biomasa bioetanol sc

8/12/2019 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


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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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


Ref: Minami et al, 2003J Wood Sci 49:158-165.


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Decomposition of Cellulose inDecomposition of Cellulose in

Supercritical MethanolSupercritical Methanol


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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Various Alcohols Available from BiomassVarious Alcohols Available from Biomass


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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


0 10 20 30

0

20

40

60

80

100

Ethanol

0 10 20 300

20

40

60

80

100

1-Octanol


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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Various AlcoholVarious Alcohol--Soluble Portions of woodSoluble Portions of wood



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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


10 15 20 25 30 35

2100050001270 580 MW (Polystyrene)

Methanol

Ethanol

1-Propanol

1-Butanol

1-Octanol1-Decanol

Elution time (min)



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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



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


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



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The Separation Scheme of LignocellulosicsThe Separation Scheme of Lignocellulosics

Treated in Supercritical WaterTreated in Supercritical Water

Treated Sample

Lignocellulosics


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



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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


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)



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The Separation Scheme of LignocellulosicsThe Separation Scheme of Lignocellulosics

Treated in Supercritical WaterTreated in Supercritical Water

Treated Sample

Lignocellulosics


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



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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




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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



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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


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


C

C

CH2 OH

O

OCH 3

OH

OCH3

H

HO H

OCH3

OH

Biphenyl Condensed Linkage

10 20 30


OH

H3CO

CH3

OH

CH3

OCH3

Untreated

Treated

-O-4 Ether LinkageGuaiacylglycerol--guaiacyl ether



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



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


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


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


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


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


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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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


Acetic Acid Fermentation for sugarsAcetic Acid Fermentation for sugars


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(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)


Concentration(g/l)


Concentration(g/l)


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


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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Bioplastics

Liquid Biofuel

Biochemicals

Bioethanol

Biodiesel

Biodiesel from Oils/Fats by Supercritical

Methanol Technology


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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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


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


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


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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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


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


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


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/


AcknowledgementsAcknowledgements

biomasa bioetanol sc

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