Energy & Fuels 2009, 23, 1089–1092 1089

Application of Sodium Aluminate As a Heterogeneous Base Catalyst

for Biodiesel Production from Soybean Oil
Tao Wan, Ping Yu, Shenggang Wang, and Yunbai Luo*
College of Chemistry and Molecular Sciences, Wuhan UniVersity, Wuhan 430072, P.R. China

ReceiVed October 19, 2008. ReVised Manuscript ReceiVed January 4, 2009

In this study, the production of biodiesel from soybean oil by transesterification was carried out over sodium
aluminate as a heterogeneous catalyst. The solid base showed high catalytic activity for methanolysis reaching
a 93.9% yield under optimal reaction conditions (reflux temperature, 1.5 wt% of catalyst, 12:1 molar ratio of
methanol/oil, and 50 min). The catalyst treated at different temperatures was characterized by inductively
coupled plasma-optical emission spectroscopy (ICP-OES), X-ray diffraction (XRD), thermogravimetry/
differential thermogravimetry (TG/DTG), and Fourier transform infrared spectroscopy (FT-IR). The reaction
contained homogeneous and heterogeneous contributions at the same time. Removing water and carbon dioxide
was an effective way to elevate the catalyst stability in methanol.

1. Introduction KNO3/Al2O3,11 K2CO3/Al2O3,12 KF/Al2O3,13 Li/CaO,14 KF/

Nowadays, biodiesel has become very attractive because of
its environmental benefits and because it is made from renewable
resources. Biodiesel has the advantages of lowering the combus-
tion emission of carbon monoxide, particulate matter, and sulfur
compounds, as well as limiting greenhouse emissions due to
its closed carbon dioxide cycle.1,2
Transesterification is the process used to make biodiesel fuel
as defined in Europe and the U.S.A.3 Most biodiesel today is
produced in the presence of homogeneous catalysts such as
sodium methoxide, sodium or potassium hydroxide.4 However,
the formation of soap lowers biodiesel yield and requires the
separation of ester and glycerol, making the washing process
difficult. To address this problem, more and more research at
present has focused on the use of heterogeneous catalysts.
Heterogeneous catalysts have several advantages including easier
operational procedures, catalyst separation, and reduction of
environment pollutants, among others. As the catalytic activity
of basic catalysts is higher than that of acid solids, they have
been preferably studied.5 However, although several basic solids
have shown promising activities such as alkali earth oxides
CaO,6-8 MgO,9 SrO,10 and so on; alkali-doped metal oxides
* To whom correspondence should be addressed. E-mail: ybai@
whu.edu.cn. Phone: +86(27)6877-2263. Fax: +86(27)68754067.
(1) Graboski, M. S.; McCormick, R. L. Prog. Energy Combust. Sci.
1998, 24, 125–164.
(2) Karmee, S. K.; Chadha, A. Bioresour. Technol. 2005, 96, 1425–
1429.
(3) Ma, F.; Hanna, M. A. Bioresour. Technol. 1999, 70, 1–15.
(4) Bak, Y. C.; Choi, J. H.; Kim, S. B.; Kang, D. W. Korean J. Chem.
Eng. 1996, 13, 242–245.
(5) Serio, M. D.; Tesser, R.; Pengmei, L.; Santacesaria, E. Energy Fuels
2008, 22, 207–217.
(6) Gryglewicz, S. Bioresour. Technol. 1999, 70, 249–253.
(7) Demirbas, A. Energy ConVers. Manage. 2007, 48, 937–941.
(8) Granados, M. L.; Zafra Poves, M. D.; Martı́n Alonso, D.; Mariscal,
R.; Cabello Galisteo, F.; Moreno-Tost, R.; Santamaría, J.; Fierro, J. L. G.
Appl. Catal. B. 2007, 73, 317-326.
(9) Dossin, T. F.; Reyniers, M.-F.; Berger, R. J.; Marin., G. B. Appl.
