Fungus-Modified Lignin and Its Use in Wood Adhesive for

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

© 2013 FPInnovations. All rights reserved. Copying and redistribution prohibited. ® FPInnovations, its marks and logos are trademarks of FPInnovations.

Contents

2

Introduction 1

Lignin & Lignin Modification 2

Methods & Experiments 3

Results & Dicussion 4

Summary 5

Challenges & Opportunities 6

Acknowledgement 7


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


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


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


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



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



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



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


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



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



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



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



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


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)


Wax dosage Face:

Core



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


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



Lignin phenolic resin properties

17

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



18

50% phenol substitution 33% phenol substitution

EA: fungal 76a; EB: fungal 332A



19



20



21



22



23



24



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


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

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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

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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]

http://www.fpinnovations.ca/

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Fungus-Modified Lignin and Its Use in Wood Adhesive for