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Transcript of Biomasa Bioetanol SC
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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
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Gasoline Engine
Biodiesel
Biorefinery from Biomass by Supercritical
Fluid Technologies
Water
Methanol
Alcohol
WasteOils/Fats
Diesel EngineBiopower
Waste Wood
WasteBiomass
CO2
BiomassH2O
Waste Wood
CO2
H2O
ThinningWood
Waste Paper
Waste oilTwig
WastePaper
Diesel Engine
Substit
utionfortheF
ossilFuels
Mitigation
oftheEnvironmentalLoading
LPG Engine
MethaneBiomethanol
Supercritical Fluid
Science
Bioplastics
Liquid Biofuel
Biochemicals
Bioethanol
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Supercritical FluidSupercritical 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 becondensed any more, even if temperature and/or pressure are increased.Such a substance is called supercritical fluid.
Temperature
Pressure
Solid Liquid
Triple Point
Critical Point
Critical
Pressure
Critical Temp.
Gas
Temperature-Pressure relationof the Pure Substance
MeOHCritical Point: 239, 8.09MPa
Under SC condition,Ionic Products: Increased(H2O Hydrolysis)
Dielectric Constant: Decreased(Hydrophilic Hydrophobic)
H2O
Critical Point: 374, 22.1MPa
SupercriticalFluid
Sakas Laboratory, Graduate School of Energy Science, Kyoto University
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Butch Continuous
Liquid-Liquid
Continuous
Solid-LiquidSakas Laboratory, Graduate School of Energy Science, Kyoto University
Supercritical Fluid Biomass Conversion SystemsSupercritical Fluid Biomass Conversion Systems
Continuous
Liquid-LiquidTwo Steps
Direct Observation
through Sapphirewindow
Gas-Charging
Unit
Butch (Two Steps)
Pilot Plant for BDF
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368 370 372 374 376
19
20
21
22
23
24
Temperature ( )
Pressur
e(MPa)
Liquid Water
C.P.
SC H2O
C
B
Gas Steam
Sakas Laboratory, Graduate School of Energy Science, Kyoto University
A
Phase Changes of Water in a VicinityPhase Changes of Water in a Vicinity
of Its Critical Pointof Its Critical Point
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Biodiesel
Organic AcidsBiomethane
Liq ue fa c tio n o f Lig no c e llu lo sic s b y Sup e rc ritic a l Alc oho l Te c hno lo g ie s
Biofuels by Supercritical Fluid TechnologiesBiofuels by Supercritical Fluid Technologies
Bioplastics
Liquid Biofuel
Biochemicals
Bioethanol
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Sakas Laboratory, Graduate School of Energy Science, Kyoto University
Supercritical MethanolSupercritical Methanol TreatmentTreatment
350350 /43MPa/43MPa
Wood flo ur MeOH MeOH- inso lub le
residue
MeOH-soluble
port ion
Ref: Minami and Saka, 2003J Wood Sci 49:73-78.
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Study by Dimeric Lignin Model CompoundsStudy by Dimeric Lignin Model Compounds
270270 /27MPa/27MPa
Condensed-Tye Linkage Ether Linkage
5-5 -1 -O-4 -O-4Structure
R=H R=CH3 R=CH3 R=H R=CH3 R=H R=CH3
Reactivity VeryLow
VeryLow
Low High High VeryHigh
High
10-3/sec 2.8 0.34 NM 0.17
Ea kJ/mol 68.9 85.2 NM 113
OR OR
OCH3H3 CO
CH3 CH3
OCH3
OCH3
C
C
CH2 OH
OCH3
OCH3
OH
H
H
OR
OCH3
C
C
CH2 OH
O
OH
OCH3
H
H
OR
OCH3
H2 C
O
OCH3
Sakas Laboratory, Graduate School of Energy Science, Kyoto University
Ref: Minami et al, 2003J Wood Sci 49:158-165.
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Decomposition of Cellulose inDecomposition of Cellulose in
Supercritical MethanolSupercritical Methanol
Sakas Laboratory, Graduate School of Energy Science, Kyoto University
O
OH
OHHO
HO O
OH
OHHO O
O O
OH
OHHO OH
n-1
O
OH
OHHO
HO O
OH
OHHO O
O O
OH
OHHO OCH3
0 3
O
OH
OHHO
HO
OC H3
O
OH
OHHO
HOOC H3
O
OH
OH
OH
O
Cellulose
Me thy la ted O l igo m ers
Methy l --D-g lucos ideMethy l --D-g lucos ide
Levog lucosan
Other Prod uc ts
Anomer iza t ion
Methanolysis
Methanolysis
Ref: Ishikawa and Saka, 2001Cellulose 8:189-195.
