Lignin as a renewable aromatic resource for the chemical industry Mini-symposium organised by Wageningen UR Lignin Platform, 6 December 2011, Wageningen Richard J.A. Gosselink
Lignin as a renewable aromatic resource
for the chemical industry
Mini-symposium organised by Wageningen UR Lignin Platform, 6 December 2011, Wageningen
Richard J.A. Gosselink
Contents
PhD program
Lignin valorization
Results
Conclusions and recommendations
PhD program
Lignin valorization for wood adhesives and aromatic chemicals
Universal method for molar mass determination of lignin
Fractionation, analysis and PCA modeling
Lignin activation
Lignin depolymerization
Promotor: Prof. J.P.M. Sanders (WUR-VPP)
Co-promotors: Prof. G. Gellerstedt, Dr. J.E.G. van Dam
Dr. E. de Jong, Dr. E.L. Scott
Lignin valorization
Biobased aromatic feedstock
Abundantly available at relatively low costs
Energy source
Versatile raw material for many applications
Additional revenues for Pulp&Paper industry and 2nd
Generation Biorefinery industry
A competitive industry can be developed
Lignin production needs to go hand in hand with application
development
Lignin valorization
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)
● Not commercially available yet, several R&D/pilot initiatives
● Organosolv lignins (eg. Lignol, CIMV, Dechema)
● Steam explosion (eg. Abengoa, ENEA)
● Hydrolysis lignins (eg. Inbicon, Chemtex)
● 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
Lignin production versus utilisation
Universal method for molar mass lignin
In EUROLIGNIN 2 size exclusion methods recommended
● organic SEC after acetylation
● alkaline SEC
Alkaline SEC method
● Alkaline solvent (0.5M NaOH)
● Directly applicable for wide range of lignins
● Disadvantage: no commercial column available
Alkaline SEC method improved for highly dispersed lignins
● 2 gels used with different pore sizes
Universal method for molar mass lignin
2 gels enables the analysis of highly dispersed lignins
Low dispersed lignins give same results
Lignin Overlay one gel and two gels
Alcell
SampleName: Alcell
SampleName: Alcell
2259 -
21.0
33
2054 -
9.5
17
AU
0.00
0.20
0.40
0.60
0.80
1.00
Minutes
1.00 2.00 3.00 4.00 5.00 6.00 7.00 8.00 9.00 10.00 11.00 12.00 13.00 14.00 15.00 16.00 17.00 18.00 19.00 20.00
Sarkanda grass F5
SampleName: S5 (=I4)
SampleName: S5 (=I4)
5758 -
20.0
70
124939 -
4.7
27
6006 -
8.7
04
AU
0.00
0.05
0.10
0.15
0.20
0.25
0.30
0.35
0.40
0.45
0.50
Minutes
1.00 2.00 3.00 4.00 5.00 6.00 7.00 8.00 9.00 10.00 11.00 12.00 13.00 14.00 15.00 16.00 17.00 18.00 19.00 20.00
Steam explosion
SampleName: Steam Explosion
SampleName: Steam Explosion
3159
- 2
0.68
6
1263
80 -
4.8
14
3248
- 9
.171
AU
0.00
0.10
0.20
0.30
0.40
0.50
0.60
0.70
Minutes
1.00 2.00 3.00 4.00 5.00 6.00 7.00 8.00 9.00 10.00 11.00 12.00 13.00 14.00 15.00 16.00 17.00 18.00 19.00 20.00
Curan 100
SampleName: Curan 100
SampleName: Curan 100
3420 -
20.6
04
3289 -
9.1
61
74 -
14.0
33
AU
0.00
0.20
0.40
0.60
0.80
Minutes
1.00 2.00 3.00 4.00 5.00 6.00 7.00 8.00 9.00 10.00 11.00 12.00 13.00 14.00 15.00 16.00 17.00 18.00 19.00 20.00
EAL
SampleName: EAL
SampleName: EAL
621605 -
14.9
70
6493 -
19.9
47
124801 -
4.7
20
6700 -
8.6
20
76 -
14.0
93
AU
0.00
0.10
0.20
0.30
0.40
0.50
0.60
0.70
Minutes
1.00 2.00 3.00 4.00 5.00 6.00 7.00 8.00 9.00 10.00 11.00 12.00 13.00 14.00 15.00 16.00 17.00 18.00 19.00 20.00
EMAL
SampleName: EMAL
SampleName: EMAL
3776
- 2
0.50
2
1269
35 -
4.8
64
4718
- 8
.888
75 -
14.
