Escolar Documentos
Profissional Documentos
Cultura Documentos
Bioresource Technology
journal homepage: www.elsevier.com/locate/biortech
a r t i c l e
i n f o
Article history:
Received 24 April 2008
Received in revised form 25 June 2008
Accepted 26 June 2008
Available online 5 August 2008
Keywords:
Biodiesel
Heterogeneous catalyst
Transesterification
Calcium oxide
Activation
a b s t r a c t
This research was aimed at studying the acceleration of the catalytic activity of calcium oxide (CaO) for
developing an effective heterogeneous catalyst for biodiesel production by the transesterification of plant
oil with methanol. CaO was activated by pretreatment with methanol and was used for the transesterification reaction. The activation and transesterification reaction conditions were examined. The obtained
optimal reaction conditions were 0.1-g CaO, 3.9-g methanol, 15-g rapeseed oil, and 1.5-h activation time
at room temperature that provided methyl ester in approximately 90% yield within a reaction time of 3 h
at 60 !C. The activation mechanism was also investigated, and the proposed mechanism is as follows. By
pretreatment with methanol, a small amount of CaO gets converted into Ca(OCH3)2 that acts as an initiating reagent for the transesterification reaction and produces glycerin as a by-product. Subsequently, a
calciumglycerin complex, formed due to the reaction of CaO with glycerin, functions as the main catalyst and accelerates the transesterification reaction.
" 2008 Elsevier Ltd. All rights reserved.
1. Introduction
In recent years, global warming, environmental pollution, and
depletion of fossil resources due to heavy consumption have become major issues of global dimensions. Biomass energy is expected to resolve these issues and has gained international
attention as a source of renewable and environment-friendly energy. Biodiesel fuel, fatty acid methyl ester (FAME), produced by
the transesterification of vegetable oils and animal fats with methanol has the following characteristics: it is a biomass-derived fuel
and is free from aromatic compounds, and it has high biodegradability and low SOx and particulate matter content in diesel fumes
(Graboski and McCormick, 1998; Schuchardt et al., 1998; Ma and
Hanna, 1999). Therefore, FAME is expected to be one of the
biomass-derived alternatives to petroleum-derived diesel fuels.
Currently, FAME is commonly produced by performing a transesterification reaction with homogeneous base catalysts such as KOH
or NaOH dissolved in methanol. This production process can provide high FAME yields under mild conditions atmospheric pressure, a temperature of 60 !C, and a reaction time of
approximately 1 h (Vicente et al., 2004; Meher et al., 2006a). However, for its safe and practical application as diesel fuel in the market, the produced FAME is required to be purified by removing
impurities such as base catalyst and glycerin using a water washing process that is cumbersome and requires the disposal of a large
amount of basic water. Moreover, the total cost of this process is
* Corresponding author. Tel.: +81 89 946 9970; fax: +81 89 946 9980.
E-mail address: a-kawa@agr.ehime-u.ac.jp (A. Kawashima).
0960-8524/$ - see front matter " 2008 Elsevier Ltd. All rights reserved.
doi:10.1016/j.biortech.2008.06.049
697
2. Experimental
2.1. Chemicals
Commercial edible-grade rapeseed oil was purchased from the
market and used without further purification. Other chemicals
such as CaO, FAME that was used as the standard substance, and
solvents were obtained from Wako Pure Chemical Industries (Osaka, Japan), Kanto Chemical Co. Inc., (Tokyo, Japan), and Sigma-Aldrich Corporation (Missouri, USA), respectively. The purchased
CaO (up to 99.9% purity) was used without further treatment.
2.2. Catalytic activation and activity measurements
The catalytic activities for the transesterification of oil were
measured by performing a batch-type reaction. The standard activation and reaction conditions were as follows. A given amount of
CaO and 3.9 g of methanol were placed in a 50-ml two-necked flask
equipped with a reflux condenser and stirred for 1 h at 25 !C for
activation. Next, 15 g of rapeseed oil was added to the mixture;
the mixture was stirred using a magnetic stirrer and subsequently
heated at 60 !C in an oil bath for 10 h. Small aliquots of this reaction mixture were sampled for studying the progress of the reaction. As for the activation by glycerin, CaO was mixed with
glycerin for a few minutes at 60 !C; subsequently, the solid phase
of the reaction mixture was separated. The transesterification reaction with methanol and rapeseed oil was then performed in a similar manner.
Quantitative determinations of the FAME yield were performed
as follows. The liquid phase of the reaction mixture was collected
and was evaporated under vacuum in order to remove the excess
methanol; then, the oil phase was separated from the reaction
mixture by centrifugation at 9170 g for 5 min. A methyl heptadecanoate solution was added as an internal standard to 100 mg of
the oil phase; this mixture was diluted to 5 ml with isooctane,
and 2 ll of the resulting solution was subjected to a high-performance liquid chromatography (HPLC) analysis for the quantitative
determination of the FAME yield. The HPLC system consisted of a
JASCO PU-2089 pump, JASCO AS-2057 auto injector, and JASCO
RI-2031 differential refractive index (RI) detector (JASCO Corp., To-
kyo, Japan). Data was collected and analyzed using JASCO Borwin
software. The mobile phase was methanol at a flow rate of
1.0 ml/min. The columns were 250 mm ! 4.6 mm Intersil ODS-3
(GL Science Inc. Japan, Tokyo, Japan) and were protected using a
10 mm ! 4 mm Intersil ODS-3 guard column. The sample injection
volume was 2 ll, and the RI analyses were conducted at 35 !C. The
HPLC analysis was carried out two times for each sample and
methyl ester yield was calculated using the average value. The
yield was defined as the ratio of the weight of methyl esters determined by HPLC to the weight of the oil phase.
