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 B45~5025~35 mesocarp fiber 4024 － stem ・ leaf － － ordinary wood － 452530 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 pulp AL (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(%) 4621 Content(%) 40~5025~35 Crude pulpA 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 g Slide glass Method Results 140 CXXXX 160 CX 180 CX 200 CX Oil palm White birchOregon 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/cm 3 ) 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 conditions Effect 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 DryWet Without pulping Bending strength (N / cm 2 ) 9 ABC
Hydrolysis of pulp from oil palm 脱アセチル化 Shaking (40 C) Pulp Hydrolysis 0 20 40 60 80 100 0612182430364248 Reaction time (hours) Yield of Glucose(%) 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 weight Low 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) 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 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 birch MethoxylAcetylHydroxyl Group (phenolic)(alcohlic) -OCH 3 -COCH 3 -OH wt %19.510.64.26.3 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-Crosslinker AL 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 Gel fraction (%) Effect of NCO / OH ratio Heating : 100 o C, 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 0.00.20.40.60.81.0 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.....