Transcript Lignocellulose refinery system must be realized for global

Lignocellulose refinery system
must be realized for
global environment and economy
Kenji Iiyama
President
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.
Changes in CO2 concentration
CO2 Concentration, ppm
380
360
CO2 concentration
Industrial
Revolution
340
320
Cold age
300
280
260
800
1000
1200
1400
Year
1600
1800
2000
Biofuel: The Savior or the Devil？
Edit from National Geographic (Japanese Ed) No.10 2007
Corn BE
(USA)
Sugarcane
BE (Brazil)
BDF
(Germany)
Cellulose
BE (USA)
Production (103kL）
18,400
15,000
Prod. Cost (JPY/L）
33.54
26.77
Fossil fuel
93.26
151.12
189.29
-
Biofuel
80.64
89.87
209.29
-
114.19
119.42
207.14
-
1.3
8
2.5
2－36
Fossil fuel
2.44
2.44
2.80
2.44
Biofuel
1.93
1.07
0.90
0.22
Reduction (%)
22
56
68
1,890
-
Retail price (JPY/L)
Energy conversion
Energy balance
GHG Emission (kg/L)
91
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
Oct. 2007：US$93.6/B
JPY70,000/kL
CIF price at port in Japan: calculation
including exchange rate
Food price rise sharply by conversion to energy
Bioethanol
Bioethanol
US$150/t
US$12/t
US$9/t
US$90/t
Biodiesel
US$357/t
US$420/t
Biodiesel
US$260/t
US$350/t
US$130/t
Wheat
US$100/t
Soybean
US$280/t
US$200/t
Production plan of bioethanol in USA
International Conference of Corn Industry (in Dalian on August 2007)
Capacity of bioethanol from corn in USA
Aug. 2007:
25.4 x 106 kL
Aug. 2009:
77.3 x 106 kL
Consumption of corn for bioethanol production
Aug. 2007:
91.9 x 106 ton（1/3 of total production）
Aug. 2009:
189.5 x 106 ton
Corn production on 2006
USA：
282 x 106 ton
World：
712 x 106 ton
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
forests?
☆ 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
the land?
☆ What bioenergy technologies are most appropriate for what
environment?
☆ Can second-generation technologies be downscaled to farm and
village levels?
☆ Are there useful genes in the international gene banks for
improved 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
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.
Refinery of bioresources
Bioactive materials introduced
from only bioresources
Cascade Utilisation of Bioresources
Felling
Pruning
Forest
Low quality
resources
Felling
Resources
Processing
Wastes
Processing
Pulp & Paper
Constructs
Furniture
Processing
Wastes
Secondary
fibre
Waste liquor
Wastes
Re-use
cycle
Wastes
Fuel, Methane,
mycelia, sugar
Final products
Wastes
Fuel, charcoal, pulp,
compost, sugar
Final products
Structural characteristics of
lignocellulosics
Polysaccharides of Plant Cell Walls
HO
O
H2COH O
OH
O
HOCH2
O
HO
OH
O
H2COH O
O
HO
OH
HOCH2
HO
OH
O
O
OH
O
O
O
HOCH2
HO
H2COH
O
OH
O
Cellulose
OAc
HO
O
H
O
O
H
HO
OH
H
O
OH
H
O
O
OH
O
O
O
O
OH
AcO
O
O
HO
OAc
H
O
O
H
O
O
OH
O
CH2
OH
O
HOCH2
Hemicellulose
Non-cellulosic wall polysaccharides
OH
OAc
CH3O
O
Structure of lignin
OCH3
H2C
O
(4) HC CH
O
HC
CH
HCOH CH2OH
O
CH2
CH3O
O
HOCH2
(7)
O
HC (1)
CH3O
OCH3
HCOH
(1) O HOCH2
HC
HOH2C
HC
HC
HC
CH3O
(1)
HOH2C
O
(3)
O
OCH3
O
HOH2C H HCOH
C
O
HCOH (6)
OCH3
OCH3
OCH3
O
CH3O
HOCH2
CH
O
(2)
CH
HCOH
(5)
O
CH
(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
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
R
CH2OH
CH CH O
O
(a) Ether linkage
C
OH2C
CH3O
CH3O
O
