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The continuous production of biodiesel (fatty acid methyl esters) by the transesterification reaction of coconut
oil and palm kernel oil was studied in supercritical methanol without using any catalyst. Experiments were
carried out in a tubular flow reactor, and reactions were studied at 270, 300, and 350 °C at a pressure of 10
and 19 MPa with various molar ratios of methanol-to-oils from 6 to 42. It was found that the best condition
to produce methyl esters from coconut oil and palm kernel oil was at a reaction temperature of 350 °C, molar
ratio of methanol-to-vegetable oil of 42, and space time 400 s. The % methyl ester conversions were 95 and
96 wt % for coconut oil and palm kernel oil, respectively. The regression models by the least-squares method
were adequate to predict % methyl ester conversion with temperature, molar ratio of methanol-to-oil, and
space time as the main effects. The produced methyl ester fuel properties met the specification of the ASTM
biodiesel standards.
TcmVcm ) ∑i ∑j xixjTcijVcij )
xi2TciVci + 2xixjTcijVcij + xj2TcjVcj (2)
Table 2. Standard Test Methods for Oil and Fuel Properties atm and 677 °C, 5.8 atm, respectively. The critical temperature
items AOCS test no. ASTM test no. and pressure of the mixtures of oil and methanol are calculated
acid value (mg of KOH/g of oil) Cd 3D-63
using eqs 2-9, and the values are shown in Table 5.
saponification value Cd 3B-76 At a molar ratio of methanol-to-oils of 6, the critical
(mg of KOH/g of oil) temperatures of mixtures of CCO and PKO with methanol were
fatty acid composition Ce 2-66 396.0 and 415.6 °C, respectively. As the methanol content in
higher heating value (MJ/kg) D240 mixture increases, the critical temperature decreases, while the
kinematic viscosity (mm2/s) D445
flash point (°C) D93 critical pressure increases. These properties are used to better
sp.gr. 15.6 °C D1298 explain the effect of operating conditions in the following
cetane No. D976 sections.
3.3. Effect of Temperature. (1) % Methyl ester conversion
Table 3. Properties of Coconut Oil, Palm Kernel Oil, and Low
Speed Diesel Fuel was calculated from GC analyses and standardization by the
following equation:
coconut palm kernel low speed
properties oil oil diesel fuel WME
sp.gr. 15.6 °C 0.919 0.925 0.836 % methyl ester conversion ) × 100 (10)
WFA
higher heating value (MJ/kg) 38.43 38.59 46.0
kinematic viscosity (mm2/s) 27.0 31.1 3.4
where WME is the weight of methyl ester in liquid product that
flash point (°C) 231 264 77
acid value (mg of KOH/g of oil) 16 31 - is obtained from gas chromatography; and WFA is the weight
saponification value 204 244 - of fatty acid in each vegetable oil (Table 4).
(mg of KOH/g of oil) (2) Space time was calculated from the oil and methanol flow
rates to obtain the real gas volumes employing the compress-
Table 4. Fatty Acid Composition in Coconut and Palm Kernel Oil
Samples (Mass % of Fatty Acids) as Analyzed by AOCS Ce - 2 - ibility factor, Z, obtained by the Pitzer method.13
66 Standard Coconut Oil. Figure 2a-d shows the effect of temperature
C in fatty coconut palm on % methyl ester conversion during various space times at
acids: C in oil % kernel oil increasing molar ratios of methanol-to-oils of 42, 24, 12, and
fatty acid formula double bonds MW mass % mass 6, respectively. By increasing the temperature from 270 to 300
caproic acid C5H11COOH C6:0 116 0.39 - and 350 °C, the % methyl ester conversion increased. At the
caprylic acid C7H15COOH C8:0 144 5.75 3.77 space time of 400 s and molar ratio of methanol-to-oil at 42, %
capric acid C9H19COOH C10:0 172 5.09 3.67
lauric acid C11H23COOH C12:0 200 44.56 48.38 methyl ester conversion increased from 50 to 85 and 95% when
myristic acid C13H27COOH C14:0 228 19.08 17.37 the reaction temperature increased from 270 to 300 and 350
palmitic acid C15H31COOH C16:0 256 10.04 9.13 °C. This indicates that, at higher temperatures of 300 and 350
stearic acid C17H35COOH C18:0 284 3.57 2.72
oleic acid C17H33COOH C18:1 282 8.8 12.56
°C, the conversion rate is higher than that at 270 °C. One can
linoleic acid C17H31COOH C18:2 280 2.72 2.4 use the calculated critical temperature (Table 5) to better explain