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Sakas Laboratory, Graduate School of Energy Science, Kyoto University
Various Alcohols Available from BiomassVarious Alcohols Available from Biomass
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Sakas Laboratory, Graduate School of Energy Science, Kyoto University
Changes in the composition of the alcoholChanges in the composition of the alcohol--insolubleinsoluble
residue under the condition of 350residue under the condition of 350ooCC
0 10 20 30
0
20
40
60
80
100
Productcompos
ition(wt%)
Methanol
Cellulose
LigninHemicelluloses
0 10 20 300
20
40
60
80
100
Treatment time (min)
1-Butanol
Productcom
positon(wt%)
0 10 20 300
20
40
60
80
100
1-Decanol
Treatment time (min)
0 10 20 30
0
20
40
60
80
100
Ethanol
0 10 20 300
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, 2006J Wood Sci 52:527-532.
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Sakas Laboratory, Graduate School of Energy Science, Kyoto University
Various AlcoholVarious Alcohol--Soluble Portions of woodSoluble Portions of wood
Ref: Yamazaki, Minami and Saka, 2006J Wood Sci 52:527-532.
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Molecular Weight Distribution of AlcoholMolecular Weight Distribution of Alcohol--SolubleSoluble
Portions after 30 min Treatment at 350Portions after 30 min Treatment at 350ooCC
Sakas Laboratory, Graduate School of Energy Science, Kyoto University
10 15 20 25 30 35
2100050001270 580 MW (Polystyrene)
Methanol
Ethanol
1-Propanol
1-Butanol
1-Octanol1-Decanol
Elution time (min)
Ref: Yamazaki, Minami and Saka, 2006J Wood Sci 52:527-532.
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Residue Mixture
Before
After
OctanolOctanol--Treated Sample (350Treated Sample (350 /19MPa/5Min) for Hot/19MPa/5Min) for Hot--
Compressed Treatment at 200Compressed Treatment at 200 for 3Sfor 3S
Precipitated
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Biodiesel
Organic AcidsBiomethane
Biofuels by Supercritical Fluid TechnologiesBiofuels by Supercritical Fluid Technologies
Bioe tha no l from Lig no c e llulosic s b y Sup e rc ritic a l Wa ter Tec hno lo g y
Bioplastics
Liquid Biofuel
Biochemicals
Bioethanol
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Various Production Types of BioethanolVarious Production Types of Bioethanol
Sakas Laboratory, Graduate School of Energy Science, Kyoto University
Wood Cellulose,
Hemicellulose
Wheat, Corn Starch
Sugarcane Molasses
Pret
reatment
Saccharification
Fermentatio
n
Distillation
Bioethano
l
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Chemical Composition of LignocelluloseChemical Composition of Lignocellulose
Glucose
Xylo se
Arabinose
Rhamnose
G a la c tose
Mannose
Fuc o se
Glucose
Ethanol
Ethanol
Ethanol
6C (Hexo se )
5C (Pe nto se )
6C (Hexo se )
By Gene t ic a l Eng ine e ring
Ba c te ria Zym o no na s m ob ilis
Co lo n b a c te ria (Esc he ric hia c o li)
Yea st(Sa c c ha rom yc e s c e re visia e )
Lig no c e llu lo se Cellulose, C rysta lline 40 50
Hem ic e llulo se s, Am o rp hou s 20 30
Lig n in, A rom a t ic 20 30
Sakas Laboratory, Graduate School of Energy Science, Kyoto University
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The Separation Scheme of LignocellulosicsThe Separation Scheme of Lignocellulosics
Treated in Supercritical WaterTreated in Supercritical Water
Treated Sample
Lignocellulosics
Sakas Laboratory, Graduate School of Energy Science, Kyoto University
Ref: Saka and Ehara, 2002
International Symposium on HighlyEfficient Use of Energy and Reduction ofits Environmental Impact :17-26.
