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Continuous Production of Biodiesel via Transesterification from

Vegetable Oils in Supercritical Methanol


Kunchana Bunyakiat, Sukunya Makmee, Ruengwit Sawangkeaw, and
Somkiat Ngamprasertsith*
Fuels Research Center, Department of Chemical Technology, Faculty of Science,
Chulalongkorn UniVersity, Bangkok 10330, Thailand

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.

1. Introduction
Biodiesel (fatty acid alkyl esters) is an alternative fuel for
diesel engines. It is an alcohol ester product from the transesterification of triglycerides in vegetable oils or animal fats.
This can be accomplished by reacting lower alcohols such as
methanol or ethanol with triglycerides. The reaction proceeds
well in the presence of some homogeneous catalysts such as
sodium hydroxide and sulfuric acid, or heterogeneous catalysts
such as metal oxides or carbonates or enzymes. Sodium
hydroxide is very well accepted and widely used because of its
low cost and high product yield, but the solubility of potassium
hydroxide in methanol is higher than that of sodium hydroxide.
Although the reaction system is simple, one drawback that
prevents wider use of biodiesel is its high energy consumption
and production cost, partly resulting from the complicated
separation and purification of the product. Therefore, to perform
the reaction without the presence of a catalyst is one effective
way to reduce the biodiesel cost. Various biodiesel production
processes employing homogeneous, heterogeneous catalytic, and
noncatalytic supercritical methods as reported in the literature
are summarized in Table 1.1-5
Recently, there have been some reports on the noncatalytic
transesterification reaction employing supercritical methanol
conditions.3,6,7 Saka and Kusdiana3,6 have proposed that the
* Corresponding author. Fax: +66-2255-5831. E-mail: somkiat@
sc.chula.ac.th.
(1) Ma, F.; Hanna, A. M. Bioresour. Technol. 1999, 70, 1-15.
(2) Branwal, B. K.; Sharma, M. P. Renewable Sustainable Energy ReV.
2005, 9, 363-378.
(3) Saka, S.; Kusdiana, D. Fuel 2001, 80, 225-231.
(4) Du, W.; Xu, Y.; Liu, D.; Zeng, J. J. Mol. Catal. B: Enzym. 2004,
30, 125-129.
(5) Noureddini, H.; Gao, X.; Philkana, R. S. Bioresour. Technol. 2005,
96, 769-777.
(6) Kusdiana, D.; Saka, S. Fuel 2001, 80, 693-698.
(7) Demirbas, A. Energy ConVers. Manage. 2002, 43, 2349-2356.

reactions of rapeseed oil were complete within 240 s at 350


C, 19 MPa, and molar ratio of methanol-to-oil at 42. Demirbas7
studied the transesterification reaction under supercritical methanol employing six potential vegetable oils (cottonseed, hazelnut
kernels, poppy seed, rapeseed, safflower seed and sunflower
seed) at varying molar ratios of alcohol-to-vegetable oil and
reaction temperatures. It was found that, when the molar ratio
of methanol-to-oil was 24, at 250 C, and at 300-s reaction time,
the best methyl ester yield from hazelnut kernels and cotton
seed oil was 95%. The properties of biodiesel were also tested
and found to be similar to those of No. 2 diesel fuel but were
slightly more viscous.
This study was carried out to investigate the effects of
temperature and molar ratio of methanol-to-oil on the biodiesel
production from palm kernel oil and coconut oil with supercritical methanol in a continuous system. The critical properties
of the mixtures at various molar ratios of methanol-to-oils were
calculated in the following manner. First, the critical properties
of a vegetable oil that is a mixture of various triglycerides is
represented by a single pseudo-triacylglyceride with the following molecular structure:8

[(CH2COO)2CHCOO](CHdCH)m(CH2)n(CH3)3

(1)

The term in brackets represents the triglyceride functional


group. The values of m and n reproduce the molecular weight
and degree of unsaturation of the vegetable oil and are calculated
from the fatty acid composition of the oil. The critical
temperature and pressure were then calculated using Lydersens
method of group contributions.9 Finally, the critical temperature
and pressure of the mixtures of oil and methanol were calculated
(8) Espinosa, S.; Fornari, T.; Bottini, S. B.; Brignole, E. A. J. Supercrit.
Fluids 2002, 23, 91-102.
(9) Chopey, N. P. Handbook of Chemical Engineering Calculation;
McGraw-Hill: New York, 1994; pp 1-8.