O
O
OH
OH
O
O
O
OH
R
(a') Ether linkage
O
O
CH
C
CH O
CH2OH
CH3O
CH3O
R
CH2OH
(b) Ester linkage
CH CH O
O
C
OOC
CH3O
CH3O
O
O
O
OH
OH
Covalent association between polysaccharides
and lignin of dicotyledonous plants
Ether linkage
(stable on alkali
treatment)
O
H
HOH2C C C
H
O
CH2OH
CH2
Lignin
Ether linkage
(stable on alkali
treatment)
O
OH
CH2OH
HC O
H
HOH2C C C
H
O
OH
C
H
HCOH
OCH3
O CH
OCH3
OCH3
O
H
C C CH2OH
H
O
H
OH
OH
H
C CH2OH
Cellolose
H H
C C CH2OH
O
H O
HO
H3CO
CH3O
CH3O
HC O
CH3O
OCH3
H COH
HC O
CH2OH
HO
O
O
HO O
HO O
O
O
Xylan
O
OCH3
O
O OH
O OH
CH3O
O
O
O
O
O OH
H2COH
CH2OH
O
OH
Covalent association between polysaccharides
and lignin of Gramineae plants
Ester linkage
(unstable on alkali
treatment)
O
Ferulic acid
CH2OH
CH2OH
HC C C O CH2
H
O
O
O
OH
O
O
O OH
O OH
CH3O
H2COH
O
HC O
C
H
HCOH
Lignin
Ester linkage
(unstable on alkali
treatment)
O
OH
CH3O
CH2OH
HC O
H
C C C
H
O
HO
H
C CH2OH
HO
H3CO
Ferulic acid
CH3O
OCH3
O CH
OCH3
OCH3
O
H
C C CH2OH
H
O
HO
O
HO O
O
O
HO O
O
OCH3
HC
O
Hemicellulose
OH
Cellulose
H H
C C CH2OH
O
H O
CH3O
OCH3
HCOH
HC O
C O
CH2OH
CH
O
OH
OH
p-Coumaric acid
OH
Examples for biomass industrial
complex (BIC) using
lignocellulosic resources
Development of effective utilisation
of agricultural wastes
Agricultural wastes: Rich in nitrogen, starch, and easily biodegraded wall components
Stockbreeding wastes: Rich in nitrogen from microflora and wall components resist to
biodegradation
Removal of dioxin
Acid
from combustion of
hydrolysis
Acid
O
o
urban wastes
210-230 C
hydrolysis
H2
Hydroxymethyl
oC
Cellulose 1-5% acid
Agric.
C
C
195-215
Levelinic
Waste
furfural +
starch
CH3
C
COOH
prod.
15-30sec
acid
15-30min
furfural
Carbonization
H2
O
with K2CO3
Bioactive chemical, polymer,
(HOCH2)
CHO
o
solvent, medicines
800-1200 C
Acid hydrolysis
120oC,
1-4%
acid
Bioactive chemical, polymer,
Activated Water
or enzymes
treatment
solvent, medicines
carbon
Carbonization
Green
with K2CO3
H2
H2
Lactase
house
C
C
fermentation
800-1200oC
C
COOH
heating
Glucose
Lactic acid CH3
Dry
H2
Biodegradable polymer
Animal
Stockbreeding
like polyethylene
feeds
wastes
Alcohol
Lactase
Anaerobic
fermentation
fermentation
fermentation
Acetic acid
fermentation
Fermentation
Anaerobic
Acetic acid CH3COOH
Ethanol
at
high
temperature
fermentation
Methane
Compost
Fuel battery
Possible utilisation of bioresources
Oil well
drilling
Carboxymethylation
Liquid
adsorbent
Soil
conditioner
Amino
acids
Light weight
Heavy metal
ceramics
chelating
Mixed
material
with clay
Crop
Heat
recovery
Water
treatment
Cereals
Cement
Carbonisation
with K2CO3
Mushroom Waste Enzyme Xylose
production liquor
Enzyme
Xylitol
Animal feed Compost
Straw
Fibre board
Glucose
Yeast
micelium
Solbitol
Ethanol
Non-woven
mat
Non-woven
Straw-plastic
composit board
Isocyanate+
sugar syrup
Yeast
Enzyme
Amino acids
Fibre
Isocyanate
Liquidified
straw
Bran
Pulp for
paper
Na2SO3+AQ
Refining
Phenol/
H2SO4
Charcoal Cement
board
Soil
conditioner
Animal feed
Activated
charcoal
Mushroom
NaOH
Hull
Carbonisation
with K2CO3
Residual compost
Adhesive
Plastics
Cement
frame board
Waste
Biodegradable
plastics
urethane form
DNA
Medicine
High protein
Animal feed
Food additives
Chemical composition of rice straw
（％ of extract-free oven dry sample）
Taichung 65
normal
Taichung 65
Dwarf d1
IR8
