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Liquefied Wood – a source
of raw materials
Asist.Prof.Dr. Matjaž Kunaver
National Institute of Chemistry, Ljubljana, SLOVENIA
And
Center of Excellence for Polymer Materials and Technologies (PoliMaT)
[email protected]
IFAT 2010 - Muenchen
17.September 2010
Geographic reasons
Slovenia
58.4% of surface is
forest.
Forest is
spreading!
IFAT 2010 - Muenchen
17.September 2010
Lignocellulosic
biomass
Cellulose
hemicellulose
Glucose
Xylose, Arabinose
Ethanol
Fuels
IFAT 2010 - Muenchen
Organic acids, textile
fibers, polymers,
adhesives, lubricants,
inks
lignin
Polymers,
fuels
17.September 2010
Lignocellulose-based materials
IFAT 2010 - Muenchen
17.September 2010
Experimental approach
Unseparated wood (polymers) to undergo partial
depolymerization with polyols to obtain complex
multifunctional oligomeric mixture – feedstocks
for polymer synthesis:
Polyesters: unsaturated and saturated
Polyurethanes
IFAT 2010 - Muenchen
17.September 2010
What is LIQUID WOOD ?
A blend of depolymerized
and solubilized wood
components obtained by
reaction with polyhydric
alcohols in the presence of
acid as a catalyst.
Liquefaction converts wood into
a feedstock for the new,
environmentally friendly
polymers
IFAT 2010 - Muenchen
17.September 2010
Liquefaction mechanism
• Wood is a complex composite of:
- highly crystalline cellulose
- polyphenolic lignin
- hemicelluloses
- minerals, resins etc.
42 - 51%
18 – 30%
24 – 40%
•Polysaccharides → glucoside→ levulinic ester
IFAT 2010 - Muenchen
17.September 2010
Liquefaction mechanism
•Lignin
→ benzyl cation
→ reaction intermediates
→ glycol ethers of
depolimerized segments
→ condensation products
IFAT 2010 - Muenchen
17.September 2010
Liquefaction process
• Glass reactor with external heating, mixing
- 0.5 to 3 hours at 150 - 180 oC
• Typical reaction mixture:
- 100 g wood (or lignocellulosic material)
- 300 g glycol (glycerol, diethylene
glycol)
- 12 g acid catalyst ( pTSA)
• Product analysis:
- gravimetric determination of
remaining wood
- FTIR, GPC analysis
- OH value determination
IFAT 2010 - Muenchen
17.September 2010
Liquefaction product
IFAT 2010 - Muenchen
17.September 2010
Liquefaction product
IFAT 2010 - Muenchen
17.September 2010
Hydroxyl content in the liquefied spruce wood
samples, taken at different time intervals.
OH groups are spent during the liquefaction reaction:
- Formation of ester and ether bonds with glycols.
IFAT 2010 - Muenchen
17.September 2010
Polyester resins from liquefied wood
The main goal: to synthesize a poliester with higher
molar mass than the liquefied wood and with the
same functionality as the commercial one.