2.3. Catalyst characterization
X-ray powder diffraction (XRD) patterns were recorded on a
MiniFlex X-ray diffractometer using monochromatic CuKa radiation (Rigaku Corp., Tokyo, Japan). Data were collected over a 2h
range of 390! with a step size of 0.02! at a scanning speed of
4!/min.
The basic strengths of the catalysts (H_) were determined by
using Hammett indicators. Approximately 25 mg of the catalyst
was shaken with 5 ml of a solution of Hammett indicators diluted
with methanol and was left to equilibrate for 2 h. After the equilibration, the color of the catalyst was noted. The following Hammett indicators were used: neutral red (H_ = 6.8), bromthymol
blue (H_ = 7.2), phenolphthalein (H_ = 9.3), Nile blue (H_ = 10.1),
Tropaeolin O (H_ = 11.1), 2,4-dinitroaniline (H_ = 15.0), and 4nitroaniline (H_ = 18.4).
3. Results and discussion
3.1. Activation of CaO
First, we investigated the catalytic activity of nonactivated CaO
for the transesterification reaction. The reactions were performed
with the addition of (0.01 or 0.05 g) CaO to 15 g of rapeseed oil
and 3.9 g of methanol at 60 !C. As shown in Fig. 1, the reaction rate
for the initial few hours was very low, but it increased gradually;
the ester yields obtained after 10 h for 0.01 and 0.05 g of CaO were
64% and 87%, respectively. This acceleration of the reaction rate in
the middle of the reaction pathway indicated that the catalyst was
somehow activated during the initial part of the reaction. Since the
catalyst coexisted only with oil and methanol in this reaction system, it was considered that it was activated by a reaction with
100
KOH 0.05 g
80
Activated
CaO, 0.05 g
60
Nonactivated
CaO, 0.05 g
Activated
CaO, 0.01 g
40
20
Nonactivated
CaO, 0.01 g
0
10
Fig. 1. Catalytic activity of nonactivated CaO (0.01 and 0.05 g), activated CaO (0.01
and 0.05 g), and KOH (0.05 g) in transesterification reaction of rapeseed oil with
methanol at 60 !C. CaO was activated with 3.9 g of methanol by stirring for 1 h at
25 !C.
698
80
80
100
100
60
24 h
40
6h
1.5 h
20
0
1h
0.5 h
60
40
0.01 g
20
0.1 g
0.05 g
Nonactivated
10
10
100
80
60
13 wt%
40
26 wt%
40 wt%
20
60 wt%
0
10
699
700
Meher, L.C., Sager, D.V., Naik, S.N., 2006a. Technical aspects of biodiesel production
by transesterification A review. Renew. Sustain. Energy Rev. 10, 248268.
Meher, L.C., Kulkarni, M.G., Dalai, A.K., Naik, S.N., 2006b. Transesterification of
karanja (Pongamia pinnata) oil by solid basic catalysts. Eur. J. Lipid Sci. Technol.
108, 389397.
Minami, E., Saka, S., 2006. Kinetics of hydrolysis and methyl esterification for
biodiesel production in two-step supercritical methanol process. Fuel 85, 2479
2483.
Narasimharao, K., Brown, D.R., Lee, A.F., Newman, A.D., Siril, P.F., Tavener, S.J.,
Wilson, K., 2007. Structure-activity relations in Cs-doped heteropolyacid
catalysts for biodiesel production. J. Catal. 248, 226234.
Nie, K., Xie, F., Wang, F., Tan, T., 2006. Lipase catalyzed methanolysis to produce
biodiesel: Optimization of the biodiesel production. J. Mol. Catal. B: Enzym. 43,
142147.
Peterson, G.R., Scarrah, W.P., 1984. Rapeseed oil transesterification by
heterogeneous catalysis. J. Am. Oil Chem. Soc. 61, 15931597.
Reddy, C.R.V., Oshel, R., Verkade, J.G., 2006. Room-temperature conversion of
soybean oil and poultry fat to biodiesel catalyzed by nanocrystalline calcium
oxides. Energy & Fuels 20, 13101314.
Schuchardt, U., Sercheli, R., Vargas, R.M., 1998. Transesterification of vegetable oils:
A review. J. Braz. Chem. Soc. 9, 199210.
Shibasaki-Kitakawa, N., Honda, H., Kuribayashi, H., Toda, T., Fukumura, T.,
Yonemoto, T., 2007. Biodiesel production using anionic ion-exchange resin as
heterogeneous catalyst. Bioresour. Technol. 98, 416421.
Shimada, Y., Watanabe, Y., Sugihara, A., Tominaga, Y., 2002. Enzymatic alcoholysis
for biodiesel fuel production and application of the reaction to oil processing. J.
Mol. Catal. B: Enzym. 17, 133142.
Suppes, G.J., Dasari, M.A., Doskocil, E.J., Mankidy, P.J., Goff, M.J., 2004.
Transesterification of soybean oil with zeolite and metal catalysts. Appl. Catal.
A: Gen. 257, 213223.
Toda, M., Takagaki, A., Okamura, M., Kondo, J.N., Hayashi, S., Domen, K., Hara, M.,
2005. Biodiesel made with sugar catalyst. Nature 438, 178.
Vicente, G., Martnez, M., Aracil, J., 2004. Integrated biodiesel production: A
comparison of different homogeneous catalysts systems. Bioresour. Technol. 92,
297305.
Xie, W., Peng, H., Chen, L., 2006. Transesterification of soybean oil catalyzed by
potassium loaded on alumina as a solid-base catalyst. Appl. Catal. A: Gen. 300,
6774.