November 22, 2006 (9:30-9:45) The 2nd Joint International Conference on Sustainable Energy and Development (SEE2006) Bangkok,

Thailand

NEDO Biodiesel Production Process by Supercritical Methanol Technologies

Shiro Saka
Graduate School of Energy Science Kyoto University Kyoto, Japan

BDF Activity in Kyoto

220 garbage trucksB100) (1.3 million liters/yr)

80 municipal busses (B20) (0.2 million liters/yr)

Sakas Laboratory, Graduate School of Energy Science, Kyoto University

Biodiesel Production Plant in Kyoto City

Method : Alkali-catalyzed Feedstock : Waste oils/fats (from household sector) Productivity : 5,000 L/day

Waste Oil/fat

Removal of water

Alkali/MeOH MeOH

Water

Removal of water

Additives

BIODIESEL

Heat Feedstock Pre-treatment

Heat

Glycerol Separation

Heat

Heat

Waste water Product

Reaction

Post-treatment

Sakas Laboratory, Graduate School of Energy Science, Kyoto University

Alkali-catalyzed Method for Commercial Biodiesel Production

Transesterification
CH2 OCOR1 | CH OCOR2 | CH2 OCOR3 Alkaline catalyst R1COOCH3 R2COOCH3 R3COOCH3 CH2 OH | CH OH | CH2 OH

3CH3OH

Triglyceride

Biodiesel

Saponification
R4COOH

KOH Alkaline catalyst

R4COOK

H2O

Free fatty acid

Saponified product
Sakas Laboratory, Graduate School of Energy Science, Kyoto University

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.

Pressure

Critical Pressure Solid Liquid Gas Triple Point

Supercritical Fluid Critical Point

H2O Critical Point: 374, 22.1MPa MeOH Critical Point: 239, 8.09MPa Under SC condition, Ionic Products: Increased (H2OHydrolysis) (MeOHMethanolysis) Dielectric Constant: Decreased (HydrophilicHydrophobic)
Sakas Laboratory, Graduate School of Energy Science, Kyoto University

Critical Temp.

Temperature Temperature-Pressure Relation of the Pure Substance

Phase Changes in a Vicinity of Critical Point in MeOH

24

LiquidMeOH MeOH SC

Pressure (MPa)

23 22 21 20 19 368

A
C.P.

GasMeOH
370 372 374 376

Temperature ()

Sakas Laboratory, Graduate School of Energy Science, Kyoto University

One-Step SC MeOH Method

(Saka Process)
MeOH recovery MeOH Oils/fats SC MeOH Separation (350oC/20MPa) Biodiesel (BDF) Glycerol

Transesterification
CH2OCOR1 CHOCOR2 CH2OCOR3 Triglyceride R4COOH + Free fatty acid CH3OH No catalyst + 3CH3OH No catalyst R1COOCH3 R2COOCH3 R3COOCH3 Biodiesel R4COOCH3 Biodiesel +

CH2OH + CHOH CH2OH

Esterification
H2O

Thermal Stability of Methyl Linolenate in SC MeOH : Untreated : Treated 270oC/20min (Two-step)

ester (C=O)

350oC/9min (One-step)
ester (C=O) ester (C-O) alkyl (C-H) cis (C=C) trans (C=C)

ester alkyl (C-O) (C-H) trans (C=C)

cis (C=C)

2000 1800 1600 1400 1200 1000

800

600 2000 1800 1600 1400 1200 1000

800

600

Wave number (cm )

-1

Wave number (cm )

Sakas Laboratory, Graduate School of Energy Science, Kyoto University

-1

Isomerization of poly-unsaturated fatty acid methyl esters

CisMethyl linolenate

O O

Supercritical Methanol (350oC/9min) CisTm= - 10 TransTm = 30

O O

TransMethyl linolenate

partly

An increase in melting point Deterioration in cold flow properties (?)

