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Oil, Gas and Chemical Engineering Department, Semnan University Opposite Sukan Park, Semnan 35195363, Iran
Engineering Department, Shahroud Islamic Azad University End of Tehran Ave, Shahrood, Iran
A R T I C L E I N F O
A B S T R A C T
Article history:
Received 4 October 2011
Received in revised form 15 January 2012
Accepted 25 January 2012
Available online 18 February 2012
Biodiesel as an alternative fuel was produced by transesterication of Malaysian RBD (Rened, Bleached,
and Deodorized) palm oil with alkaline catalysts. Potassium and sodium hydroxide were used as catalysts
in this reaction at temperature of 60 8C in a stirred tank reactor with 600 rpm stirring. Gas
chromatography was used to determine the fatty acid methyl ester (FAME) contents in the produced
biodiesel. Yield of reaction which was carried out with KOH as a catalyst is a higher value than the
reaction when NaOH was used as a catalyst. A second-order reaction mechanism which was purposed by
Leevijit et al. (2004) was applied to calculate the product concentrations. There was a good agreement
between the methyl ester concentrations measured experimentally and what was predicted from the
kinetic model. Finally important fuel properties of produced biodiesels were obtained and compared with
petro diesel and the ASTM standards which indicate that the biodiesel with acceptable quality was
synthesized experimentally.
Crown Copyright 2012 Taiwan Institute of Chemical Engineers. Published by Elsevier B.V. All rights
reserved.
Keywords:
Biodiesel
Transesterication
Methyl ester
RBD palm oil
Catalysts
1. Introduction
Nowadays increasing in application of fossil fuels in different
elds caused increasing concern about using these fuels and what
happens after use or the global warming issues. In addition,
depletion of this great source of energy causes looking for
alternative and efcient fuels by many researchers. Indeed
removing disadvantages of conventional diesel fuel is another
relative subject. One of these alternative fuels is biodiesel, which
with respect to its benets such as non-toxicity, biodegradability,
and renewability has attracted many views. In addition to these
benets, greenhouse gas reduction and less pollution generation of
this type of fuel compared with other fuels are other major reasons
to use the biodiesel [13]. A life cycle analysis of the biodiesel
showed that the overall CO2 emissions were reduced by 78%
compared with the petroleum based diesel fuel [3,4].
Biodiesel or fatty acid methyl ester (FAME) is produced by the
transesterication reaction among vegetable oils, animal fats or
waste cooking oils with an alcohol in presence of a catalyst. A
strong alkali, a strong acid, and an enzyme are three kinds of
catalysts which can be used in the transesterication reaction. The
1876-1070/$ see front matter . Crown Copyright 2012 Taiwan Institute of Chemical Engineers. Published by Elsevier B.V. All rights reserved.
doi:10.1016/j.jtice.2012.01.009
M.R. Shahbazi et al. / Journal of the Taiwan Institute of Chemical Engineers 43 (2012) 504510
Nomenclature
A
As
Cs
CN
DG
FID
GC
GL
k
mi
ME
MG
MW
ROH
RBD
TG
wt%
Yester
peak area
peak area of standard solution
concentration of standard solution
cetane number
diglyceride
ame ionization detector
gas chromatography
glycerin
reaction rate constant of Eqs. (2)(4) (L/mol s)
weight of component i
methyl ester
monoglyceride
molecular weight
alcohol
Rened, Bleached, Deodorized
triglyceride
weight percent
biodiesel content (%)
505
M.R. Shahbazi et al. / Journal of the Taiwan Institute of Chemical Engineers 43 (2012) 504510
506
k1
Table 1
Products from the harvested crops and world supply of vegetable oils [11].
