Lignocellulose refinery system must be realized for

global environment and economy

Kenji IiyamaPresident

Japan International Research Center for Agricultural Sciences (JIRCAS)

Lignocellulose refinery system is essential for global environment and economy

☆ Global warming requires strongly the great reduction of consumption of fossil resources. Biomass carbon is “Carbon Neutral”. ☆ Sharp rise of petroleum price is getting threat for world economy, especially economy of non-petroleum produce countries, which may cause similar situation to the “Asian Economic Crisis” on few years ago. ☆ Price of food crops is getting the conflict with food supply by halfway measures for biomass utilization, such as production of biofuels → “Expert Consultation on Biofuel” at IRRI (International Rice Research Institute) in the Philippines together with worldwide agricultural scientists. ☆ Thus sustainable society will be established by only lignocellulose refinery system.

260

280

300

320

340

360

380

800 1000 1200 1400 1600 1800 2000

Year

CO

2 C

on

cen

trat

ion

, pp

m

CO2 concentrationIndustrial

Revolution

Cold age

Changes in CO2 concentration

Biofuel: 　 The Savior or the Devil ？

Corn BE(USA)

Sugarcane BE (Brazil)

BDF(Germany)

Cellulose BE (USA)

Production (103kL ） 18,400 15,000 1,890 -

Prod. Cost (JPY/L ） 33.54 26.77 -

Retail price (JPY/L)

Fossil fuel 93.26 151.12 189.29 -

Biofuel 80.64 89.87 209.29 -

Energy conversion 114.19 119.42 207.14 -

Energy balance 1.3 8 2.5 2 － 36

GHG Emission (kg/L)

Fossil fuel 2.44 2.44 2.80 2.44

Biofuel 1.93 1.07 0.90 0.22

Reduction (%) 22 56 68 91

Edit from National Geographic (Japanese Ed) No.10 2007

In case of corn, it has been pointed out to be accounted GHG emission from land use change.

Changes in price of petroleum （ US$/B ）

Changes in price of petroleum

CIF price at port in Japan: calculation including exchange rate

Oct. 2007 ：US$93.6/B JPY70,000/kL

Food price rise sharply by conversion to energy

Bioethanol Bioethanol

Biodiesel Biodiesel

US$90/t

US$150/t

US$12/t

US$9/t

US$357/t

US$420/t

US$260/t

US$350/t

US$100/t

US$130/t

US$200/t

US$280/t

Wheat

Soybean

Production plan of bioethanol in USA

Capacity of bioethanol from corn in USA　 Aug. 2007: 　　　 25.4 x 106 kL Aug. 2009: 　　 77.3 x 106 kLConsumption of corn for bioethanol production　 Aug. 2007: 　　 91.9 x 106 ton （ 1/3 of total productio

n ）　 Aug. 2009: 　 189.5 x 106 tonCorn production on 2006　 USA ：　　　　　　　 282 x 106 ton　 World ：　　　　　　　 712 x 106 ton

International Conference of Corn Industry (in Dalian on August 2007)

Changes in crop demand & production

Under-nourished population

United Nations Millennium Developing Goals (2001): Eradicate extreme poverty & hunger

Expert Consultation on Biofuel at IRRI (27-29 Aug)

Aim of “Expert Consultation on Biofuel”

☆ How can we design integrated, sustainable food-bioenergy production systems?

☆ Will there be enough cheap food for the poor? ☆ Will the expansion of feed stocks threaten the remaining tropical f

orests? ☆ Will carbon trading foster more sustainable land management?☆ Will the biofuel industry mitigate climate change?☆ Will poor farmers in developing countries benefit?☆ Will consumers gain or lose?☆ Will soils deteriorate because less crop residues are returned to t

he land?☆ What bioenergy technologies are most appropriate for what envir

onment?☆ Can second-generation technologies be downscaled to farm and

village levels?☆ Are there useful genes in the international gene banks for improv

ed feed stocks for biofuel production

The possibility of lignocellulosic refinery system has been proposed more than 50 years ago. However, it has not been realized because of political, economic and technological reasons. Issues to be conquered:☆ Further technological developments regarding prices of products and also lif

e cycle assessment are required.

