Shiro Saka

Graduate School of Energy Science

Kyoto University
Kyoto, Japan
January 29, 2009
Biorefinica Conference Workshop
Osnabruck, Germany
Recent Progress in Biorefineries as Introduced by
Supercritical Fluid Science and Technology
Gasoline Engine
Biodiesel
Biorefinery from Biomass by Supercritical
Fluid Technologies
Water
Methanol
Alcohol
Waste
Oils/Fats
Diesel Engine
Biopower
Waste Wood
Waste
Biomass
CO
2
Biomass
H
2
O
Waste Wood
CO
2
H
2
O
Thinning
Wood
Waste Paper
Waste oil
Twig
Waste
Paper
Diesel Engine
S
u
b
s
t
i
t
u
t
i
o
n

f
o
r

t
h
e

F
o
s
s
i
l

F
u
e
l
s
M
i
t
i
g
a
t
i
o
n

o
f

t
h
e

E
n
v
i
r
o
n
m
e
n
t
a
l

L
o
a
d
i
n
g
LPG Engine
Methane
Biomethanol
Supercritical Fluid
Science
Bioplastics
Liquid Biofuel
Biochemicals
Bioethanol
Supercritical Fluid
Supercritical Fluid
A pure substance may be changed into 3 phases such as gas, liquid and
solid. Among these, the critical point exists between the gas and liquid.
Above the critical point, there exists the high-density fluid which cannot be
condensed any more, even if temperature and/or pressure are increased.
Such a substance is called supercritical fluid.
Temperature
P
r
e
s
s
u
r
e
Solid
Liquid
Triple Point
Critical Point
Critical
Pressure
Critical Temp.
Gas
Temperature-Pressure relation
of the Pure Substance
MeOH
Critical Point: 239, 8.09MPa
Under SC condition,
Ionic Products: Increased
(H
2
OHydrolysis)
Dielectric Constant: Decreased
(Hydrophilic Hydrophobic)
H
2
O
Critical Point: 374, 22.1MPa
Supercritical
Fluid
Sakas Laboratory, Graduate School of Energy Science, Kyoto University
Butch Continuous
Liquid-Liquid
Continuous
Solid-Liquid
Sakas Laboratory, Graduate School of Energy Science, Kyoto University
Supercritical Fluid Biomass Conversion Systems
Supercritical Fluid Biomass Conversion Systems
Continuous
Liquid-Liquid
Two Steps
Direct Observation
through Sapphire
window
Gas-Charging
Unit
Butch (Two Steps)
Pilot Plant for BDF
368 370 372 374 376
19
20
21
22
23
24


Temperature ( )
P
r
e
s
s
u
r
e
(
M
P
a
)
Liquid Water
C.P.
SC H
2
O
C
B
Gas Steam
Sakas Laboratory, Graduate School of Energy Science, Kyoto University
A
Phase Changes of Water in a Vicinity
Phase Changes of Water in a Vicinity
of Its Critical Point
of Its Critical Point
Biodiesel
Organic Acids
Biomethane
Liquefaction of Lignocellulosics by Supercritical Alcohol Technologies
Biofuels by Supercritical Fluid Technologies
Biofuels by Supercritical Fluid Technologies
Bioplastics
Liquid Biofuel
Biochemicals
Bioethanol
Sakas Laboratory, Graduate School of Energy Science, Kyoto University
Supercritical Methanol
Supercritical Methanol
Treatment
Treatment
350
350
/43MPa
/43MPa

Wood flour MeOH MeOH-insoluble

residue
MeOH-soluble
portion
Ref: Minami and Saka, 2003
J Wood Sci 49:73-78.
Study by Dimeric Lignin Model Compounds
Study by Dimeric Lignin Model Compounds
270
270
/27MPa
/27MPa

Condensed-Tye Linkage Ether Linkage

5-5 -1 -O-4 -O-4
Structure
R=H R=CH
3
R=CH
3
R=H R=CH
3
R=H R=CH
3
Reactivity Very
Low
Very
Low
Low High High Very
High
High
10
-3
/sec 2.8 0.34 NM 0.17
E
a
kJ/mol 68.9 85.2 NM 113
OR OR
OCH
3
H
3
CO
CH
3
CH
3
OCH
3
OCH
3
C
C
CH
2
OH
OCH
3
OCH
3
OH
H
H
OR
OCH
3
C
C
CH
2
OH
O
OH
OCH
3
H
H
OR
OCH
3
H
2
C
O
OCH
3
Sakas Laboratory, Graduate School of Energy Science, Kyoto University
Ref: Minami et al, 2003
J Wood Sci 49:158-165.
Decomposition of Cellulose in
Decomposition of Cellulose in
Supercritical Methanol
Supercritical Methanol
Sakas Laboratory, Graduate School of Energy Science, Kyoto University
O
OH
OH
HO
HO
O
OH
OH
HO O
O
O
OH
OH
HO OH
n-1
O
OH
OH
HO
HO
O
OH
OH
HO O
O
O
OH
OH
HO OCH
3
0 `3
O
OH
OH
HO
HO
OCH
3
O
OH
OH
HO
HO
OCH
3
O
OH
OH
OH
O
Cellulose
Methylated Oligomers
Methyl--D-glucoside Methyl--D-glucoside
Levoglucosan
Other Products
Anomerization
Methanolysis
Methanolysis
Ref: Ishikawa and Saka, 2001
Cellulose 8:189-195.
Sakas Laboratory, Graduate School of Energy Science, Kyoto University
Various Alcohols Available from Biomass
Various Alcohols Available from Biomass
Sakas Laboratory, Graduate School of Energy Science, Kyoto University
Changes in the composition of the alcohol
Changes in the composition of the alcohol
-
-
insoluble
insoluble
residue under the condition of 350
residue under the condition of 350
o o
C
C
0 10 20 30
0
20
40
60
80
100
P
r
o
d
u
c
t

c
o
m
p
o
s
i
t
i
o
n

(
w
t
%
)
Methanol
Cellulose
Lignin
Hemicelluloses


0 10 20 30
0
20
40
60
80
100
Treatment time (min)
1-Butanol
P
r
o
d
u
c
t

c
o
m
p
o
s
i
t
o
n

(
w
t
%
)