TG ROH @ DG ME
k2
Palm
Soybean
Rapeseed
29.7
34.8
19.1
4.8
29.85
33.87
2.3
0.4
14.2
16.59
3
1.2
k3
DG ROH @ MG ME
k4
k5
MG ROH @ GL ME
k6
transparent one if more times have been given for settling. Usually,
the complete separation could take as long as 818 h. The methyl
ester which was the upper layer in the decanter was washed three
times with the warm distilled water to remove excess methanol,
catalyst, and remained glycerol. In the washing stage, water to
methyl ester ratio was considered to be 2:1.Washed biodiesel was
dried using heating up approximately to 110 8C in an open
container until making sure that no more steam rises from it.
Indeed the heating process can also drive off any traces of moisture
and remained methanol [24]. Finally the mixture was ltrated and
cooled down to the room temperature and the pure biodiesel was
stored for any further tests.
2.4. Analysis
The gas chromatography analyzer (Shimadzu 2010 Brand)
equipped with a ame ionization detector (FID) and a capillary
column (SP 2330 polar column 2 60 m ID: 0.32 mm; Supelco
Inc.) was used for analyzing the produced biodiesel. Helium was
used as an inert carrier gas at a ow rate of 1 ml/min. Oven
temperature started at 160 8C, kept for 5 min, and then it increased
to 210 8C at a rate of 2 8C/min and held at this temperature for
10 min. Methyl myristate and n-hexane were used as internal
standard and solvent, respectively [26].
The FAME content (mass concentration) in the product was
measured by the GC analysis according to the EN 14103 test
method [27]. In this test method the methyl heptadecanoate and nheptane were replaced with methyl myristate and n-hexane as
internal standard and solvent, respectively. To measure the
biodiesel content in the nal product, a standard solution was
prepared as 10 mg/ml methyl myristate with hexane solution at
rst. Then 250 mg of the sample was added to 5 ml of standard
solution and the mixture was injected to the GC column.
Different standard tests were applied to measure some of the
important physical properties of the produced biodiesel. The EN
ISO 3675 [28] for density measurement, ASTM D445 [29] for
kinematic viscosity measurement, ASTM D93 [30] for ash point
measurement, EN ISO 660 [31] for acidity number measurement,
and ASTM 2709 [32] for humidity measurement were applied. The
cetane number was also calculated from the correlation (1) given
in [33].
CN 33:6 0:539C18 : 0 0:303C18 : 1 0:0878C18
: 2 0:233C22 : 1
(1)
(2)
(3)
(4)
(5)
(6)
dMG
k3 DGROH k4 MGME k5 MGROH
dt
k6 GLME
dGL
k5 MGROH k6 GLME
dt
(7)
(8)
dME
k1 TGROH k2 DGME k3 DGROH
dt
k4 MGME k5 MGROH k6 GLME
dROH
dME
dt
dt
(9)
(10)
M.R. Shahbazi et al. / Journal of the Taiwan Institute of Chemical Engineers 43 (2012) 504510
Table 2
The reaction rate constants (L/mol s) [15].
1.057 102
0.000
1.184 101
8.187 102
1.310 101
2.011 103
k1
k2
k3
k4
k5
k6
507
where MWi and %mi are the molecular weight and the weight
percent of fatty acid i obtained from the GC analysis, respectively,
and constant value of 14 is the molecular weight of CH2 in the
methyl ester molecular structure without considering the fatty
acid.
The methyl ester concentrations in two cases of using NaOH and
KOH as catalyst were measured experimentally as 2.31 mol/L and
2.43 mol/L, respectively, after 60 min. There is a good agreement
between the experimental results and what was predicted from
the kinetic model when using the rate constants of Table 2.
Therefore a second-order kinetic mechanism using the mentioned
reaction rate constants can justify the palm oil transesterication
reaction, properly. Mathematical models that used for kinetic
studies can be applied to predict the product concentrations,
design the experiments, and optimize the biodiesel production
processes. The kinetics of palm transesterication reaction studied
by different researchers and the second-order kinetics presented
for this reaction [15,16]. The second-order kinetics proposed on
transesterication reaction of soybean, sunower, brassica carinata oils as well [14,3638]. In some studies the mass transfer
controlling step on the rate of transesterication reaction was
investigated and the sigmoidal kinetics shape was analyzed
[39,40]. The kinetics of transesterication reaction of triglycerides
with methanol was compared with interesterication reaction
with methyl acetate in a recent work [41]. In this study 15
reactions including the transesterication reactions with secondorder kinetics scheme were considered.
