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Lignin valorization towards materials,
chemicals and energy
Dr. Richard Gosselink
2nd Lund symposium on lignin and hemicellulose valorisation, November 3-4, 2015 Lund
Contents
Lignin valorization
Biorefineries
Conversion technologies for lignin
Take home messages
2
Lignin valorization
Lignin = glue in woody type of biomass
Abundantly available at relatively low costs
Energy source
Versatile raw material for many applications
Additional revenues for Pulp&Paper industry (focus on
cellulose) and 2nd Generation Biorefinery industry (focus on
fuels)
3
Chemicals and materials driven biorefineries
- Developing biobased chemicals will increase the profitability of second
generation biofuels production
- Biobased chemicals and materials driven biorefineries can also be created
alongside traditional vegetable oil, starch, sugar and paper producers
- Agrifood industries are diversifying their product slate; increasingly engaging in
non-food products
- Traditional pulp and paper industry focus on side stream valorization (lignin
initiatives of Domtar, Stora Enzo, West Fraser, ...)
4
Lignin structure
Lignin
5 Model softwood lignin: Brunow 2001
Lignocellulose architecture: Rubin 2008
Composition of lignocellulosic (LC) feedstocks (wt% dm)
Origin Species Carbo-hydrates
C6 sugars
C5 sugars
Lignin
Hardwoods Mixed (stem)
60-75 40-50 16-20 18-25
Softwoods Mixed (stem)
60-67 40-50 15-18 27-33
Grasses Sugar cane bagasse
60-70 33-36 20-25 19-24
Agricultural residues
Corn cobs 75 40 30-34 15
Wheat straw
55-60 30-35 20-23 16-21
Rice husks 50-55 30-35 20-22 20-22
6
Technical lignin availability (dry ton/y)
Pulp & Paper industry
● 50 M ton lignin extracted, 2% commercial lignins
● 1 M ton lignosulfonates, 0.1 M ton kraft lignins, 5-10 kton sulfur-free lignins
● Efficient processing and extraction in 2020 2-4 M ton extra kraft lignin
Biomass conversion (Biorefinery)
● Some commercially available, but no current lignin production
● Steam explosion (eg. Biochemtex, Abengoa)
● Organosolv lignins (eg. Lignol, CIMV, Dechema)
● Hydrolysis lignins (eg. POET-DSM, Inbicon/DONG, SEKAB)
● Large quantities expected in EU in 2020 (4-5 M ton)1; in 2030 (12 M ton)1
1EU directive
10% biofuels in 2020, 25% in 2030
7
Lignin production versus utilisation
Aromatic chemicals & materials derived from lignin
Binders/resins
Polymerisation Depolymerisation
Composites Coatings Surfactants Bitumen (asphalt, roofing)
Monomeric chemicals Chemical/ Enzymatic upgrading
(Bio-)catalysis
Fractionation Oligomeric fragments
Confidential 9 9
Chemistry Biotechnology
Fractionation Varied biomass
Hemicellulose
Lignin
Cellulose
Intermediates
Final products
PVC, polyolefins, polyurethanes, polyesters
Thermoplastics
Ethanol
2nd generation fuels
Application sectors
Materials
Energy
Adhesives and paints
Food additives
Wood panels
Resins/Adhesives
Detergents
Building
Packaging
SRC wood
Forestry waste
Cereal by-products
10
INTERMEDIATE PRODUCTS
11
Cellulose (glucose) Hemicelluloses (xylose and arabinose)
Lignins
11
FURTHER VALUE CHAIN ASSESSMENT
Lignin- PU elastomer coatings
Rigid lignin-PU foams
Biobased lignin-phenol-formaldehyde resins
Itaconic acid for paint
Bio-ethanol for fuel or
PVC
12
Lignin application in asphalt (macromolecule)
Bitumen = asphalt binder
In future more scarcity and lower quality; increase of price level
Lignin in combination with vegetable oil
Substitution of 50% bitumen by lignin in low temperature asphalt
testroad (Biobased Infra project Zeeland NL; July 2015)
Monitoring of road quality / performance / durability coming years
13
Relevance of (bio)aromatics
Aromatic chemicals used in a lot of consumer products:
● high performance polymers, resins, fuel additives, flavours,
agrochemicals, fragrances, coatings, bottles etc.