Table 1. Various Biodiesel Production Processes1-5


homogeneous
catalytic method

heterogeneous
catalytic method

enzymatic
method

SC MeOH
method

0.5-3 h
0.1-5.0 MPa, 30-200 C
metal oxide or carbonate
methyl esters
normal
methanol

1-8 h
0.1 MPa, 35-40 C
immobilized lipase
methyl esters
low to high
methanol or methyl acetate

120-240 s
>8.09 MPa, >239.4 C
none
methyl esters
high
methanol

waste
glycerin purity

0.5-4 h
0.1 MPa, 30-65 C
acid or alkali
saponified products
normal to high
methanol, catalyst,
and saponified product
wastewater
low

none
low to normal

none
high

process

complicated

complicated

none
normal or triacetylglycerol
as byproduct
complicated

reaction time
reaction conditions
catalyst
free fatty acids
yield
removal for purification

simple

by Lorentz-Berthelot-type mixing rules10 as the following


equations:

TcmVcm )

i j xixjTcijVcij )
xi2TciVci + 2xixjTcijVcij + xj2TcjVcj (2)

Vcm )

i j xixjVcij ) xi2Vci + 2xixjVcij + xj2Vcj

(3)

i j xixjzcij ) xi2zci + 2xixjzcij + xj2zcj

(4)

zcmRTcm
Vcm

(5)

zcm )

Pcm )

The terms Vcij, Tcij, and zcij were calculated by the combining
rules as the following equations:

Tcij ) xTciTcj
Pcij )

1
P P V V
Vcijx ci cj ci cj

(6)
(7)

zcij ) 0.5(zci + zcj)

(8)

1
Vcij1/3 ) (Vci1/3 + Vcj1/3)
2

(9)

where i and j are subscripts for vegetable oil and methanol,


respectively, x is the mole fraction of vegetable oil or methanol,
Tc is the critical temperature of vegetable oil or methanol, Vc is
the molar volume of vegetable oil or methanol, zc is the
compressibility factor of vegetable oil or methanol, Tcm is the
critical temperature of vegetable oil and methanol mixture, Vcm
is the molar volume of vegetable oil and methanol mixture, zcm
is the compressibility factor of vegetable oil and methanol
mixture, and Pcm is the critical pressure of vegetable oil and
methanol mixture.
2. Experimental Methods
Two potential vegetable oils were studied: coconut oil (CCO)
and palm kernel oil (PKO). The CCO was supplied by Tab Sakae
Co. Ltd., and the PKO was supplied by Cheeva Mongkol Co. Ltd.
Both samples were warmed and filtered prior to use. Analytical
grade methanol (Fisher) was used with no further purification. The
experiments were performed using a tubular flow reactor shown
in Figure 1.
The oil and methanol were pumped in two different lines by
high-pressure high-performance liquid chromatographic pumps
(Jasco, model PU-1580) up to 19 MPa (total flow rate of 1.5-9.0
(10) Walas, S. M. Phase Equilibria in Chemical Engineering; Butterworth: Boston, 1985; pp 29-33.

Figure 1. Schematic diagram of the continuous transesterification


reactor system. 1. High-pressure pumps, 2. methanol reservoir, 3.
vegetable oil reservoir, 4. nitrogen cylinder, 5. preheaters, 6. reactor,
7. salt bath, 8. temperature monitoring system, 9. cooling bath, 10.
inline filter, 11. pressure monitoring system, 12. back pressure regulator,
and 13. sample collector.

