Production of carbon fibres from

kraft lignin for composites

Per Tomani, Darren Baker, Anders Uhlin
and Mrten kerstrm
ZELLCHEMING 2016-06-29
LignoBoost Demo plant & The LignoCity project

Owned by Innventia
Max capacity: 6 000 - 8 000 tonnes/year
Today mainly R&D activities
Production manager & 4 process operators

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Lignin opportunities
Higher lignin values
Carbon nanofibres, CNF
Carbon fibers, CF

Dispersants
Activated CF & CNF

Hydrofobic & active surfaces

Resins
Green aromatics Bio-carbons
Adhesives
Binders Asphalt emulsions Transportation fuels

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Estimated market price & world market volumes
for some products possible to produce from lignin.
Market price World market
Product (2015) (2015) Lignin potential - comment
EUR/kg kton/year
Low value on product made from green
Activated carbon 1.5 1500
material (coconut shell)
Activated carbon Small market but potentially high value for
20-100 4
fibre lignin
Large volumes average value economy
BTX 1-1.2 110 000
depends on yield and modification
High value and potentially a large market if
Carbon fibre 20-35 (Industrial) 70
automotive usage increase
Carbon nano fibres 300 700 <1 Very high value on lignin if feasible

Fuel 0.3 >10 000 Enormous market but low value

Good value and environmental beneficial.
PF Resins 2-3 5 000
Uncertainty in cost for increasing reactivity
PU-foams 2-3.5 15 000 High value and large market
High value and large market. Uncertainties in
Thermoplastics 1.5-2 130 000
need for pre-treatment
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Different ways to form fibres where we are active

Melt spinning
Solvent spinning (cooperation project with Swerea)

Electrospinning (nanofibres diamenter 10 nm to 1 mm - forms a web)

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Different ways to form fibres where we are active

Melt spinning
Solvent spinning (cooperation project with Swerea)
Electrospinning

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Typical scheme for carbon fibre production

We consider lignin a precursor to

making an engineering polymer

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 Purification: Lignin is not usually just lignin
Lignins are recovered as a result of processes designed for carbohydrate recovery

Impurities are usually included

Impurities must be removed or controlled as they give rise to flaws in later processing

Problems during filament formation and oxidative Flaws during Main spinning
thermostabilization carbonization problem

INORGANICS VOLATILES
CELLULOSE HEMICELLULOSE EXTRACTIVES
Lignin problem

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Typical scheme for carbon fibre production

We consider lignin a precursor to

making an engineering polymer

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 Refining: Lignin is not just any old lignin
A family of polymers whose structures depend on
the biomass, delignification process, and recovery conditions used
p-Coumaryl alcohol Defined by chemical properties
HO
monomer
(hydroxyphenyl)
X=Y=H
O composition
Coniferyl alcohol
(guaiacyl alcohol)
linkages
X = OCH3 and Y = H pendent groups
HO elemental composition
X Y Sinapyl alcohol
(syringyl alcohol)
O X = Y = OCH3
Defined by macromolecular properties
n
molecular mass
glass transition
Softwood Lignin Hardwood Lignin softening temperature
> 90% coniferyl alcohol, ratios of coniferyl
plus p-coumaryl alcohol and sinapyl alcohols
melt viscosity
thermogravimetric response

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Typical scheme for carbon fibre production

We consider lignin a precursor to

making an engineering polymer

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 Filaments: Melt spinning of lignin
Low melt
temperature

3 weeks
to carbon fibre

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Typical scheme for carbon fibre production

We consider lignin a precursor to

making an engineering polymer

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 Thermostabilization: melt spinning v. conversion
Low Tg High Tg

Spins well Conversion

Low diameter Carbon yield
High quality X: Fibre melts during conversion
Y: Fibre retained during conversion Strength

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Typical scheme for carbon fibre production

We consider lignin a precursor to

making an engineering polymer

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 Conversion of lignin fibre to carbon fibre is complex
Each thermal processing step has an optimum for extracting the best possible properties