0 10 20 30
0
20
40
60
80
100
1-Decanol
Treatment time (min)


0 10 20 30
0
20
40
60
80
100
Ethanol




0 10 20 30
0
20
40
60
80
100
1-Octanol
Treatment time (min)

0 10 20 30
0
20
40
60
80
100
1-Propanol

Ref: Yamazaki, Minami and Saka, 2006
J Wood Sci 52:527-532.
Sakas Laboratory, Graduate School of Energy Science, Kyoto University
Various Alcohol
Various Alcohol
-
-
Soluble Portions of wood
Soluble Portions of wood
Ref: Yamazaki, Minami and Saka, 2006
J Wood Sci 52:527-532.
Molecular Weight Distribution of Alcohol
Molecular Weight Distribution of Alcohol
-
-
Soluble
Soluble
Portions after 30 min Treatment at 350
Portions after 30 min Treatment at 350
o o
C
C
Sakas Laboratory, Graduate School of Energy Science, Kyoto University
10 15 20 25 30 35
2100050001270580 MW (Polystyrene)
Methanol
Ethanol
1-Propanol
1-Butanol
1-Octanol
1-Decanol
Elution time (min)

Ref: Yamazaki, Minami and Saka, 2006
J Wood Sci 52:527-532.
Residue Mixture
Before
After
Octanol
Octanol
-
-
Treated Sample (350
Treated Sample (350
/19MPa/5Min) for Hot
/19MPa/5Min) for Hot
-
-
Compressed Treatment at 200
Compressed Treatment at 200
for 3S
for 3S
Precipitated
Biodiesel
Organic Acids
Biomethane
Biofuels by Supercritical Fluid Technologies
Biofuels by Supercritical Fluid Technologies
Bioethanol from Lignocellulosics by Supercritical Water Technology
Bioplastics
Liquid Biofuel
Biochemicals
Bioethanol
Various Production Types of Bioethanol
Various Production Types of Bioethanol
Sakas Laboratory, Graduate School of Energy Science, Kyoto University
Wood Cellulose,
Hemicellulose
Wheat, Corn Starch
Sugarcane Molasses
P
r
e
t
r
e
a
t
m
e
n
t
S
a
c
c
h
a
r
i
f
i
c
a
t
i
o
n
F
e
r
m
e
n
t
a
t
i
o
n
D
i
s
t
i
l
l
a
t
i
o
n
B
i
o
e
t
h
a
n
o
l
Chemical Composition of Lignocellulose
Chemical Composition of Lignocellulose
Glucose
Xylose
Arabinose
Rhamnose
Galactose
Mannose
Fucose
Glucose
Ethanol
Ethanol
Ethanol
6C (Hexose)
5C (Pentose)
6C (Hexose)
By Genetical Engineering
Bacteria Zymononas mobilis
Colon bacteria (Escherichia coli)
Yeast(Saccharomyces cerevisiae)
Lignocellulose Cellulose, Crystalline 40 50
Hemicelluloses, Amorphous 20 30
Lignin, Aromatic 20 30
Sakas Laboratory, Graduate School of Energy Science, Kyoto University
The Separation Scheme of Lignocellulosics
The Separation Scheme of Lignocellulosics
Treated in Supercritical Water
Treated in Supercritical Water
Treated Sample
Lignocellulosics
Sakas Laboratory, Graduate School of Energy Science, Kyoto University
Ref: Saka and Ehara, 2002
International Symposium on Highly
Efficient Use of Energy and Reduction of
its Environmental Impact :17-26.
Water
Water
-
-
Soluble Portion
Soluble Portion
Sakas Laboratory, Graduate School of Energy Science, Kyoto University
HPLC HPLC C Chromatograms of hromatograms of W Water ater- -S Soluble oluble P Portions from ortions from
C Cellulose as ellulose as T Treated in reated in S Supercritical upercritical W Water (380 ater (380
o o
C, 40 MPa) C, 40 MPa)
0 5 10 15 20 25
Retention time (min)
Glucose
5-HMF
Methylglyoxal
Erythrose
Fructose
Glycolaldehyde
Dihydroxyacetone
Levoglucosan
Oligomers
0.12 s
0.24 s
0.48 s
Furfural
Hydrolyzed
Fragmented
Dehydrolyzed
Sakas Laboratory, Graduate School of Energy Science, Kyoto University
Ref: Ehara and Saka, 2002
Cellulose 9:301-311.
500 1000 1500 2000
Water-soluble
Cellododecaose
1
0
1
4
.
7
8
5
2
.
7
6
9
0
.
7
5
2
8
.
0
1
1
7
7
.
1
Cello-oligosaccharides
Mass/charge
5
2
8
.
0
6
9
0
.
5
8
5
2
.
6
1
0
1
5
.
1
1
1
7
7
.
1
1
3
3
9
.
5
1
5
0
1
.
1
1
6
6
3
.
7
1
8
2
5
.
6
1
9
8
8
.
8
O
HO
HO
OH
OH
O
O
HO
OH
O
OH
O
HO
OH
OH
OH
n-2
162
Gl
1
5
4
3
.
5
1
7
0
5
.
5 1
2
1
9
.
2
1
3
8
1
.
3
8
9
4
.
7
1
0
5
6
.
6
7
3
2
.
4
5
7
0
.
1
O
HO
HO
OH
OH
O
O
HO
OH
O
OH
n
O
-1
162
GA
1
6
0
3
.
3
1
2
7
9
.
2
1
4
4
1
.
2
9
5
4
.
7
1
1
1
7
.
1
7
9
2
.
6
6
1
6
.
1
O
HO
HO
OH
OH
O
O
HO
OH
O
OH
n
O
OH
OH
-1
162
Er
1
6
4
6
.
4
1
3
2
1
.
3
1
4
8
4
.
4
9
9
6
.
7
1
1
5
8
.
9
8
3
4
.
7
6
7
2
.
4
162
LG
O
HO
HO
OH
OH
O
O
HO
OH
O
OH
n
O
O
OH
HO
-1
Celloheptaose
MALDI MALDI- -TOFMS analyses of the water TOFMS analyses of the water- -soluble portion soluble portion
(Flow (Flow- -type system, 380 type system, 380
o o
, 40 MPa, 0.24 s) , 40 MPa, 0.24 s)
Ref: Ehara and Saka, 2002
Cellulose 9:301-311.
The Separation Scheme of Lignocellulosics
The Separation Scheme of Lignocellulosics
Treated in Supercritical Water
Treated in Supercritical Water
Treated Sample
Lignocellulosics
Sakas Laboratory, Graduate School of Energy Science, Kyoto University
Ref: Saka and Ehara, 2002
International Symposium on Highly
Efficient Use of Energy and Reduction of
its Environmental Impact :17-26.
SC water-soluble
After 12 h
Precipitates
Dielectric constant; 10
Hydrophobic
Dielectric constant; 80
Hydrophilic
SC water Ordinary water
Precipitates from Supercritical Water
Precipitates from Supercritical Water
-
-
soluble Portion
soluble Portion
5 15 25 35 45
2