mL/min depending on space time and molar ratio of methanol-tooil), preheated while flowing in the preheat lines (SUS316 tubing
of 1/8-in. o.d., 0.035-in. thickness, and 2-m length). After being
preheated, the two lines were mixed at the reactor inlet using a
SUS316 mixing tee, and the temperature of the fluid was monitored
directly using a thermocouple located within this mixing tee. The
reactor was constructed from a 5.5-m length of 3/8-in. o.d., 0.035in. thickness SUS316 tubing. The preheat lines and the reactor were
immersed in an electrically heated salt bath. The fluid product
exiting from the reactor was promptly cooled by an external watercooling bath and depressurized using a back-pressure regulator.
After pressure and temperature were constant, approximately 10
mL of liquid product was collected, and then methanol was
evaporated by a rotary evaporator. The liquid product was checked
for % methyl esters by gas chromatography to ensure that the system
reached steady state, which was indicated by a constant value, after
more than 90 min. The product was then collected until the total
volume was sufficient for further analysis.
The final liquid product was collected and left to settle for several
hours, preferably overnight, to ensure complete separation. Two
liquid phases were obtained: ester and crude glycerin. The top ester
layer was separated by a separatory funnel and put in a rotary
evaporator to remove any excess methanol. The % methyl ester in
liquid product was then analyzed by gas chromatography (Shimadzu
model GC14BSPL) with a flame ionization detector. A 30-m-long,
0.25-mm-diameter capillary column coated with poly(ethylene
glycol) was used with helium as a carrier gas. The ester product
was diluted with n-heptane (analytical grade) before injection and
standardized by standard methyl esters. Chemical analyses of the
oil samples were performed according to AOCS standards,11 while
the other standard test methods for fuel properties were performed
according to ASTM standards,12 as shown in Table 2.
(11) Methods Cd 3d-63, Cd 3b-73, and Ce 2-66. American Oil Chemical
Society: Champaign, IL, 1997.
(12) Methods D1298, D976, D93, D240, and D445. American Society
for Testing and Materials Annual Book of ASTM Standards, Part 26;
ASTM: Philadelphia, PA, 2004.

Table 2. Standard Test Methods for Oil and Fuel Properties


items

AOCS test no.

acid value (mg of KOH/g of oil)


saponification value
(mg of KOH/g of oil)
fatty acid composition
higher heating value (MJ/kg)
kinematic viscosity (mm2/s)
flash point (C)
sp.gr. 15.6 C
cetane No.

Cd 3D-63
Cd 3B-76

ASTM test no.

Ce 2-66
D240
D445
D93
D1298
D976

Table 3. Properties of Coconut Oil, Palm Kernel Oil, and Low


Speed Diesel Fuel
properties

coconut
oil

palm kernel
oil

low speed
diesel fuel

0.919
38.43
27.0
231
16
204

0.925
38.59
31.1
264
31
244

0.836
46.0
3.4
77
-

sp.gr. 15.6 C
higher heating value (MJ/kg)
kinematic viscosity (mm2/s)
flash point (C)
acid value (mg of KOH/g of oil)
saponification value
(mg of KOH/g of oil)

Table 4. Fatty Acid Composition in Coconut and Palm Kernel Oil


Samples (Mass % of Fatty Acids) as Analyzed by AOCS Ce - 2 66 Standard

fatty acid

formula

C in fatty
acids: C in
double bonds

caproic acid
caprylic acid
capric acid
lauric acid
myristic acid
palmitic acid
stearic acid
oleic acid
linoleic acid

C5H11COOH
C7H15COOH
C9H19COOH
C11H23COOH
C13H27COOH
C15H31COOH
C17H35COOH
C17H33COOH
C17H31COOH

C6:0
C8:0
C10:0
C12:0
C14:0
C16:0
C18:0
C18:1
C18:2

MW

coconut
oil %
mass

palm
kernel oil
% mass

116
144
172
200
228
256
284
282
280

0.39
5.75
5.09
44.56
19.08
10.04
3.57
8.8
2.72

3.77
3.67
48.38
17.37
9.13
2.72
12.56
2.4

total

100

100

3. Results and Discussion


3.1. Vegetable Oil Properties. The vegetable oil properties,
together with low speed diesel fuel, are given in Table 3, and
fatty acid compositions of the vegetable oil samples are given
in Table 4.
From Table 3, it is clear that both CCO and PKO had lower
heating values and much higher viscosities than those of low
speed diesel fuel. This would indicate troublesome atomization
and poor engine performance if these oils are used as neat fuels.
Table 4 shows that both the CCO and PKO samples contained
lauric acid as the major fatty acid. The CCO sample contained
44.56% lauric, 19.08% myristic, and 10.04% palmitic acids,
while the PKO sample contained 48.38% lauric, 17.37%
myristic, and 12.56% oleic acids, respectively.
3.2. Critical Property Estimation. The critical temperatures
and pressures of CCO and PKO were calculated as 629 C, 6.1

