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
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
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)
Under-nourished population
United Nations Millennium Developing Goals (2001): Eradicate extreme poverty & hunger
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.
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
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
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
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
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
Nepia grass ( Zhejiang, China: Hemudo ruin )
Silver grass (Auckland, New Zealand )
June, 2006 January, 2007
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
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
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
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.
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