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WaterWater--Soluble PortionSoluble Portion
Sakas Laboratory, Graduate School of Energy Science, Kyoto University
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HPLCHPLC CChromatograms ofhromatograms of WWaterater--SSolubleoluble PPortions fromortions from
CCellulose asellulose as TTreated inreated in SSupercriticalupercritical WWater (380ater (380 ooC, 40 MPa)C, 40 MPa)
0 5 10 15 20 25
Retention time (min)
Glucose
5-HMF
Methylglyoxal
Erythrose
FructoseGlycolaldehyde
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, 2002Cellulose 9:301-311.
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500 1000 1500 2000
Water-soluble
Cellododecaose
1014.78
52
.7
690.7
528.0
1177.1
Cello-oligosaccharides
Mass/charge
528.0
690.5
852
.6
1015.1 1
177.1
1339.5
1501.1
1663.7
1825.6
1988.8
OHO
HO OH
OH
O
OHO
OHO
OH
O
HOOH
OH
OH
n - 2
162
Gl
1543.5
1705.51
219.2
1381.3
894.7
1056.6
732.4
570.1
OHO
HOOH
OH
O
OHO
OHO
OH
n
O
- 1
162GA
1603.3
1279.2
1441.2
954.7 1
117.1
792.6
616.1
OHO
HOOH
OH
O
OHO
OHO
OH
n
O
OH
OH
- 1
162Er
1646.4
1321.3
1484.4
996.7
1158.9
834.76
72.4
162LG
OHO
HOOH
OH
O
OHO
OHO
OH
n
OO
OH
HO-1
Celloheptaose
MALDIMALDI--TOFMS analyses of the waterTOFMS analyses of the water--soluble portionsoluble portion(Flow(Flow--type system, 380type system, 380 oo , 40 MPa, 0.24 s), 40 MPa, 0.24 s)
Ref: Ehara and Saka, 2002Cellulose 9:301-311.
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The Separation Scheme of LignocellulosicsThe Separation Scheme of Lignocellulosics
Treated in Supercritical WaterTreated in Supercritical Water
Treated Sample
Lignocellulosics
Sakas Laboratory, Graduate School of Energy Science, Kyoto University
Ref: Saka and Ehara, 2002
International Symposium on HighlyEfficient Use of Energy and Reduction ofits Environmental Impact :17-26.
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SC water-soluble
After 12 h
Precipitates
Dielectric constant; 10
HydrophobicDielectric constant; 80
Hydrophilic
SC water Ordinary water
Precipitates from Supercritical WaterPrecipitates from Supercritical Water--soluble Portionsoluble Portion
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5 15 25 35 45
2 ( )
Intensity
Dried Precipitates
Cellulose
(avicel)
Sak as Lab oratory, Gradu ate Sc hoo l of Energy Sc ienc e, Kyoto
XX--rayray DDiffractograms ofiffractograms of Dried PDried Precipitatesrecipitates afterafter
SSupercriticalupercritical WWaterater TTreatment at 380reatment at 380 ooC for 0.24 sC for 0.24 s
Cellulose II
Cellulose I
Ref: Ehara and Saka, 2002Cellulose 9:301-311.
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Others
Oligomers
Polysaccharides(precipita
0
20
40
60
80
100
0.48 s0.12 s 0.24 s
Yield(%) Dihydroxyacetone
Glycolaldehyde
5-
HydroxymethylfurfuralLevoglucosan
Fructose
Glucose
MethylglyoxalErythrose
Hydrolyzed
Fragmented
Dehydrated
Chemical Composition of Cellulose TreatedChemical Composition of Cellulose Treated
in Supercritical Water (380in Supercritical Water (380 , 40MPa), 40MPa)
Glycolic acidLactic acid
Formic acid
Acetic acid
Organic acid
Sakas Laboratory, Graduate School of Energy Science, Kyoto University
Ref: Ehara and Saka, 2002Cellulose 9:301-311.
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OHO
HOOH
OH
OO HO
OHO
OH
n
O
OHO
HOOH
OH
OO HO
OH
O
OH
n
O
OH
OH
OHO
HOOH
OH
OO HO
OHO
OH
n
OO
OH
HO
OHO
HO OH
OH
O
O HOOH
O
OH
O
HOOH
OH
OH
n
OHO
HO OH
OH
O
O HO OH O
OH
O
HOOH
OH
OH
n
O
HO
HO
OH
OH
OH
CH2 OH
HOH 2C
HO
OH
O
Organic Acids etc
+
+
+
0~10
0~9
0~9
+ H 20
H20+
>10
Dehydration Fragmentation
Fragmentation
Dehydration0~9
OH
OH OH
O
OH
OH OH
O
CH2OH
C
H
O
Hydrolysis
Hydrolysis
O
O
OH
OH
OH
OHOH2C CHO
CH2OH
C
H
O
CHO
HC
CH2OH
OH
CH2OH
C
CH2OH
O
HC
C
CH3
O
O
LG
Er
GA Er
GA
FrGl
LG5-HMF
Er GA DA
MG
PA
The Proposed Pathway of CelluloseThe Proposed Pathway of Cellulose
Decomposition in FlowDecomposition in Flow--Type Supercritical WaterType Supercritical Water
Ref: Ehara and Saka, 2002Cellulose 9:301-311.