atm and 677 C, 5.8 atm, respectively. The critical temperature


and pressure of the mixtures of oil and methanol are calculated
using eqs 2-9, and the values are shown in Table 5.
At a molar ratio of methanol-to-oils of 6, the critical
temperatures of mixtures of CCO and PKO with methanol were
396.0 and 415.6 C, respectively. As the methanol content in
mixture increases, the critical temperature decreases, while the
critical pressure increases. These properties are used to better
explain the effect of operating conditions in the following
sections.
3.3. Effect of Temperature. (1) % Methyl ester conversion
was calculated from GC analyses and standardization by the
following equation:

% methyl ester conversion )

WME
100
WFA

(10)

where WME is the weight of methyl ester in liquid product that


is obtained from gas chromatography; and WFA is the weight
of fatty acid in each vegetable oil (Table 4).
(2) Space time was calculated from the oil and methanol flow
rates to obtain the real gas volumes employing the compressibility factor, Z, obtained by the Pitzer method.13
Coconut Oil. Figure 2a-d shows the effect of temperature
on % methyl ester conversion during various space times at
increasing molar ratios of methanol-to-oils of 42, 24, 12, and
6, respectively. By increasing the temperature from 270 to 300
and 350 C, the % methyl ester conversion increased. At the
space time of 400 s and molar ratio of methanol-to-oil at 42, %
methyl ester conversion increased from 50 to 85 and 95% when
the reaction temperature increased from 270 to 300 and 350
C. This indicates that, at higher temperatures of 300 and 350
C, the conversion rate is higher than that at 270 C. One can
use the calculated critical temperature (Table 5) to better explain
this effect. At the molar ratio of methanol-to-oil of 42, the
critical temperature of the mixture is 282 C. This means that
the system at 270 C was a little below the critical temperature.
At this temperature, the conversion rate would be low, presumably due to the subcritical state or the instability of the
supercritical state of mixture.14
Palm Kernel Oil. Figure 3a-d shows the effect of temperature on % methyl ester conversion during various space times
at palm kernel molar ratios of methanol-to-oil of 42, 24, 12,
and 6, respectively. By increasing the temperature from 270 to
300 and 350 C, % methyl ester conversions increased. At the
space time of 400 s and molar ratios of methanol-to-oil at 42,
% methyl ester conversions increased from 38 to 94 and 96%
when the reaction temperature increased from 270 to 300 and
350 C, respectively. Again, this indicates that, at higher
temperatures of 300 and 350 C, the conversion rate is higher
than that at 270 C.
3.4. Effect of Molar Ratio of Methanol-to-Oil. At 350 C,
% 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
Tc, C
Pc, atm
Vc, L/mol
zc

688.60
415.45
37.22
0.33
0.22

669.02
395.87
37.26
0.32
0.22

632.72
359.57
50.36
0.23
0.22

619.08
345.93
50.31
0.22
0.22

587.75
314.60
61.80
0.17
0.22

579.00
305.85
61.68
0.17
0.22

561.10
287.95
68.52
0.15
0.22

555.35
282.20
68.39
0.15
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.

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,
as shown in Figure 4. When the methanol content in the
supercritical fluids increased, % methyl ester conversion also
increased. The higher methanol content is favorable not only
because more molecules of methanol surround the oil molecules
but also because it contributes to the lower critical temperature
of the mixture.
(13) C engel, Y. A.; Boles, M. A. Thermodynamics: An Engineering
Approach; McGraw-Hill: Boston, 1998; p 81.
(14) Cao, W.; Han H.; Zhang J. Fuel 2005, 84, 347-351.