☆ Analysis of accurate and scientific characteristics of biomass to be supplied as resources is essential to find out proper combination of resources, because of seasonal supply of bioresources.

☆ The deliberate layout of lignocellulosic industrial system, namely the division to local processes for basic treatment of bioresources and intensive process for final products based on high technology, has to be constructed to warrant regional economics.

☆ Some political and financial support such as carbon tax or environmental tax are essential to compete petroleum refinery system, which is turning huge profit on mass production, because lignocellulosic refinery system is to be small scale system at the beginning stage and restriction of resource supply.

Refinery of bioresources

Bioactive materials introduced from only bioresources

Final products Final products

Wastes

Processing

Processing

ConstructsFurniturePulp & Paper

Waste liquorWastes

WastesWastes

Processing

Wastes

Fuel, Methane,mycelia, sugar

Fuel, charcoal, pulp,compost, sugar

Low qualityresources

FellingPruning

Felling

Forest

Resources

Secondaryfibre

Re-usecycle

Cascade Utilisation of Bioresources

Structural characteristics of lignocellulosics

O

OH

OH

CH2HO

O

OO

OAcHO

H

O

O

O

OH

HO

O

OAcHO

H

O

OH

O

AcO

H

OO

OAcO

H

O

OH

O

O

H

O

OH

OH

HOCH2

O

OO

HO OH

HOCH2

OO

OHHO

H2COHO

O

HOOH

H2COH

O

OH

O

HO

HOCH2

OO

OOH

H2COH

O

OH

O

HO

HOCH2

Cellulose

Hemicellulose

Polysaccharides of Plant Cell Walls

Non-cellulosic wall polysaccharides

O

OCH3

H

O

CH3O

O

CH3O

HCOHC

O

HOH2C

HCOH

O

C

O

HOH2C

OCH3

H

H

C

HC

O

HOH2C

OCH3

CH3O

CO

CO HOCH2

H OCH3

HCOH

HCOHOCH2

OCH3CH3O

HCOHCH

O

CH2OH

H

H

CH3O

HC

O

HC

H2C

OCH2

CH

CO

OCH3

HCOH

CHHOCH2

(4)

(6)

(7)

(1)

(1)

(2)

(3)(1)

(5)

(1) Arylglycerol--aryl ether (-O-4)(2) Non-cyclic benzyl aryl ether (-O-4)(3) Phenylcoumaran(4) Pinoresinol(5) Biphenyl(6) 1,2-Diarylpropane(7) Diphenyl ether

Structure of lignin

3D structure of lignin

Importance of covalent linkages between

cell wall polysaccharides and lignin

for establishment of lignocellulosic refinery system

Economical, environmental and technological Importance of linkages

between wall polysaccharides and lignin

➣ Delignification during pulping ➡ requirement of bleaching using chlorine ➡ regional environment

➣ Digestibility by ruminants ➡ limitation of productivity of ruminants.

➣ Biomodification of plant residues ➡ carbon circulation ➡ global environment.

➣ Durability of woody construction ➡ external or internal usages Iiyama et al., 2002

Covalent linkages between polysaccharides and lignin

(b) Ester linkage

(a) Ether linkage

(a') Ether linkage

O CH

OH2C

CH

CH2OH

O

CH3O

R

CH3O

C

OO

O

OH

OH

OH OO

O

CH3O

CO CH CH O

CH3O

R

CH2OH

O

OH

OH OOO

CH3O

CO CH CH

CH2OH

O

CH3O

R

OOC

Covalent association between polysaccharides and lignin of dicotyledonous plants

CH3O

C OC

O

HOH2C

OOO OH

OH

O

CH2OH

OOH

OH

O

CH2OH

OOH

OH

H

OCH3CH3O

COH

HC

CH2OH

O

H

H

H

OCH3

OHC

CH2OH

CHO

O

OCH3

CH3O

C

O

O

OHO

C

O

HOH2CH

Lignin

Cellolose

HCOH

HC

H2COH

O

OCH3CH3O

O

C CH2OHC

O

OCH3

C C CH2OH

H3CO

C C CH2OH

O

OH

H

O

H

H

HO

CH2H

H

H

OHO OO

OH

O

OH

O HO

Xylan

H

Ether linkage(stable on alkali treatment)