Wheat
12.2
10.9
15.6
16.8
Rhamnose
0.6
0.4
0.6
0.0
Arabinose
3.1
3.6
3.3
2.5
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
54.7
49.7
43.5
30.9
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
Lignin
Neutral sugar
Xylose
Glucose
Total
Acetyl content: 2.8-3.6％（Substituted at C2 or C3 of xylose residue）
Lam & Iiyama, J. Wood Sci., 46:376-380 (2000)
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
0.9
1.2
1.5
2.2
10.4
11.6
18.2
28.6
Terminal
0.0
0.0
0.0
0.0
1,3-/1,4-
0.5
0.8
1.0
0.2
2.8
3.8
1.6
2.0
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
1.8
Xylose
Terminal
1,2,4-/1,3,4Galactose
Glucose
Terminal
1,4-(cellulose)
Lam & Iiyama, J. Wood Sci., 46:376-380 (2000)
Non-coniferous wood (Incd. waste
furniture)
Fuel
Pellet
Fuel Water
treatment
Sorbitol
Soil conditioner
Charcoal
Enzyme
Heavy metal absorbent
Saw dust
Furniture
Saw
wood
Acid or
enzymes
Tree
Leaves Fuel
Low quality
tree
Branch
Chip
Liquid
absorbent
Enzyme
Ethanol
Waste plastics
+ papers
Fibre board
Refining
Fibre
Concrete-frame
Wood-plastics
Carboxypanel
composit
methylation
Bridging
Non-woven mat
agent
Water-insol.
Base of immobilised enzyme
CM-fibre
Paper
Compost Particle
(mulching) board
Soil
conditioner
Glucose
Amino acid
Heavy metal absorbent
Heavy metal
Chelating
trapping
materials
Fuel
Peat
Animal Amino
feeds acids DNA
BIC
Fertilizer
(NH3+K)
Rubber
tree
Lectin
Enzymes
Yeast
Latex production
Mangrove
Waste
liquor
Serum
Rubber
Kenaf
Cacao
bean
Pulp
Soil
Timber Charcoal
Chip Water treatment
Bark
Soil improvement
Compost
Glue
Mushroom
Cacao
Wood
HCHO
tar
Polyphenol
Fiber Particle
board board Animal Cellulosic
resources
feeds
Husk Pod
Animal
feeds
Biodegradable
Container
Oil
Trank
Animal
feeds
Coir
Roofing
Fruit
Royal
palm
Fruits
Sugar
Leaves Stems
Oil palm
Straw Hull
Bran
Animal
feeds
Nipa palm
Crop
Rice
Fig. 1 Example of material flow of biomass industrial complex
(BIC) using plantation and agricultural wastes
Ethanol production from lignocelluloses
Separable?
Possible?
Bioethanol production from lignocellulose
Woody
materials
Gramineae
plants
Woody
materials
72% H2SO4 +
4% H2SO4
121℃, 60min
Unbleach pulp
Pentose
Hexose
0.2M NaOH, 60-80oC, 30-60min
defibrator
1M NaOH + Na2S
150-170oC,
for 60-90 min
Unbleach pulp
O3/NaOH
treatment
ClO2/O2/H2O2
treatment
Klason
lignin
Bleached pulp
Bleached pulp
Wash with water
Cellulase treatment
H2SO4
Recovery
H2, CH4 trapping
Tetrahydrofurane Solvent
Hexose
H2SO4
Pentose
Heating with
dilute acid
Yeast
H2SO4
Ethylene
Ethanol
Reduction
Enzyme
Distillation
Dehydration
Buthanol Biodiesel
Buthene
Polybuthylene
Propylene
Polypropylene
Propanol
Enzyme
99.5% Ethanol
Furfural Solvent, polymers
Xylitol Sweetner
H2SO4
95% Ethanol
Polyethylene
Hydrogenation
H2SO4
C4 plants
C3 plants
Photosynthesis of various 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
Woody
materials
Gramineae
plants
Woody
materials
72% H2SO4 +
4% H2SO4
121℃, 60min
Unbleach pulp
Pentose
Hexose
0.2M NaOH, 60-80oC, 30-60min
defibrator
1M NaOH + Na2S
150-170oC,
for 60-90 min
Unbleach pulp
O3/NaOH
treatment
ClO2/O2/H2O2
treatment
Klason
lignin
Bleached pulp
Bleached pulp
Wash with water
Cellulase treatment
H2SO4
Recovery
H2, CH4 trapping
Tetrahydrofurane Solvent
Hexose
H2SO4
Pentose
Heating with
dilute acid
Yeast
H2SO4
Ethylene
Ethanol
