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

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.

.

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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

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Thank you for your kind attention