Catal., B 2006, 67, 136–148.
(10) Xuejun, L.; Huayang, H.; Yujun, W.; Shenlin, Z. Catal. Commun.
2007, 8, 1107–1111.
ZnO,15 and so on; basic hydrotalcites Mg-Al,16 Li-Al,17 and
so on; anion-exchange resins;18 basic zeolites;19 A-B-O type
metal oxides, where A is an alkaline-earth metal, alkaline metal,
or rare earth metal and B is a transition metal;20 and solid
Brønsted bases,21 the basic heterogeneous catalysts were not
satisfactory in the industrial field to date.
Because of the versatility of its technological applications,
sodium aluminate (SA) is an important commercial inorganic
chemical. It is formulated as NaAlO2, Na2O · Al2O3, or
Na2Al2O4. SA is mainly in demand for use in effective water
treatment systems. It is also used by producers of paper, paint
pigments, alumina-containing catalysts, dishwasher detergents,
ingot molds, and molecular sieves, concrete, and so on.22 It is
generally believed that NaAlO2 is water soluble and shows
strong basicity in water, insoluble in alcohol.
To the best of our knowledge, there has been no published
study yet using NaAlO2 as a heterogeneous catalyst to produce
biodiesel from vegetable or animal oils. In this study, we
(11) Wenlei, X.; Hong, P.; Ligong, C. Appl. Catal., A 2006, 300, 67–
74.
(12) Alonso, D. M.; Mariscal, R.; Moreno-Tost, R.; Zafra Poves, M. D.;
Granados, M. L. Catal. Commun. 2007, 8, 2080–2086.
(13) Bo, X.; Guomin, X.; Lingfeng, C.; Ruiping, W.; Lijing, G. Energy
Fuels 2007, 21, 3109–3112.
(14) Watkins, R. S.; Lee, A. F.; Wilson, K. Green Chem. 2004, 6, 335–
340.
(15) Wenlei, X.; Xiaoming, H. Catal. Lett. 2006, 107, 53–59.
(16) Cantrell, D. G.; Gillie, L. J.; Lee, A. F.; Wilson, K. Appl. Catal.,
A 2005, 287, 183–190.
(17) Corma, A.; Abd Hamid, S. B.; Iborra, S.; Velty, A. J. Catal. 2005,
234, 340–347.
(18) Shibasaki-Kitakawa, N.; Honda, H.; Kuribayashi, H.; Toda, T.;
Fukumura, T.; Yonemoto, T. Bioresour. Technol. 2007, 98 (2007)), 416–
421.
(19) Leclercq, E.; Finiels, A; Moreau, C. JAOCS 2001, 78, 1161–1165.
(20) Kawashima, A.; Matsubara, K.; Honda, K. Bioresour. Technol.
2008, 99, 3439–3443.
(21) Yijun, L.; Loterob, E.; Goodwin, J. G., Jr,; Changqing, L. J. Catal.
2007, 246, 428–433.
(22) Rayzman, V.; Filipovich, I.; Nisse, L.; Vlasenko, Y. JOM 1998,
50, 32–37.

10.1021/ef800904b CCC: $40.75  2009 American Chemical Society

Published on Web 02/04/2009
1090 Energy & Fuels, Vol. 23, 2009
Table 1. Operation Parameters for Spectro Genesis EOP
ICP-OES
RF generator power (W) 1400
frequency of RF generator (MHz) 27.12
nebulizer type crossflow
carrier gas flow rate (L min -1) 1 drying under infrared
coolant gas flow rate (L min -1) 14
auxiliary gas flow rate (L min -1) 1 200 °C
netto time (sec) 12
analytical wavelength (nm) Na 589.592
investigated its catalytic activity and the durability of soybean
oil to fatty acid methyl ester.
