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M a y 2 5 , 2 0 0 9 , H e l s i n k i , Comprehensive Utilization of Comprehensive Utilization of Comprehensive Utilization of Woody Biomass components Woody Biomass components Woody Biomass components Yasumitsu Uraki

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SLIDE 1

M a y 2 5 , 2 9 , H e l s i n k i ,

Comprehensive Utilization of Woody Biomass components Comprehensive Utilization of Comprehensive Utilization of Woody Biomass components Woody Biomass components

Yasumitsu Yasumitsu Uraki Uraki, Dr. , Dr. Sci Sci. .

Professor of Forest Chemistry, Professor of Forest Chemistry, Research Faculty of Agriculture, Research Faculty of Agriculture, Hokkaido University, Japan Hokkaido University, Japan E E-

  • mail:

mail: uraki uraki@for. @for.agr agr. .hokudai hokudai.ac. .ac.jp jp

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SLIDE 2

the most abundant natural resource on the earth. carbon neutral. comprised of hydrophilic polysaccharides, cellulose and hemicellulose (glucomannan, glucuronoxylan, and arabinogalactan). and hydrophobic lignin (polyphenylpropanoid). Woody biomass is An alternative resource to fossil resources

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SLIDE 3

Objectives: Comprehensive utilization of woody biomass

Minor components Major components (cell wall components)

Extractives

Antibiotics, Antioxidants, etc.

Wood

(<10% )

Acetic acid Pulp

(ca. 50%)

Lignin

Carbon fibers, Adhesives, Polyurethane resins, Ion exchangers,

(20- 30% )

Hemicellulose

Sugar syrups Furfural, Diet sweetening materials,

(30-20%)

Pretreatment Reflux for 1h in 90-95% AcOH aq. Pulping Addition of 0.32% sufuric acid

  • r 0.1% hydrochloric acid

Reflux for 3-4 h Insolubles Insolubles Water-insolubles Water-solubles

Papers, Cellulose derivatives,

Cellulose (AP)

Atmospheric Acetic acid Pulping

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SLIDE 4

Birch chips Birch outer bark

Filtration Washing Dry Centrifu- gation

Unbleached Unbleached Pulp (AP) Pulp (AP)

Concentration

Black liquor

Precipitation Filtration

20-L Evaporator

Filtration

Sugars

  • Fig. Separation scheme of woody biomass (birch) using a large reactor

Freezing Lignin (AL) Lignin (AL) Freeze- dry Reduction

Crystalli- zation

Xylitol Xylitol

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SLIDE 5

Table Material balance on the atmospheric acetic acid pulping. Cooking conditions Material balance (% on chips) Species AcOH Catalyst Pulp (KL) Reject Lignin WS 47.5 (7.2) 90% 0.32-SA 0.4 49.9 (3.5) 90% 0.32-SA 0.0 22.9 22.3 51.9 (4.7) 95% 0.1-HCl 0.0 19.0 27.1 46.3 (5.6) 90% 0.32-SA 0.8 24.9 27.7 51.8 (5.3) 90% 0.32-SA 0.1 22.2 30.2 51.7 (7.3) 95% 0.1-HCl 0.2 24.5 25.9 Birch Beech Poplar Todo-fir

1)

SA, sulfuric acid; Pulp, screened pulp; KL, Klason lignin (% on pulp).

1) The pulping was performed in a 100-L reactor (Chips, o.d. 9 kg; Liquor, about 60 kg)

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SLIDE 6

Lignin utilization I.

  • Finding fusibility and

Preparation of carbon fibers -

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SLIDE 7 .

30 50 100 150 200 25

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SLIDE 8
  • Fig. Laboratory spinning apparatus for fusion spinning of lignin.

Winder Heater Thermocouple Nozzle Lignin fiber Nozzle heater Nitrogen (N2) Temperature: 330 - 380℃ Maximum winding rate: 140 m min-1 Extrusion pressure: 3 - 5 kgf cm-1 Spinning condition

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SLIDE 9
  • Fig. Scanning electron micrographs of AL-CF.