A typical formulation:
- 300g of neutralized liquefied wood
- 60g of adipic acid
- 0.1g of dibutyl tin oxide
Temp: 190-220oC , reaction time: approx. 4 hours
IFAT 2010 - Muenchen
17.September 2010
SYNTHESIS OF LINEAR, SATURATED
POLYESTERS FOR POLYURETHANE FOAMS
Mn
Dalton
LW
300g LW, 60g AA
300g LW, 60g PAA
300g LW, 30g AA,
30g PAA
IFAT 2010 - Muenchen
OH value
mgKOH/g
Viscosity
Pa.s
19400
1043
3.0
24.5
39900
798
1.9
22.7
60000
378
1.8
23.3
79500
437
2.1
23.1
Mw
Dalton
% of
wood
(w/w)
4790
10300
4590
7980
17.September 2010
SYNTHESIS OF POLYURETHANE FOAMS
FOAM PREPARATION:
COMPONENTS:
Parts by Weight
Liquefied wood
Catalysts
100.0
KOC
DMEA
2.0
2.5
Silicone surfactant
1.5
Water, ethanol, hexane
3.0
PMDI*
180.0
PMDI : diphenylmethane diisocyanate polymer
DMEA: N,N-Dimethyl ethanolamine
KOC: potassium octoate
IFAT 2010 - Muenchen
17.September 2010
SYNTHESIS OF POLYURETHANE FOAMS
Polyurethane foams
based on liquid wood
poliols,
Density = 0.03 -0.05 g/ cm3
Compressive strength at
10% strain:
46kPa – 74kPa
Thermal conductivity:
0.036 W/mK
Addition of glycerol
IFAT 2010 - Muenchen
17.September 2010
SYNTHESIS OF POLYURETHANE FOAMS
Properties of polyurethane foams differ depending
on the variations of the linear polyester formulation
as well as final foam formulation.
Pigments for coloration, additives to improve
durability can easily be incorporated into the final
foam formulation.
Wood content:
- 50% - 25 % in liquefied wood
- 45% - 25% in linear polyester
- 20% - 10% in polyurethane foam
IFAT 2010 - Muenchen
17.September 2010
Wood content: a practical example
75 pairs of disposable chopsticks give 500gr of
wood and together with alcohols -> 1000gr of
LIQUEFIED WOOD (50% wood content).
From 1000gr of L.W. we can synthesize 1170gr of
LINEAR POLYESTER (still 43% of wood)
From 1170gr of polyester with addition of PMDI,
2930gr of rigid POLYURETHANE FOAM can be
prepared (17% of wood )
2930gr of PUR = 58 Lit of volume!
1 chopstick gives 0.78 Lit of PUR foam!
1 chopstick with wrap paper gives 0.90 Lit of PUR
foam!
IFAT 2010 - Muenchen
17.September 2010
PANEL BOARD PRODUCTION - OPPORTUNITIES
Global Panel board production 2011: 75 Mio m3
– Europe:37 Mio m3
– Asia: 32 Mio m3
37 Mio m3:
17
12
4
4
Mio m3 particle board
Mio m3 MDF (Medium density fiber board)
Mio m3 Plywood boards
Mio m3 OSB (Oriented strand boards)
10% Adhesive
30% Adhesive
~15% Adhesive
5% Adhesive
17 Mio m3 = 12 Mio Tons = 1.2 Mio Tons of adhesive
IFAT 2010 - Muenchen
17.September 2010
Liquefied wood, paper, bark –
adhesives for plywood and wood chip panels
Standard adhesives:
Melamine –formaldehyde resins,
melamine – urea – formaldehyde resins
Up to 50% of adhesive can be replaced with
liquefied wood.
The temperature can be lowered to 160° C.
Formaldehyde release: less than 5mg/100g
European standard EN 312:2003 compliant.
IFAT 2010 - Muenchen
17.September 2010
SINGLE LAYER PARTICLE BOARD
Standard adhesives:
Melamine –formaldehyde,
melamine – urea –
formaldehyde resins
Hot pressed at 180° C, 3
N/mm2, for 5 minutes
IFAT 2010 - Muenchen
17.September 2010
Liquefied wood, paper, bark –
adhesives for plywood and wood chip panels
Mechanical and physical properties of particle boards prepared
using an adhesive that contained the addition of 50 % (w/w)
liquefied spruce wood.