2. Experimental Section
2.1. Chemicals. Commercial edible-grade soybean oil was
purchased from the supermarket and used without further purifica-
tion. SA, methanol and n-hexane were obtained from Sinopharm
Chemical Reagent Co., Ltd., (Shanghai, China). Lauric acid methyl
ester, used as an internal standard, was purchased from Sigma-
Aldrich Corporation (Missouri, U.S.A.).
2.2. Reaction Procedures. The reaction was conducted in a 250
mL one-neck flask equipped with a water-cooled condenser and a
magnetic stirrer charged with 15 g of soybean oil, different volumes
of methanol, and varied amounts of catalysts freshly prepared in
different conditions. Each reaction was carried out at a methanol
reflux temperature with vigorous stirring for the required time.
We performed catalyst durability tests by repeating the transes-
terification reaction several times with used catalysts. Catalysts were
separated from the previous reaction mixture by centrifugation and
calcined at 600 °C.
2.3. Catalyst Characterization. The catalysts were character-
ized using several techniques of the Hammett indicator, inductively
coupled plasma-optical emission spectroscopy (ICP-OES), X-ray
diffraction (XRD), thermogravimetry/differential thermogravimetry
(TG/DTG), and Fourier transform infrared spectroscopy (FT-IR).
The Hammett indicator is used to determine the basic strength
of the solid bases (H_). About 200 mg of sample was shaken with
10 mL methanol solution of the Hammett indicator and left for 1 h
to achieve equilibration. The concentrations of 0.02 mol/L bro-
mthymol blue (H_ ) 7.2), phenolphthalein (H_ ) 9.8), 2,
4-dinitroaniline (H_ ) 15.0), and 4-nitroaniline (H_ ) 18.4) were
used for Hammett indicators. Methanol was used as a solvent.
Sodium solubility in methanol was determined by a Spectro
Genesis EOP ICP-OES (Keleve, Germany). The ICP-OES-
Spectrometer settings are shown in Table 1.
The XRD measurements were performed on a XRD-6000 powder
diffraction using Cu-KR radiation over a 2θ range of 10-80° with
a step size of 0.02° at a scanning speed of 4°/min. The data were
analyzed with the DiffracPlus software, and phases were identified
according to the Powder Diffraction (PDF) database (JCPDS,
International Centre for Diffraction Date).
Thermal analysis of NaAlO2 was carried out on an AETARAM
SETSYS 16TG/DTA/DSC apparatus operating under a flow of air
at a 10 K/min heating rate up to 800 °C.
Avatar 360 FT-IR was used for the infrared analysis of the solids
with the KBr pellet technique. The range of scanning was from
400 cm-1 to 4000 cm-1.
2.4. Method of Analysis. The samples were analyzed with
Varian-3900 gas chromatography with an automatic injection
system. Data collection and analysis were performed with a Varian-
3900 workstation. A capillary column (HP5, 30m × 0.32 mm ×
0.25 µm) was used for separation. Nitrogen was used for the carrier
gas, and the split ratio was 10:1. Samples were prepared by
dissolving about 15 mg of biodiesel sample into a 10 mL of
n-hexane. About 5 mg of lauric acid methyl ester was added as a
reference of crude biodiesel.23 Samples were placed in a gas
(23) Yong, W.; Shiyi, O.; Pengzhan, L.; Feng, X.; Shuze, T. J. Mol.
Catal. A. 2006, 252, 107–112.
Wan et al.
Table 2. Basic Strengths, Solubility, and Catalytic Activities
with Different Calcination Temperatures of NaAlO2
basic solubilityb yieldc
thermal treatmenta strength (H_) (µg · mL-1) (%)
no 18 < H_ 120.7 89.9%
15 < H_ <18 68.1 62.7%
light
15 < H_ <18 127.8 83.0%
400 °C 15 < H_ <18 83.3 72.0%
600 °C 15 < H_ <18 81.6 66.2%
800 °C 9.8 < H_ <15 45.3 56.7%
600 °C used and recalcined not analyzed 40.0 62.9%
at 600 °C
a All thermal treatments were carried out for 4 h. b A 0.45 g quantity
of SA dissolved in 15 mL of methanol, stirred for 30 min, then
centrifuged, and the methanol transferred into a 1000 mL volumetric
flask filled with deionized water. c The reactions were performed with a
methanol/oil molar ratio of 12:1 and 1.5% catalyst at reflux temperature
for 30 min.