( )
I
n
t
e
n
s
i
t
y
Dried Precipitates
Cellulose
(avicel)
Sakas Laboratory, Graduate School of Energy Science, Kyoto
U i it
X
X
-
-
ray
ray
D
D
iffractograms of
iffractograms of
Dried P
Dried P
recipitates
recipitates
after
after
S
S
upercritical
upercritical
W
W
ater
ater
T
T
reatment at 380
reatment at 380
o o
C for 0.24 s
C for 0.24 s
Cellulose II
Cellulose I
Ref: Ehara and Saka, 2002
Cellulose 9:301-311.
Others
Oligomers
Polysaccharides(precipitat
0
20
40
60
80
100
0.48 s 0.12 s 0.24 s
Y
i
e
l
d

(
%
)
Dihydroxyacetone
Glycolaldehyde
5-
Hydroxymethylfurfural Levoglucosan
Fructose
Glucose
Methylglyoxal
Erythrose
Hydrolyzed
Fragmented
Dehydrated
Chemical Composition of Cellulose Treated
Chemical Composition of Cellulose Treated
in Supercritical Water (380
in Supercritical Water (380
, 40MPa)
, 40MPa)
Glycolic acid
Lactic acid
Formic acid
Acetic acid
Organic acid
Sakas Laboratory, Graduate School of Energy Science, Kyoto University
Ref: Ehara and Saka, 2002
Cellulose 9:301-311.
O
HO
HO
OH
OH
O
O
HO
OH
O
OH
n
O
O
HO
HO
OH
OH
O
O
HO
OH
O
OH
n
O
OH
OH
O
HO
HO
OH
OH
O
O
HO
OH
O
OH
n
O
O
OH
HO
O
HO
HO
OH
OH
O
O
HO
OH
O
OH
O
HO
OH
OH
OH
n
O
HO
HO
OH
OH
O
O
HO
OH
O
OH
O
HO
OH
OH
OH
n
O
HO
HO
OH
OH
OH
CH
2
OH
HOH
2
C
HO
OH
O
Organic Acids etc
+
+
+
0~10
0~9
0~9
+
H
2
0
H
2
0
+
>10
Dehydration
Fragmentation
Fragmentation
Dehydration
0~9
OH
OH
OH
O
OH
OH
OH
O
CH
2
OH
C
H
O
Hydrolysis
Hydrolysis
O
O
OH
OH
OH
O
HOH
2
C
CHO
CH
2
OH
C
H
O
CHO
HC
CH
2
OH
OH
CH
2
OH
C
CH
2
OH
O
HC
C
CH
3
O
O
LG
Er
GA Er
GA
Fr
Gl
LG
5-HMF
Er
GA
DA
MG
PA
The Proposed Pathway of Cellulose The Proposed Pathway of Cellulose
Decomposition in Flow Decomposition in Flow- -Type Supercritical Water Type Supercritical Water
Ref: Ehara and Saka, 2002
Cellulose 9:301-311.
The Separation Scheme of Lignocellulosics
The Separation Scheme of Lignocellulosics
Treated in Supercritical Water
Treated in Supercritical Water
Treated Sample
Lignocellulosics
Sakas Laboratory, Graduate School of Energy Science, Kyoto University
Ref: Saka and Ehara, 2002
International Symposium on Highly
Efficient Use of Energy and Reduction of
its Environmental Impact :17-26.
Oily substances
Methanol-soluble
Water-insoluble residue
Methanol
extraction
Oily Substances (Methanol
Oily Substances (Methanol
-
-
soluble Portion)
soluble Portion)
GC
GC
-
-
MS Analysis of the Monomeric Compounds in
MS Analysis of the Monomeric Compounds in
the MeOH
the MeOH
-
-
Soluble Portion
Soluble Portion
2
0
6
2
0
2
1
8
8 1
9
2
1
7
4
O
CHO HOH
2
C
OH
OCH
3
CH
3
OH
OCH
3
OH
OCH
3
CHO
OH
OCH
3
CH
CH
2
OH
OCH
3
CH
2
CH
3
OH
OCH
3
C
CH
3
O

OH
OCH
3
CH
2
COOH
OH
CH
2
CHO
OCH
3
OH
OCH
3
CH
CH
COOH
OH
OCH
3
CH
2
CH
2
CH
3
OH
OCH
3
CH
2
CH
CH
2
OH
OCH
3
CH
CH
CH
3