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Oily substances
Methanol-soluble
Water-insoluble residue
Methanolextraction
Oily Substances (MethanolOily Substances (Methanol--soluble Portion)soluble Portion)
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GCGC--MS Analysis of the Monomeric Compounds inMS Analysis of the Monomeric Compounds in
the MeOHthe MeOH--Soluble PortionSoluble Portion
206
2021
881
921
74
O CHOHOH2C
OH
OCH3
CH 3
OH
OCH3
OH
OCH3
CHO
OH
OCH3
CH
CH 2
OH
OCH3
CH 2
CH 3
OH
OCH3
C
CH3
O
OH
OCH3
CH2
COOH
OH
CH2
CHO
OCH3
OH
OCH3
CH
CH
COOH
OH
OCH3
CH 2
CH 2
CH 3
OH
OCH3
CH 2
CH
CH 2
OH
OCH3
CH
CH
CH3
OH
OCH3
CH
CH
CHO
CH
CH
CH 2
OH
OCH3
OH
OH
C
CH2
OCH3
CH3
O
OH
CH2
C
OCH3
CH3
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, 2004J Wood Sci 50:253-259.
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Study of Lignin Model CompoundsStudy of Lignin Model CompoundsSupercritical water (400Supercritical water (400 ooC, 115MPa)C, 115MPa)
10 20 30
Retention time (min)
C
C
CH2 OH
O
OCH 3
OH
OCH3
H
HO H
OCH3
OH
Biphenyl Condensed Linkage
10 20 30
Retention time (min)
OH
H3CO
CH3
OH
CH3
OCH3
Untreated
Treated
-O-4 Ether LinkageGuaiacylglycerol--guaiacyl ether
Sakas Laboratory, Graduate School of Energy Science, Kyoto University
Ref: Takada, Ehara and Saka, 2004J Wood Sci 50:253-259.
GC MS Ch f Di i C d
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10 15 20 25 30 35 40 45 50
Retention time [min]
GCGC--MS Chromatogram of Dimeric CompoundsMS Chromatogram of Dimeric Compounds
in the MeOHin the MeOH--Soluble PortionSoluble PortionDimers
OH
OCH3
CH
H2C
OOCH3
OH
OCH3
CH
OH
OCH3
HC
OH
CH2
H3CO
OH
OCH3
CH2
CH3 CH 3
OH
OCH3
CH2
H2C OH
OCH3
OH
CH
H3CO
CH
CH2OH
OH
OCH3
CHO
Biphenyl type
Biphenyl type
Diphenyl ethane typeStilbene type
Phenyl coumaran
type
Sakas Laboratory, Graduate School of Energy Science, Kyoto University
Ref: Takada, Ehara and Saka, 2004J Wood Sci 50:253-259.
Various aromatic compounds by the GCVarious aromatic compounds by the GC MS in the methanolMS in the methanol
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Retention time min
SCH
CH
CHO
SCH2
C
CH3
O
SC
CH2
CH3
O
SC
CH3
O
SCH
CH
CH2 OH
SCH
CH
CH3
SCHO
SCH2
CH
CH2
SCH2
CHO
SCH
CH2
SCH2
CH3
SCH3
SOHOCH3H3 CO
Various aromatic compounds by the GCVarious aromatic compounds by the GC--MS in the methanolMS in the methanol--
soluble portion fromsoluble portion from Japanese beechJapanese beech treatedtreated
in supercritical waterin supercritical water
G GCHCH
C O O H
GCHCH
CHO
GCH 2C
CH 3
O
GCCH 2
CH 3
O
GCCH 3
O
GCH 2CHO
GCHCH
CH 3
GCH 2CH 3
GCH 3
GCHO
OH
OCH3
Sakas Laboratory, Graduate School of Energy Science, Kyoto University
Ref: Ehara, Takada and Saka, 2005J Wood Sci 51:256-261.
