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ReceiVed August 29, 2007. ReVised Manuscript ReceiVed NoVember 20, 2007
In this work, calcium ethoxide is proposed as a catalyst for the transesterication of soybean oil to biodiesel
with methanol and ethanol. First, calcium ethoxide was synthesized through a calcium reaction with ethanol.
Then, its physical and chemical characteristics were determined using instrumental methods such as
Brunauer-Emmett-Teller surface area measurements, scanning electron micrographs, and particle size
distribution measurements. The effects of the mass ratio of catalyst to oil, the molar ratio of methanol to oil,
and the reaction temperature were studied to optimize the reaction conditions. The experimental results showed
that the optimum conditions are a 12:1 molar ratio of methanol to oil, the addition of 3% Ca(OCH2CH3)2
catalyst, and a 65 C reaction temperature. A 95.0% biodiesel yield was obtained within 1.5 h in these conditions,
and the activation energy was 54 149 J/mol. It also indicated that the catalysis performance of calcium ethoxide
is better than that of CaO. Besides, a 91.8% biodiesel yield was obtained when it catalyzed soybean oil to
biodiesel with ethanol.
The physical and chemical characterizations of calcium ethoxide was as follows: First, the catalyst was dispersed in methanol under
were analyzed with some instrumental methods. Then, the magnetic stirring. Then, the soybean oil was added into the mixture
effects of various reaction conditions on the biodiesel yields and heated by water circulation. The amount of soybean oil was 28
were investigated. mL every time. After the reaction, the excess methanol was distilled
off under vacuum and the Ca(OCH2CH3)2 catalyst was separated
by centrifugation. After removal of the glycerol layer, the biodiesel
2. Experimental Section was collected for chromatographic analysis.
2.1. Materials and Catalyst Preparation. Ca(OCH2CH3)2 was 2.4. Analysis. The biodiesel samples were analyzed in an HP
synthesized in a 100 mL glass reactor with a condenser. The
magnetic stirring rate was 800 rpm. The reaction procedure was as
follows: First, calcium was dispersed in ethanol under magnetic
stirring. Then, it was heated to 65 C by water circulation. The (2)
reaction can be expressed by eq 1. After 8 h of reaction, ethanol
was rst distilled off under vacuum. Then, the catalyst was dried
in an oven at 105 C for 1 h.
65 C 5890 gas chromatograph equipped with a ame ionization detector
Ca + 2CH3CH2OH ) Ca(OCH2CH3)2 + H2v (1) and a capillary column HP-INNOWAX (30 m 0.15 mm 0.25
Rened soybean oil was purchased from Tianjin Jiali Oil Plant. m). Four microliters of the upper oil layer were dissolved in 300
The fatty acid composition consisted of 12.5% palmitic acid, 5.2% L of n-hexane and 100 L of the internal standard solutions
stearic acid, 23.5% oleic acid, 47.8% linoleic acid, 10% linolenic (heptadecanoic acid methyl ester-n-hexane solution) for gas
acid, and traces of other acids. Methanol was analytical reagent chromatography (GC) analysis. Samples (1 L) were injected by a
grade and was purchased from Beihua Fine Chemical Co., Beijing. sampler at an oven temperature of 220 C. After an isothermal
Analytical reagents (e.g., standards for high performance liquid period of 4 min, the GC oven was heated at 10 C/min to 230 C
chromatography (HPLC)) were of high grade and were obtained and held for 7.5 min. Nitrogen was used as the carrier gas at a
from Sigma Chemical Co. All other chemicals were analytical ow rate of 2 mL/min measured at 20 C and as the detector make
reagents and were purchased from Beihua Fine Chemical Co., up gas at a ow rate of 30 mL/min. The inlet pressure was 96.4
Beijing. kPa. The split ratio was 10:1. The injector temperature and detector
2.2. Apparatus and Procedure. The Brunauer-Emmett-Teller temperatures were 300 and 320 C, respectively.
(BET) surface area, total pore volume, and pore size distribution The biodiesel yield in each experiment was calculated by the
of Ca(OCH2CH3)2 were measured with a Quantachrome Autosorb- following expression:
1-C chemisorption-physisorption analyzer. A weighed sample of
the catalyst was prepared by outgassing for 1.5 h at 423 K on the mactual Cesters n Vesters
yield ) 100% 100%
degas port. Adsorption isotherms were generated by dosing nitrogen mtheoretical moil
onto the catalyst in a bath of liquid nitrogen at approximately 77 Cesters n Voil Cesters n
K. The BET surface area was calculated from the adsorption 100% 100%
branches in the relative pressure range of 0.050.25 bar, and the moil Foil
total pore volume was evaluated at a relative pressure of about 0.99 where both mactual [g] and mtheoretical [g] are the masses of methyl
bar. The pore size distribution was calculated from the desorption ester; moil [g] is the mass of the vegetable oil that was used in the
branches using the BarrettJoynerHalenda (BJH) method. The reaction; Cester [g/mL] is the mass concentration of methyl ester
particle size distribution was measured using a Malvern Mastersizer which was acquired by GC; n is the diluted multiple of methyl
MICRO-PLUS laser particle size analyzer and evaluated by a ester; Foil [g/mL] is the density of the vegetable oil; and Vesters [mL]
volume concentration. An FTIR-8201 (PC) infrared spectropho- and Voil [mL] are the volumes of crude ester layer and vegetable
tometer was used to identify the surface group of the catalyst. oil, respectively.