At last the biodiesel conversion can be calculated as [42]
conversion%
Fig. 1. The concentration proles of methyl ester (ME), methanol (MeOH), glycerol
(GL), triglyceride (TG), diglyceride (DG), and monoglyceride (MG) during the
transesterication of palm oil at temperature of 60 8C, methanol/oil molar ratio of
6:1, catalyst concentration of 1 wt% oil and mixing speed of 600 rpm.
Y ester % 100
P
A As
As
CsV s
m
(12)
P
where A is the summation of the GC peak areas for all methyl
esters (C14:0C24:1), As is the increasing amount of the GC peak
area of methyl myristate after adding standard solution, Cs is the
concentration of standard solution as 10 mg/ml, Vs is the volume of
standard solution (5 ml), and m is the amount of sample (250 mg).
Based on this relation, methyl ester contents in the nal biodiesels
were calculated as 88 and 93 wt% for cases when NaOH and KOH
used as catalyst, respectively. This value obtained as 9798% for
Karanja oil (a non-edible oil) transesterication with methanol and
KOH as a catalyst under the optimized conditions [35].
Fig. 2(a)(c) shows the chromatograms of fatty acid of feedstock
and produced biodiesel by transesterication of palm oil using
potassium hydroxide and sodium hydroxide as catalyst mixed
with the standard solution. The results of analysis have been given
in Table 3.
As it is given in Table 3, according to the gas chromatographic
analysis there are no signicant changes in the concentration of
mB =MWB Y ester
mO =3MWO
(14)
M.R. Shahbazi et al. / Journal of the Taiwan Institute of Chemical Engineers 43 (2012) 504510
508
Fig. 2. The GC chromatograms of (a) RBD palm oil, (b) biodiesel, using NaOH as a catalyst mixed with the standard solution, (c) biodiesel, using KOH as a catalyst mixed with
the standard solution.
cooking oil [43,44] when alkali catalyst used in the course of the
transesterication reaction.
The quality of synthesized alkyl esters was evaluated by
measuring some important fuel properties and comparing with the
ASTM standards for biodiesel and the properties of conventional
diesel fuel. The quality of biodiesel is signicant from the engine
point of view. Different factors have been specied to check the
quality. The results have been given in Table 4.
Table 3
Fatty acid compositions in RBD palm oil and produced biodiesel in presence of
NaOH and KOH as a catalyst.
FAME
*
Myristic (C14:0)
Palmitic (C16:0)
Palmitoleic (C16:1)
Stearic (C18:0)
Oleic (C18:1)
Linoleic (C18:2)
Linolenic (C18:3)
Arachidic (C20:0)
1.06
42.56
0.21
4.76
40.08
10.69
0.53
0.11
1.14
42.04
0.14
4.43
39.97
11.74
0.44
0.09
1.0
42.54
0.16
4.39
39.83
11.60
0.39
0.08
*
Numbers in parenthesis indicate the numbers of carbons and unsaturated
bonds.
M.R. Shahbazi et al. / Journal of the Taiwan Institute of Chemical Engineers 43 (2012) 504510
509
Table 4
Physical properties of produced biodiesels and conventional diesel.
Property
2
Palm oil
ASTM Stand.
Using NaOH
Using KOH
Petro diesela
39.4
256
0.881
0.1
0.03
40
1.96
Min. 130
Max. 0.5
Max. 0.050
Min. 47
4.59
164
0.875
0.24
0.042
49.13
49.5c
4.61
166
0.876
0.16
0.036
49.05
3.06
69
0.855
0.11
50
Ref. [45].
Calculated from the correlation presented in Ref. [33] using fatty acid methyl esters proles.
Measured by The National Iranian Oil Products Distribution Company (NIOPDC).
