Vanguard Case

Bio-aromaticsLeader: Flanders (Ludo Diels)

Co-leaders: South Netherlands, NRW

National Bio-economy DayMilan, 23 May 2019

Why bio-aromatics?

2

1

Powered by: TNO, VITO, ECN & Green Chemistry Campus

6/20/2019 3

CRACKING

Powered by: TNO, VITO, ECN & Green Chemistry Campus

6/20/2019 4

Powered by: TNO, VITO, ECN & Green Chemistry Campus

6/20/2019 5

COSTS

FUNCTIONALITY

6

DRIVERS AND OPPORTUNITIES FOR DEVELOPMENT OF ‘LIGNOCELLULOSIC FEEDSTOCK TO

AROMATICS’

❑ Societal driver for transition to bio-economy (i.e. renewable feedstock)

❑ Reducing footprint of industrial processes

❖ Use of biomass

❖ Use of functionality (less steps)

❑ Innovation in chemicals & materials

❖ Safer, performance-based products

❖ Through disruptive enabling process technologies

❑ Economic drivers

❖ 40% of chemicals are aromatic (>23 mln tons BTX-fenol)

❖ Inability to valorize lignin is a lost opportunity in biorefining

❖ Recovery boiler (P&P) is limited in solids content, removal of lignin solves this problem

❖ Shale gas does not deliver higher than C3

❖ 25% of world production in Europe (large amount of jobs)

7

Sustainable & renewable

feedstocks

geopolitics

climate

price volatility

environment

HOW CAN BIOMASS REPLACE AROMATIC CHARACTERISTICS?

Based on the lignocellulose biorefinery

8

Replace by lignin-based aromatics

Replace by sugar-based aromatics via

fermentation

Replace by sugar-based furan chemistry or via

Diels-Alder chemistry

Bio-economy as part

of the circular

economy

9

2

BIO-ECONOMY AS PART OF THE CIRCULAR ECONOMY

❑ MSW at 520 kg/p/y of which 50% is biodegradable

❑ Still huge amounts end up in landfills

❑ Global food loss and waste generate 4.4 Gtons CO2eq, i.e. 8 % if anthropogenic GHG emissions

❑ Only 5% of sewage sludge is converted into CH4

Food & feed processing and domestic use leads to large amounts of waste

10

OECD, Realising the circular bioeconomy, Nov 2018, No. 60

WASTE-SUGARS TO FURANICS

Biphasic reactor for conversionof waste into furans (kg/hr)

FURANS TO AROMATICS

12

Bio-economy as part

of negative emissionsForests in climate change mitigation

13

3

NEGATIVE EMISSIONS AND THE PARIS-GAP

14

Prof. RadermacherUni. Neu-Ulm

NEGATIVE EMISSIONS

From three trillions of trees to four trillions of trees! (Tom Crowther, Yale Univ., ETH-Zurich)

One trillion of trees can be added without changing biotopes

Action by UNEP and ¨Plant for the Planet”

15

How to proceed from

lignin to aromatics?

16

4

ORIGIN OF LIGNIN

❑ Lignin from pulp & paper industry

▪ Lignosulfonate lignin (wood)

▪ Kraft lignin (wood)

▪ Soda lignin (non-wood)

❑ Lignin modifications

▪ Lignoboost (CO2-precipitation)

▪ Lignoforce (oxidation + CO2-precipitation)

▪ Ligniox (alkaline oxidation step)

▪ Ecolig

▪ ….

❑ H-lignin from cellulose ethanol production

▪ Steam/ammonia explosion + enzymes

▪ …

❑ New lignins

▪ scCO2, scAlcohols

▪ Alkali or acid (LXP, Zambezi, Chempolis)

▪ Autohydrolysis (hot water)

▪ Organic solvents: Lignol, FhG, CIMV

▪ Ionic Liquids/DES/ NADES

▪ …

Pulp & paper industry (+ upgraded lignins) or from Cellulose ethanol

17

LIGNIN VALUE VS LIGNIN-BASED PRODUCT VALUE

18

Lignin-based product potential market value ($/ton)

Lignin actual value ($/ton)