Ether linkage(stable on alkali treatment)

Covalent association between polysaccharides and lignin of Gramineae plants

CH3O

HC C C

O

O CH2H

OOO OH

OH

O

CH2OH

OOH

OH

O

CH2OH

OOH

OH

H

OCH3CH3O

COH

HC

CH2OH

O

H

H

H

OH

OCH3

OHC

CH2OH

CHO

O

OCH3

CH3O

CCC

O

O H

H

OHO OO

O

HO

OHOO

OH

O HO

HCOH

HC

H2COH

O

OCH3CH3O

O

C CH2OHC

O

C O

CH

HC

OCH3

C C CH2OH

H3CO

C C CH2OH

O

OH

H

O

H

H

HO

Ester linkage(unstable on alkalitreatment)

Ester linkage(unstable on alkalitreatment)

Cellulose

Lignin

Hemicellulose

Ferulic acid

Ferulic acid

p-Coumaric acid

Examples for biomass industrial complex (BIC) using lignocellulo

sic resources

CH3COOH

CC

CCOOHCH3

OH2

H2

CC

CCOOHCH3

H2

H2

H2

OCHO(HOCH2)

Agricultural wastes: Rich in nitrogen, starch, and easily biodegraded wall componentsStockbreeding wastes: Rich in nitrogen from microflora and wall components resist to