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SC W t P f Eth l P d tiSC Water Process for Ethanol Production
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Lignocellulosics
Extra
yeast Residue
Alcoholfermentation
Ethanol
tank
SC water
Cooling water
Enzymaticsaccharification
Lignin-derived
products tank
Methanol-soluble portion
Water-soluble portion
Methanol extraction
D
istillation
SCwater
treatm
ent
380
40 MPa
15 , 40 MPa
Poly-saccharides, Oligo-saccharidesGlucose, Fructose, Mannose, Xylose
Cellulose-derived products
Hemicellulose-derived products
Lignin-derived
products
Mixed
sugars
400 , 40 MPa
SC Water Process for Ethanol ProductionSC Water Process for Ethanol Production
from Lignocellulosicsfrom Lignocellulosics
100% 95%
75~80%
95%
Separation
Sakas Laboratory, Graduate School of Energy Science, Kyoto University
Ref: Saka and Ehara, 2003Energy Res. 24:178-182.
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AcOH Fermentation Esterification Hydrogenolysis
Anaerobic Ethanol Fermentation by YeastAnaerobic 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 + H 2O
D-Glucose Hydrogen Ethanol water
Indirect Ethanol Fermentation by Acetic AcidIndirect Ethanol Fermentation by Acetic Acid
FermentationFermentation
NEDO D l f P B i Bi T h l i
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Ethanol Production by Acetic Acid Fermenation withEthanol Production by Acetic Acid Fermenation withHydrogenolysis from LignocellulosicsHydrogenolysis 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 TechnologiesNEDO Development of Preparatory Basic Bioenergy Technologies
Ref: NEDO Pamphlet, p.20 (Oct 12,2007)
H d d X l (H i ll l )Hardwood Xylan (Hemicellulose)
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Hardwood Xylan (Hemicellulose)Hardwood Xylan (Hemicellulose)
and Celluloseand Cellulose
Sakas Laboratory, Graduate School of Energy Science, Kyoto University
Microfibril
Hydrogen bonds
Hardwood Xylan 90%O-Acetyl-4-O-methylglucuronoxylan
O
HO O
OHO
HOO
OH
O
O
HOO
O
OH 3CO
OH
O
HOHO
O
O
OH
O
CH3
O
O
HO
OHOO
HO
OHOO
HO
OHOO
OO
OHO
CH 3
O
HO
OH( 21 )
4-O-Methyl-D-glucuronic acid
Cellulose
Ref: Wood Chemistry, Kyoritsu Publisher,1968.
B W d H d l i T t d b TB W d H d l i T t d b T St H tSt H t
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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
Xylooligosaccharidesand Xylose
Cellooligosaccharides
and Glucose
Acetic Acid
Levoglucosan
Temp.(
oC)
Y
ield(basedonwood,wt%)
Buna Wood Hydrolysis as Treated by TwoBuna Wood Hydrolysis as Treated by Two--Step HotStep Hot--
CompressedCompressed (230(230 --270270 /10MPa/10mL/min)/10MPa/10mL/min)
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Substrates for Acetic Acid FermentationSubstrates for Acetic Acid Fermentation
O
OHHO OH
HO
OH
D-Glucose
(C6)
O
OHHO OH
HO
D-Xylose(C5)
O
HO OH
HO
OHOH
D-Mannose
(C6)
O
OH
OH
HOH 2C
OH
L-Arabinose(C5)
OOH
OHHO OH
OH
D-Galactose
(C6)
OHO
HO
OH
COOH
OH
Uronic acids(Acid Sugar)
Cellooligosaccharide
Xylooligosaccharide
O
(R )(S )
(R )(R )
C H 2O H C H 2O H
H O
O HO
D-Fructose
(C6)
O
OH
HO
HO
OH
OO
HO
OH
O
O
OH
HO
OH
OO
HO
OH
O
O
OH
HO
OH
OO
HO
OH
OH
OH OH OH
OHO
HO
OH
O
O
HO
OH
O
HO
OH
OO
O
HO
OH
O
HO
OH
OO
O
HO
OH
OH
Sakas Laboratory, Graduate School of Energy Science, Kyoto University
Acetic Acid Fermentation for sugarsAcetic Acid Fermentation for sugars
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Sakas Laboratory, Graduate School of Energy Science, Kyoto University