0

600

1300

6500

0 300 650 1000

Low purity lignin

Lignosulfonates

Kraft lignin

LignoboostEcolig

Organo-solv

Lignin

High purity ligninHydrolysis

Lignin

EnergyBitumen

Plasticizer

Carbon fibres

Vanillin, API

Depol.Lignin

PU

AdditivesUV, Bact, FR, AO

Resins

Polymers

CoatingsAdhesives

Flocculant

DispersantFenols

CAT-lignin

Low purity lignin

Lignosulfonates

Kraft lignin

LignoboostEcolig

Organo-solv

Lignin

High purity ligninHydrolysis

Lignin

EnergyBitumen

Plasticizer

Carbon fibres

Vanillin, API

Depol.Lignin

PU

AdditivesUV, Bact, FR, AO

Resins

Polymers

CoatingsAdhesives

Flocculant

DispersantFenols

CAT-lignin

PHYSICOCHEMICAL FACTORS PROMISE A BRIGHT FUTURE FOR LIGNIN-BASED

PRODUCTS

❑ presence of aromatic rings reactive functional groups

❑ good rheological and visco-elastic properties and good film-forming ability

❑ compatibility with a wide range of industrial chemicals

❑ hydrophilic or hydrophobic character depending on origin

19

20

MONOMER MODIFICATION AND REACTIVE SITES!

phenol guaiacol

syringol methyl guaiacolvanillin vinyl guaiacol

vinyl syringolmethyl syringol syringaldehyde

Aromatic ortho site

Aromatic para site

Major

monomeric

products

obtained

during lignin

fractionation

3 2

1

0

1

0

1 1

0

# reactive groupsx

21

OLIGOMERS AND REACTIVE SITES!

1

0

3

2

Typical

structures

(dimers &

oligomers)

obtained

from the

BCD

process

Oligomeric

structures are

intrinsically more

suitable than

monomers for

resin development

(higher # of

reactive groups).

Reactivity of

the dimers

is better

compared to

monomers,

but it is not

always

sufficient

Lignin

depolymerization

22

5

DEPOLYMERIZATION & FOCUS ON FUNCTIONALITY

23

- Reductive- Oxidative- Solvolytic- Thermal- Catalytic- Enzymatic

Voettekst invulling24

MOLECULES THAT ARE OBTAINED

Downstream

separation of lignin

streams25

6

Powered by: TNO, VITO, ECN & Green Chemistry Campus

26

(Modified) filler

LigninO

O

O

HO

OH

O

O

OH

O

OO

O

OHO

HO

O

O

HO

O

O

OH

O

O OH

O

O OH O

O O

OH

HO

O

HO

O

O

O

O

O

O

OH

O

OH

O

O

O

Polymeric lignin as such

Fractionation

Oligomer based mix

Monomer based mix

Specific fractionation / affinity-based separation

Pure, single molecules/ chemicals

O

OCH3

R2

R1

R

O

R' CH3

O

OCH3

Rx

Ry

OH

CH3O

OH

R'

R

Depolymerization

Chemicals Mix

Powered by: TNO, VITO, ECN & Green Chemistry Campus

Pretreatment by alkaline oxidation

Input Process Output

❑ [Na+] : 8.1 g/L

❑ [CO32-] : 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

❑ [CO32-] : 0.2 g/L

❑ [Lignin] : 67 g/L

❑ [organic acids] < 0.7 g/L

❑ UF/NF

❑ Diafiltration

❑ Concentration

12 g/L 17 g/L[Lignin] Quasi-

complete

removal of

CO32-,

organic acids

and residual

sugars

44 % removal

of Na+

67 g/L

Initial DV 1 DV 2 DV 3 DV 40

2

4

6

8

10

Conc

entr

atio

n (g

/L)

Na+ CO3

2-

Acetic acid Formic acid

Oxalic acid Glycolic acid

Glucose Xylose

ESP04 (PCI - Xylem)

27

2 SEPARATION OF LIGNIN DEGRADATION PRODUCTS

Base catalysed degradation (BCD)

28

Current DSP process

Lower Mw phenolics Higher Mw phenolics

2 SEPARATION OF LIGNIN DEGRADATION PRODUCTS

Base catalysed degradation of lignin

29

Alternative membrane process

pH-stable NF membrane

Powered by: TNO, VITO, ECN & Green Chemistry Campus

Grafted ceramic membranes: unique separation capabilities thanks to surface tailoring