biodegradation

Agric. prod. Waste

Cellulosestarch

Acid hydrolysis210-230oC1-5% acid Hydroxymethyl

furfural +furfural

Acidhydrolysis195-215oC

15-30sec 15-30minLevelinicacid

Acid hydrolysis120oC, 1-4% acidor enzymes

Glucose

Lactasefermentation

Lactic acid

Lactasefermentation

Alcohol fermentation

Ethanol

Acetic acidfermentation

Acetic acid

Stockbreedingwastes

Fermentation at high temperature

Compost

Anaerobicfermentation

Methane

Anaerobicfermentation

Animal feeds

Dry

Carbonizationwith K2CO3

800-1200oC

Activatedcarbon

Carbonizationwith K2CO3

800-1200oC

Watertreatment

Fuel battery

Greenhouseheating

Removal of dioxinfrom combustion ofurban wastes

Biodegradable polymerlike polyethylene

Bioactive chemical, polymer,solvent, medicines

Bioactive chemical, polymer,solvent, medicines

Development of effective utilisation of agricultural wastes

Possible utilisation of bioresources

Carbonisationwith K2CO3

Activatedcharcoal

Carbonisationwith K2CO3

Oil welldrilling

Aminoacids

Heavy metalchelatingmaterial

Mushroom

Cereals StrawHull

Bran

Crop Animal feed

Pulp for paper

Phenol/H2SO4

AdhesivePlastics

Biodegradableurethane form

Na2SO3+AQ

Compost

Mushroomproduction

Refining Fibre

Wasteplastics

Straw-plasticcomposit board

Cement frame board

Liquidifiedstraw

Isocyanate

Isocyanate+sugar syrup

Non-woven

Non-wovenmat

NaOH

Waste liquor Xylose

Xylitol

Enzyme

Enzyme

Charcoal

Heatrecovery

Soil conditioner

Mixed with clay

Light weightceramics

Cement

Cementboard

Watertreatment

Animal feed

Enzyme

GlucoseAmino acids

Solbitol

Ethanol

Yeast

DNA Medicine

High proteinAnimal feed

Food additives

Soilconditioner

Residual compostCarboxymethylationLiquidadsorbent

Yeastmicelium

Fibre board

Chemical composition of rice straw（％ of extract-free oven dry sample ）

Taichung 65 normal

Taichung 65 Dwarf d1

IR8 Wheat

Lignin 12.2 10.9 15.6 16.8

Neutral sugar

Rhamnose 0.6 0.4 0.6 0.0

Arabinose 3.1 3.6 3.3 2.5

Xylose 17.5 17.9 22.9 19.9

Mannose 0.0 0.0 0.3 0.3

Galactose 1.7 1.7 1.3 0.4

Glucose 54.7 49.7 43.5 30.9

Total 77.6 73.3 71.9 54.0

GalA+GlcA 0.7 0.8 1.1 1.4

p-Coumaric acid 1.3 1.1 1.2 1.1

Ferulic acid 1.1 0.9 1.2 1.3

Lam & Iiyama, J. Wood Sci., 46:376-380 (2000)

Acetyl content: 2.8-3.6 ％（ Substituted at C2 or C3 of xylose residue ）

Structural characteristics of cell wall polysaccharides

TC65 normal TC65 dwarf d1 IR8 Wheat

Arabinose

Terminal 4.5 5.6 8.5 3.8

1,2-/1,3-/1,5- 1.5 1.8 1.7 1.1

Xylose

Terminal 0.9 1.2 1.5 2.2

1,2,4-/1,3,4- 10.4 11.6 18.2 28.6

Galactose

Terminal 0.0 0.0 0.0 0.0

1,3-/1,4- 0.5 0.8 1.0 0.2

Glucose

Terminal 2.8 3.8 1.6 2.0

1,4-(cellulose) 74.0 68.7 62.3 57.2

1,3-(store sugar ）

2.0 2.3 0.8 0.7

Others 1.8 2.2 1.7 1.8Lam & Iiyama, J. Wood Sci., 46:376-380 (2000)

Non-coniferous wood (Incd. waste furniture)

Sorbitol

Enzyme

EthanolEnzyme

Glucose

Waste plastics+ papers

Heavy metal absorbent

Soil conditioner

Acid orenzymes

Fibre board

Wood-plasticscomposit

Concrete-framepanel

Non-woven mat

Fibre

Carboxy-methylationBridgingagent

PaperParticleboard

Compost(mulching)

FuelLeaves

SawwoodFurniture

Saw dust

PelletFuelFuel

Tree Branch

ChipRefining

Charcoal

Water treatment

Low qualitytree

Water-insol.CM-fibre

Amino acid

Heavy metal absorbent

Base of immobilised enzymeLiquidabsorbent

Soilconditioner

Rubber tree

Latex

Rubber Serum

Yeastproduction

DNAAminoacids

Animalfeeds

Chelatingmaterials

Peat

Heavy metaltrapping

CharcoalTimber

ChipBark Woodtar

Compost

Fiberboard

Particleboard

Pulp

Kenaf

Wasteliquor

TrankFruit

Oil palm

Oil Coir

Animalfeeds

Cellulosicresources

Soil

Mushroom

Straw Hull Bran

Crop

Rice

Animalfeeds

Animalfeeds

Cacaobean

Cacao

PodHuskPoly-phenolGlue

Animalfeeds

Fruits

Roofing

Leaves Stems

Sugar

Nipa palm

Fuel

Mangrove

Royalpalm

HCHO

Enzymes

Fig. 1 Example of material flow of biomass industrial complex (BIC) using plantation and agricultural wastes

LectinFertilizer(NH3+K)

ContainerBiodegradable

Water treatmentSoil improvement

BIC

Ethanol production from lignocelluloses

Separable?

Possible?

