Yaolin Zhang, Dian-Qing Yang, Xiang-Ming Wang, Martin Feng,
Guangbo He,
Location: InterContinental Toronto Centre
Date: October 11, 2013
Fungus-Modified Lignin & Its Use in
Wood Adhesives for Wood
Composites
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Contents
2
Introduction 1
Lignin & Lignin Modification 2
Methods & Experiments 3
Results & Dicussion 4
Summary 5
Challenges & Opportunities 6
Acknowledgement 7
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1. Introduction: Phenolic Resins
Global PF Resins
▫ Capacity: 5.4 MT
in 2011
▫ Consumption: 3.2
MT in 2010
- One third of PF for
wood adhesives
3
World consumption of PF resin in 2011
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1. Introduction: Wood Composites
4
Panel Type Adhesives
Oriented strand board (OSB) PF, MDI, MDI/PF, MUPF
Particleboard (PB) UF, MUF, PF
Medium density fiberboard (MDF) UF, MUF, PF, MDI
Plywood PF, UF, PVAc
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1. Introduction: Wood Adhesives
Consumption: 1.6-1.8
MT in 2000
Consumption: 1.5 MT
in 2009
▫ PF resin 28.5%
Demand in 2012:
similar as 2009
5
North America consumption of wood
adhesives in 2009
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2. Lignin & Lignin Modification
The lignin content in wood varies
▫ 25%-31% in softwoods
▫ 16%-24% in hardwoods
The lignin can be divided into two categories
▫ Conventional or sulfur-containing lignin
- Kraft lignin and lignosulfonate from pulp and paper
industry
▫ Non-sulfur lignin
- Soda lignin, organosolv lignin, steam explosion lignin,
hydrolysis lignin and oxygen delignification
6
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2. Lignin & Lignin Modification
Liquefaction with phenol
▫ Non-catalyzed liquefaction; Acid-catalyzed
liquefaction; Alkali-catalyzed liquefaction
▫ Liquefaction by supercritical phenol
▫ Acid-catalyzed liquefaction in phenol is more
effective at moderate temperatures
Liquefaction with low aliphatic alcohol
Liquefaction in hydrogen-donor solvents
▫ Such as 9,10-dihydroanthracene (AnH2) and 7H-
benz[de]anthracene (BzH)
7
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2. Lignin & Lignin Modification
The fungi can be categorized into the
following three groups (Hatakka, 1994)
▫ Lignin-manganese peroxidase group.
- Phanerochaete chrysosporium and Phlebia radiata
▫ Manganese peroxidase-laccase group
- Dichomitus squalens and Rigidoporus lignosus
▫ Lignin peroxidase-laccase group.
- Phlebia ochraceofulva and Junghuhnia separabilima
8
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2. Lignin & Lignin Modification
Wood-decomposing fungi
▫ Brown-rot fungi
- degrade wood polysaccharides and leave behind a
brown, partially modified (oxidized) lignin residue
▫ White-rot fungi
- degrade polysaccharides and lignin simultaneously or
degrade lignin selectively, leaving a cellulose-enriched
white material
▫ Soft-rot fungi
- show a wide variety of effects on cell wall constituents
9
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3. Methods & Experiments
Screening the fungi (over 50 species) for
modifying the lignin
▫ Select few fungi for lignin modification
Characterize the modified lignin
▫ Phenolic hydroxyl groups by UV
Lignin phenolic resin development as wood
adhesive
Wood composites manufacturing &
evaluation
10
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3. Methods & Experiments
Type of Fungi Fungal species
Brown-rot Pycnoporellus alboluteus (Ellis & Everh.)
Kotl. & Pouz. (FTK 76A)
White-rot Phanerochaete cremea (Bres.) Parmasto
(FTK 332A)
White-rot Lenzites elegans (Spreng.) Pat. (FTK 329A)
Brown-rot Meruliopsis taxicola (Pers.) Bondartsev
(FTK 122B)
11
Within over 50 fungi species, selecting 4 more efficient for further investigations
Zhang Y, Yang DY, Wang XM, Feng M, Brunette G, Process for Fungal Modification of Lignin and Preparing Wood Adhesives with the
Modified Lignin and Wood Composites Made from Such Adhesives, WO 2012/113058 A1, 2012, Aug. 30
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3. Methods & Experiments
Determination of phenolic hydroxyl groups
▫ based on the absorbance values at 300 nm, and
350nm-365 nm with different buffer solution at
pH 6, pH 12, and with 0.2N NaOH
12
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3. Methods & Experiments
Lignin modification by fungi
▫ Preparing the fungi species for lignin modification
▫ Preparing lignin for fungal modification
▫ Mixing/incubation of lignin with the prepared
fungal species, and further culturing the mixture
for few weeks under shaking
▫ Separating the incubated suspension, and
collecting the bio-modified lignin
13
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3. Methods & Experiments
Synthesis of lignin phenolic resin
▫ Replacing phenol by lignin from 1/3 to half
▫ Adjust the molar ratio of formaldehyde to phenol
to around 2.2-2.54
▫ First methylolation, and then condensation
▫ Solid content around 45% and viscosity 100-
200cps for OSB, 250-300 for plywood, and 60-
100 cps for powder resin application
14
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3. Methods & Experiments Target panel density (OD basis) 40 lbs/ft3
Mat dimensions 20 in x 23 in
Target panel thickness 11.1 mm (7/16 in)
Mat composition: face/core/face 25/50/25
Resin dosage Face:
Core
3% (solids on dry wood basis)
3% (solids on dry wood basis)
Wax dosage Face:
Core
1% (solids on dry wood basis)
1% (solids on dry wood basis)
Face wafer moisture before resin and wax 2%
Core wafer moisture before resin and wax 2.5%
Core moisture after resin and wax 3.5%
Face moisture after resin and wax 7-8%
Press platen temperature (°C) 220°C
Total press time 150 seconds (daylight to daylight)
Close time 25 seconds
Degas 25 seconds
15
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4. Results & Discussion
Unmodifie
d lignin
Modified
by 76A
Modified
by 332A
Modified
by 329A
Modified
by 122B
Total Ph-
OH
2.05 1.60 1.62 2.71 2.41
I, % 0.72 0.74 1.10 0.96 1.19
II, % 0.18 0.16 0.21 0.20 0.25
III, % 1.10 0.68 0.33 1.46 0.92
IV, % 0.05 0.02 0 0.10 0.04
16
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4. Results & Discussion
Lignin phenolic resin properties
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Lignin
modified by
fungi
Replace
phenol by
lignin (%)
Solid content
(%)
Gel time
(sec)
76A 33 40.69 690±11
332A 33 41.70 644±16
No 33 40.20 656±19
76A 50 41.70 877±31
332A 50 39.66 756±25
No 50 40.94 792±17
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4. Results & Discussion
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50% phenol substitution 33% phenol substitution
EA: fungal 76a; EB: fungal 332A
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4. Results & Discussion
19
© 2013 FPInnovations. All rights reserved. Copying and redistribution prohibited. ® FPInnovations, its marks and logos are trademarks of FPInnovations.
