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812 Energy & Fuels 2006, 20, 812-817

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

ReceiVed October 6, 2005. ReVised Manuscript ReceiVed December 8, 2005

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 reactions of rapeseed oil were complete within 240 s at 350


°C, 19 MPa, and molar ratio of methanol-to-oil at 42. Demirbas7
Biodiesel (fatty acid alkyl esters) is an alternative fuel for studied the transesterification reaction under supercritical metha-
diesel engines. It is an alcohol ester product from the trans- nol employing six potential vegetable oils (cottonseed, hazelnut
esterification of triglycerides in vegetable oils or animal fats. kernels, poppy seed, rapeseed, safflower seed and sunflower
This can be accomplished by reacting lower alcohols such as seed) at varying molar ratios of alcohol-to-vegetable oil and
methanol or ethanol with triglycerides. The reaction proceeds reaction temperatures. It was found that, when the molar ratio
well in the presence of some homogeneous catalysts such as of methanol-to-oil was 24, at 250 °C, and at 300-s reaction time,
sodium hydroxide and sulfuric acid, or heterogeneous catalysts the best methyl ester yield from hazelnut kernels and cotton
such as metal oxides or carbonates or enzymes. Sodium seed oil was 95%. The properties of biodiesel were also tested
hydroxide is very well accepted and widely used because of its and found to be similar to those of No. 2 diesel fuel but were
low cost and high product yield, but the solubility of potassium slightly more viscous.
hydroxide in methanol is higher than that of sodium hydroxide. This study was carried out to investigate the effects of
Although the reaction system is simple, one drawback that temperature and molar ratio of methanol-to-oil on the biodiesel
prevents wider use of biodiesel is its high energy consumption production from palm kernel oil and coconut oil with super-
and production cost, partly resulting from the complicated critical methanol in a continuous system. The critical properties
separation and purification of the product. Therefore, to perform of the mixtures at various molar ratios of methanol-to-oils were
the reaction without the presence of a catalyst is one effective calculated in the following manner. First, the critical properties
way to reduce the biodiesel cost. Various biodiesel production of a vegetable oil that is a mixture of various triglycerides is
processes employing homogeneous, heterogeneous catalytic, and represented by a single pseudo-triacylglyceride with the fol-
noncatalytic supercritical methods as reported in the literature lowing molecular structure:8
are summarized in Table 1.1-5
Recently, there have been some reports on the noncatalytic [(CH2COO)2CHCOO](CHdCH)m(CH2)n(CH3)3 (1)
transesterification reaction employing supercritical methanol
conditions.3,6,7 Saka and Kusdiana3,6 have proposed that the
The term in brackets represents the triglyceride functional
group. The values of m and n reproduce the molecular weight
* Corresponding author. Fax: +66-2255-5831. E-mail: somkiat@
sc.chula.ac.th.
and degree of unsaturation of the vegetable oil and are calculated
(1) Ma, F.; Hanna, A. M. Bioresour. Technol. 1999, 70, 1-15. from the fatty acid composition of the oil. The critical
(2) Branwal, B. K.; Sharma, M. P. Renewable Sustainable Energy ReV. temperature and pressure were then calculated using Lydersen’s
2005, 9, 363-378. method of group contributions.9 Finally, the critical temperature
(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, and pressure of the mixtures of oil and methanol were calculated
30, 125-129.
(5) Noureddini, H.; Gao, X.; Philkana, R. S. Bioresour. Technol. 2005, (8) Espinosa, S.; Fornari, T.; Bottini, S. B.; Brignole, E. A. J. Supercrit.
96, 769-777. Fluids 2002, 23, 91-102.
(6) Kusdiana, D.; Saka, S. Fuel 2001, 80, 693-698. (9) Chopey, N. P. Handbook of Chemical Engineering Calculation;
(7) Demirbas, A. Energy ConVers. Manage. 2002, 43, 2349-2356. McGraw-Hill: New York, 1994; pp 1-8.

