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Naonori MIYATA (Kansai Paint Co.,Ltd.)
Shinich OGINO (Kansai Paint Co.,Ltd.)
Yasumitsu URAKI (Hokkaido University)
Makoto UBUKATA (Hokkaido University)
A study on industrial utilization of acetic acid lignin
1. The back ground of this study
2. Efficient use of palm oil residues
by acetic acid pulping at ambient pressure
3. Innovative application of acetic acid lignin. ~Application of acetic acid lignin derived from wood to termiticide and coatings material~
4. Conclusions
Contents
Oil palm is one of the most useful plants
It is necessary to use AL for efficient use of hole oil palm
Fruit bunch Fruit
Empty fruit bunch
Oil
Acetic acid
lignin (AL)
Pulp
?
?
Glucose (fermentation sauce)
Background ~Efficient use of woody biomass ~
Paper
Cooking
Acetic acid pulping process
Pulp
A L
Pulping
Woody
biomasses
Soluble to organic solvents
Bio diesel
Oil palm AL has similar properties to ALs form woods?
1
Sulfuric acid lignin is not soluble
Efficient use of oil palm residues
by acetic acid pulping
2
Possibility of using palm oil residues The amount of palm oil residues (in Malaysia)
Several ten million ton / year
stem ・ leaf 48
others
20
EFB
20
trunk
12
Fruit bunch
Details of wastes(%)
Good materials from the view point of not only their total amount
but also their resource density
Empty fruit bunch fiber as sauce for pulping
Fruit
Empty fruit bunch fiber(EFB)
3
Composition of EFB
Composition of wastes from oil palm
*composition:weight% of each component (dry)
shape cellulose( % ) ( % ) ( % )
E F B 45~50 25~35 25~35
mesocarp fiber 40 24 24
-stem ・ leaf -
-ordinary wood - 45 25 30
no data
hemicellulose lignin
shell
trunk
long fiber
short fiber
Composition of EFB is similar to that of ordinary wood
The pulping condition for wood was applied to EFB
4
from a reference
Solubility to organic solvents
Fusion characteristics
Material that can be coated
(e.g. “Paint”)
Molding
Important properties of AL
Basic Policy of Development
From the view point of “efficient” use
It’s preferable that not only pulp but also lignin can be used
Suitable use for AL from EFB
5
.
.
.
.
Results of pulping
EFB(dry) 150 g
Acetic acid 3465 g
Distilled water 373 g
Sulfuric acid 11.5 g
Concentration of acetic acid : 90 wt %
Concentration of sulfuric acid : 0.3 wt %
Crude pulpAL (powder)
reflux over 4hr
Pulping
Solubility of AL from EFB (1 wt % to each solvent*)
(completely soluble):Tetrahydrofuran , Dimethyl Sulfoxide , Cyclohexanone
( partially soluble ):Acetone , Chloroform
Yield(%)
46 21
Content(%)
40~50 25~35
Crude pulp A L
Cellulose Lignin
(Experimental value)
(from a reference)( Condition for hard woods)
*Solvents: alcohols, ketones, esters, ethers, alkanes, aromatics….
6
Fusing Temperature of AL
140 C
:Fused :Partially fused X:Unfused
180 C
Oil palm AL after heating
Heating(20min.)
AL(powder) 0.1 gSlide glass
Method Results
140 C X X X X
160 C X
180 C X
200 C X
Oil palm White birch Oregon pine S L *
* S L : Lignin obtained from hard wood and soft wood
by sulfuric acid pulping
Oil palm AL fused at 180 C
I tried to use oil palm AL
as material for molding
7
Preparation of fiber board
A precedence work of fiberboard :
Fiber board from wastepaper and white birch AL
(J.Nemoto,Y.Uraki, Y.Sano; Mokuzaigakkaishi, 49, 4, p287 )
An attempt to prepare board from EFB only
・・・・・・・・・170 C 25 MPa
Mixing Heating and pressurization Fiberboard
(density :1.3~1.4 g/cm3)
Procedure of preparing fiberboard
8
.
Oil palm board ( )
from oil palm pulp and AL
Without pulping ( )
from raw EFB
(without pulping process)
Typical pressurizing condition
pulp / AL = 80 / 20 ( by weight )
temperature:170 C
pressure:25MPa
pressurizing time:15min.