4. Results & Discussion
20
© 2013 FPInnovations. All rights reserved. Copying and redistribution prohibited. ® FPInnovations, its marks and logos are trademarks of FPInnovations.
4. Results & Discussion
21
© 2013 FPInnovations. All rights reserved. Copying and redistribution prohibited. ® FPInnovations, its marks and logos are trademarks of FPInnovations.
4. Results & Discussion
22
© 2013 FPInnovations. All rights reserved. Copying and redistribution prohibited. ® FPInnovations, its marks and logos are trademarks of FPInnovations.
4. Results & Discussion
23
© 2013 FPInnovations. All rights reserved. Copying and redistribution prohibited. ® FPInnovations, its marks and logos are trademarks of FPInnovations.
4. Results & Discussion
24
© 2013 FPInnovations. All rights reserved. Copying and redistribution prohibited. ® FPInnovations, its marks and logos are trademarks of FPInnovations.
4. Results & Discussion
OSB Panels Made with Biomodified Lignin PF
25
Fungi
used
Ph.
(%)
TS
(%)
WA
(%)
IB
(MPa)
MOE
(MPa)
MOR
(MPa)
76A 33 20.5±2.2 31.9±1.8 0.41±0.07 3711±544 33.9±3.3
332A 33 19.1±1.4 31.1±1.7 0.43±0.08 3854±585 34.6±6.6
No 33 31.6±3.4 57.3±4.8 0.46±0.08 4054±536 37.3±5.1
Com.PF - 25.6±0.9 45.2±4.3 0.42±0.08 3535±419 27.4±4.7
76A 50 18.2±1.3 29.8±1.7 0.46±0.08 3510±276 28.9±6.2
332A 50 29.8±4.2 53.0±3.0 0.48±0.05 3651±620 31.6±4.5
No 50 32.0±2.8 53.9±7.2 0.35±0.07 4124±328 32.8±5.1
Zhang Y, Yang DY, Wang XM, Feng M, Brunette G, Process for Fungal Modification of Lignin and Preparing Wood Adhesives with the
Modified Lignin and Wood Composites Made from Such Adhesives, WO 2012/113058 A1, 2012, Aug. 30
© 2013 FPInnovations. All rights reserved. Copying and redistribution prohibited. ® FPInnovations, its marks and logos are trademarks of FPInnovations.
5. Summary
Lignin modified by different fungi ▫ Resulting phenolic hydroxyl group changes
Modified lignin incorporated into phenolic
resin via in-situ polymerization ▫ 33% and 50% phenol replacement
▫ At 33% replacement, the gel time is similar among unmodified and
modified lignin phenolic resin
▫ At 50% phenol replacement by lignin, the gel time is similar among
unmodified and modified lignin phenolic resin
▫ Gel time of lignin PF with 50% phenol replacement is longer than that
with 33% of phenol replacement
26
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5. Summary
OSB made with lignin phenolic resin
▫ Comparable MOE, MOR and IB between
commercial PF and modified lignin PF
▫ Thickness swelling and water absorption of some
OSB made with modified lignin PF are lower than
OSB panel made with commercial PF
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6. Challenges & opportunities
Lots of research on lignin-based resins have
been reported ▫ Resin applicability, cure speed and durability are still the main
technical issues
Commercial applications are still uncommon
to date ▫ Economic viability is another issue to apply these environmental
friendly products for wood composite manufacturing.
More research is needed to focus on the
commercial applications of these products ▫ for both technical and economic reasons
28
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7. Acknowledgement
Natural Resources Canada (Canadian Forest
Service) financial support
Industry members for their guidance and
financial support
Gilles Brunette, John Schmidt, Michael
Paleologou, Lamfeddal Kouisni, Kirsten Maki
support
Technical staff working on this project
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Thank you! For more information:
Yaolin Zhang, PhD
Tel: 418 781-6749
Email: [email protected]