(a) Glucose (b) Xylose
(c) Fructose
Acetic acid
Xylose
Fructose
Acetic Acid Fermentation for sugarsAcetic Acid Fermentation for sugars
Clostridium thermoaceticumClostridium thermoaceticum
Glucuronic acid
(d) Glucuronic acid
Concentration(g/l)
Fermentation time (h)
Concentration(g/l)
Fermentation time (h)
Concentration(g/l)
Fermentation time (h)
Concentration(g/l)
Fermentation time (h)
Acetic acid
Acetic acid
Acetic acid
Glucose
NEDO Development of Preparatory Basic Bioenergy TechnologiesNEDO Development of Preparatory Basic Bioenergy Technologies
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3 H2O
O
Sakas Laboratory, Graduate School of Energy Science, Kyoto University
3 CH3COH
O
Fermentation
Esterification
Hydrogenolysis
Net
3 ROH3 CH3COH
O
3 CH3COR
O
3 CH3COR
6 H2 3 CH3CH2OH 3 ROH +
C6H12O6+
6 H2 3 CH3CH2OH +
3 H2O+
+
+
C6H12O6
Ethanol Production by Acetic Acid FermenationEthanol Production by Acetic Acid Fermenation
with Hydrogenolysis from Lignocellulosicswith Hydrogenolysis from Lignocellulosics
NEDO Development of Preparatory Basic Bioenergy Technologiesp p y gy g
Ref: NEDO Pamphlet, p.20 (Oct 12,2007)
Bi f l b S iti l Fl id T h l iBi f l b S iti l Fl id T h l i
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Biofuels by Supercritical Fluid TechnologiesBiofuels by Supercritical Fluid Technologies
Bioplastics
Liquid Biofuel
Biochemicals
Bioethanol
Biodiesel
Biodiesel from Oils/Fats by Supercritical
Methanol Technology
Organic AcidsBiomethane
A V i f V bl Oil d A i l F
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A Variety of Vegetable Oils and Animal FatsA Variety of Vegetable Oils and Animal Fats
Sakas Laboratory, Graduate School of Energy Science, Kyoto
Sunflower Rapeseed Soybean Cottonseed Olive Peanut Palm Copra Beef tallow
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Sakas Laboratory, Graduate School of Energy Science, Kyoto
Trio le in
Oils/Oils/FFatsats asas FFeedstockseedstocks for Biodieselfor Biodiesel
O le ic a c id
Fre e fa t ty a c id m ino r c om p o ne nt (2-5%)
Wa ste o il 25%
Trig lyc e rid e m a jo r c om p onent
CH2
OCOCH2CH2CH2CH2CH2CH2CH2CH=CHCH2CH2CH2CH2CH2CH2CH2CH3|
CH OCOCH2CH2CH2CH2CH2CH2CH2CH=CHCH2CH2CH2CH2CH2CH2CH2CH3|
CH2OCOCH2CH2CH2CH2CH2CH2CH2CH=CHCH2CH2CH2CH2CH2CH2CH2CH3
HOOCCH2CH2CH2CH2CH2CH2CH2CH=CHCH2CH2CH2CH2CH2CH2CH2CH3
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C t l tC t l t ff
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Sakas Laboratory, Graduate School of Energy Science, Kyoto University
CatalystCatalyst--freefree
Supercritical Methanol (SC MeOH) MethodsSupercritical Methanol (SC MeOH) Methods
One-Step SC MeOH Method :(Saka Method)Transesterification
Two-Step SC MeOH Method :(Saka-Dadan Method)
Hydrolysis + EsterificationRef: Kusdiana and Saka, 2004,
Appl Biochem Biotech 115:781-791.
Ref: Saka and Kusdiana, 2001,Fuel 80:225-231.
OneOne--Step SC MeOH MethodStep SC MeOH Method
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pp
(Saka Process)(Saka Process)
Oils/fats
MeOH
Biodiesel
(BDF)
GlycerolSC MeOH
(350oC/20MPa)
MeOH recovery
Separation
CH2 OCOR1CH OCOR2
CH2 OCOR3+ 3CH3OH
R3COOCH3
R2COOCH3
R1COOCH3
+
CH2 OHCH OH
CH2 OHTriglyceride Biodiesel
Este rific a tio n
R4COOH + CH3OH R4COOCH3 + H2O
Free fatty acid Biodiesel
Tra nse ste rific a tio n
No catalyst
No catalyst
Ref: Saka and Kusdiana, 2001, Fuel 80:225-231.