total 100 100 this effect. At the molar ratio of methanol-to-oil of 42, the
critical temperature of the mixture is 282 °C. This means that
3. Results and Discussion the system at 270 °C was a little below the critical temperature.
At this temperature, the conversion rate would be low, presum-
3.1. Vegetable Oil Properties. The vegetable oil properties, ably due to the subcritical state or the instability of the
together with low speed diesel fuel, are given in Table 3, and supercritical state of mixture.14
fatty acid compositions of the vegetable oil samples are given Palm Kernel Oil. Figure 3a-d shows the effect of temper-
in Table 4. ature on % methyl ester conversion during various space times
From Table 3, it is clear that both CCO and PKO had lower at palm kernel molar ratios of methanol-to-oil of 42, 24, 12,
heating values and much higher viscosities than those of low and 6, respectively. By increasing the temperature from 270 to
speed diesel fuel. This would indicate troublesome atomization 300 and 350 °C, % methyl ester conversions increased. At the
and poor engine performance if these oils are used as neat fuels. space time of 400 s and molar ratios of methanol-to-oil at 42,
Table 4 shows that both the CCO and PKO samples contained % methyl ester conversions increased from 38 to 94 and 96%
lauric acid as the major fatty acid. The CCO sample contained when the reaction temperature increased from 270 to 300 and
44.56% lauric, 19.08% myristic, and 10.04% palmitic acids, 350 °C, respectively. Again, this indicates that, at higher
while the PKO sample contained 48.38% lauric, 17.37% temperatures of 300 and 350 °C, the conversion rate is higher
myristic, and 12.56% oleic acids, respectively. than that at 270 °C.
3.2. Critical Property Estimation. The critical temperatures 3.4. Effect of Molar Ratio of Methanol-to-Oil. At 350 °C,
and pressures of CCO and PKO were calculated as 629 °C, 6.1 % methyl ester conversions at the molar ratio of methanol-to-
Table 5. Calculated Critical Properties of Oil and Methanol Mixture at Various Compositionsa
molar ratio of methanol-to-oil
6 12 24 42
properties PKO CCO PKO CCO PKO CCO PKO CCO
Tc, K 688.60 669.02 632.72 619.08 587.75 579.00 561.10 555.35
Tc, °C 415.45 395.87 359.57 345.93 314.60 305.85 287.95 282.20
Pc, atm 37.22 37.26 50.36 50.31 61.80 61.68 68.52 68.39
Vc, L/mol 0.33 0.32 0.23 0.22 0.17 0.17 0.15 0.15
zc 0.22 0.22 0.22 0.22 0.22 0.22 0.22 0.22
a T , P , V , and z of methanol: 512.6 K, 79.9 atm, 118.0 L/mol, and 0.224, respectively. Calculated T , P , V , and z of coconut oil: 879.93 K, 6.21
c c c c c c c c
atm, 2.366 L/mol, and 0.20; palm kernel oil: 926.12 K, 5.936 atm, 2.476 L/mol, and 0.19, respectively.
Production of Biodiesel from Vegetable Oils Energy & Fuels, Vol. 20, No. 2, 2006 815
Figure 2. Effect of temperature on the % methyl ester conversion at various molar ratios of methanol-to-coconut oil, P ) 19 MPa. (a) 42, (b) 24,
(c) 12, (d) 6.
Figure 3. Effect of temperature on the % methyl ester conversion at various molar ratios of methanol-to-palm kernel oil, P ) 19 MPa. (a) 42, (b)
24, (c) 12, (d) 6.
coconut oil of 42, 24, 12, and 6 are plotted against space time, At a space time of 450 s, % methyl ester conversions
as shown in Figure 4. When the methanol content in the increased from 50, 52, 93, to 95% when molar ratio of methanol-
supercritical fluids increased, % methyl ester conversion also to-oil increased in the mixture from 6, 12, 24, to 42, respectively.
increased. The higher methanol content is favorable not only The same conclusion holds true for palm kernel oil, as shown
because more molecules of methanol surround the oil molecules in Figure 5. When the methanol content in the supercritical fluid
but also because it contributes to the lower critical temperature increased, % methyl ester conversion also increased. At a space
of the mixture. time of 450 s, % methyl ester conversions increased from 48,
50, and 85 to 96% when molar ratio of methanol-to-oil increased
(13) Çengel, Y. A.; Boles, M. A. Thermodynamics: An Engineering
Approach; McGraw-Hill: Boston, 1998; p 81. in the mixture from 6, 12, and 24 to 42, respectively. The
(14) Cao, W.; Han H.; Zhang J. Fuel 2005, 84, 347-351. maximum methyl ester conversion is 96% at a molar ratio of