078
AU
0.00
0.05
0.10
0.15
0.20
0.25
Minutes
1.00 2.00 3.00 4.00 5.00 6.00 7.00 8.00 9.00 10.00 11.00 12.00 13.00 14.00 15.00 16.00 17.00 18.00 19.00 20.00
R.J.A. Gosselink et al. (2010)
Holzforschung 64:193-200
Alkaline SEC with 2 columns (gels)
Fractionation, analysis and PCA modeling
Lignin characterization is important for selection of suitable application
Fractionation of lignin can be used to tailor the properties of a lignin fraction
By Principle Component Analysis lignins can be clustered and selected for an application
Analyses:
● Carbohydrates and ash (lignin impurities)
● Molar mass
● Degree of condensation
● Functional groups (phenolic OH, free ortho)
Fractionation, analysis and PCA modeling
Fractionation performed by organic solvents leading to fractions with increasing molar mass
High – molar mass - low
Indulin AT
0
5000
10000
15000
20000
25000
30000
35000
40000
45000
* F1 F2 F3 F4 F5
Mw
(D
alto
n)
Organic SEC
Alkaline SEC
Curan 100
0
10000
20000
30000
40000
50000
60000
* F1 F2 F3 F4 F5
Mw
(D
alto
n) * Unfractionated lignin
Sarkanda grass soda lignin
0
5000
10000
15000
20000
25000
30000
35000
* F1 F2 F3 F4 F5
Mw
(D
alto
n)
Hardwood soda lignin
0
10000
20000
30000
40000
50000
60000
70000
* F1 F2 F3 F4 F5M
w (
Da
lto
n)
Fractionation, analysis and PCA modeling
PCA modeling results in different clusters of lignins or their fractions
Each clusters has its own poperties and application potential
Biplot (axes PC1 and PC2: 80.15 %)
Indulin ATCuran 100
Sarkanda grass soda
Hardwood soda
Organosolv
P1000
Sarkanda grass soda F1Sarkanda grass soda F2
Sarkanda grass soda F3
Sarkanda grass soda F4Sarkanda grass soda F5
log_(1/carb)
log_(1/ash)
log_molar_massFree_ortho
log(1/condensation)
log(phenolicOH)
-3
-2
-1
0
1
2
3
-3 -2 -1 0 1 2 3
-- axis PC1 (57.61 %) -->
-- a
xis
PC
2 (
22
.54
%)
-->
R.J.A. Gosselink et al. (2010)
Holzforschung 64:193-200
Lignin as wood adhesive
Lignin is a natural glue
● Binders are used in panel & boards
● 1 M tonnes phenol formaldehyde (PF) resins globally
Why lignin?
● Substitution of expensive phenol part
● Reduction in emission of carcinogenic formaldehyde
Partial substitution of PF resin by modified lignin
Lignin structure resembles PF structure
Development of emission-free renewable binders
Lignin-furan resins (ECOBINDERS)
Ocobinders
Ocobinders
Lignin valorization
Bakelite (PF resin) Lignin
Activation needed
PF resin can be substituted up to 50% by lignin
Ocobinders
Ocobinders
Lignin activation
Sodium periodate oxidises lignin moieties
Lignin treated under mild conditions
Lignin quinones have the ability to react with furfuryl alcohol
(furan derivatives) via a Diels-Alder reaction
Ocobinders
Ocobinders
Proposed mechanism
Lignin activation
Ocobinders
Ocobinders
0
0.2
0.4
0.6
0.8
1
1.2
900100011001200130014001500160017001800
Wavenumber (cm-1)
Ab
so
rba
nce
15
98
16
58
17
01
15
12
14
58
14
21
13
26
12
63
12
18
11
24
10
87
10
29
91
4
13
59
0
0.2
0.4
0.6
0.8
1
1.2
900100011001200130014001500160017001800
Wavenumber (cm-1
)
Ab
so
rba
nce
Untreated
1% periodate
10% periodate
50% periodate
17
14
16
62 15
95
15
12
14
65
14
52
14
20
13
67
12
69
12
13
11
36
11
26
10
80
10
26
55°C during 10 min at pH 5
1658 cm-1 corresponds to quinoid structures
Soda lignin
Kraft lignin
Lignin based wood adhesive
Ocobinders
Ocobinders
Furan resin with 10% lignin
0.0
0.5
1.0
1.5
2.0
2.5
3.0
3.5
Str
ength
(N
/mm
2)
0
25
50
75
100
Furan
resin
(no
ligni
n)
Gra
ss/s
traw
Gra
ss/s
traw 1
0% o
xid.