Effects of preparing conditionsEffect of Mixing condition
0
10
20
30
40
50
60
A: pulp / AL = 80 / 20 , 15min.
B: pulp / AL = 70 / 30 , 15min.
C: pulp / AL = 80 / 20 , 8min.
Effect of ratio of materials and pressurizing time
0
10
20
30
40
50
60
ドライ混合 ウェット混合 新聞紙ボード 空果房繊維のみDry Wet Withoutpulping
Ben
ding
str
eng
th (
N /
cm
2)
Ben
ding
str
eng
th (
N /
cm
2)
9
A B C
Hydrolysis of pulp from oil palm
脱アセチル化
Shaking (40 C)Pulp
Hydrolysis
0
20
40
60
80
100
0 6 12 18 24 30 36 42 48
Reaction time (hours)
Yie
ld o
f Glu
cose
(%)
Reference:Y.Uraki, Y.Sano(1998)
Treatment with NaOH
With NaOH treatment
Without NaOH treatment
EFB(without pulping)
Filter paper powder
Oil palm pulp can be used to produce glucose.
・ Cellulase
・ β-Glucosidase
Measurement of
glucose concentration
10
Innovative Application of AL
~Application to termiticide and coatings material~
11
Application of AL to termiticide
Molecular weightLow High
Molecular weight of phenolic compounds
and their properties as termiticide
Presumed structure of lignin
針葉樹リグニンの推定構造
アルコールOH
フェノールOH
アルデヒドOH(alcohlic)
OH(phenolic)
Effect of AL upon termites is unknown
A L(3000 ~ 4000)
OH OH
CH3
Natural lignins(over 10000)
Properties as termiticide? X
12
Repellency of AL to termites
Behavior of termites at repellency test (6days)
a) b) c)
AL:from white birch Treatment method:coated twice by brush (solvent:acetone)
Wood tip
a) Treated with AL
b) Untreated
c) Treated(right) and
Untreated(left)
13
Termites avoid AL, though this tendency is not so strong
.
.
Termiticide Property of Wood Tip Treated with AL
0
20
40
60
80
100
0 10 20 30
Time(days)
ratio
of
dea
d te
rmite
s (%
)
Result of termiticide property test of AL treated wood tips
Refluxing & Dipping
Dipping
Without AL treatment
Hunger condition
(blank test)
Method of treatment
AL showed termiticide property
Effect as termiticideis was influenced by treatment method
14
.
.
Amount of functional groups in AL derived from white birchMethoxyl Acetyl Hydroxyl Hydroxyl
Group (phenolic) (alcohlic)
-OCH3 -COCH3 -OH -OH
wt % 19.5 10.6 4.2 6.3
Y.Sano; Kinouzairyou, 21, 12, p41 (2001)
It is well known that hydroxyl groups of lignin
react with isocyanates or epoxides
Investigation of potential of AL for “Paint Binder”
Application of AL to coatings material 15
Reaction of AL with NCO-CrosslinkerAL solution in cyclohexanone with crosslinker*
Heating(100 C, 60 min.)
Crosslinker : Hexamethylenediisocyanate derivative (bi-functional) Catalyst : Dibutyltin dilaurate
OH
NCO
Urethane
Confirmation of reaction ( by FT-IR analysis )
In refluxing acetone (4hours)
Decreasing of peaks from
OH and NCO group, and
appearance of a new peak
from urethane bonding
were confirmed
Measurement of
gel fraction ratio
Before heating
After heating
16
Curability of film from AL with NCO-Crosslinker G
el f
ract
ion
(%)
Effect of NCO / OH ratio Heating : 100 oC , 60min.
Film from AL with crosslinker showed good curability
( NCO / OH ratio > 0.4 )
If enough heating time can be secured, it may be
possible to use this system for paint.
17
0
20
40
60
80
100
0.0 0.2 0.4 0.6 0.8 1.0
NCO / OH ratio
.
.=
Conclusions
Pulp and AL were yielded by 46% and 21%
by acetic acid pulping of oil palm EFB
Fiberboards were prepared from oil palm pulp and AL
Oil palm pulp was converted to glucose in high yield
by enzymatic hydrolysis.
AL from white birch showed termiticide property
Film from AL with NCO-crosslinker showed good curability
18
.
.
.
.
.
Thank you for your kind attention