Scanning electron microscopy (SEM) observations were performed
on a Hitachi JEOL JSM 7401F microscope operating at 1.0 kV.
Thermogravimetry (TG) was performed with a Netzsch TA-449C 3. Results and Discussion
TG analyzer from 25 to 1000 C at a heating rate of 10 C/min 3.1. Characterizations of the Ca(OCH2CH3)2 Solid Base
under air atmosphere. The solubility of the catalyst in methanol
Catalyst. The analyzed results indicate that calcium ethoxide
and ethanol was determined by measuring the calcium concentration
with a HITACHI Z-5000 polarized zeeman atomic absorption possesses a surface area of 15.02 m2/g and a total pore volume
spectrophotometer. of 0.100 cm3/g. It is favorable for use in a slurry reactor. Fig-
2.3. Reaction Procedures. The transesterication reactions (eq ure 1 shows the SEM image of the Ca(OCH2CH3)2 catalyst. It
2) were carried out in a 100 mL glass reactor with a condenser. shows that the surfaces comprise a large number of small pores.
The magnetic stirring rate was 800 rpm. The reaction procedure Figure 2 shows the pore size distribution. It can be seen that a
Transesterication of Soybean Oil to Biodiesel Energy & Fuels, Vol. 22, No. 2, 2008 1315
Figure 10. Reaction mechanism for the transesterication of triglyceride with ethanol over the Ca(O CH2CH3)2 catalyst, where R1, R2, and R3
represent the long chain alkyl group.
the plot of ln k versus 1/T, the slope is equal to (-Ea/R). Thus, mechanism could be assumed to be one where that the catalytic
a value for Ea of 54 149 J/mol (12 954 cal/mol) was calculated reactions take place on the surface of calcium ethoxide. The
for the reaction. It indicates that the experimental value of the proposed mechanism of the transesterication reaction by
activation energy in this study is consistent with that reported calcium methoxide with ethanol is given in Figure 10. Alcohol
in the literature for this transesterication using homogeneous and triglyceride are adsorbed on two neighboring free catalytic
catalysts, such as NaOH, KOH, NaOCH3, NaOBu, H2SO4, and sites (O- and Ca+). The surface O- extracts an H+, and Ca+
so on.1517 Noureddini reported activation energies for the adsorbs CH3CH2O- from alcohol. The adsorbed triglyceride
reaction involved in the transesterication of soybean oil to be forms a surface intermediate with the catalyst. The two
in the range of 6400-20 000 cal/mol, and Bernard and neighboring adsorbed species react to result in the formation
co-workers reported these in the range of 800020 000 cal/mol. of a fatty acid methyl and a diglyceride. The diglyceride reacts
3.2.4. Transesterication of Soybean Oil to Biodiesel with with alcohol along similar processes on the surface of the
Ethanol. Biodiesel can be produced by the transesterication catalyst to form glycerol and biodiesel.
of soybean oil with ethanol. The experimental results are shown
in Table 2. It indicates that the reaction rate was slow at low 4. Conclusions
temperature. It cost 3 h to reach a 91.8% biodiesel yield at 75
C. Therefore, calcium ethoxide can also catalyze the transes- From the experimental results, it can be seen that
terication soybean oil to biodiesel with ethanol. It has strong Ca(OCH2CH3)2 has excellent catalytic abilities as a solid base
basicity and can catalyze many transesterication reactions. catalyst. It has a moderate surface area, a relatively broader
Some researchers have proposed some possible mechanisms in particle size distribution, and a better low solubility in methanol
chemical reactions over solid base catalysts.5,1113,18,19 When and ethanol. When it catalyzes the transesterication of soybean
calcium ethoxide is used as a solid base catalyst, the catalysis oil to biodiesel with methanol, the optimal conditions are a 12:1
molar ratio of methanol to oil, the addition of 3.0%
(15) Darnoko, D.; Cheryan, M. Kinetics of palm oil transesterication Ca(OCH2CH3)2 catalyst, a 65 C reaction temperature, and about
in a batch reactor. J. Am. Oil Chem. Soc. 2000, 77, 12631267.
(16) Noureddini, H.; Zhu, D. Kinetics of Transesterication of soybean
1.5 h of reaction time. The reactions are completed under mild
oil. J. Am. Oil Chem. Soc. 1997, 74, 14571463. temperature and pressure conditions. This catalyst can also be
(17) Bernard, F.; Royden, O. B.; Evereff, H. P. Transesterication applied in other chemical reactions as a solid base catalyst.
kinetics of soybean oil. J. Am. Oil Chem. Soc. 1986, 63, 13751380.
(18) Dossin, T. F.; Reyniers, M. F.; Marin, G. B. Kinetics of hetero-
geneously MgO-catalyzed transesterication. Appl. Catal., B 2006, 61, 35 Acknowledgment. The authors would like to thank Professor
45. Yigui Li for his kind help. This work was supported by the National
(19) Hideto, T.; Fuyuki, Y.; Hideshi, H.; Hideaki, K. Self-condensation Basic Research Program (973 Plan, No. 2007CB714302).
of n-butyraldehyde over solid base catalysts. J. Catal. 1994, 148, 759
770. EF700518H