chromatography (GC) auto sampler vial and 1.0 µL was injected
for GC analysis. The oven temperature program consisted of the
following: start at 120 °C (3 min), ramp at 30 °C/min to 170 °C (2
min), and ramp at 30 °C/min to 265 °C (20min). The purity of
crude biodiesel was calculated based on the area of FAME over
the reference by the following equation:
area of FAME
× weight of reference
area of reference
purity(%) ) × 100
weight of crude biodiesel
3. Results and Discussion
3.1. Basic Strength, Solubility, and Catalytic Activity
with Different Calcination Temperatures. Table 2 summarizes
the basic strength, solubility, and catalytic activities of SA
calcined at different temperatures. The NaAlO2 sample with no
treatment could change the color of 4-nitroaniline (H_ ) 18.4)
from yellow to orange and had the highest activity in the
transesterification. However, the dissolved quantity achieved
120.7 µg mL-1, about 26.8% of the loading amount. As the
temperature had a significant influence on the composition of
equilibrium crystalline, we treated NaAlO2 at high temperatures.
These samples (H_ > 15.0) could be regarded as strong bases
according to the definition of acids and bases by Tanabe.24 With
the increase in calcination temperatures, the basic strength,
solubility, and catalytic activities were decreased. However, we
still need to mention that the maximum solubility is at 200 °C
calcined sample. It probably belongs to chemisorbed H2O and
CO2 in air at low temperature calcination. The sample dried
with infrared light was more stable in methanol than the sample
calcined at 600 °C. The result indicated that water was the main
factor for the stability, whereas the negative effect of CO2 is
less important. When the temperature was higher than 600 °C,
the stability increase could be the phase transformation detected
by XRD. The following instrumental investigation supported
these hypotheses. The reactivity was closely related with
NaAlO2 solubility in methanol, suggesting that the catalytic
reaction was the result of the heterogeneous and homogeneous
contributions. Part of the reaction took place on basic sites at
the surface of the catalyst; the rest was due to the dissolution
of the activated NaAlO2 in methanol that creates homogeneous
leached active species. We also tested the catalyst that repeated
the transesterification reaction for one time, which was shown
to have highest stability but not the lowest reactivity. The reason
(24) Tanabe, K.; Imelik, B. In Catalysis by Acids and Bases; Imelik,
B., Nacceche, C., Condurier, G., Taarti, Y. B., Vedrine, J. C., Eds.; Elsevier:
Amsterdam, 1985; p 1.
Sodium Aluminate As a Heterogeneous Base Catalyst
Figure 1. TG/DTG traces of initial SA (a) and the sample used for
one time (b).
Figure 2. XRD patterns for SA calcined at different temperatures, (a)
initial sample with no calcination, (b) sample calcined at 200 °C, (c)
sample calcined at 400 °C, (d) sample calcined at 600 °C, (e) sample
calcined at 800 °C, (f) sample calcined at 600 °C used and recalcined
at 600 °C. All samples’ calcination was carried out for 4 h.
for this may be due to organic materials adsorbed, which led to
carbonization on the catalyst surface at a high temperature, and
then changed the catalytic character.
3.2. Thermal Analysis. The TG/DTG traces of SA and the
sample used for one time are reported in Figure 1. The NaAlO2
sample presents two weight losses at temperature ranges of
28-160 °C and 160-220 °C. The total weight loss amounted
to 18.51% and could be attributed to the elimination of carbon
dioxide and water from the sample. The curves of the used solid
exhibit three weight losses in the temperature ranges of 28-200
°C, 200-250 °C, and 250-500 °C. The first two weight losses
amounting to 16.16% correspond to the elimination of carbon
dioxide and water, whereas the second one is due to the organic
materials adsorbed on the catalyst surface decomposed at a high
temperature.