Sakas Laboratory, Graduate School of Energy Science, Kyoto University

Two-Step SCMeOH Method

(Saka-Dadan Process)
MeOH recovery
MeOH Water Sub-C Water (270oC/7MPa) Oils/fats Water layer Oil layer SC MeOH (270oC/7MPa) Waste water Glycerol

Purification

Biodiesel BDF

CH2 | CH OCOR2 | CH2 OCOR3 OCOR1

Step I: Hydrolysis
R1COOH

3H2O

R2COOH R3COOH

Triglyceride
R4COOH

Fatty acids

CH2 OH | CH OH | CH2 OH

Step II: Esterification

Fatty acid +
CH3OH R4COOCH3

Biodiesel

H2O

Arrhenius Plots for Transesterification, Hydrolysis and Esterification of Rapeseed Oil

Reaction rate constant (1/sec) 10
-1

350

300

250

200 ( C)
Tc (MeOH)

Tc (Water)
-2

10

270oC Hydrolysis Esterification

10

-3

Transesterification

10

-4

1.4

1.6

1.8

2.0

2.2

Temperature (1000/K)
Sakas Laboratory, Graduate School of Energy Science, Kyoto University

Direct Observation through Sapphire Window

MeOH Oil 240 Water Oil 280 MeOH + Fatty Acid 160 260 340 300 340 280 340

Transesterification
2 Phase Phase
(Low Temp)

(High Temp)

Hydrolysis
2 Phase
(Low Temp)

2 Phase

(High Temp)

Esterification
1 Phase Phase
(Low Temp)

(High Temp)

Sakas Laboratory, Graduate School of Energy Science, Kyoto University

Two-Step Biodiesel Production Process

(Hydrolysis Esterification Re-esterification)
Distillation Hydrolysis Water Hi Pres. Pump Phase Separation Re-Esterification Methanol Oil Phase (Fatty Acids) Water Phase (Glycerin) BDF Distillation Methanol Oils Esterification Methanol/ Water

Step II: Esterification

R4COOH

Fatty acid

CH3OH

Biodiesel

R4COOCH3

H2O

Reactions Involved in SC MeOH Methods

Oils/fats

Triglycerides

Fatty acids

Transesterification

Hydrolysis Fatty acids Esterification

One-Step (Saka) Two-Step (Saka-Dadan)

Methyl esters (BDF)

Sakas Laboratory, Graduate School of Energy Science, Kyoto University

Effect of Free Fatty Acid on Transesterification/ Esterification by Various Methods

100 Methyl esters (%) 80 60 40 20 0 0 10

SC MeOH Lipase-catalyzed Ion-Ex-catalyzed Acid-catalyzed

Alkali-catalyzed
20 30

Free fatty acid (%)

Sakas Laboratory, Graduate School of Energy Science, Kyoto University

Effect of Water on Transesterification/Esterification by Various Methods

100 Methyl esters (%) 80 60 40 20 0 0 5

SC MeOH

Alkali-catalyzed Acid-catalyzed Lipase-catalyzed Ion-ex-catalyzed

10 15 20 25 Water (%)
Sakas Laboratory, Graduate School of Energy Science, Kyoto University

Applicable Range of Different Methods in Water and Free Fatty Acid Contents in Various Oils/Fats
100
Fatty acids (wt%)
Lipase-catalyzed Ion-ex-catalyzed Dark oil Waste SC MeOH

oil

Waste palm oil

10 Acid-catalyzed
Used frying oil Virgin 1 oil Alkali-catalyzed

10 Water (wt%)

100

Sakas Laboratory, Graduate School of Energy Science, Kyoto University

Specification Standards of Biodiesel Fuel

Density (15oC) Viscosity (40oC) Pour point CFPP Carbon residue (10%) Cetane number Water ppm oC Flash point MG % DG % TG % G % Total glycerol % Methanol % Na+K mg/kg Acidic value Iodine value Unit g/mL mm2/s oC oC % Kyoto 0.86 ~ 0.90 3.5 ~ 5.0 < 7.5 <5 < 0.30 > 51 < 500 > 100 < 0.8 < 0.2 < 0.2 < 0.02 < 0.25 < 0.2 <5 < 0.5 < 120 EU 0.86 ~ 0.90 3.5 ~ 5.0 < 0.30 > 51 < 500 > 101 < 0.8 < 0.2 < 0.2 < 0.02 < 0.25 < 0.2 <5 < 0.5 < 120 US 0.88 1.9 ~ 6.0 < 0.50 (100%) > 47 < 500 > 130 < 0.02 < 0.24 -

Sakas Laboratory, Graduate School of Energy Science, Kyoto University

Thank you for your attention!

Kyoto University 21 COE Program Grant-in-Aid for Scientific Research (B)(2) NEDO for High Efficiency Bioenergy Conv Projects

Sakas Laboratory, Graduate School of Energy Science, Kyoto University