Bioethanol production from lignocellulose

72% H2SO4 +4% H2SO4121℃, 60min

1M NaOH + Na2S150-170oC, for 60-90 min

O3/NaOH treatment

0.2M NaOH, 60-80oC, 30-60mindefibrator

ClO2/O2/H2O2

treatment

H2SO4

H2SO4

H2SO4

Woodymaterials

Klasonlignin

H2SO4

Recovery

H2SO4

PentoseHexose

Woodymaterials

Gramineaeplants

Unbleach pulp Unbleach pulp

Bleached pulp Bleached pulp

Wash with waterCellulase treatment

Hexose Pentose

Yeast

Ethanol

Ethylene

Polyethylene

Distillation

95% Ethanol

Dehydration

99.5% Ethanol

Heating with dilute acid

Reduction

Enzyme

EnzymeButhanol Biodiesel

Buthene Polybuthylene

Propanol

Propylene Polypropylene

Xylitol

Furfural

Tetrahydrofurane

Hydrogenation

Solvent, polymers

Solvent

Sweetner

H2, CH4 trapping

Photosynthesis of various plants

C4 plants

C3 plants

Nepia grass （ Zhejiang, China: Hemudo ruin ）

Silver grass (Auckland, New Zealand ）

June, 2006 January, 2007

Defibrator

Laboratory scale defibrator Plant scale defibrator

Bioethanol production from lignocellulose

72% H2SO4 +4% H2SO4121℃, 60min

1M NaOH + Na2S150-170oC, for 60-90 min

O3/NaOH treatment

0.2M NaOH, 60-80oC, 30-60mindefibrator

ClO2/O2/H2O2

treatment

H2SO4

H2SO4

H2SO4

Woodymaterials

Klasonlignin

H2SO4

Recovery

H2SO4

PentoseHexose

Woodymaterials

Gramineaeplants

Unbleach pulp Unbleach pulp

Bleached pulp Bleached pulp

Wash with waterCellulase treatment

Hexose Pentose

Yeast

Ethanol

Ethylene

Polyethylene

Distillation

95% Ethanol

Dehydration

99.5% Ethanol

Heating with dilute acid

Reduction

Enzyme

EnzymeButhanol Biodiesel

Buthene Polybuthylene

Propanol

Propylene Polypropylene

Xylitol

Furfural

Tetrahydrofurane

Hydrogenation

Solvent, polymers

Solvent

Sweetner

H2, CH4 trapping

Synthesis of alkene by dehydration of alcohol

RCH2CH2OH RCH=CH2concH2SO4

160-170oC

RCH2CH2OH + MsCl RCH2OMs + (Ms- = CH3SO2-)HCl

RCH2OMs + R'3N RCH=CH2 + R'3N-MsOH

RCH2CH2OH + CS2 CH3I NaOH+ + RCH2CH2OC(=S)SCH3 + +NaI H2O

RCH2CH2OC(=S)SCH3 RCH=CH2 + O=C(SH)SCH3

CH3CH2CH2OH CH3CH=CH2

CC

CC

CH3 CH3

CC

CC

CH3 CH3

CC

CC

CH3 CH3

HH

HH

HH

HH H H H

HH

H

HH

H

HPolypropyrene

BIC for biodiesel production

Palm oil complex

Palm oilmill

Crudeoil

Alkali/acid/enzyme

Methanol

Glycerin

ElectricitySteam

Xylitol

BoilerFiber

Emptyfruit bunch

Steamexplosion

Methanolextraction

Acid

FurfuralBoard

Levulinicacid

Polymersmedicines

Adhesive

Vitamine E

CH4Anaerobicfermentation

Methanol

Hydrogen

Fuel cell battery

Boiler

Electricity Steam

Polyurethane

Phenol(lignin)Isocyanate

Biodiesel

Jatropha curcas Linn. (Kasetsart Univ., Thailand)

Harvest

1kg/tree2.5t/ha/y

4kg/tree10t/ha/y

10kg/tree(OD weight:

2.5t/ha/y)

15kg/tree(OD weight:

7.5t/ha/y)

Oil: 250g

0.63kl/ha/y

Cake: 750g

Bark

5kg/tree(OD weight:

2.5t/ha/y)

Forage Board

Fuel

Paper2t/ha/y

Soil improvement

US$2,000/ha/y

BDFUS$1.75/lUS$1,100

/ha/y

Price of diesel oilThailand ：　

US$0.7/lJapan ：　 US$1.0/l

Price of BDF from palm oilUS$0.82 円 /l (Pilot plant)US$0.55/ ｌ (400,000kl

scale)

?

??

?