Gra
ss/s
traw 5
0% o
xid.
SKL
SKL
10%
oxid.
Gra
ss
Gra
ss 1
0% o
xid.
Wood f
ailu
re (
%)
0.0
0.5
1.0
1.5
2.0
2.5
37% DM 47% DM Grass/straw Grass/straw 10%
oxid.
Grass/straw 50%
oxid.
SKL SKL 10% oxid. Grass Grass 10% oxid.
Str
en
gth
(N
/mm
2)
0
25
50
75
100
37%
DM
47%
DM
Gra
ss/straw
Gra
ss/straw
10%
oxid.
Gra
ss/straw
50%
oxid.
SKL
SKL 10
% oxid.
Gra
ss
Gra
ss 10%
oxid.
Wo
od
fa
ilu
re (
%)
10% lignin in PF resin
30% lignin in PF resin
PF resin
PF resin with 10 and 30% lignin
R.J.A. Gosselink et al.
(2011) Holzforschung
65:155-162
Further developments wood adhesives
Currently 30% P replacement by soda lignin in commercial PF
resins (Lora, 2008)
Ultimate goal 100% P replacement
Near 100% Ecofriendly boards (isocyanates)
Lignin + tannin + glyoxal (non-toxic, non-volatile) (Pizzi,
2009; Mansouri, 2011)
Binderless boards (Van Dam, 2006)
Lignin depolymerization
Production of value added AROMATIC chemicals
Replacement of petrochemical based phenol or derivatives
Replacement of fossil based polymers (polycarbonate,
polyurethanes, polyesters..) and phenol based resins (PF)
Lignin conversion to phenol can decrease the production costs
of cellulose ethanol substantially
Lignin depolymerization
Lignin needs to be defunctionalised and char formation needs to be depressed
Lignin depolymerization under supercritical
conditions
Process development under high P and T (100 bar, 300°C)
ScCO2 with co-solvents
Non-toxic, industrial experience, easy downstream processing
Phenolic oil separated from residual lignin/char by expansion
Labscale process development
Lignin in acetone/water 8:2 (v/v) + scCO2
Formic acid as hydrogen donor
Mixed hardwoods organosolv lignin (Alcell)
Wheat straw organosolv lignin (ECN)
Supercritical depolymerization of lignin
Gas
Lignin oil
Char
Lignin
Reactor
Lignin depolymerization under supercritical
conditions
Mono-phenolics 3-12% in phenolic oil 20-30%
Char 40-55%; gases 6-12%: CO, CH4, C2H4, MeOH; water 15%
Formic acid favours formation of monomers
Straw and hardwood lignin comparable conversion, but different phenolic
mixture
R.J.A. Gosselink et al.
(2011) Biores.
Technol. accepted
Conclusions and recommendations (1)
Today there is an increased demand for green alternatives to
materials and products made from fossil resources.
Plant biomass offers this alternative. However to realise this,
biomass needs to be used in an optimal way including the
rest-stream lignin.
My research focused on the utilisation of lignin for value-added
applications such as wood adhesive and production of aromatic
chemicals as building blocks for polymers.
By measuring the lignin properties, its suitable application can
be predicted.
Lignin fractionation lead to fractions with different properties
and application potential
Conclusions and recommendations (2)
Lignin needs to be activated to reach the desired glue
strength. Furthermore novel glues fully based on biomass and
without using formaldehyde were studied and show good
potential.
Production of aromatic building blocks from lignin is an
important future development as a large part of our daily
consumer products can be made from these. The results of
this research showed that promising opportunities are
identified.
Supercritical depolymerization of lignin should be further
optimised focusing on lowering the formation of char
More info: [email protected]