At a space time of 450 s, % methyl ester conversions


increased from 50, 52, 93, to 95% when molar ratio of methanolto-oil increased in the mixture from 6, 12, 24, to 42, respectively.
The same conclusion holds true for palm kernel oil, as shown
in Figure 5. When the methanol content in the supercritical fluid
increased, % methyl ester conversion also increased. At a space
time of 450 s, % methyl ester conversions increased from 48,
50, and 85 to 96% when molar ratio of methanol-to-oil increased
in the mixture from 6, 12, and 24 to 42, respectively. The
maximum methyl ester conversion is 96% at a molar ratio of

Table 7. Analysis of Variance of Palm Kernel Oil Regression Model

Figure 4. Effect of the molar ratio of methanol-to-coconut oil on the


% methyl ester conversion at 350 C, 19.0 MPa.

source

sum of squares

DF

mean square

F value

P value

model
A
B
C
A2
B2
C2
AB
AC
BC
residual

23160
4206
1805
1964
2781
1.13
91.69
216.0
202.6
322.3
3388

9
1
1
1
1
1
1
1
1
1
31

2573
4206
1805
1964
2781
1.13
91.69
216.0
202.6
322.3
109.3

23.54
38.48
16.52
17.97
25.45
0.01
0.84
1.98
1.85
2.95

<0.0001
<0.0001
0.0003
0.0002
<0.0001
0.9197
0.3668a
0.1697
0.1832
0.0959

total

26550

40

Significant when ignoring the interaction effect.


Table 8. Statistical Values of Regression Models
coconut oil regression model

SD
mean
CV
PRESS

12.93
44.39
29.13
11720

R2
adjusted R2
predicted R2
adequate precision

0.81
0.79
0.77
25.52

palm kernel oil regression model

Figure 5. Effect of the molar ratio of methanol-to-palm kernel oil on


the % methyl ester conversion at 350 C, 19.0 MPa.

SD
mean
CV
PRESS

10.77
51.73
20.82
7124

R2
adjusted R2
predicted R2
adequate precision

0.85
0.83
0.73
22.29

Table 6. Analysis of Variance of Coconut Oil Regression Model


source

sum of squares

DF

mean square

F value

P value

model
A
B
C
A2
B2
C2
AB
AC
BC
residual

41780
4862
4127
8345
2755
128.7
2974
53.10
536.1
314.9
8935

9
1
1
1
1
1
1
1
1
1
54

4641
4862
4127
8345
2755
128.7
2974
53.10
536.1
314.9
165.5

28.05
29.38
24.94
50.44
16.65
0.78
17.97
0.32
3.24
1.90

<0.0001
<0.0001
<0.0001
<0.0001
0.0001
0.3817
<0.0001
0.5734
0.0775
0.1734

total

50710

63

methanol-to-oil of 42. However, it is possible to obtain high


conversion at molar ratio of methanol-to-oil of 24, by increasing
space time to around 800 s. Nevertheless, at a higher molar
ratio of methanol-to-oil of 42, it also needed almost twice as
much methanol and longer separation and evaporation steps than
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
production. Taking this into consideration, the methyl ester
sample obtained at a molar ratio of methanol-to-oil of 24 was
used for fuel properties testing.
3.5. Effect of Pressure. The effect of pressure was investigated 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%,
while at higher pressure of 19 MPa, % methyl ester conversion
increased only slightly to 67.64%. Nonetheless, in this work,
the experiments were carried out at the higher pressure of 19
MPa, and as at higher pressure, fluid density is also high,
providing a more favorable condition for the interaction between
molecules.
3.6. Fitting Regression Model by the Least-Squares
Method. The regression model of experimental data with respect
to % methyl ester conversion can be determined by the leastsquares method.15 From Tables 6 and 7, the analysis of variance

table shows that both main effects (temperature, molar ratio of


methanol-to-oil, and space time) and second-order effect (temperature and space time) are significant in the regression model
but have no interaction effect. Thus, the regression model with
respect to % methyl ester conversion in terms of coded variables
as shown in eqs 11-13 for coconut oil and palm kernel oil are
simplified as shown in eqs 14 and 15, respectively, where

(350 +2 270) )
(350 -2 270)

Temperature (C) A)

Temperature (C) - 310


(11)
40

Molar ratio of MeOH-to-oil B)

(42 2- 6)

(42 2+ 6) )

Molar ratio of MeOH-to-oil - 24


(12)
18

(20002+ 30) )
(20002- 30)

Space time (s) C)

Space time (s) - 1015


(13)
985

and

xCCO % ME conversion ) 10.82 + 1.31A + 1.25B +


2.46C - 1.45A2 - 2.87C2 (14)
xPKO % ME conversion ) 10.21 + 1.62A + 1.48B +
2.14C - 1.65A2 - 2.17C2 (15)