3.3. XRD analysis. The crystalline phases of SA treated at
different temperatures were identified by X-ray diffraction
analysis whose pattern is shown in Figure 2. All of the samples
show the diffraction peaks of NaAlO2. Especially, the observed
powder pattern of the sample calcined at 800 °C corresponds
well with the Powder Diffraction file pattern (PDF 33-1200)
(2θ ) 20.7, 21.1, 30.3, 33.2, 34.3, 34.9, 37.6, 42.2, 46.4, 48.5,
52.0, 57.6, 61.9, 63.1, 63.8, 65.9, 68.8, 72.4). The NaAlO2 with
no thermal treatment demonstrated that these materials are three-
Energy & Fuels, Vol. 23, 2009 1091
Figure 3. Infrared spectra of SA with different thermal treatment, (a)
drying under infrared light, (b) calcined at 200 °C, (c) calcined at 400
°C, (d) calcined at 600 °C, (e) calcined at 800 °C, (f) calcined at 600
°C used and recalcined at 600 °C. All thermal treatments were carried
out for 4 h.
phase mixtures of sodium Dawsonite NaAl(OH)2CO3,25
NaAlO2 · χH2O (PDF 41-638), and NaAlO2 (PDF 33-1200).
When we elevated the temperature from 200 °C to 400 °C, the
intensity of the peaks (2θ ) 16.7, 25.3, 26.8, 29.3, 31.7, 39.0,
55.3, 55.7) shrunk gradually, and the peaks (2θ ) 21.0, 30.4,
46.5, 48.5, 62.1, 64.5, 69.1) grew with the temperature. The
process consisted of hydrated SA on heating in situ in air as
studied by Kaduk and Shiyou.26 SA began to lose water and
carbon dioxide from when the temperature elevated, and only
showed single-phase NaAlO2 at 800 °C. No intermediate phases
are detected. Regarding the dissolution changing with the
temperature in Table 2, XRD analysis confirmed that the main
reason for SA dissolution in methanol was that water and carbon
dioxide changed its composition. Dehydration is an efficient
way to enforce the stability of SA in methanol. The sample
calcined at 600 °C used for one time and recalcined at 600 °C
showed some difference with other samples. A new crystalline
phase of γ-NaAlO2 (PDF 19-1179) (2θ ) 20.9, 26.8, 30.4, 33.8,
34.6, 36.0, 42.0, 45.4, 46.0, 48.3, 50.2, 54.5, 54.8, 58.1, 61.0,
63.2, 65.8, 68.7, 69.1) was formed, suggesting there was a phase
transformation.
3.4. Infrared Analysis of the Solid. To further understand
the correlation between the solid catalyst composition and
calcination temperature, characterization by FT-IR was also
carried out. From the spectra in Figure 3, we can see that the
absorption bands corresponding to O-H at 3300 to 3700 cm-1
and 1650 cm-1, and to carbonate at 1450 cm-1 gradually
decreased in intensity when we elevated the temperature from
200 to 800 °C. The sample dried by infrared light shows the
lowest O-H bands in intensity and the second lowest carbonate
peak. It can be concluded that thermal treatment eliminates water
and carbon dioxide at the same time, but infrared light is more
efficient for the elimination of water. The absorption peaks at
810 cm-1, 610 cm-1, 560 cm-1, and 490 cm-1 are associated
with the coordination state of the aluminum present in the
system.27 The sample calcined at 600 °C used for one time and
recalcined at 600 °C exhibits very small peaks at 1450 cm-1
and 810 cm-1 indicating that the surface of the solid is covered
(25) Serna, J.; White, J. L.; Hem, S. L. Clays Clay Miner. 1977, 25,
384–391.
(26) Kaduk, J. A.; Shiyou, P. J. Solid State Chem. 1995, 115, 126–139.
