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Gran Gellerstedt
Wageningen 2011
H3CO
H3CO
HO
OH
O
HO
HO
OH H3CO
CH2OH
CH2OH
CHOH
2OH
H3CO
Lignin structure
OH
OH
O
O
HO
OH
H3CO
H3CO
OCH3
OH
HO
OH
OH
H3CO
O
O
OH
OCH3
Lignin
HO
OH
HO
H3CO
CH2OH
p-Coumaryl alcohol
H3CO
O
OH
H3CO
O
Coniferyl alcohol
OH
Sinapyl alcohol
HO
O
O
HO
H3CO
O
OH
H3CO
O
Plant
Type
H3CO
OCH3
OH
1 OCH3
HO
H3CO
OCHOH
3
OH
Coniferous; Softwoods
H3CO
O
HO
OH
<5
HO
Monocotyledonous;
Grasses
H CO
3
Lignin
Wageningen 2011
O
OH
H3CO
OH
0-8
O
5-35
HO
Per cent
H3CO
OCH3
25-50
35-80
OCH3
HO
OCH3
HO
>95
O
OH
Eudocotyledonous; Hardwoods
O
HO
HO
Lignin
OH
0
H3CO
OH
45-75
H3CO
20-55
CHO
Lignin Content
Scientific/Common Name
Gymnosperms
(compression wood)
28
39
28
Angiosperms - Eudicotyledons
Betula verrucosa, Siver birch
20
22
19
Angiosperms - Monocotyledons
Saccharum species, Bagasse
Wageningen 2011
14
Biodiesel
Pulp
4 (+9) Mtoe
11 Mtoe
Lignin
13 (+1) Mtoe
DME, FT-diesel
Ethanol
5 Mtoe
Wageningen 2011
Hemicell.
suprabio
19.0 M
Biocore
20.3 M
Wageningen 2011
Phenols
Vanillin
Org. S-comp.
Macromolecule in
solution systems
Dispersants
Emulsion stab.
Macromolecule in
material systems
Resins
Polyblends
Antioxidant
Rubber reinf.
Lignin
Energy
Wageningen 2011
Technical lignins
Commercial
Lignosulfonates (softwood, hardwood)
Kraft lignins (softwood, hardwood)
Soda lignins (annual plants)
Component
Spruce
Birch
Lignosulfonate, tot.
Mw > 5,000
Carbohydrates
- Arabinose
- Xylose
- Mannose
- Galactose
- Glucose
Aldonic acids
Acetic acid
Extractives
Misc. compounds
4801)
245
280
10
60
120
50
40
50
40
40
40
3701)
55
375
10
340
10
10
5
95
100
40
60
1) calculated as lignin
Wageningen 2011
Ethanol
Aq. lignosulfonate
Wageningen 2011
Pine
Birch
Lignin
Carbohydrate derived
- Hydroxy acids
- Acetic acid
- Formic acid
Turpentine
Resin and/or fatty acids
Misc. products
490
330
320
50
80
10
50
60
230
120
50
40
80
Wageningen
2011
Fibre processing
Black
liquor
Recovery
boiler
The LignoBoost
process
Lignin
Wageningen
2011
Conversion
Chemicals
Conversion
Biofuels
Carbon: 61-65%
Hydrogen: 5-7%
Oxygen: 28-30%
Sulfur: 1-3%
Ash: 0.2-0.4%
Carbohydrates: 1-2%
Wageningen 2011
88
100
O
62
82
84
72
85
CH
CH3
59
O
H
85
Wageningen 2011
99
D, [H]
Wageningen 2011
C8.35 H7.27 O1.89 S0.08 (OCH3)0.89 + 12.73H C6H6O + 3.24(CH4) + 1.78(H2O) + 0.08(H2S)
Product
Water
C5H12
% by weight
25.2
Neutrals
Mono-
High Mw
<240 oC
phenols
>240 oC
14.0
37.5
11.1
17.9
Hydrogen
5.7
CH3
CH3
CH3
CH3
CH3
CH3
CH3
Yield, %:
OH
OH
OH
OH
22
OH
33
H3C
OH
OH
OH
20
Spruce
Birch
E. globulus
4.1
4.3
3.3
3.1
1.7
1.5
0.5
0.5
0.2
4500
1600
2300
Polydispersity, Mw/Mn
4.5
3.6
4.3
148
119
133
3.1
1.2
n.a.
Molecular mass, Mw
Wageningen 2011
Lignosulfonates
upgrading
Lignin
2)
reactive aldehyde
OCH3
Reactive
position
OH
sulfite
dispersing agents
amine
chelating agents
phenol
adhesives
3)
Wageningen
2011
polyurethane
Sulfomethylation of lignin
Lignin
Lignin
~140 C
+ NaHSO3 + CH2O
OCH3
OH
NaOH
NaO3S
C
OCH3
H H OH
Wageningen 2011
13C-NMR
Spruce tannin
160
OH
RO
140
130
120
110
ppm
140
130
120
110
ppm
120
110
ppm
A
OH
OH
catechol
150
B D
resorcinol
OR
160
150
D
RO
Spruce lignin
OH
phloroglucinol
OCH3
O
160
Wageningen
2011
guaiacol
150
140
130
Wageningen 2011
O
HO
HO
O
OCN
KOH
OCH3
OCH3
OH
O
CH2OH
R NCO
OCH3
O
CH2O
O
NH
R
O
HN
O
Wageningen 2011
Starting material:
Wageningen 2011
Wageningen 2011
Wageningen 2011
converted to
16,000 tonnes of CF
Wageningen 2011
SWL
EL
SP5
EP5
SR5
ER5
dw/d log M
dw/d log M
softwood
Wageningen 2011
Conclusions
Large quantities of lignins will be formed in future biorefineries
Most of the lignin will be used as internal process fuel or subjected to
gasification (CO + H2)
A partial out-take of (purified) lignin is technically feasible in different
types of processes
Carbon fibre would be an interesting option but will require new
knowledge about the structure-property relationship
Other uses: biofuels, adhesives and other polymers (esters, ethers,
urethanes), BTX chemicals, activated carbon
There is still a long way to go
Wageningen 2011