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Lignin Structure and

Applications
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 in plants


Plant

Lignin Content

Scientific/Common Name
Gymnosperms

Picea abies, Norway spruce


"

(compression wood)

Pinus sylvestris, Scots pine

28
39
28

Angiosperms - Eudicotyledons
Betula verrucosa, Siver birch

20

Eucalyptus globulus, Blue gum eucalyptus

22

Populus tremula, European aspen

19

Angiosperms - Monocotyledons
Saccharum species, Bagasse

Wageningen 2011

14

From biomass to liquid fuels in 2020


(5.38 43 Mtoe within EU)

Biodiesel

Pulp

4 (+9) Mtoe

11 Mtoe

Lignin
13 (+1) Mtoe

DME, FT-diesel

Ethanol
5 Mtoe
Wageningen 2011

Hemicell.

Current Biorefinery Activities (EU)


EuroBioRef
37.4 M

suprabio
19.0 M

Biomass Processing Lignin Processing surfactants


emulsifiers
antioxidants

Biocore
20.3 M

CIMV-process Lignin resins, adhesives,

Wageningen 2011

Suggested uses for lignin


Fragmentation

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)

Pilot plant scale


Organosolv lignins (hardwood, softwood)
Steam explosion lignins (annual plants)
Acid hydrolysis lignins (softwood)
Wageningen 2011

Compounds in spent sulfite liquor


(kg/ton of pulp)

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

Lignosulfonate as dispersing agent


(Borregaard Lignotech)

Aq. lignosulfonate

Wageningen 2011

Compounds in kraft black liquor


(kg/ton of pulp)
Component

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

Modern kraft pulping A lignin outtake can be accepted


Pulpwood

Fibre processing

Black
liquor

Pulp & paper

Recovery
boiler

The LignoBoost
process
Lignin

Wageningen
2011

Conversion

Chemicals

Conversion

Biofuels

Precipitated kraft lignin

Carbon: 61-65%
Hydrogen: 5-7%
Oxygen: 28-30%
Sulfur: 1-3%
Ash: 0.2-0.4%
Carbohydrates: 1-2%

Wageningen 2011

Bonding energies, kcal/mol


H

88

100
O

62

82
84

72

85
CH

CH3
59

O
H
85
Wageningen 2011

99

van Krevelen diagram showing different biomass


and fossil materials

D, [H]

Wageningen 2011

Phenol from kraft lignin at 340-450 oC


Theoretical:

cat: Fe-oxide; Co-oxide;

C8.35 H7.27 O1.89 S0.08 (OCH3)0.89 + 12.73H C6H6O + 3.24(CH4) + 1.78(H2O) + 0.08(H2S)

560 kg/ton lignin


Volatiles

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

Ref: Huibers and Parkhurst Jr, 1983


Wageningen 2011

Kraft lignins; Analytical data


Functionality

Spruce

Birch

E. globulus

Aromatic OH, mmol/g

4.1

4.3

3.3

Aliphatic OH (total), mmol/g

3.1

1.7

1.5

Carboxyl groups, mmol/g

0.5

0.5

0.2

4500

1600

2300

Polydispersity, Mw/Mn

4.5

3.6

4.3

Glass transition temp. Tg, oC

148

119

133

Free aromatic C5, mmol/g

3.1

1.2

n.a.

Molecular mass, Mw

Wageningen 2011

Some lignin reactions


1)

Lignosulfonates

upgrading

Lignin

2)

reactive aldehyde
OCH3

Reactive
position

OH

sulfite

dispersing agents

amine

chelating agents

phenol

adhesives

(Softwood) kraft lignin

3)

Kraft lignin (low Mw-fraction) + polyol + isocyanate

Wageningen
2011

polyurethane

Sulfomethylation of lignin

Lignin

Lignin

~140 C
+ NaHSO3 + CH2O
OCH3
OH

NaOH

NaO3S

C
OCH3
H H OH

A maximum of ~2 mmol sulfonate groups/g of lignin


can be obtained ~33% reactive positions

Wageningen 2011

13C-NMR

of tannin and lignin


B

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

Reactivity towards formaldehyde


Phloroglucinol: highly reactive
Resorcinol: intermediate
Catechol/phenol: low
Tannins are presently used as wood adhesives,
lignins are not
In the future, formaldehyde-free adhesives
based on lignin might be developed
Wageningen
2011

Lignin uniform reactivity

Wageningen 2011

Polyurethane from oxypropylated kraft lignin

O
HO

HO
O

OCN

KOH
OCH3

OCH3
OH

O
CH2OH

R NCO

OCH3
O
CH2O

O
NH
R
O
HN
O

Wageningen 2011

Manufacturing process for CF

Starting material:

Polyacrylonitrile (PAN; ~90% of CF)


Petroleum/coal pitch
Regenerated cellulose (rayon)

Wageningen 2011

Carbon fiber use .towards the automotive industry

Driving force: lower price of CF


Advantage: lower weight of
vehicle, less gas consumption

Wageningen 2011

Even a small lignin withdrawal can be interesting


650,000 tonnes
of pulp

Wageningen 2011

Lignin withdrawal of 10%


yields 33,000 tonnes

converted to
16,000 tonnes of CF

to support 160,000 cars


with CF-composite
(~40% replacement)

SEC of kraft lignins before/after


fractionation
E. globulus

log M (relative polystyrene)

Wageningen 2011

SWL

EL

SP5

EP5

SR5

ER5

dw/d log M

dw/d log M

softwood

log M (relative polystyrene)

Carbon fibre characteristics

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

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