HAL carbon fiber (LAL-CF) BET surface area of HAL-CF= 190 m2 g-1 SAL carbon fiber (NAL-CF) BET surface area of SAL-CF = 370 m2 g-1

bar = 30 µm bar = 30 µm

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SLIDE 10

Softwood

Steam exploded lignin Acetic acid lignin Pitch

Woody biomass Woody biomass Steam explosion Atmospheric Acetic acid pulping

hot water alkaline water

Exploded lignin Hygrogenolysis

  • r Phenolation

Filtration Acidification Solvent fractionation

Polymerization upon heating Melt spinning Thermostabilization Acetic acid lignin Removal of volatile substance Melt spinning Thermostabilization Petroleum or Coal pitch Polymerization upon heating to heavy oil Melt spinning Thermostabilization

Extraction with Concentration of black liquor Precipitation

Carbonization to carbon fibers Hydrogenation Pitch for spinning

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SLIDE 11

40 30 20 10 5 5 100 200 300 400 500 600 50

Tensile strength (MPa) Diameter (µm)

  • Fig. Effect of Diameter on tensile

strength of AL based CFs.

SAL CF-1 SAL CF-2 HAL CF (air)

Note; SAL CF-1; prepared without thermostabilized, SAL CF-2; prepared with thermostabilization in air, HAL CF; prepared with thermostabilization in air.

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SLIDE 12

Lignin utilization II.

  • Preparation of activated carbon fibers

and Hot-melt type adhesive-

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SLIDE 13

Vaccum pump Trap

Sample

Heater Flow meter N2

Pump

Water trap Ice trap

  • Fig. Steam activation system for producing activated carbon moldings
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SLIDE 14

Surface area Iodine Methylene blue

650

  • Fig. Adsorption performance of AL-based ACF

Activation time (min)

Specific surface area (m2 g-1) 20 40 60 80

500

1,000 1,500 2,000 2,500

1,930 1,400 1,550 1,180 370 190

; HAL

Adsorption capacity (mg g-1)

Activation time (min)

20 40 60 80 500

1,600 1,830 1,510

2,000

Activation time (min)

600 1,500 1,000 20 40 60 80

PAN Tar pitch 410 320 370

400 200

; SAL

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SLIDE 15

Preparation scheme of dry Preparation scheme of dry-

  • formed board

formed board

Dry mixture

Paper Lignin

(from birch)

Thermal press with a mold

+

Mixed

Medium density

Fiberboard

High density

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SLIDE 16
  • Fig. Influence of lignin content
  • n flexural strength

20 40 60 80 20 40 60 80 HAL content (%) Flexural strength (MPa)

S35

Pressure : 230 kgf/cm2 Press temp : 130℃

  • Fig. Influence of lignin content
  • n water absorption

Press temp : 130℃ Pressure : 230 kgf/cm2

100 200 300 400 500 600 700 20 40 60 80 24h water soaking Water absorption (％) HAL content (%)

Properties of lignin-wastepaper fiberboard

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SLIDE 17

Lignin utilization III.

  • Support for Water-soluble immobilized

cellulase system and Surfactants-

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SLIDE 18

1)Stirring at room temperature for 5 min 2)Standing still at 80℃ for 1hr 3)pH4.0 with AcOH 4)Washing with hot water 5)Lyophilization

AL 10g AL 10g Saponified AL

3.3 M NaOH 30 ml Stirring for 24hr

Saponified AL

1)Stirring at 70℃ for 3hr 2)Stirring at room temperature for 3 days 3)pH4.0 with AcOH 4)Ultrafiltration 5)Lyophilization

Amphiphilic product (PE-AL sol) Amphiphilic product (PE-AL sol) PE-AL gel PE-AL gel PE 16 g PE 4 g