New flexible functionalization platform: FunMem®

❖ Unique, direct M-R bond

❖ Stable, non-hydrolysable

❖ Commercial membranes

❖ Broad variety of functional groups

❖ Tailored membrane surfaces

FunMem4Affinity – Exploration of Functional Ceramic Membranes in Organic Solvent

Nanofiltration (2012-14)

Membrane

Solvent Solute

New possibilities for affinity-based separations:

❖ Tuning of interactions

❖ Beyond size-exclusion

❖ Selectivity by design

30

Analytics and

conversion

31

7

C/O mapping 5/31

20/06/2019

©VITO – Not for

32

CO mapping

*NMR database of Lignin and cell wall model compounds (Ralph J. 2009)

C23O2 NF in biological manetic resonance data bank

C22O6 NF in biological manetic resonance data bank

C18O6 C18H22O6 http://www.bmrb.wisc.edu/metabolomics/mol_summary/show_data.php?id=bmse010045

C17O5 C17H18O5 http://www.bmrb.wisc.edu/metabolomics/mol_summary/show_data.php?id=bmse010456

C14O3 NF in biological manetic resonance data bank

C13O2 NF in biological manetic resonance data bank

C18H22O6*C17H18O5*

33

DE AND REFUNCTIONALISATION

▪ Removal of propyl-, methyl-groups (O- & C-dealkylation)

▪ Removal of methoxy groups

▪ From alkylfenol mixture to application mixture

▪ Other modifications

▪ Developed on monomers

Applications34

8

CAN THE BIO-ECONOMY BE PART OF CARBON STORAGE

Biological carbon storage is different from a circular economyStorage in engineered bio-based construction materialsNot only by using wood or bamboo in a direct way

35

Rüdiger Lainer + Partner

CLT

TRANSFORM BIO-WASTE INTO FURNITURE

But you need a hardener and a resin!!!!

36

BIOAROMATICS VALUE CHAIN

37

Vanguard approach38

9

39

40

time

Thanks to Triple Helix bio-aromatics is nog verywell on the regional, but also international agenda. It starts from the strong chemical region Antwerp-Amsterdam-Rhein-ruhrRegionIdeal starting point

41

0

5

10

15

20

25

30

Horizon 1 Horizon 2 Horizon 3

Ho

rizo

n f

inan

cin

g [M

€]

RTO

partners

Horizon financing

42

2025: 1st Commercial bio-aromatic production

2021: 1st Demo plant (50 ton/year)

2040: Array of commercial bio-aromatic production facilities.2040: Array of commercial bio-aromatic production facilities.

2040: Array of commercial bio-aromatic production facilities.2040: Array of commercial bio-aromatic production facilities.

Array of commercial bio-aromatic production facilities

2018: Pilot skids

Lignovalue Pilot plant

43

Lignin-based business plan for

Thematic Smart Specialization Platform

44

Innovative

Biorefinery

2G Ethanol

Biorefinery

Pulp & Paper

Lignin

e.g. Organosolv,

ionic liquid, ……

Hydrolysis-Lignin

Black Liquor

LignoValue

Lignin

e.g. lignoBoost

CatLignin

LignoValue Oil

fractions

Additives

Resins

Adhesives

Polymers

Coatings

Polyurethane

Dispersants

Building Blocks

Lignovalue: thermal solvolysis, catalytic hydrolysis, membrane fractionation

“The Vanguard network brings

stakeholders together in

different value chains from

feedstock to processes to

material development & via

brand owners to consumers

45

Different value chains

▰Over all lignocellulose biorefinery

▰Sugar + lignin

▰Natural lignin to cosmetics & fragrances

▰Lignin to glues and adhesives

▰Lignin to fenols for cyclohexanon &

Bisphenol-A

▰Combination of timber – pulp –performance

fibers –resins

▰Tannins-based value chain

46

▰Agriculture waste for extraction of specific molecules

▰Bio-composites

▰Bio-asphalt

▰Lignin in 3D-printing

▰Carbon fibers

▰New pulping systems via ILs

47

THANKS!Any questions?

You can find me at

Ludo.diels@vito.be