional materials
  • Nanoscale characterisation
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Laboratory of Fibre and Cellulose Technology

www.abo.fi

Acknowledgements

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Laboratory of Fibre and Cellulose Technology

www.abo.fi

“Polysaccharides as a Source

  • f Advanced Materials”

CONFERENCE 2009

Turku, Finland September 21-24, 2009

http://congress.utu.fi/epnoe2009

Important dates Last minute abstract submission: March 30, 2009 Early bird registration: June 30, 2009