OH
OCH
3
CH
CH
CHO

CH
CH
CH
2
OH
OCH
3
OH
OH
C
CH
2
OCH
3
CH
3
O
OH
CH
2
C
OCH
3
CH
3
O
Coniferyl aldehyde
Coniferyl alcohol
Acetoguaiacone
Eugenol
Vanillin
Guaiacol
Methyl guaiacol
5-HMF
Vinyl guaiacol
Feruric acid
Ethyl guaiacol
Isoeugenol
Propyl guaiacol
Homovanillin
Propioguaiacone
Homovanillic acid
Guaiacyl
acetone
Sakas Laboratory, Graduate School of Energy Science, Kyoto University
Ref: Takada, Ehara and Saka, 2004
J Wood Sci 50:253-259.
Study of Lignin Model Compounds
Study of Lignin Model Compounds
Supercritical water (400 Supercritical water (400
o o
C, 115MPa) C, 115MPa)
10 20 30
Retention time (min)
C
C
CH
2
OH
O
OCH
3
OH
OCH
3
H
HO H
OCH
3
OH
Biphenyl Condensed Linkage
10 20 30
Retention time (min)
OH
H
3
CO
CH
3
OH
CH
3
OCH
3
Untreated
Treated
-O-4 Ether Linkage
Guaiacylglycerol--guaiacyl ether
Sakas Laboratory, Graduate School of Energy Science, Kyoto University
Ref: Takada, Ehara and Saka, 2004
J Wood Sci 50:253-259.
10 15 20 25 30 35 40 45 50
Retention time [min]
GC
GC
-
-
MS Chromatogram of Dimeric Compounds
MS Chromatogram of Dimeric Compounds
in the MeOH
in the MeOH
-
-
Soluble Portion
Soluble Portion
Dimers
OH
OCH3
CH
H2C
O
OCH3
OH
OCH3
CH
OH
OCH3
HC
OH
CH
2
H
3
CO
OH
OCH
3
CH
2
CH
3
CH
3
OH
OCH
3
CH
2
H
2
C OH
OCH
3
OH
CH
H
3
CO
CH
CH
2
OH
OH
OCH
3
CHO
Biphenyl type
Biphenyl type
Diphenyl ethane type
Stilbene type
Phenyl coumaran
type
Sakas Laboratory, Graduate School of Energy Science, Kyoto University
Ref: Takada, Ehara and Saka, 2004
J Wood Sci 50:253-259.
Retention time min
S
CH
CH
CHO
S
CH
2
C
CH
3
O
S
C
CH
2
CH
3
O
S
C
CH
3
O
S
CH
CH
CH
2
OH
S
CH
CH
CH
3
S
CHO
S
CH
2
CH
CH
2
S
CH
2
CHO
S
CH
CH
2
S
CH
2
CH
3
S
CH
3
S
OH
OCH
3
H
3
CO
Various aromatic compounds by the GC Various aromatic compounds by the GC- -MS in the methanol MS in the methanol- -
soluble portion from soluble portion from Japanese beech Japanese beech treated treated
in supercritical water in supercritical water
G G
CH
CH
COOH
G
CH
CH
CHO
G
CH
2
C
CH
3
O
G
C
CH
2
CH
3
O
G
C
CH
3
O
G
CH
2
CHO
G
CH
CH
CH
3
G
CH
2
CH
3
G
CH
3
G
CHO
OH
OCH
3
Sakas Laboratory, Graduate School of Energy Science, Kyoto University
Ref: Ehara, Takada and Saka, 2005
J Wood Sci 51:256-261.
Direct
Polymers & gums
C2
Analogous Model of a Biobased Product
Analogous Model of a Biobased Product
Flow
Flow
-
-
chart for Biomass Feedstocks
chart for Biomass Feedstocks
Ammonia synthesis, hydrogenation products
Methyl esters, Formaldehyde, Acetic acid, Dimethylether,
Dimethylcarbonate, Methyl amines, MTBE, olefins, gasoline
Linear and branched 1 alcohols, and mixed higher alcohols
Olefin hydroformylation products: aldehydes, alcohols, acids
Iso-C4 molecules, isobutene and its derivatives
-olefins, gasoline, waxes, diesel
-olefins, gasoline, waxes, diesel
Acrylates, Acrylamides, Esters, 1,3-Propanediol,
Malonic acid and others
THF, 1,4-Butanediol, -butyrolactone, pyrrolidones,
esters, diamines, 4,4-Bionelle, hydroxybutyric acid
Fermentation products, Propylene glycol, malonic,
1,3-PDO, diacids, propyl alcohol, dialdehyde, epoxides
Acrylates, L-Propylene glycol, Dioxanes, Polyesters, Lactide
Reagent, propionol, acrylate
Pharma. Intermediates
2-amino-1,3-PDO, 2-aminomalonic, (amino-3HP)
Unsaturated succinate derivatives (see above)
Hydroxy succinate derivatives (above), hydroxybutyrolactone
Amino succinate derivatives (see above)
Hydroxybutyrates, epoxy--butyrolactone, butenoic acid
Butanediols, butenols
Diols, ketone derivatives, indeterminant
Methyl succinate derivatives (see above), unsaturated esters
Many furan derivatives
-aminolevulinate, 2-Methyl THF, 1,4-diols, esters, succinate
Amino diols, glutaric acid,substituted pyrrolidones
Lactones, esters
EG, PG, glycerol, lactate, hydroxy furans, sugar acids
1,5-pentanediol, itaconic derivatives, pyrrolidones, esters
Numerous furan derivatives, succinate, esters, levulinic acid
Caprolactam, diamino alcohols, 1,5-diaminopentane
Gluconolactones, esters
Dilactones, monolactones, other products
Glycols (EG, PG), glycerol, lactate, isosorbide
Phenolics, food additives
H
2
Methanol
Oxo synthesis
products
Mixed alcohols
Higher alcohols
Iso-synthesis
products
Fischer-Tropsch
Liquids
Glycerol
Lactic
Malonic acid
Serine
Propionic acid
3-Hydroxy-
propionate
Succinic acid
Fumaric acid
Malic acid
Aspartic acid
Acetoin
Threonine
3-Hydroxy-
butyrolactone
Itaconic acid
Levulinic acid
Xylonic acid
Furfural
Glutamic acid
Xylitol/Arabitol
Citric/Aconitic acid
Glucaric acid
Lysine
Gluconic acid
Sorbitol
5-Hydroxymethy-
lfurfural
Gallic acid
Ferulic acid
Biomass
Feedstocks
Intermediate
Platforms
Building
Blocks
Secondary
Chemicals
Intermediates Products/Uses
SG
C4
C5
C6
Specialty chemical intermediate
Emulsifiers
Chelating agents
Amines
Plasticizers
Polyvinyl acetate
pH control agents
Resins, crosslinkers
Polyvinyl alcohol
Polyacrylates
Polyacrylamides
Polyethers
Polypyrrolidones
Phthalate polyesters
PEIT polymer
Polyhydroxypolyesters
Nylons (polyamides)
Polyhydroxypolyamides
Bisphenol A replacement
Polycarbonates
Polyurethanes
Phenol-formaldehyde resins
polyhydroxyalkonoates
polysaccharides
poyaminoacids
Green solvents
Solvents
Antifreeze and deicers
Reagents-building unit
Fuel oxygenates
Starch
Oil
Protein
Biobased
Syn Gas
Industrial
Corrosion inhibitors, dust control,
boiler water treatment, gas
purification, emission abatement,
specialty lubricants, hoses, seals
Transportation
Fuels, oxygenates, anti-freeze, wiper
fluids molded plastics, car seats, belts
hoses, bumpers, corrosion inhibitors
Textiles
Carpets, Fibers, fabrics, fabric
coatings, foam cushions, upholstery,
drapes, lycra, spandex
Safe Food Supply
Food packaging, preservatives,
fertilizers, pesticides, beverage
bottles, appliances, beverage can
coatings, vitamins
Environment
Water chemicals, flocculants,
chelators, cleaners and detergents
Communication
Molded plastics, computer casings,
optical fiber coatings, liquid crystal
displays, pens, pencils, inks, dyes,
paper products
Housing
Paints, resins, siding, insulation,
cements, coatings, varnishes, flame
retardents, adhesives, carpeting
Recreation
Footgear, protective equipment,
camera and film, bicycle parts & tires,
wet suits, tapes-CDs-DVDs, golf
equipment, camping gear, boats
Health and Hygiene
Plastic eyeglasses, cosmetics,
detergents, pharmaceuticals, suntan
lotion, medical-dental products,
disinfectants, aspirin
Cellulose
Lignin
Ar
Sugars
Glucose
Fructose
Xylose
Arabinose
Lactose
Sucrose
Starch
C3
Hemicellulose
Ref: Biomass U.S. DOE, 2004, 1-76.
Lignocellulosics
Extra
yeast
Residue
Alcohol
fermentation
Ethanol
tank
SC water
Cooling water
Enzymatic
saccharification
Lignin-derived
products tank
Methanol-soluble portion
Water-soluble portion
Methanol extraction
D
i
s
t
i
l
l
a
t
i
o
n
S
C

