Bunyakiat 2006 Bueno
Bunyakiat 2006 Bueno
Bunyakiat 2006 Bueno
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.
[(CH2COO)2CHCOO](CHdCH)m(CH2)n(CH3)3
(1)
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
TcmVcm )
i j xixjTcijVcij )
xi2TciVci + 2xixjTcijVcij + xj2TcjVcj (2)
Vcm )
(3)
(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)
(8)
1
Vcij1/3 ) (Vci1/3 + Vcj1/3)
2
(9)
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.
Cd 3D-63
Cd 3B-76
Ce 2-66
D240
D445
D93
D1298
D976
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)
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
WME
100
WFA
(10)
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.
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
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
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
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
(350 +2 270) )
(350 -2 270)
Temperature (C) A)
(42 2- 6)
(42 2+ 6) )
(20002+ 30) )
(20002- 30)
and
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
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
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.