1M NaOH 100 ml Stirring for 24hr

PE13

CH2CH-CH2-O-(CH2-CH2-O)13-CH2-CHCH2 O O CH2CH-CH2-O-(CH2-CH2-O)13-CH2-CHCH2 O O

AL： 25.9 wt% PE : 74.1 wt% AL: 40.7 wt% PE : 59.3 wt%

HO HO HO OH

AL AL AL PE PE PE AL PE PE PE

HO HO HO OH

AL AL AL AL AL AL PE PE PE PE PE AL AL PE PE PE PE

HO HO HO OH

AL AL AL PE PE PE AL PE PE PE

HO HO HO OH

AL AL AL AL AL AL PE PE PE PE PE AL AL PE PE PE PE

HO HO HO OH

AL AL AL AL AL AL PE PE PE PE PE AL AL PE PE PE PE

HO HO HO OH

AL AL AL AL AL AL PE PE PE PE PE AL AL PE PE PE PE PE PE PE

Blanched polymer chain Three-dimensional network structure

AL AL AL AL PE AL AL AL AL PE PE PE PE PE AL AL AL AL PE PE PE PE PE PE PE PE PE PE PE PE

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SLIDE 19

Glass filter

P r e s s u r e

（Enzyme fraction ） Cellulose etc . Enzymic hydrolysis

Cellulase or EX-AL - cellulase derivatives in Acetate buffer

Filtration

Incubator with shaker ( 40 ℃ )

F i l t r a t e Measurement of weight of residue

Measurement of ratio of hydrolysis

Polysulfone membrane filter Instrument of ultrafiltration

Analysis of sugar

( HPLC column for analysis of sugar ) Residue high molecular mass ( enzyme ) low molecular mass ( sugar )

Sugar solution by enzymic hydrolysis

Separation

Repeated use of recovery enzyme

( cut off 1.0 X 10 k Da )

4

  • Scheme. Repeating hydrolysis of cellulosic materials by cellulase
  • r PE-AL - cellulase complex using ultrafiltration.
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SLIDE 20

Repeating hydrolysis of filter paper (A) and PHA-pulp (B) by cellulase and PE-AL - cellulase complex. Repeating hydrolysis of filter paper (A) and PHA-pulp (B) by cellulase and PE-AL - cellulase complex.

Relative cellulase activity (%) 40 60 80 100 20

8 6 4 2 10 8 6 4 2

40 60 80 100 20

Reaction time (day)

(A) (B)

Reaction time (day) ) Hydrolysis conditions: Substrate, 3 g; Cellulase, 240 mg; PE-AL, 0 wt.% ( and 0.2 wt% ( ) based on 300 mL of the buffer solution .

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SLIDE 21

PEGDE-AL(13,1)

Conc./g mL-1

EPEG-AL(13,2)

mono-functionalize

Conc./g mL-1

EPEG-AL(13,4)

increase in PEG

Conc./g mL-1

Introduction

Time /sec

TritonX-100

28 mN/m

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SLIDE 22

Preparation LAEO-AL , LAEO-KL

H3C

CH2 O CH

2

CH2O CH2CH O CH2

11 15

lauryl alcohol ( EO ) 15 glycidylether

LAEO

EO ( % ) HLB LAEO-AL(3) 63.0 12.6 LAEO-AL(6) 68.4 13.7 LAEO-KL(5) 65.4 13.1 LAEO-KL(10) 70.5 14.1

Conc./g mL-1

* Parenthesis is a weight ratio of LAEO/lignin

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SLIDE 23

20 30 40 50 60 70 80 Surface tension (mN/m)

1.3 × 10-4g/mL 31 mN/m

10-6 10-4 10-2 1

Conc./g mL-1

LAEO

20 30 40 50 60 70 80

Surface tension (mN/m)

7.8 × 10 -4 g/mL 34 mN/m

10-6 10-4 10-2

Conc./g mL-1 1

20 30 40 50 60 70 80

Surface tension (mN/m)

2.0 × 10 -4 g/mL 34 mN/m

10-6 10-4 10-2

Conc./g mL-1 1

LAEO-AL(3) LAEO-AL(6)

Surface Activity

LAEO-AL , LAEO-KL

Conc./g mL-1

LAEO-KL(5)

Conc./g mL-1

LAEO-KL(10)

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SLIDE 24

Utilization of unbleached pulp.

  • Inclusion compounds and

Stimuli-responsive gel-

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SLIDE 25

Chemical properties of HP Chemical properties of HP-

  • samples

samples

Mw2) MS3) LCST(°C)4) Lignin content(%)1) 3.40×105 38 HPC‐ L 6.63 7.09×105 43 HPC 4.2 ― 3.2

1)The lignin content was estimated by UV absorption. 2)Mw is weight

average molecular-mass determined by high performance size-exclusion chromatography.

3)Degree of molar substitution. 4)Lower critical solution temperature.