TwoTwo--Step SCMeOH MethodStep SCMeOH Method
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(Saka(Saka--Dadan Process)Dadan Process)
Oils/fats
Sub-C Water(270oC/7MPa)
Glycerol
MeOH
BiodieselBDF
Waterlayer
Oil layer
SC MeOH(270oC/7MPa)
Waste water
MeOH recovery
Purification
Step I: Hydrolysis
Step II: Esterification
Fa tty a c id sTrig lyc e ride
Fa tty a c id
+
CH2 OCOR1|
CH OCOR2
|
CH2
OCOR3
3H2O
R1COOH
R2COOH
R3
COOH
CH2 OH|CH OH|
CH2
OH
Biodiesel
R4COOH CH3OH H2O++ R4COOCH3
+
Water
Ref: Kusdiana and Saka, 2004, Appl Biochem Biotech 115:781-791.
Reactions Involved in SC MeOH MethodsReactions Involved in SC MeOH Methods
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Oils/fats
Triglycerides Fatty acids
Transesterification Hydrolysis
Fatty acids
Methyl estersOne-Step (Saka)Two-Step (Saka-Dadan)
Esterification
Sakas Laboratory, Graduate School of Energy Science, Kyoto University
Reactions Involved in SC MeOH MethodsReactions Involved in SC MeOH Methods
Ref: Kusdiana and Saka, 2004Appl Biochem Biotech 115:781-791.
Direct Observation through Sapphire WindowDirect Observation through Sapphire Window
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Direct Observation through Sapphire WindowDirect 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
+FattyAcid
MeOH
Oil
Ref: Kusdiana and Saka, 2004Appl Biochem Biotech 115:781-791.
Arrhenius Plots for Transesterification,Arrhenius Plots for Transesterification,
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1.4 1.6 1.8 2.0 2.210
-4
10-3
10-2
10-1 350 300 250 200 (
oC)
Reactionrateco
nstant(1/
sec)
Temperature (1000/K)
,,
Hydrolysis and Esterification of Rapeseed OilHydrolysis and Esterification of Rapeseed Oil
Transesterification
Esterification
Hydrolysis
Tc (MeOH)Tc (Water)
270oC
Sakas Laboratory, Graduate School of Energy Science, Kyoto UniversityRef: Kusdiana and Saka, 2004
Appl Biochem Biotech 115:781-791.
Applicable Range of Methods for Various Oils/FatsApplicable Range of Methods for Various Oils/Fats
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1 10 1001
10
100
Fattyacids(wt%
)
Water (wt%)
Dark oil
Waste oil
Used frying oil
Virginoil
Acid-catalyzed
Alkali-catalyzed
Waste palm oil
Sakas Laboratory, Graduate School of Energy Science, Kyoto University
SC MeOH Methods
with different Water and Fatty Acid Contentswith different Water and Fatty Acid Contents
Ref: Saka, 2005Japan Inst Energy 84:413-419.
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Biodiesel Production from Oils and Fats without ProducingBiodiesel Production from Oils and Fats without Producing
GlycerolGlycerol by Carcoxylate Estersby Carcoxylate Esters
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Esterification
R4COOH + CH3COOCH3 R4COOCH3 + CH3COOH
Fatty Acid FAME(BDF)
Interesterification
No catalyst
CH2 OCOR1
CH OCOR2
CH2 OCOR3
+ 3CH3COOCH3
R3COOCH3
R2COOCH3
R1
COOCH3+
Triglyceride FAME(BDF)
No catalyst
Triacetin
(BDF)
CH2 OCOCH3CH OCOCH3
CH2 OCOCH3
Methyl Acetate
Methyl Acetate
Oils
Methyl Acetate
BDF
(FAME+Triacetin)Supercritical Cond.