w
a
t
e
r

t
r
e
a
t
m
e
n
t
380
40 MPa
15 , 40 MPa
Poly-saccharides, Oligo-saccharides
Glucose, Fructose, Mannose, Xylose
Cellulose-derived products
Hemicellulose-derived products
Lignin-derived
products
Mixed
sugars
400 , 40 MPa
SC Water Process for Ethanol Production
SC Water Process for Ethanol Production
from Lignocellulosics
from Lignocellulosics
100% 95%
75~80%
95%
S
e
p
a
r
a
t
i
o
n
Sakas Laboratory, Graduate School of Energy Science, Kyoto University
Ref: Saka and Ehara, 2003
Energy Res. 24:178-182.
AcOH FermentationEsterificationHydrogenolysis
Anaerobic Ethanol Fermentation by Yeast
Anaerobic Ethanol Fermentation by Yeast
C6H12O6 2 CH3CH2OH + 2 CO2
D-Glucose Ethanol Carbon Dioxide
Sakas Laboratory, Graduate School of Energy Science, Kyoto University
C6H12O6 + H2 3 CH3CH2OH + H2O
D-Glucose Hydrogen Ethanol water
Indirect Ethanol Fermentation by Acetic Acid
Indirect Ethanol Fermentation by Acetic Acid
Fermentation
Fermentation
Ethanol Production by Acetic Acid Fermenation with
Ethanol Production by Acetic Acid Fermenation with
Hydrogenolysis from Lignocellulosics
Hydrogenolysis from Lignocellulosics
Sakas Laboratory, Graduate School of Energy Science, Kyoto University
Hot-Compressed
Water Hydrolysis
Acetic Acid
Fermentation
Esterification/
Hydrogenolysis
Acetic Acid
NEDO Development of Preparatory Basic Bioenergy Technologies NEDO Development of Preparatory Basic Bioenergy Technologies
Ref: NEDO Pamphlet, p.20 (Oct 12,2007)
Hardwood Xylan (Hemicellulose)
Hardwood Xylan (Hemicellulose)
and Cellulose
and Cellulose
Sakas Laboratory, Graduate School of Energy Science, Kyoto University
Microfibril
Hydrogen bonds
Hardwood Xylan 90%
O-Acetyl-4-O-methylglucuronoxylan
O
HO
O
OH
O
HO
O
OH
O
O
HO
O
O
O
H
3
CO
OH
O
HO
HO
O
O
OH
O
CH
3
O
O
HO
OH
O
O
HO
OH
O
O
HO
OH
O
O
O O
OH
O
CH
3
O
HO
OH
( 21 )
4-O-Methyl-D-glucuronic acid
Cellulose
Ref: Wood Chemistry, Kyoritsu Publisher,1968.
Sakas Laboratory, Graduate School of Energy Science, Kyoto University
0 10 20 30 40 50
140
160
180
200
220
240
260
280
0
2
4
6
8
10
Treatment Time (min)
Glucuronic Acid
Fructose
Xylooligosaccharides
and Xylose
Cellooligosaccharides
and Glucose
Acetic Acid
Levoglucosan
T
e
m
p
.