10.1021/ef050329b CCC: $33.50 © 2006 American Chemical Society


Published on Web 02/04/2006
Production of Biodiesel from Vegetable Oils Energy & Fuels, Vol. 20, No. 2, 2006 813

Table 1. Various Biodiesel Production Processes1-5


homogeneous heterogeneous enzymatic SC MeOH
catalytic method catalytic method method method
reaction time 0.5-4 h 0.5-3 h 1-8 h 120-240 s
reaction conditions 0.1 MPa, 30-65 °C 0.1-5.0 MPa, 30-200 °C 0.1 MPa, 35-40 °C >8.09 MPa, >239.4 °C
catalyst acid or alkali metal oxide or carbonate immobilized lipase none
free fatty acids saponified products methyl esters methyl esters methyl esters
yield normal to high normal low to high high
removal for purification methanol, catalyst, methanol methanol or methyl acetate methanol
and saponified product
waste wastewater none none none
glycerin purity low low to normal normal or triacetylglycerol high
as byproduct
process complicated complicated complicated 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)

zcm ) ∑i ∑j xixjzcij ) xi2zci + 2xixjzcij + xj2zcj (4)


Figure 1. Schematic diagram of the continuous transesterification
reactor system. 1. High-pressure pumps, 2. methanol reservoir, 3.
zcmRTcm vegetable oil reservoir, 4. nitrogen cylinder, 5. preheaters, 6. reactor,
Pcm ) (5) 7. salt bath, 8. temperature monitoring system, 9. cooling bath, 10.
Vcm inline filter, 11. pressure monitoring system, 12. back pressure regulator,
and 13. sample collector.
The terms Vcij, Tcij, and zcij were calculated by the combining
rules as the following equations: mL/min depending on space time and molar ratio of methanol-to-
oil), preheated while flowing in the preheat lines (SUS316 tubing
Tcij ) xTciTcj (6) 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
1
Vcijx ci cj ci cj
Pcij ) P P V V (7) 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., 0.035-
zcij ) 0.5(zci + zcj) (8) in. thickness SUS316 tubing. The preheat lines and the reactor were
immersed in an electrically heated salt bath. The fluid product
1
Vcij1/3 ) (Vci1/3 + Vcj1/3) (9) exiting from the reactor was promptly cooled by an external water-
2 cooling bath and depressurized using a back-pressure regulator.
After pressure and temperature were constant, approximately 10
where i and j are subscripts for vegetable oil and methanol, mL of liquid product was collected, and then methanol was
respectively, x is the mole fraction of vegetable oil or methanol, evaporated by a rotary evaporator. The liquid product was checked
Tc is the critical temperature of vegetable oil or methanol, Vc is for % methyl esters by gas chromatography to ensure that the system
the molar volume of vegetable oil or methanol, zc is the reached steady state, which was indicated by a constant value, after
compressibility factor of vegetable oil or methanol, Tcm is the more than 90 min. The product was then collected until the total
critical temperature of vegetable oil and methanol mixture, Vcm volume was sufficient for further analysis.
is the molar volume of vegetable oil and methanol mixture, zcm The final liquid product was collected and left to settle for several
is the compressibility factor of vegetable oil and methanol hours, preferably overnight, to ensure complete separation. Two
mixture, and Pcm is the critical pressure of vegetable oil and liquid phases were obtained: ester and crude glycerin. The top ester
methanol mixture. layer was separated by a separatory funnel and put in a rotary
evaporator to remove any excess methanol. The % methyl ester in
2. Experimental Methods liquid product was then analyzed by gas chromatography (Shimadzu
model GC14BSPL) with a flame ionization detector. A 30-m-long,
Two potential vegetable oils were studied: coconut oil (CCO) 0.25-mm-diameter capillary column coated with poly(ethylene
and palm kernel oil (PKO). The CCO was supplied by Tab Sakae glycol) was used with helium as a carrier gas. The ester product
Co. Ltd., and the PKO was supplied by Cheeva Mongkol Co. Ltd. was diluted with n-heptane (analytical grade) before injection and
Both samples were warmed and filtered prior to use. Analytical standardized by standard methyl esters. Chemical analyses of the
grade methanol (Fisher) was used with no further purification. The oil samples were performed according to AOCS standards,11 while
experiments were performed using a tubular flow reactor shown the other standard test methods for fuel properties were performed
in Figure 1. according to ASTM standards,12 as shown in Table 2.
The oil and methanol were pumped in two different lines by
high-pressure high-performance liquid chromatographic pumps (11) Methods Cd 3d-63, Cd 3b-73, and Ce 2-66. American Oil Chemical
(Jasco, model PU-1580) up to 19 MPa (total flow rate of 1.5-9.0 Society: Champaign, IL, 1997.
(12) Methods D1298, D976, D93, D240, and D445. American Society
(10) Walas, S. M. Phase Equilibria in Chemical Engineering; Butter- for Testing and Materials Annual Book of ASTM Standards, Part 26;
worth: Boston, 1985; pp 29-33. ASTM: Philadelphia, PA, 2004.
814 Energy & Fuels, Vol. 20, No. 2, 2006 Bunyakiat et al.

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.

