Beruflich Dokumente
Kultur Dokumente
Thailand
Shiro Saka
Graduate School of Energy Science Kyoto University Kyoto, Japan
Waste Oil/fat
Removal of water
Alkali/MeOH MeOH
Water
Removal of water
Additives
BIODIESEL
Heat
Glycerol Separation
Heat
Heat
Reaction
Post-treatment
3CH3OH
Triglyceride
Biodiesel
Saponification
R4COOH
R4COOK
H2O
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
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.
24
LiquidMeOH MeOH SC
Pressure (MPa)
23 22 21 20 19 368
A
C.P.
GasMeOH
370 372 374 376
Temperature ()
Transesterification
CH2OCOR1 CHOCOR2 CH2OCOR3 Triglyceride R4COOH + Free fatty acid CH3OH No catalyst + 3CH3OH No catalyst R1COOCH3 R2COOCH3 R3COOCH3 Biodiesel R4COOCH3 Biodiesel +
Esterification
H2O
350oC/9min (One-step)
ester (C=O) ester (C-O) alkyl (C-H) cis (C=C) trans (C=C)
cis (C=C)
800
800
600
-1
-1
CisMethyl linolenate
O O
O O
TransMethyl linolenate
partly
Purification
Biodiesel BDF
Step I: Hydrolysis
R1COOH
3H2O
R2COOH R3COOH
Triglyceride
R4COOH
Fatty acids
CH2 OH | CH OH | CH2 OH
Biodiesel
H2O
350
300
250
200 ( C)
Tc (MeOH)
Tc (Water)
-2
10
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
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)
Fatty acid
CH3OH
Biodiesel
R4COOCH3
H2O
Triglycerides
Fatty acids
Transesterification
Alkali-catalyzed
20 30
SC MeOH
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
10 Acid-catalyzed
Used frying oil Virgin 1 oil Alkali-catalyzed
10 Water (wt%)
100
Kyoto University 21 COE Program Grant-in-Aid for Scientific Research (B)(2) NEDO for High Efficiency Bioenergy Conv Projects