(
o
C
)
Y
i
e
l
d

(
b
a
s
e
d

o
n

w
o
o
d
,

w
t
%
)
Buna Wood Hydrolysis as Treated by Two
Buna Wood Hydrolysis as Treated by Two
-
-
Step Hot
Step Hot
-
-
Compressed
Compressed
(230
(230
-
-
270
270
/10MPa/10mL/min)
/10MPa/10mL/min)
Substrates for Acetic Acid Fermentation
Substrates for Acetic Acid Fermentation
O
OH
HO
OH
HO
OH
D-Glucose
(C6)
O
OH
HO
OH
HO
D-Xylose
(C5)
O
HO
OH
HO
OH
OH
D-Mannose
(C6)
O
OH
OH
HOH
2
C
OH
L-Arabinose
(C5)
O
OH
OH
HO
OH
OH
D-Galactose
(C6)
O
HO
HO
OH
COOH
OH
Uronic acids
(Acid Sugar)
Cellooligosaccharide
Xylooligosaccharide
O
(R)
(S)
(R)
(R)
CH
2
OH
CH
2
OH
H O
OH
O
D-Fructose
(C6)
O
OH
HO
HO
OH
O
O
HO
OH
O
O
OH
HO
OH
O
O
HO
OH
O
O
OH
HO
OH
O
O
HO
OH
OH
OH
OH
OH
O
HO
HO
OH
O
O
HO
OH
O
HO
OH
O
O
O
HO
OH
O
HO
OH
O
O
O
HO
OH
OH
Sakas Laboratory, Graduate School of Energy Science, Kyoto University
Sakas Laboratory, Graduate School of Energy Science, Kyoto University
(a) Glucose
(b) Xylose
(c) Fructose
Acetic acid
Xylose
Fructose
Acetic Acid Fermentation for sugars
Acetic Acid Fermentation for sugars

Clostridium thermoaceticum
Clostridium thermoaceticum

Glucuronic acid
(d) Glucuronic acid
C
o
n
c
e
n
t
r
a
t
i
o
n

(
g
/
l
)
Fermentation time (h)
C
o
n
c
e
n
t
r
a
t
i
o
n

(
g
/
l
)
Fermentation time (h)
C
o
n
c
e
n
t
r
a
t
i
o
n

(
g
/
l
)
Fermentation time (h)
C
o
n
c
e
n
t
r
a
t
i
o
n

(
g
/
l
)
Fermentation time (h)
Acetic acid
Acetic acid
Acetic acid
Glucose
3 H
2
O
O
Sakas Laboratory, Graduate School of Energy Science, Kyoto University

3 CH
3
COH
O
Fermentation
Esterification
Hydrogenolysis
Net
3 ROH
3 CH
3
COH
O

3 CH
3
COR
O

3 CH
3
COR

6 H
2
3 CH
3
CH
2
OH 3 ROH +
C
6
H
12
O
6
+
6 H
2
3 CH
3
CH
2
OH +
3 H
2
O +
+
+
C
6
H
12
O
6
Ethanol Production by Acetic Acid Fermenation
Ethanol Production by Acetic Acid Fermenation
with Hydrogenolysis from Lignocellulosics
with Hydrogenolysis from Lignocellulosics
NEDO Development of Preparatory Basic Bioenergy Technologies NEDO Development of Preparatory Basic Bioenergy Technologies
Ref: NEDO Pamphlet, p.20 (Oct 12,2007)
Biofuels by Supercritical Fluid Technologies
Biofuels by Supercritical Fluid Technologies
Bioplastics
Liquid Biofuel
Biochemicals
Bioethanol
Biodiesel
Biodiesel from Oils/Fats by Supercritical
Methanol Technology
Organic Acids
Biomethane
A Variety of Vegetable Oils and Animal Fats
A Variety of Vegetable Oils and Animal Fats
Sakas Laboratory, Graduate School of Energy Science, Kyoto
U i it
Sunflower Rapeseed Soybean Cottonseed Olive Peanut Palm Copra Beef tallow
Sakas Laboratory, Graduate School of Energy Science, Kyoto
U i it
Triolein
Oils/
Oils/
F
F
ats
ats
as
as
F
F
eedstocks
eedstocks
for Biodiesel
for Biodiesel
Oleic acid
Free fatty acid minor component (2-5%)
Waste oil 25%
Triglyceride major component
CH
2
OCOCH
2
CH
2
CH
2
CH
2
CH
2
CH
2
CH
2
CH=CHCH
2
CH
2
CH
2
CH
2
CH
2
CH
2
CH
2
CH
3
|
CH OCOCH
2
CH
2
CH
2
CH
2
CH
2
CH
2
CH
2
CH=CHCH
2
CH
2
CH
2
CH
2
CH
2
CH
2
CH
2
CH
3
|
CH
2
OCOCH
2
CH
2
CH
2
CH
2
CH
2
CH
2
CH
2
CH=CHCH
2
CH
2
CH
2
CH
2
CH
2
CH
2
CH
2
CH
3
HOOCCH
2
CH
2
CH
2
CH
2
CH
2
CH
2
CH
2
CH=CHCH
2
CH
2
CH
2
CH
2
CH
2
CH
2
CH
2
CH
3
Sakas Laboratory, Graduate School of Energy Science, Kyoto
U i it
Alkali
Alkali
-
-
catalyzed Method
catalyzed Method
for Commercial Biodiesel Production
for Commercial Biodiesel Production
Transesterification
Saponification
Biodiesel Triglyceride
Free fatty acid
Alkaline
catalyst
+
CH
2
OCOR
1
|
CH OCOR
2
|
CH
2
OCOR
3
3CH
3
OH
Alkaline
catalyst
R
1
COOCH
3
R
2
COOCH
3
R
3
COOCH
3
CH
2
OH
|
CH OH
|
CH
2
OH
+
Saponified
product
R
4
COOH KOH H
2
O + + R
4
COOK
Sakas Laboratory, Graduate School of Energy Science, Kyoto University
Catalyst
Catalyst
-
-
free
free
Supercritical Methanol (SC MeOH) Methods
Supercritical Methanol (SC MeOH) Methods
One-Step SC MeOH Method :
(Saka Method)
Transesterification
Two-Step SC MeOH Method :
(Saka-Dadan Method)
Hydrolysis + Esterification
Ref: Kusdiana and Saka, 2004,
Appl Biochem Biotech 115:781-791.
Ref: Saka and Kusdiana, 2001,
Fuel 80:225-231.
One
One
-
-
Step SC MeOH Method
Step SC MeOH Method
(Saka Process)
(Saka Process)
Oils/fats
MeOH
Biodiesel
(BDF)
Glycerol
SC MeOH
(350
o
C/20MPa)
MeOH recovery
Separation
CH
2
OCOR
1
CH OCOR
2
CH
2
OCOR
3
+ 3CH
3
OH
R
3
COOCH
3
R
2
COOCH
3
R
1
COOCH
3
+
CH
2
OH
CH OH
CH
2
OH
Triglyceride
Biodiesel
Esterification
R
4
COOH + CH
3
OH R
4
COOCH
3
+
H
2
O
Free fatty acid Biodiesel
Transesterification
No catalyst
No catalyst
Ref: Saka and Kusdiana, 2001, Fuel 80:225-231.
Two
Two
-
-
Step SCMeOH Method
Step SCMeOH Method
(Saka
(Saka
-
-
Dadan Process)
Dadan Process)
Oils/fats
Sub-C Water
(270
o
C/7MPa)
Glycerol
MeOH
Biodiesel
BDF
Water
layer
Oil layer
SC MeOH
(270
o
C/7MPa)
Waste water
MeOH recovery
Purification
Step I: Hydrolysis
Step II: Esterification
Fatty acids Triglyceride
Fatty acid
+
CH
2
OCOR
1
|
CH OCOR
2
|
CH
2
OCOR
3
3H
2
O
R
1
COOH
R
2
COOH
R
3
COOH
CH
2
OH
|
CH OH
|
CH
2
OH
Biodiesel
R
4
COOH CH
3
OH H
2
O + + R
4
COOCH
3
+
Water
Ref: Kusdiana and Saka, 2004, Appl Biochem Biotech 115:781-791.
Oils/fats
Triglycerides Fatty acids
Transesterification Hydrolysis
Fatty acids
Methyl esters
One-Step (Saka)
Two-Step (Saka-Dadan)
Esterification
Sakas Laboratory, Graduate School of Energy Science, Kyoto University
Reactions Involved in SC MeOH Methods
Reactions Involved in SC MeOH Methods
Ref: Kusdiana and Saka, 2004
Appl Biochem Biotech 115:781-791.
Direct Observation through Sapphire Window
Direct Observation through Sapphire Window
Sakas Laboratory, Graduate School of Energy Science, Kyoto University
240 280 340
Transesterification
2 Phase 1 Phase
(Low Temp) (High Temp)
160 260 340
280 300 340
Hydrolysis
2 Phase 2 Phase
(Low Temp) (High Temp)
Esterification
1 Phase 1 Phase
(Low Temp) (High Temp)
Water
Oil
MeOH
+
Fatty
Acid
MeOH
Oil
Ref: Kusdiana and Saka, 2004
Appl Biochem Biotech 115:781-791.
1.4 1.6 1.8 2.0 2.2
10
-4
10
-3
10
-2
10
-1
350 300 250 200 (
o
C)