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

properties

method of
analysis

low speed
diesel

biodiesel
(B100)

low speed
diesel

CCO
biodiesel

PKO
biodiesel

specific gravity (15.6 C)


cetane No.
flash point (C)
higher heating value (MJ/kg)
kinematic viscosity (mm2/s)

ASTM D1298
ASTM D976
ASTM D93
ASTM D240
ASTM D445

0.92 max
45 min
52 min
45.2 min
8 max

40 min
100 min
1.9-6.5

0.836
55
77
46.0
3.4

0.8796
42
120
39.4
3.81

0.8801
44
156
38.3
4.8

Figure 6. Relationship between predicted % methyl ester conversion


from regression model of coconut oil versus % methyl ester conversion
from the experiment.

From eqs 14 and 15, all coefficients have a plus sign in the
first-order term, indicating that % methyl ester conversion
increases with these factors, conforming with the experimental
result shown in sections 3.3 and 3.4. The second-order terms
of A and C (temperature and space time) illustrate that there
are optimum points within the experimental condition range.
The regression models for coconut oil and palm kernel oil in
actual variables are shown in eqs 16 and 17, respectively.

xCCO % ME conversion ) -93.43 + 0.59T + 0.07M +


8.51 10-3 - 9.08 10-4T2 - 2.96 10-62 (16)
xPKO % ME conversion ) -107.91 + 0.68T + 0.08M +
6.72 10-3 - 1.03 10-3T2 - 2.24 10-62 (17)
where T ) temperature (270 to 350 C), M ) molar ratio of
methanol-to-oil (6 to 42), and ) space time (30-2000 s).
The statistical values of both regression models are given in
Table 8. From Table 8, the coefficients of determination (R2)
are 0.81 and 0.85 for coconut oil and palm kernel oil regression
model, respectively. The predicted % methyl ester conversions
from regression models of coconut oil and palm kernel oil versus
experimental result are shown in Figures 6 and 7, respectively.
In Figures 6 and 7, the relationship lies on the diagonal line,
and hence both regression models are adequate to predict %
methyl ester conversion from given factors (temperature, molar
ratio of methanol-to-oil, and space time).
3.7. Methyl Ester Properties. The final methyl ester products
at 350 C, 19.0 MPa, molar ratio of methanol-to-oil at 24, also
known as biodiesel, together with a low speed diesel fuel sample,
were tested for their fuel properties and compared to the
(15) Montgomery, D. C. Design and Analysis of Experiments; Wiley &
Sons: New York, 2001; pp 392-415.

Figure 7. Relationship between predicted % methyl ester conversion


from regression model of palm kernel oil versus % methyl ester
conversion from the experiment.

specification of low speed diesel fuel and biodiesel (B 100) as


specified in ASTM D6751-02. The results are shown in Table
9. Hence, CCO and PKO biodiesel properties are much
improved from those of vegetable oils, as the flash points and
viscosities are much reduced, and the specific gravities are
lower. All properties meet the biodiesel standard. This indicates
that biodiesel from CCO and PKO can readily replace low speed
diesel fuel.
4. Conclusions
Continuous transesterification of coconut oil and palm kernel
oil in supercritical methanol was successfully attempted. The
best conditions are 350 C, 19.0 MPa, molar ratio of methanolto-oil of 42, at a space time of 400 s. Percent methyl ester
conversions are 95 and 96% for coconut oil and palm kernel
oil, respectively. The regression models by the least-squares
method to predict % methyl ester conversion from coconut oil
and palm kernel oil show that the main effects (temperature,
molar ratio of methanol-to-oil, and space time) and secondorder effects (temperature and space time) are significant with
no interaction effect, and the coefficients of determination (R2)
are 0.81 and 0.85, respectively. Methyl ester products were
analyzed, and it was confirmed that their fuel properties met
the specification of biodiesel (B 100) as specified in ASTM
D6751-02.
Acknowledgment. We express our sincere appreciation to Tab
Sakae Co. Ltd. and Cheeva Mongkol Co. Ltd. for supplying the
coconut oil and palm kernel oil samples. We are also grateful for
the financial support from The Graduate School of Chulalongkorn
University, The Petroleum and Petrochemical Technology Consortium, Ministry of University Affairs, and the National Energy
and Policy Office.
EF050329B