LIGNIN, ONE OF THE WAYS TO BIO-BASED AROMATICS?

Heleen De Wever, VITO, Belgium Ludo Diels, VITO, Antwerp University, Belgium World Congress on Industrial Biotechnology, Montreal, July 23 – 26, 2017

Chapter 1 Why Aromatics?

AROMATICS: REALLY IMPORTANT?

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benzene

styrenics PSty

Disposable ustensils

Food containers

Packaging, electronics

PSty foam

cumene Phenols

Pharma, cosmetics

cyclohexane BPA

Polyesters, flame retardance

PC

Soda bottles, lenses

aniline Nylon

Fabric, carpets, medical implants

PUR

Foam insulation, adhesives

alkylbenzenes Detergents

Footwear

Laundry detergents, glass

cleaner

1st line derivatives

2nd line derivatives

Raw material

toluene

xylene

AROMATICS TODAY AND CHALLENGES OF TOMORROW

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40 % of bulk chemicals are aromatics

BTX: 120 Bio $ market 14,6 Mio tons

Phenol : 8 Mio tons

Europe: 25 % of world production

20,000 (direct)– 70,000 (plastics) – 1,000,000 (wider industry chain)

Innovative support for SME’s

Brandowners, producer consumer (Ikea, Nike, Coca-Cola, Lego)

Sustainability driver

Socio-economic impact, contribution to everyday’s life

MARKET SIZE EMPLOYMENT IN EUROPE SUPPLY DEMAND & SECURITY

DRIVERS AND OPPORTUNITIES FOR DEVELOPMENT OF LIGNOCELLULOSE TO BIO-AROMATICS

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New sustainable feedstocks towards bio-economy

Reducing footprint of industrial processes

Innovation in chemicals & materials

Safer, performance-based products

Through disruptive enabling process technologies

Economic and societal drivers for transition to bio-economy

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Sustainable & renewablefeedstocks

geopolitics

climate

price volatility

environment

Chapter 2 Why lignin as feedstock for aromatics?

International Lignin Institute

ORIGIN OF LIGNIN

Pulp & paper industry Lignosulfonate lignin Kraft lignin Soda lignin

New lignins Lignoboost Lignol Lignoforce LXP ….

Cellulose ethanol Steam/ammonia explosion sc alcohols Alkali or acid Autohydrolysis Organic solvents Ionic Liquids/DES/ NADES

More than 50 million tons produced/a Pulp & paper industry Cellulose ethanol

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LIGNIN-BASED AROMATICS

presence of aromatic rings stability good mechanical properties broad range of chemical transformations

presence of reactive functional groups allows preparation of graft copolymers

good rheological and visco-elastic properties good film-forming ability compatibility with a wide range of industrial chemicals small particle size hydrophilic or hydrophobic character depending on origin

Allows the production of a wide range of blends But low reactivity!!!!!

Physicochemical factors promise a bright future for lignin-based products

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LIMITED REACTIVITY OF LIGNIN

- Only 20-40 % phenol can be replaced with lignin in PF-resins - Methoxyl groups limit the reactivity (especially hardwood lignins) - Not really a technical feasible activation process

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(Marie Anheden RISE)

Chapter 3 The lower hanging fruit Use of lignin as fibre or polymer

RISE

LIGNIN AS FIBRE

Lignosulfonate in concrete Bitumen and asphalt applications replacing low quality petro-based bitumen Direct use and low processing Resins via combination with formaldehyde Glues Filler material Replacement is limited (20%) due to low reactivity Carbon fibres High tech application, but more delicate processing (still ongoing development)

Extraction of lignin and use as fibre in applications

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Chapter 4 The higher hanging fruit Use of lignin for chemicals need for mild depolymerization need for fractionation & separation

FOCUS ON FUNCTIONALITY

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DEPOLYMERIZATION PROCESSES

Base Catalysed Depolymerization (BCD, Fraunhofer)

Lignin-First Process (KULeuven)

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LIGNIN PURIFICATION AND FRACTIONATION OF LIGNIN MONO- & OLIGOMERS

(Modified) filler

Depolymerization

Lignin

O

OO

HO

OH

OO

OH

O

OO

O

OHO

HO

OO

HO

OO

OHO

O OH

O

O OH O

O O

OH

HOO

HOO

O

OO

OO

OH

O

OH

O

OO

Lignin material as such

e.g. additive for bitumens, rubber, resins, polymer matrices…

Fractionation

Chemicals Mix

Oligomer based mix

Monomer based mix

Specific fractionation / affinity-based separation

Pure, single molecules/ chemicals

O

OCH3

R2

R1

R

O

R' CH3

OOCH3

Rx

Ry

OH

CH3O

OH

R'

R

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(1) PURIFICATION-CONCENTRATION OF LIGNIN-BASED STREAMS

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Input Process Output

[Na+] : 8,1 g/L [CO3

2-] : 11,5 g/L [Lignin] : 12 ± 2 g/L MW : 200 – 4500 g/mol [organic acids] : 7,75 g/L