R
e
a
c
t
i
o
n

r
a
t
e

c
o
n
s
t
a
n
t

(
1
/
s
e
c
)
Temperature (1000/K)
Arrhenius Plots for Transesterification,
Arrhenius Plots for Transesterification,
Hydrolysis and Esterification of Rapeseed Oil
Hydrolysis and Esterification of Rapeseed Oil
Transesterification
Esterification
Hydrolysis
T
c
(MeOH) T
c
(Water)
270
o
C
Sakas Laboratory, Graduate School of Energy Science, Kyoto University
Ref: Kusdiana and Saka, 2004
Appl Biochem Biotech 115:781-791.
1 10 100
1
10
100
F
a
t
t
y

a
c
i
d
s

(
w
t
%
)
Water (wt%)
Dark oil
Waste oil
Used frying oil
Virgin
oil
Acid-catalyzed
Alkali-catalyzed
Waste palm oil
Sakas Laboratory, Graduate School of Energy Science, Kyoto University
SC MeOH Methods
Applicable Range of Methods for Various Oils/Fats
Applicable Range of Methods for Various Oils/Fats
with different Water and Fatty Acid Contents
with different Water and Fatty Acid Contents
Ref: Saka, 2005
Japan Inst Energy 84:413-419.
Worldwide Glycerol Production Worldwide Glycerol Production
Worldwide Glycerol Production
Sakas Laboratory, Graduate School of Energy Science, Kyoto University
(forecast)
0
500
1,000
1,500