816 Energy & Fuels, Vol. 20, No. 2, 2006 Bunyakiat et al.
SD 12.93 R2 0.81
mean 44.39 adjusted R2 0.79
CV 29.13 predicted R2 0.77
PRESS 11720 adequate precision 25.52
SD 10.77 R2 0.85
mean 51.73 adjusted R2 0.83
Figure 5. Effect of the molar ratio of methanol-to-palm kernel oil on CV 20.82 predicted R2 0.73
the % methyl ester conversion at 350 °C, 19.0 MPa. PRESS 7124 adequate precision 22.29
Table 6. Analysis of Variance of Coconut Oil Regression Model
table shows that both main effects (temperature, molar ratio of
source sum of squares DF mean square F value P value
methanol-to-oil, and space time) and second-order effect (tem-
model 41780 9 4641 28.05 <0.0001 perature and space time) are significant in the regression model
A 4862 1 4862 29.38 <0.0001
B 4127 1 4127 24.94 <0.0001 but have no interaction effect. Thus, the regression model with
C 8345 1 8345 50.44 <0.0001 respect to % methyl ester conversion in terms of coded variables
A2 2755 1 2755 16.65 0.0001 as shown in eqs 11-13 for coconut oil and palm kernel oil are
B2 128.7 1 128.7 0.78 0.3817
C2 2974 1 2974 17.97 <0.0001
simplified as shown in eqs 14 and 15, respectively, where
AB 53.10 1 53.10 0.32 0.5734
AC
BC
residual
536.1
314.9
8935
1
1
54
536.1
314.9
165.5
3.24
1.90
0.0775
0.1734
A)
Temperature (°C) - (350 +2 270) )
total 50710 63 (350 -2 270)
methanol-to-oil of 42. However, it is possible to obtain high
Temperature (°C) - 310
(11)
conversion at molar ratio of methanol-to-oil of 24, by increasing 40
(42 2+ 6) )
space time to around 800 s. Nevertheless, at a higher molar
ratio of methanol-to-oil of 42, it also needed almost twice as Molar ratio of MeOH-to-oil -
much methanol and longer separation and evaporation steps than B)
at molar ratio of methanol-to-oil of 24, and this might not be a
favorable condition when putting this process into a larger scale
(42 2- 6)
Molar ratio of MeOH-to-oil - 24
production. Taking this into consideration, the methyl ester (12)
sample obtained at a molar ratio of methanol-to-oil of 24 was 18
used for fuel properties testing.
3.5. Effect of Pressure. The effect of pressure was investi-
C)
Space time (s) - (20002+ 30) )
gated for transesterification of coconut oil at 350 °C, molar ratio
of methanol-to-oil of 24, and a space time of 440 s. At lower
pressure of 10 MPa, % methyl ester conversion was 65.82%,
(20002- 30)
Space time (s) - 1015
while at higher pressure of 19 MPa, % methyl ester conversion (13)
increased only slightly to 67.64%. Nonetheless, in this work,
985
the experiments were carried out at the higher pressure of 19
MPa, and as at higher pressure, fluid density is also high, and
providing a more favorable condition for the interaction between
molecules. xCCO % ME conversion ) 10.82 + 1.31A + 1.25B +
3.6. Fitting Regression Model by the Least-Squares 2.46C - 1.45A2 - 2.87C2 (14)
Method. The regression model of experimental data with respect
to % methyl ester conversion can be determined by the least- xPKO % ME conversion ) 10.21 + 1.62A + 1.48B +
squares method.15 From Tables 6 and 7, the analysis of variance 2.14C - 1.65A2 - 2.17C2 (15)
Production of Biodiesel from Vegetable Oils Energy & Fuels, Vol. 20, No. 2, 2006 817
Table 9. Properties of CCO and PKO Biodiesel Products at 350 °C and 19.0 MPa; Molar Ratio of Methanol-to-Oil Is 24 in Comparison with
Low Speed Diesel and Standard Biodiesel Fuels (ASTM D6751-02)
specification obtained samples
method of low speed biodiesel low speed CCO PKO
properties analysis diesel (B100) diesel biodiesel biodiesel
specific gravity (15.6 °C) ASTM D1298 0.92 max - 0.836 0.8796 0.8801
cetane No. ASTM D976 45 min 40 min 55 42 44
flash point (°C) ASTM D93 52 min 100 min 77 120 156
higher heating value (MJ/kg) ASTM D240 45.2 min - 46.0 39.4 38.3
kinematic viscosity (mm2/s) ASTM D445 8 max 1.9-6.5 3.4 3.81 4.8