Reduction
Enzyme
Distillation
Dehydration
Buthanol Biodiesel
Buthene
Polybuthylene
Propylene
Polypropylene
Propanol
Enzyme
99.5% Ethanol
Furfural Solvent, polymers
Xylitol Sweetner
H2SO4
95% Ethanol
Polyethylene
Hydrogenation
H2SO4
Synthesis of alkene by dehydration of
alcohol
RCH2CH2OH
concH2SO4
o
160-170 C
RCH=CH2
RCH2CH2OH + MsCl
RCH2OMs + HCl (Ms- = CH3SO2-)
RCH2OMs + R'3N
RCH=CH2 + R'3N-MsOH
RCH2CH2OH + CS2 + CH3I + NaOH
RCH=CH2 + O=C(SH)SCH3
RCH2CH2OC(=S)SCH3
CH3CH2CH2OH
RCH2CH2OC(=S)SCH3 + NaI + H2O
CH3CH=CH2
CH3
CH3
C H C
H C H
H
CH3
CH3
H C H C H
C H C H C
H
H
H
Polypropyrene
CH3
CH3
C H C H
H C H C
H
H
BIC for biodiesel production
Biodiesel
Glycerin
Phenol
(lignin)
Isocyanate
Palm oil complex
Alkali/acid/enzyme
Methanol
Crude
oil
Steam Electricity
Xylitol
Polyurethane
Fiber
Palm oil
mill
CH4
Empty
fruit bunch
Vitamine E
Anaerobic
fermentation
Methanol
Boiler
Steam
explosion
Methanol
extraction
Acid
Board
Furfural
Adhesive
Hydrogen
Boiler
Fuel cell battery
Levulinic
acid
Electricity Steam
Polymers
medicines
Jatropha curcas Linn.
(Kasetsart Univ., Thailand)
Jatropha curcas Linn.
Biodiesel from
Jatropha curcas
Harvest
Bark
1kg/tree
2.5t/ha/y
10kg/tree
(OD weight:
2.5t/ha/y)
4kg/tree
10t/ha/y
Soil
improvement
Forage
?
?
Oil: 250g
BDF
US$1.75/l
US$1,100
/ha/y
Fuel
?
Board
?
5kg/tree
(OD weight:
2.5t/ha/y)
Paper
2t/ha/y
US$2,000/ha/y
Cake: 750g
0.63kl/ha/y
15kg/tree
(OD weight:
7.5t/ha/y)
Price of diesel oil
Thailand： US$0.7/l
Japan： US$1.0/l
Price of BDF from palm oil
US$0.82円/l (Pilot plant)
US$0.55/ｌ (400,000kl scale)
Preliminary study of utilization of Jatropha Industrial Complex
based on Zero-Emission Initiative
Jatropha curcas
Seed
Shell
Trunk
Leaf
Extraction
Milling
of o il
Ground
Bark
Fertilizer
Stem
Animal
meal
Oil
Cake
o
Steam
feed
Press at 150 C
TransNaOH/AQ
Used as
explosion
for
20-30
min
esterification
Cracking
fuel
Hand mad e Unbleach
Press
Extract
Binderless
Strip
o
Biodiesel
with H2O paper
pulp
150 C, 4MPa
board
Ash
Electricity
Zeph a
H2O2 bleach
(Rich in K)
& steam
board
Pulp
H2O
Bleached
soluble
Hydrolysis
Fertilizer
Digestion pulp
dehydration
Air dried
with NaOH,
Xylitol
Press at
H2O2 bleach
Furfural 150oC,
Fou ndamental studies
-Cellulose pulp Rayon
4MPa,
1. Analyses of chemical composition
15-20min
2. Physicochemical characteristics
Cellulase
such as viscosity, molecular weight etc.
Yiest
Binderless
Glucose
3. Physical & mechanical studies of
Ethanol
board
Lactase
products
4. Toporagical invetigation of original
Lactic acid
aterials & produ cts
Polymerization
5. Biochemical researches for fertilizer,
Polylactate
feedstaff
Biodegradable
polymer
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)/L
Environment tax
Finland:(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/L
UK：(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 Japan
Demand
1,000kL
Unit price
JPY/L
Tax total CO2 Emission
109 JPY
106 ton
Tax/CO2
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
9,141
0
0
25.5
0
4,980
693.4
7,182
569
777.2
732
Others
Total
278,897
Fuel tax*
278,897
Tax Total
2.04
5,549
*: Fuel tax is import duties for petroleum.
The tax is only used for road construction and maintenance.
7,914
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 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