Required values
Achieved values
Meldur H-97
Achieved values
Meldur MS-1
16,0 ± 0,3
16.1
16.2
-
0.68
0.67
Above 0.35
0.40
0.49
Surface soundness
EN 311 (N/mm2)
Above 0.8
1.0
0.9
Bending strength
EN 310 (N/mm2)
Above 13
15.9
16,5
Swelling in Thickness
EN 317 (%)
Below 15
11.6
15.9
Below 8
5.7
3.6
Board thickness EN 324 (mm)
Density EN 323 (g/cm3)
Internal bond strength
EN 319 (N/mm2)
Formaldehyde release
Perforator method
EN 120 (mg/100g board)
IFAT 2010 - Muenchen
17.September 2010
THREE - LAYERS PARTICLE BOARD
Standard adhesives:
Melamine –
formaldehyde,
melamine – urea –
formaldehyde resins
Hot pressed at 180° C,
3 N/mm2, for 5 minutes
IFAT 2010 - Muenchen
17.September 2010
Mechanical and physical properties of particle boards
prepared using an adhesive that contained the addition
of 30 % (w/w) liquefied spruce wood – industrial process
simulation
Required values
Achieved values
16,0 ± 0,3
16.1
-
0.72
Above 0.35
0.94
Surface soundness
EN 311 (N/mm2)
Above 0.8
1.96
Bending strength
EN 310 (N/mm2)
Above 13
21.1
Swelling in Thickness
EN 317 (%)
Below 15
8.2
Below 8
3.2
Board thickness EN 324 (mm)
Density EN 323 (g/cm3)
Internal bond strength
EN 319 (N/mm2)
Formaldehyde release
Perforator method
EN 120 (mg/100g board)
IFAT 2010 - Muenchen
17.September 2010
Liquefied wood – polyester:
adhesives for plywood panels
A combination of polyester based on liquefied wood with a
melamin-formaldehyde resin (1:1 ratio).
POLYESTER:
500g L.W.
50g APA
0.3g F4201
4.5 hours at 180oC-220oC
OH value: 333.5mgKOH/g
IFAT 2010 - Muenchen
17.September 2010
Liquefied wood – polyester:
adhesives for plywood panels
A combination of polyester based on liquefied wood with a
melamin-formaldehyde resin (1:1 ratio).
STANDARD EN 12765:
Classification of thermosetting
wood adhesives for non-structural
applications...
More than 12N/mm2 of the
bond strength can be
achieved.
CLASS C1 and C2 compliant
IFAT 2010 - Muenchen
17.September 2010
Liquefied wood – liquid fuel
Liquid fuel with more than 22 MJ/kg heat of combustion
(brown coal: 14 MJ/kg, dry wood: 15 MJ/kg)
High viscous liquid
at room temperature
(3 Pa.s), but soluble
in ethanol.
Sulfur content: 0.25%
IFAT 2010 - Muenchen
17.September 2010
Conclusions
• Different lignocellulosic materials were liquefied with yields
higher than 95%, (Lignin – with additional use of the
ultrasound).
• Polyesters were synthesized using liquefied wood, waste
paper or other lignocellulosic materials as a feedstock where
liquefied wood/paper replaced a certain amount of polyhydric
alcohols – produced form crude oil.
• The properties of polyurethane foams were similar to
commercially available samples.
• Liquefied lignocellulosic materials were used as adhesives for
particle boards production – with reduced formaldehyde
emission and excellent mechanical properties.
• Efficient lignocellulosic waste recycling and use of renewable
resources, including glycerol from biodiesel production.
IFAT 2010 - Muenchen
17.September 2010
Future:
• Liquefaction with the use of the ULTRASOUND
• Liquefied wood – MUF adhesives: new applications
• Energy source and fuel
• Effective wood waste recycling
IFAT 2010 - Muenchen
17.September 2010
Acknowledgments:
Authors wish to gratefully acknowledge the support for the
presented work received from :
- Ministry of Higher Education, Science and Technology of the
Republic of Slovenia within Program P2-0145 and through the
contract No. 3211-10-000057 (Center of Excellence Polymer
Materials and Technologies).
- Colleagues at the Polymer chemistry and technology laboratory
- GGP for their financial and material support,
- Melamin, for their general help and material support
IFAT 2010 - Muenchen
17.September 2010