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


source sum of squares DF mean square F value P value
model 23160 9 2573 23.54 <0.0001
A 4206 1 4206 38.48 <0.0001
B 1805 1 1805 16.52 0.0003
C 1964 1 1964 17.97 0.0002
A2 2781 1 2781 25.45 <0.0001
B2 1.13 1 1.13 0.01 0.9197
C2 91.69 1 91.69 0.84 0.3668a
AB 216.0 1 216.0 1.98 0.1697
AC 202.6 1 202.6 1.85 0.1832
BC 322.3 1 322.3 2.95 0.0959
residual 3388 31 109.3
Figure 4. Effect of the molar ratio of methanol-to-coconut oil on the total 26550 40
% methyl ester conversion at 350 °C, 19.0 MPa. a Significant when ignoring the interaction effect.

Table 8. Statistical Values of Regression Models


coconut oil regression model

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

palm kernel oil regression model

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

Figure 7. Relationship between predicted % methyl ester conversion


Figure 6. Relationship between predicted % methyl ester conversion from regression model of palm kernel oil versus % methyl ester
from regression model of coconut oil versus % methyl ester conversion conversion from the experiment.
from the experiment.
specification of low speed diesel fuel and biodiesel (B 100) as
From eqs 14 and 15, all coefficients have a plus sign in the specified in ASTM D6751-02. The results are shown in Table
first-order term, indicating that % methyl ester conversion 9. Hence, CCO and PKO biodiesel properties are much
increases with these factors, conforming with the experimental improved from those of vegetable oils, as the flash points and
result shown in sections 3.3 and 3.4. The second-order terms viscosities are much reduced, and the specific gravities are
of A and C (temperature and space time) illustrate that there lower. All properties meet the biodiesel standard. This indicates
are optimum points within the experimental condition range. that biodiesel from CCO and PKO can readily replace low speed
The regression models for coconut oil and palm kernel oil in diesel fuel.
actual variables are shown in eqs 16 and 17, respectively.
4. Conclusions
xCCO % ME conversion ) -93.43 + 0.59T + 0.07M +
Continuous transesterification of coconut oil and palm kernel
8.51 × 10-3 τ - 9.08 × 10-4T2 - 2.96 × 10-6τ2 (16) oil in supercritical methanol was successfully attempted. The
xPKO % ME conversion ) -107.91 + 0.68T + 0.08M + best conditions are 350 °C, 19.0 MPa, molar ratio of methanol-
to-oil of 42, at a space time of 400 s. Percent methyl ester
6.72 × 10-3τ - 1.03 × 10-3T2 - 2.24 × 10-6τ2 (17) conversions are 95 and 96% for coconut oil and palm kernel
where T ) temperature (270 to 350 °C), M ) molar ratio of oil, respectively. The regression models by the least-squares
methanol-to-oil (6 to 42), and τ ) space time (30-2000 s). method to predict % methyl ester conversion from coconut oil
The statistical values of both regression models are given in and palm kernel oil show that the main effects (temperature,
Table 8. From Table 8, the coefficients of determination (R2) molar ratio of methanol-to-oil, and space time) and second-
are 0.81 and 0.85 for coconut oil and palm kernel oil regression order effects (temperature and space time) are significant with
model, respectively. The predicted % methyl ester conversions no interaction effect, and the coefficients of determination (R2)
from regression models of coconut oil and palm kernel oil versus are 0.81 and 0.85, respectively. Methyl ester products were
experimental result are shown in Figures 6 and 7, respectively. analyzed, and it was confirmed that their fuel properties met
In Figures 6 and 7, the relationship lies on the diagonal line, the specification of biodiesel (B 100) as specified in ASTM
and hence both regression models are adequate to predict % D6751-02.
methyl ester conversion from given factors (temperature, molar
ratio of methanol-to-oil, and space time). Acknowledgment. We express our sincere appreciation to Tab
3.7. Methyl Ester Properties. The final methyl ester products Sakae Co. Ltd. and Cheeva Mongkol Co. Ltd. for supplying the
coconut oil and palm kernel oil samples. We are also grateful for
at 350 °C, 19.0 MPa, molar ratio of methanol-to-oil at 24, also
the financial support from The Graduate School of Chulalongkorn
known as biodiesel, together with a low speed diesel fuel sample, University, The Petroleum and Petrochemical Technology Con-
were tested for their fuel properties and compared to the sortium, Ministry of University Affairs, and the National Energy
and Policy Office.
(15) Montgomery, D. C. Design and Analysis of Experiments; Wiley &
Sons: New York, 2001; pp 392-415. EF050329B