G
l
y
c
e
r
o
l

p
r
o
d
u
c
t
i
o
n

(

~1
,
0
0
0
t
)
BDF
Fatty acid
Fatty alcohol
Soap
Others
2008 2005 2003 1995
Ref: 2006, Yushi 59:24-25.
Esterification
R
4
COOH + CH
3
COOCH
3
R
4
COOCH
3
+ CH
3
COOH
Fatty Acid FAME(BDF)
Interesterification
No catalyst
CH
2
OCOR
1
CH OCOR
2
CH
2
OCOR
3
+ 3CH
3
COOCH
3
R
3
COOCH
3
R
2
COOCH
3
R
1
COOCH
3
+
Triglyceride FAME(BDF)
No catalyst
Triacetin
(BDF)
CH
2
OCOCH
3
CH OCOCH
3
CH
2
OCOCH
3
Methyl Acetate
Methyl Acetate
Oils
Methyl Acetate
BDF
(FAME+Triacetin)
Supercritical Cond.
(350
o
C/20MPa)
Recycle
Separation Purification
Acetic Acid
Tc=233
o
C
Pc=4.69MPa
Tc=233
o
C
Pc=4.69MPa
Biodiesel Production from Oils and Fats without Producing Biodiesel Production from Oils and Fats without Producing
Glycerol Glycerol by Carcoxylate Esters by Carcoxylate Esters
- -One One- -Step Supercritical Methyl Acetate Method Step Supercritical Methyl Acetate Method- -
Sakas Laboratory, Graduate School of Energy Science, Kyoto University Ref: NEDO Pamphlet, p.21 (Oct 12,2007), Fuel in Press (2009)
Sakas Laboratory, Graduate School of Energy Science, Kyoto University
Properties Unit FAME TA
Model
BDF
a
Kyoto JASO
b
EU US
Density
(15
o
C)
g/ml
0.88 1.16 0.92
0.86
~0.90
0.86
~0.90
0.86
~0.90
-
Kinematic
viscosity
(40
o
C)
mm
2
/s
4.4 7.3 4.5 3.5-5.0 3.5-5.0 3.5-5.0 1.9-6.0
Cetane
number
-
86.3 < 15 64.5 51 51 51 47
Carbon
Residue
(100%)
wt%
0.02 0.01 0.03
0.30
(10%)
0.30
(10%
0.30
(10%)
0.05
Pour point
o
C
-16.0 -40.0 -18.0 7.5 - - -
Cold filter
plugging
point
o
C
-16.0 13.5 -17.0 5 - - -
Flash point
(closed
cup)
o
C
170.5 158.5 154.5 100 120 101 > 130
a
Methyl Oleate/Triacetin 3:1 (mol/mol)
b
Japan Automobile Standards Organization JASOStandard Later JISStandard JIS K2390
Fuel Properties of Model Fuel and BDF Standards Fuel Properties of Model Fuel and BDF Standards
Fuel Properties of Model Fuel and BDF Standards
Fuel in Press (2009)
Triglyceride
(Rapeseed Oil)
Dimethyl Carbonate
(DMC)
Upper
Biodiesel
FAME
Supercritical Dimethyl Carbonate
Tc=274.9
o
C/Pc=4.6 MPa
DMC Recycle
Separation/Purification
Lower
Glycerol carbonate +
Citramalic Acid
Biodiesel Production by Transesterification
Biodiesel Production by Transesterification
with Supercritical Dimethyl Carbonate
with Supercritical Dimethyl Carbonate
Non-Catalyst
350
o
C/20MPa
:DMC= 1:42 (mol)
Triglyceride Dimethyl
carbonate
Fatty acid
methyl ester
Glycerol
carbonate
Citramalic
Acid
CH
2
OCOR
1
CHOCOR
2
CH
2
OCOR
3
3 CH
3
OCOOCH
3
R
1
COOCH
3
R
2
COOCH
3
R
3
COOCH
3
CH
CH
2
OH
O
O
C O
CH
2
C
5
H
8
O
5
Non-Catalyst
Sakas Laboratory, Graduate School of Energy Science, Kyoto University
Ref: Ilham and Ehara, 2009
Biores Technol 100:1793-1796.
By
By
-
-
Products of Biodiesel Produced by
Products of Biodiesel Produced by
Supercritical Dimethyl Carbonate
Supercritical Dimethyl Carbonate
CH
CH
2
OH
O
O
C O
CH
2
C
CH
2
C
C
CH
3
O
O
HO
OH
OH
Glycerol
Carbonate
Citramalic Acid
Glyoxal
Solvents for paints, dyes
and adhesives.
New source of polymeric
materials.
Cosmetic and dermatologic.
Emulsifier
Pharmaceutical applications. Printing.
Textile dyeing.
Rust and scale
removal.
(Cheol et al., 2003,2004; Rolf et al., 2000; Joerg et al., 1999;
Ruey et al., 1997; Kiyoura and Kogure, 1997)
HC
O
CH
O
Sakas Laboratory, Graduate School of Energy Science, Kyoto University
Ref: Ilham and Ehara, 2009
Biores Technol 100:1793-1796.
Biomass Lignocellulosics
Cellulose Hemicellulose-Derived
Products
Lignin-Derived products
Sugars
Organic Acids
Value-Added
Aromatic Products
Formic Acid
Bio-
hydrogen
Bio-
methanol
Bio-
ethanol
Super/Subcritical
water
Fatty Acid Methyl Esters
Biodiesel
Glycerol/Triacin
Supercritical Methanol
Supercritical Carboxylate
Esters
Supercritical Dimethyl
arbonate
Anaerobic
Fermtn
Alcoholic
Fermtn
Oils/Fats
Methane
Biofuels and Biochemicals from lignocellulosics
Biofuels and Biochemicals from lignocellulosics
by Supercritical Fluid Technologies
by Supercritical Fluid Technologies
Sakas Laboratory, Graduate School of Energy Science, Kyoto University
Acetic Acid
Hydrogenolysis
Ref: Saka, 2007
Ad Tech for Chem from Wood Res
p.56, CMC Publisher.
Paper Waste
Garbage
Waste
Oils/Fats
Bioethanol
Biomethane
Biodiesel
Sludge
Excresions
Kitchen Waste
Forest Residues
Woody Waste
Agr. Waste
Biomethanol
Sakas Laboratory, Graduate School of Energy Science, Kyoto University
Glycerol
Biomethanol
Liquid Fuel
MTBE ETBE
Plant
SS
Home Gas
SS
Heat
Local
Heating
SS
Oil Factory
CNG Car
Diesel Car
Bioethanol
Biomethane
Zero
Zero
-
-
Emission Type Biorefinery for Chemicals and
Emission Type Biorefinery for Chemicals and
Bioenergy and its Utilization System
Bioenergy and its Utilization System
Biochemicals
Bioplastics
Value-added
Products
Gasoline Car
Members of Saka
Members of Saka

s Laboratory
s Laboratory
Sakas Laboratory, Graduate School of Energy Science, Kyoto University
Thank you for your kind attention!
Shiro SAKA
Kyoto University
Graduate School of Energy Science
Kyoto, JAPAN
Phone/Fax:075-753-4738
E-mail:saka@energy.kyoto-u.ac.jp
Homepage:http://www.ecs.energy.kyoto-u.ac.jp/
Sakas Laboratory, Graduate School of Energy Science, Kyoto University
Acknowledgements
Acknowledgements