(350oC/20MPa)
Recycle
Separation Purification
Acetic Acid
Tc=233oC
Pc=4.69MPa Tc=233oC
Pc=4.69MPa
GlycerolGlycerol by Carcoxylate Estersby Carcoxylate Esters
--OneOne--Step Supercritical Methyl Acetate MethodStep Supercritical Methyl Acetate Method--
Sakas Laboratory, Graduate School of Energy Science, Kyoto UniversityRef: NEDO Pamphlet, p.21 (Oct 12,2007), Fuel in Press (2009)
Fuel Properties of Model Fuel and BDF StandardsFuel Properties of Model Fuel and BDF StandardsFuel Properties of Model Fuel and BDF Standards
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Sakas Laboratory, Graduate School of Energy Science, Kyoto University
Properties Unit FAME TAModelBDFa
Kyoto JASOb EU US
Density(15oC)
g/ml 0.88 1.16 0.92 0.86~0.900.86~0.90
0.86~0.90 -
Kinematic
viscosity(40oC)
mm2
/s 4.4 7.3 4.5 3.5-5.0 3.5-5.0 3.5-5.0 1.9-6.0
Cetanenumber
- 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 oC -16.0 -40.0 -18.0 7.5 - - -
Cold filterpluggingpoint
oC -16.0 13.5 -17.0 5 - - -
Flash point(closedcup)
oC 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 StandardsFuel Properties of Model Fuel and BDF Standardsue ope t es o ode ue a d Sta da ds
Fuel in Press (2009)
Biodiesel Production by TransesterificationBiodiesel Production by Transesterification
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Triglyceride
(Rapeseed Oil)
Dimethyl Carbonate
(DMC)Upper
BiodieselFAME
Supercritical Dimethyl Carbonate
Tc=274.9oC/Pc=4.6 MPa
DMC RecycleSeparation/Purification
Lower
Glycerol carbonate +
Citramalic Acid
with Supercritical Dimethyl Carbonatewith Supercritical Dimethyl Carbonate
Non-Catalyst350
oC/20MPa
:DMC= 1:42 (mol)
Triglyceride Dimethyl
carbonate
Fatty acid
methyl ester
Glycerol
carbonateCitramalic
Acid
CH2OCOR1
CHOCOR2
CH2OCOR3
3 CH3OCOOCH3
R1COOCH3
R2COOCH3
R3COOCH3
CH
CH2OH
O
O
C O
CH2
C5H8O5
Non-Catalyst
Sakas Laboratory, Graduate School of Energy Science, Kyoto UniversityRef: Ilham and Ehara, 2009
Biores Technol 100:1793-1796.
ByBy--Products of Biodiesel Produced byProducts of Biodiesel Produced by
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Supercritical Dimethyl CarbonateSupercritical Dimethyl Carbonate
CH
CH2OH
O
O
C O
CH2
C
CH2
C
C
CH3
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 UniversityRef: Ilham and Ehara, 2009
Biores Technol 100:1793-1796.
Biofuels and Biochemicals from lignocellulosicsBiofuels and Biochemicals from lignocellulosics
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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 CarboxylateEsters
Supercritical Dimethyl
arbonate
Anaerobic
Fermtn
Alcoholic
Fermtn
Oils/Fats
Methane
by Supercritical Fluid Technologiesby Supercritical Fluid Technologies
Sakas Laboratory, Graduate School of Energy Science, Kyoto University
Acetic Acid
Hydrogenolysis
Ref: Saka, 2007
Ad Tech for Chem from Wood Resp.56, CMC Publisher.
ZeroZero--Emission Type Biorefinery for Chemicals andEmission Type Biorefinery for Chemicals and
Bioenergy and its Utilization SystemBioenergy and its Utilization System
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PaperWaste
Ga rbage
Waste
Oils/Fats
Bioethanol
Biomethane
Biodiesel
SludgeExcresionsKitchen Waste
Forest Residues
Woody WasteAgr. Waste
Biomethanol
Sakas Laboratory, Graduate School of Energy Science, Kyoto University
Glycerol
Biomethanol
Liquid FuelMTBE ETBE
Plant
SS
Home Gas
SS
Heat Local
Heating
SS
Oil Factory
CNG Car
Diesel Car
Bioethanol
Biomethane
Bioenergy and its Utilization SystemBioenergy and its Utilization System
BiochemicalsBioplastics
Value-addedProducts
Gasoline Car
Members of SakaMembers of Sakas Laboratorys Laboratory
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yy
Sakas Laboratory, Graduate School of Energy Science, Kyoto University
AcknowledgementsAcknowledgements
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Tha nk you fo r your k ind a tte ntio n!
Shiro SAKA
Kyoto University
Graduate School of Energy Science
Kyoto, JAPAN
Phone/Fax:075-753-4738
E-mail:[email protected]
Homepage:http://www.ecs.energy.kyoto-u.ac.jp/
Sakas Laboratory, Graduate School of Energy Science, Kyoto University
AcknowledgementsAcknowledgements