Jatropha curcas Linn. Biodiesel from Jatropha curcas

Foundamental studies1. Analyses of chemical composition2. Physicochemical characteristics such as viscosity, molecular weight etc.3. Physical & mechanical studies of products4. Toporagical invetigation of original aterials & products5. Biochemical researches for fertilizer, feedstaff

Preliminary study of utilization of Jatropha Industrial Complex based on Zero-Emission Initiative

Jatropha curcas

Stem

Trunk

CrackingPress

Strip

Zephaboard Pulp

Hydrolysisdehydration

Binderlessboard

-Cellulose pulp Rayon

Cellulase

Glucose YiestEthanol

Lactase

Lactic acidPolymerization

PolylactateBiodegradablepolymer

LeafMilling

Groundmeal

Binderlessboard

Fertilizer Animalfeed

SeedExtractionof o il

Oil CakeTrans-esterification

Used asfuel

Ash(Rich in K)

Biodiesel

Electricity& steam

Fertilizer

Shell

Press at 150oCfor 20-30 min

Hand madepaper

Unbleachpulp

Bleachedpulp

Bark

150oC, 4MPa

H2Osoluble

NaOH/AQ

H2O2 bleach

XylitolFurfural

SteamexplosionExtractwith H2O

Digestionwith NaOH,H2O2 bleach

Air driedPress at 150oC,4MPa,15-20min

Taxation to promote lignocellulosic refinery systems

Environmental taxes in Europe

Preference taxation system for biofuels　　 France ： 0.38Eur(JPY55.1)/L ， Spain ： 0.39Eur(JPY56.6)/LEnvironment taxFinland:(1990-) Carbon tax + Electricity tax JPY6.657/t-C (1998)Netherlands ： (1990-) Fuel tax + Energy regulation tax JPY6,600/t-C Sweden: (1991-) Carbon tax JPY5,330/t-C (1998)Norway ： (1991-) Carbon tax JPY4,990/t-C (1998)Denmark: (1992-) Carbon tax JPY2,620/t-C (1993)Germany ： (1999-) Vehicle fuel tax JPY21.5/L (2003) + Gasoline tax

JPY66/L or Diesel tax JPY41/LUK ： (2001-) Climate change tax (Annual total JPY157.6 billion （ 2002)Italy ： (1998 年 -) Environmental tax

Environmental tax is used for reduction of “Social Insurance Expense”

Taxation for petroleum and CO2 emission in JapanDemand Unit price Tax total CO2 Emission Tax/CO2

1,000kL JPY/L 109 JPY 106 ton JPY/t-CO2

Gasoline 61,469 53.8 3,307 144.2 22,926

Kerosene 27,977 0 0 69.8 0

Jet fuel 4,906 26.0 128 12.2 10,428

Diesel 38,203 32.1 1,226 95.3 12,874

Heavy oil 55,658 0 0 155.1 0

Naphtha 48,992 0 0 115.0 0

ＬＰＧ 32,551 9.8 319 76.4 4,176

Others 9,141 0 0 25.5 0

Total 278,897 4,980 693.4 7,182

Fuel tax* 278,897 2.04 569 777.2 732

Tax Total 5,549 7,914*: Fuel tax is import duties for petroleum.The tax is only used for road construction and maintenance.

The possibility of lignocellulosic refinery system has been proposed more than 50 years ago. However, it has not been realized because of political, economic and technological reasons.

Issues to be conquered:☆ Further technological developments regarding prices of products an

d also life cycle assessment are required.

☆ Analysis of accurate and scientific characteristics of biomass to be supplied as resources is essential to find out proper combination of resources, because of seasonal supply of bioresources.

☆ The deliberate layout of lignocellulosic industrial system, namely the division to local processes for basic treatment of bioresources and intensive process for final products based on high technology, has to be constructed to warrant regional economics.

☆ Some political and financial support such as carbon tax or environmental tax are essential to compete petroleum refinery system, which is turning huge profit on mass production, because lignocellulosic refinery system is to be small scale system at the beginning stage and restriction of resource supply.

Thank you for your attention