49.5 that is very close to what was calculated from the correlation
(1). The minimum value of cetane number based on the ASTM
D6751 [46] is 47, that fullled the values obtained in the present
work. Therefore the properties of produced biodiesel in the present
work were found within the limits of standards.
5. Conclusions
The Malaysian palm oil as a good source of FAME was used to
produce biodiesel in the present work. Sodium and potassium
hydroxides were used as catalysts in the transesterication
reaction. The potassium hydroxide was a better catalyst to reach
to the higher yields on the transesterication of palm oil. Indeed
the conversion of Malaysian palm oil to the produced biodiesel
shows higher value than that reported by the other researches
regarding to the operating temperature. The molar concentration
of fatty acid methyl esters (FAME) was compared with what was
predicted from a second-order kinetics model that it justied the
results of the present work at the time duration of 60 min.
The kinematic viscosity, ash point, and the cetane number of
the produced biodiesel were measured and showed as acceptable
values based on the ASTM standards. The biodiesel properties also
were compared with the conventional diesel fuel properties and it
shows that the synthesized biodiesel has the properties comparable with the conventional diesel fuel and can be considered as an
alternative to mix with it and use in motors.
Acknowledgments
We would like to appreciate the research laboratory operators
of Margarin Mfg. Co. for the gas chromatography analyses. Indeed
many thanks to the personnel of research laboratory of Tarbiat
Modarres University for measuring the ash point and the
kinematic viscosity of the produced biodiesel.
References
[1] Kumar Agarwal A. Biofuel (alcohol and biodiesel) applications as fuels for
combustion engines. Progress in Energy and Combustion Science 2007;33:
23371.
[2] Demirbas A. Biofuel sources, biofuel policy, biofuel economy and global biofuel
projections. Energy Conversion and Management 2008;49:210616.
[3] Duz MZ, Saydut A, Ozturk G. Alkali catalyzed transesterication of safower
seed oil assisted by microwave irradiation. Fuel Processing Technology
2011;92:30813.
[4] Saydut A, Duz MZ, Kaya C, Kafadar AB, Hamamci C. Transesteried sesame
(Sesamum indicum L.) seed oil as a biodiesel fuel. Bioresource Technology
2008;99:665660.
[5] Rashid U, Anwar F. Production of biodiesel through optimized alkaline-catalyzed transesterication of rapeseed oil. Fuel 2008;87:26573.
[6] Kawashima A, Matsubara K, Honda K. Development of heterogeneous base
catalysts for biodiesel production. Bioresource Technology 2008;99:343943.
[7] Lang X, Dalai AK, Bakhshi NN, Reaney MJ, Hertz PB. Preparation and characterization of bio-diesels from various bio-oils. Bioresource Technology
2001;80:5362.
[8] Mendow G, Veizaqa NS, Querini CA. Ethyl ester production by homogeneous
alkaline transesterication: inuence of catalyst. Bioresource Technology
2011;102:638591.
510
M.R. Shahbazi et al. / Journal of the Taiwan Institute of Chemical Engineers 43 (2012) 504510
[37] Gemma V, Martinez M, Aracil J, Estaban A. Kinetics of sunower oil methanolysis. Industrial Engineering Chemistry Research 2005;44:544754.
[38] Gemma V, Martinez M, Aracil J. Kinetics of Brassica carinata oil methanolysis.
Energy and Fuels 2006;20:17226.
[39] Stamenkovic OS, Todorovic ZB, Lazic ML, Veljkovic VB, Skala DU. Kinetics of
sunower oil methanolysis at low temperatures. Bioresource Technology
2008;99:113140.
[40] Bambase ME, Nakamura N, Tanaka J, Matsumura M. Kinetics of hydroxidecatalysed methanolysis of crude sunower oil for the production of fuel-grade
methyl esters. Journal of Chemical Technology and Biotechnology 2007;82:
27380.
[41] Casas A, Ramos MJ, Perez A. Kinetics of chemical interesterication of sunower oil with methyl acetate for biodiesel and triacetin production. Chemical
Engineering Journal 2011;171:132432.