(27) Contreras, C. A.; Sugita, S.; Ramos, E. AdV. Technol. Mater. 2006,
8 (2), 122–129.
1092 Energy & Fuels, Vol. 23, 2009
Figure 4. Effect of reaction time on the methyl ester yield. Reaction
condition: catalyst amount 1.5%, methanol/oil molar ratio of 12:1,
methanol reflux temperature.
Figure 5. Effect of methanol/oil molar ratio on the methyl ester yield.
Reaction condition: catalyst amount of 1.5%, reaction time of 30 min,
methanol reflux temperature.
with carbon. The sharp absorption peaks at 610 cm-1, 560 cm-1,
and 490 cm-1 show the same component of aluminum species.
3.5. Catalytic Properties. The effects of reaction time,
methanol/oil molar ratio, and catalyst amount were studied. The
catalysts with no pretreatment were used in the catalysts’
variables test. The influences of reaction time are illustrated in
Figure 4. The reaction rate for the initial 10 min was very fast
and reached 93.9% at 50 min. The reason may partly be due to
the dissolution of the catalyst active species in methanol and
the formation of CH3O in the system.
The influences of methanol/oil molar ratio are shown in
Figure 5. In heterogeneous catalysis, mass transfer and reactant
adsorption on the catalyst is very important; thus, a molar ratio
higher than the stoichiometric molar ratio of methanol is needed
to shift the equilibrium for the reaction. When the methanol/oil
molar ratio reached 15:1, the maximum conversion was
obtained, which was distinguished from the value for the
homogeneous system.28 The production yield only improved a
little when the methanol/oil molar ratio was elevated from 12:1
(28) Freedman, B.; Pryde, E. H.; Mounts, T. L. JAOCS 1984, 61, 1638–
1643.
Wan et al.
Figure 6. Effect of catalyst amount on the methyl ester yield. Reaction
conditions: methanol/oil molar ratio of 12:1, reaction time of 30 min,
methanol reflux temperature.
to 15:1. The result indicated that excessive use of methanol had
no significant effect on the production yield.
In Figure 6, the influences of catalyst loading amount are
presented. The optimum catalyst amount was found to be 1.5%,
and the yield reached 89.9%. The extra loading of the catalyst
did not lead to an increase in production yield. This was
probably because the slurry became too viscous, giving rise to
a problem of mixing and a demand of higher power consumption
for adequate stirring.
Reusability tests were also performed. The catalyst calcined
at 600 °C reused without recalcination would achieve 47.4%
yield for the second round, and 12.1% for the third round.
Otherwise, the catalyst calcined at 600 °C before each cycle
was used for three cycles. The yield was 66.2%, 62.9%, and
61.4%. It is reasonable that calcination is very important for
the catalyst’s reusability.
4. Conclusions
We aimed to investigate if SA was an effective heterogeneous
catalyst for biodiesel production. The solid base showed high
activity for the alcoholysis of soybean oil. The reaction was
carried out at a reflux temperature with a 12:1 molar ratio of
oil to methanol and 1.5% catalyst loading for a reaction time
varying from 10 to 60 min, in which the methyl ester yield
reached 82.9-93.9%. In particular, catalytic durability tests
showed slight decrease in activity by repeating the transesteri-
fication reaction for three times.
We also investigated the stability mechanism of SA. NaAlO2
adsorbed water and carbon dioxide, then changed the superficial
composition like NaAlO2 · χH2O and NaAl(OH)2CO3. They were
easy to dissolve in methanol. At the same time, there was also
probably a small part of NaAlO2 leaching into methanol.
Acknowledgment. The authors are grateful to Associate Profes-
sor Man He in the centre of analysis and test of Wuhan University
for assistance with ICP tests.
Supporting Information Available: Further details about the
gas chromatography analysis are given in Figures S1 and S2.
This material is available free of charge via the Internet at
http://pubs.acs.org.
EF800904B