[Na+] : 0,8 g/L [CO3

2-] : 0,2 g/L [Lignin] : 17 g/L (67* g/L) [organic acids] < 0,7 g/L

Ultra/Nanofiltration Diafiltration Up-concentration*

Na2CO3, impurities (low Mw lignin species)

High Mw lignin species

Initial DV 1 DV 2 DV 3 DV 40

2

4

6

8

10Co

ncen

trat

ion

(g/L

)

Na+ CO32-

Acetic acid Formic acid Oxalic acid Glycolic acid Glucose Xylose

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(1) PURIFICATION-CONCENTRATION OF LIGNIN-BASED STREAMS

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Input Process Output

[Na+] : 8,1 g/L [CO3

2-] : 11,5 g/L [Lignin] : 12 ± 2 g/L MW : 200 – 4500 g/mol [organic acids] : 7,75 g/L

[Na+] : 0,8 g/L [CO3

2-] : 0,2 g/L [Lignin] : 17 g/L (67* g/L) [organic acids] < 0,7 g/L

Ultra/Nanofiltration Diafiltration Up-concentration*

Feed

Purified lignin-rich stream

Impurities & low MW lignin

in permeate

Results published in Ind. Crops. Prod. (in press)

12 g/L 17 g/L 67 g/L [Lignin]

100 % removal of sugars and organic acids

44% removal of Na+ions WCIB2017

(2) FRACTIONATION OF LIGNIN OILS

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Lignin

Ethanol

Catalytic depolymerization scEtOH + catalyst CuMgAlOx

Lignin crude

oil

OH

O

OH

O

OH

O

OH

O

Composition of lignin crude oil

Monomers in lignin crude oil

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(2) FRACTIONATION OF LIGNIN OILS

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UF/NF 6 polymeric membranes 1 ceramic membranes Influence of pressure Influence of MWCO

BIO-HArT-5 (400 Da)

15 bar 35 bar

Retention of lignin (derivatives) Mw profile of membrane fractions

Screening trials

Selection of BIO-HArT-5 membrane

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FUNMEM: NEW FLEXIBLE FUNCTIONALIZATION PLATFORM

FunMem : Functionalized membranes

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Meynen et al., PCT/EP2010/053616 (2010).

Van Heetvelde et al., Chem. Commun. 2013, 49, 6998.

M MgBr salts R

+ R Mg Br M OH

+

Unique, direct M-R bond Stable, non-hydrolysable On commercial membranes Wide variety of functional groups Tailored membrane surfaces:

o Fouling mitigation o Hydrophobization o Affinity separations

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WRAP-UP

Membranes powerful tool for biomass separation in future biorefineries: Energy-efficient Flexible Scalable

Applicable to technical/modified lignins as well as to (modified) lignin depolymerisation products

Tailored membrane surface design for affinity-based fine separation Produce fractions with enhanced functionality/reactivity

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Fire retardants

Flocculants

Polyurethanes

Surfactants

Fertilizers

Dispersants Aromas

Phenolic resins

Wood plastic composites

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Chapter 5 Valorization

POTENTIAL APPLICATIONS

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OOCH3

Rx

Ry

OH

CH3O

OH

R'

R

OH

OH

O

OHO

HO

pure, single molecules

monomers mix

oligomers mix

Chemical building blocks

API’s, aroma’s, chemical building blocks

Epoxy resins

Phenolic resins

POTENTIAL APPLICATIONS

Ex. Phenolics derivatives

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45-100 €/ton wet wood Up to 250 €/ton dry wood

50 – 750 €/ton

Fire retardants

Flocculants

Polyurethanes

Surfactants

Fertilizers

Dispersants Aromas

Phenolic resins

Wood plastic composites

Chapter 6 Regional Development in Europe via: Biorizon (see panel this morning) BIG-Cluster (see panel yesterday) Vanguard

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Mission: to enable commercial production of bio-aromatics by 2025

BIG - Bio-Innovation for Growth mega-Cluster

Mega-cluster: NL-NRW-Fl

Fred du Plessis, (Executive Advisor, Sabic)

F2P Flagship Aromatics & Fine Chemicals from woody biomass

VANGUARD INITIATIVE

Biobased aromatics Leading region: Flanders Co-leading regions:

South Netherlands – Randstad NordRhein Westfalia Emilia Romagna Scotland Brandenburg Värmland Central Finland Upper Austria Wallonia Slovenia Basque Country

Regional collaboration via smart specialisation Different pilots: additive manufacturing, nanomaterials, Biobased economy

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CONCLUSIONS

Lignin is becoming more and more available

Lignin valorization is cornerstone for economic viability of lignocellulose biorefining

Lignin use as polymer: more and more established technology

Next approach functionalised aromatic molecules: Need for depolymerization process Need for technically efficient and economically viable fractionation process Need for efficient conversion processes including telescopic conversions

Developments in Europe via Biorizon, BIG-Cluster and Vanguard

Attention to REACH regulation in Europe

Further developments: Materials of the future (e.g. 3D-printing) Extractives Non-aromatic derivatives Composite materials …

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Further information

ludo.diels@vito.be

Join us at

www.biorizon.eu/community

Visit Biorizon at the Holland Pavillion

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