Thermox 1 Thermox n Carbon 1 Carbon 2

Lignin fibre
(R1 / T1 / t1 / 1) (Rn / Tn / tn / n) (R3 / T3 / t3 / 3) (R4 / T4 / t4 / 4)

R1 Rate at which temperature is reached (dependent on t1)

Fibre tow enter furnace and have a balistic temperature change

T1 Isothermal temperature set point

Temperature is set to initiate crosslinking of the lignin fibres

t1 Isothermal temperature dwell time

Dwell time is set to optimally crosslink the lignin fibres

1 Strain controlled by relative fibre speed at start and end of process

Strain is induced at an optimal level once other parameters optimized

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Published state of the art (so far) melt spinning of lignin
Process All reported data for lignin CF development uses batch conversion processes

Strength Around 1.2 GPa tensile strength is the maximum so far reported (Hardwood+additive)

Modulus Around 85 GPa tensile modulus is the maximum so far reported (Hardwood+additive)

Extension Around 1.2 to 2.2% extensibility before break

Future? Most studies performed without tensioning and property development is optimized
during continuous conversion

Our progress? Going very well!

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The Innventia Research Programme
Example: work at Innventia on meltspun SW lignin, no additives

E-modulus Tensile

Source: Innventia Research Progrmme 2015-2017

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Target for lignin-based CF in structural applications
- Good progress towards the target

DOE target for

CF in automotives

Published lignin
CF data

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Example of lignin-based CF:s in applications
Demonstration - goals

Manufacture a roof for a radio controlled toy car.

100% softwood lignin-based CF, without additives

Manufacture a battery to power the car using electrode material

based on lignin-CFs

Propose opportunities to increase the market value of lignin

Financed by: Innventia Research Programme 2015-2017 & BioInnovation

 The GreenLight project covers the whole value chain
Renewable raw material Kraft pulp mill Lignin recovery

End use CF reinforced Lignin-based CF

polymer

667501 GreenLight Cost effective lignin-based carbon fibres for innovative light-weight applications 21
 The GreenLight Consortium
Innventia (Coordinator)
Sdra

FIBRE (Faserinstitut Bremen)

Fourn Machinenbau

STFI (Saechsisches Textilforschungsinstitut)

SWEREA Sicomp

NetComposites

Blatraden

CRF (Centro Ricerche Fiat)

667501 GreenLight Cost effective lignin-based carbon fibres for innovative light-weight applications
Different ways to form fibres where we are active

Melt spinning
Solvent spinning (made by Swerea in a joint R&D project)
Electrospinning

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The Prefiber project

Cellulose was used as a fiber forming polymer and

support for lignin during wet spinning of dopes
using the ionic liquid EMIMAc as solvent.

Diam Elong. TS E-mod.

Precursor
(m) (%) (MPa) (GPa)

SKL:D-SKP (70:30) 18 1.8 590 34

SKL:SKP (70:30) 12 2.2 610 29

Source: Cooperation Innventia & Swerea

Financed by the Swedish Energy Agency,
within LIGHTer, and by Valmet AB

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Different ways to form fibres where we are active

Melt spinning
Solvent spinning (cooperation project with Swerea)
Electrospinning

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Electrospinning of ligninbased carbon nanofibres (CNF)

Pilotscale electrospinning
with 100% SW lignin.

A 0.5 m wide CNF mat is formed

Source: Innventia Research Progrmme 2015-2017

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 Carbon
nanofibres*
Bonded filament web
Good for applications in electronics?

Adjusting the oxidative

thermostabization time from
5 minutes to 20 minutes

Free filaments

*sub-micron for productivity, as shown

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Roadmap for upscaling of lignin-based CF
Plan for 2014-2025

Source: Cooperation Innventia & Swerea

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 Thank you!
& We thank all our cooperation partners & financers:
Industrial financers
Different grant offices;
Vinnova, Swedish Energy Agency, Formas, BioInnovation, Horizon 2020, BBI

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