Water molecule Polymer chain Shrinking and aggregation of polymer Hydroxypropylcellulose （ HPC） ( Ex. DS=2, MS=4 ) OH OCH2CHCH3 H H OH O n CH2OCH2CHCH3 CH3CHCH2O OCH2CHCH3 OH O

LCST

Heating Cooling

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SLIDE 26

Thermoresponse Thermoresponse and and thermoreversibility thermoreversibility of gel

  • f gel

～ ～Epoxy type Epoxy type～ ～

Volume (%) 20 30 40 Temperature (°C) 50 20 40 60 80 100

Initial polymer concentration: 3.0% (w/v), Addition of EGDE: 50% based on polymer. HPC gel ( ) and HPC-L gel ( ).

20 40 60 80 100 Volume (%) 72 144 168 Retention time (h) 36 108

20ºC 20ºC 50ºC 50ºC 50ºC

20ºC 36ºC 42ºC

A drastic volume transition of the HPC-L gel occurred at 38oC

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SLIDE 27

Hemicellulose utilization and Artificial woody cell wall using honeycomb-patterned cellulose .

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SLIDE 28
  • Fig. Purification sheme of water-solubles

Applying to column (Activated carbon : celite = 1 : 1) At least three times Washing with water Fractionation by liquid-liquid extraction EtOH Extraction with acetone C6H14-ext Et2O-ext EtOAc-ext EtOH-ext ・ CH3ONa/CH3OH Stirring for 24 h ・ Neutralization with cation exchanger

Effluent (PWS) Deacetylated WS (RWS) Adsorbed materials

(Activated carbon layer)

Acetone extracts

Yield (% on chips) Hardwood WS (HWS): 37.6 Softwood WS (SWS) : 21.0 Yield Sugar constituents (%) (%) Ara Xyl Man Gal Glc HPWS 22.0 4.0 79.7 8.2 5.2 2.9 SPWS 8.8 5.5 10.1 53.3 14.5 16.6

Water-solubles (WS)

sugars, lignin-derived materials etc.

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SLIDE 29

R-HPWS

  • r

Xyl Conc., 20% pH 8.0 adjusted with NaOH Flow rate, 30 ml/h 10 g of Suitase (Glucose isomerase, Supplied by Nagase Seikagaku) 7 ℃ water 35cm

Su-HPWS

  • r

xylulose

CH 2OH CH 2OH OH C O C C HO H H

D-xylulose

1 2 3 4 5

  • 10

20 30 40 50 60 70 80 0.00 0.25 0.50 0.75 1.00 1.25 1.50 Concentration of Xyl and xylulose (mol/l) Elution time (h)

D-xylulose

Glucose isomerase

  • Fig. Xyl conversion to xylulose by glucose

isomerase (Suitase)

CH 2OH CH 2OH OH C O C C HO H H

D-xylulose

1 2 3 4 5

HCOH

2

D-xylose

Modification of Xyl and hardwood WS (HPWS)

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SLIDE 30

100 100 6.7 6.9 13.4 31.4 6.812.7 9.2 15.7 46.4 139 8.1 18.4 5.4 20.6 22.6 22.5 74.4 25.5 120 8.9 33.0 15.2 8.2 49.4 8.2 88.1 8.9 11.6

50 100 150 Glc Man Gal Xyl Ara mannitol xylitol SPWS D-SPWS R-SPWS R-SPWS HPWS D-HPWS Su-HWS 4) Su-Xyl 4) No sugar BC Yield (%)

ATCC 53582 ATCC 10245

  • Fig. Bacterial cellulose production from various sugars.
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SLIDE 31

ハニカ ムパタ ーン化フ ィ ルムの予 想構造（ 上)と 実態像（ 下)

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SLIDE 32

Recent study is to Create Artificial Cell Wall

Regenrated cellulose honeycomb

20 µm 20 20 µ µm m

Bacterial cellulose honeycomb

Mimic Lignin deposition

50 µm

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SLIDE 33

高温高湿条件 常温条件 高温高湿条件 MOR(MPa)

20 40 60 80

MOE(GPa)

0.2 0.4 0.6 0.8 1

MOE(GPa) 常温条件 高温高湿条件

23oC, RH50% 30oC, RH90% 23oC, RH50% 30oC, RH90%

Effect of lignin adsoprtion on the tensile strength

  • f honeycomb-patterned cellulose film.

Honey-patterned BC Honey-patterned BC with lignin

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SLIDE 34