Production capacity is over 100 Mton annually and demand is growing
Shale gas leads to less production of aromatics
Alternative sources are needed
Lignin, the largest aromatic biopolymer in nature, is a good option
14
Conversion technologies for lignin to chemicals
15
Lignin
B/A hydrolysis
phenylpropane (C9)
combustion
pyrolysis
char
BTX (C6,C8)
vanillin (C7)
oxydation
fermentation
Heat
gasification CO, CO2, H2, CH4
hydrogenolysis oil
chemicals
electricity
Mixed aromatics
reduction
solvolysis
supercritical
Ionic liquids /DES
Phenols (C6)
Sub- and supercritical water / hydrothermalin to
Target defunctionalised aromatics (BTX, phenolics)
Moderate temperature for hydrothermal (200-300°C)
High temperature / pressure (300-400°C, > 220 bar) at sc conditions
Green solvent
Various catalysts showing higher selectivity
Moderate yields of monomers (typically >20%)
Added phenols yield complete conversion in dimers
Demonstrated at R&D
16
Hydrothermal lignin depolymerization
Turn lignin into high value aromatics (BTX) and building blocks (phenol)
Approach: Selective catalytic hydrothermal depolymerisation without external hydrogen; Prevent re-condensation
17
Aromatics and phenolics Focus: Biorefinery lignins
Biomass
O H
17 Van Es, D.S., Van der Klis, F., Van Haveren, J.,
Gosselink, R.J.A., Method for the
depolymerization of lignin, WO2014/168473
18
Hydrothermal lignin conversion
Lignin depolymerization is 20% over Pd/C
Limited product distribution; 1 compound (guaiacol) in 50%
Monomers further converted into BTX, cyclohexanone for
chemicals and fuel additives
Relatively limited number of different monomeric compounds
Also supported by NMR
Guaiacol is formed as main compound
RT: 4.00 - 23.00
4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23
Time (min)
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Re
lative
Ab
un
da
nce
10.84
12.02 20.4214.68
15.2913.048.54 8.62 16.09 20.37
14.0311.17 16.27 22.3212.59 19.108.84 17.804.04 19.199.90 20.4713.297.224.38 21.005.81 7.277.08
NL:7.59E6
TIC MS Lignin160311
Lignin/biomass conversion to aromatics
19
Technology Company Type of
development
Feedstock Scale Product portfolio
Pyrolysis ECN (NL) RTD lignin 1 kg/h Lignin oil, char, gas
Catalytic
pyrolysis
Biobtx (NL) RTD biomass 1 kg/h Pyrolysis oil, BTX
Catalytic
fast
pyrolysis
Anellotech
(US)
Pilot biomass 1 kg BTX, hydrocarbons,
gas
BCD Borregaard
(No)
Commercial Lignosulfonate 1500
t/y
Vanillin
HDO UOP (US) RTD lignin 25 g Lignin oil
Take home messages
LC biorefineries will generate large amounts of lignin
Lignin valorization can lead to more profit
Lignin conversion to valuable products (fuel additives,
chemicals and materials) is expanding area
Technologies for deriving aromatic base –and specialty
chemicals are leaving the “initial stages of infancy”
Catalytic conversion of lignin is leading
A number of viable concepts to get to biobased fuels,
chemicals and materials have been demonstrated
Lignin biorefinery leads to multiple outlets including chemicals,
materials and energy
20
Wageningen UR Lignin Platform
Focus on lignin to bioaromatics + materials
● NL knowledge institutes + industrial partners
EU projects:
NL projects:
Industry sponsored projects: coatings, resins, life sciences, ...
Networks:
Ocobinders
Ocobinders
More info: Wageningenur.nl/ligninplatform
LigniFAME
