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Sodium zirconate (Na2ZrO3) as a catalyst in a

soybean oil transesterification reaction for
biodiesel production
ARTICLE in FUEL PROCESSING TECHNOLOGY APRIL 2014
Impact Factor: 3.02 DOI: 10.1016/j.fuproc.2013.11.018

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Fuel Processing Technology 120 (2014) 3439

Contents lists available at ScienceDirect

Fuel Processing Technology

journal homepage: www.elsevier.com/locate/fuproc

Sodium zirconate (Na2ZrO3) as a catalyst in a soybean oil

transesterication reaction for biodiesel production
Nicols Santiago-Torres, Issis C. Romero-Ibarra, Heriberto Pfeiffer
Instituto de Investigaciones en Materiales, Universidad Nacional Autnoma de Mxico, Circuito Exterior s/n Cd. Universitaria, Del. Coyoacn, CP 04510 Mexico DF, Mexico

a r t i c l e

i n f o

Article history:
Received 7 February 2013
Received in revised form 24 November 2013
Accepted 24 November 2013
Available online xxxx
Keywords:
Basic catalyst
Biodiesel
Sodium zirconate
Soybean oil

a b s t r a c t
Sodium zirconate (Na2ZrO3) was tested as a basic catalyst for the production of biodiesel using a soybean
oil transesterication reaction. Initially, Na2ZrO3 was synthesized via a solid-state reaction. The structure and
microstructure of the catalyst were characterized using X-ray diffraction, scanning electron microscopy and N2
adsorption. Various transesterication reactions were then conducted using soybean oil and methanol under
differing reaction conditions. The inuence of some parameters, such as the reactant concentrations (molar
ratios), catalyst percentage, reaction time, temperature and re-use of the catalyst, on the transesterication
process in the presence of Na2ZrO3 was investigated. The maximum FAME conversion efciency was 98.3% at
3 h of reaction time and 3% of catalyst. Additionally, the produced biodiesel was characterized using infrared
spectroscopy, gas chromatography coupled to mass spectrometry and proton nuclear magnetic resonance. The
resulting biodiesel showed good purity, composition and degree of unsaturation in comparison to previous
reports. According to these results, Na2ZrO3 could become an alternative solid base catalyst for scalable and
cost-effective biodiesel production.
2013 Elsevier B.V. All rights reserved.

1. Introduction
One promising approach to mitigate global energy problems is
the use of biomass bio-fuels, such as bioethanol and biodiesel, as abundant and environmentally friendly energy sources. Biodiesel is a nonpetroleum based, alternative diesel fuel that is relatively clean burning,
non-toxic, biodegradable and renewable [16]. It consists of a mixture
of esters composed of mono-methyl esters of long chain fatty acid derivatives [79]. The combustion of biodiesel can decrease carbon monoxide (CO) emissions by 46.7%, particulate matter emissions by 66.7%
and unburned hydrocarbons by 45.2% [9].
The most common method for producing biodiesel is via triglyceride
(TG) transesterication from vegetable oils and animal fats in the
presence of short-chain alcohols and homogeneous acid or base catalysts; these yield fatty acid methyl esters (FAME) or fatty acid ethyl
esters (FAEE) and glycerol (also called glycerin) as products [10].
Every triglyceride molecule reacts with 3 equivalents of alcohol to
produce glycerol and three fatty acid (methyl) ester molecules
[1113]. The alcohols (R-OH) used in the transesterication are normally methanol or ethanol, where methanol is the most common because of
its low cost, low reaction temperatures, fast reaction times and higher
quality methyl ester products [911].
The most commonly used method for triglyceride transesterication
relies on the use of batch plants, where homogeneous base-catalyzed
reactions are used [10,14]. NaOH, KOH or methoxides are typically
Corresponding author. Tel.: +52 55 5622 4627; fax: +52 55 5616 1371.
E-mail address: pfeiffer@iim.unam.mx (H. Pfeiffer).
0378-3820/$ see front matter 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.fuproc.2013.11.018

used as the homogenous catalyst due to their high activity, among

other advantages that make them economically superior over mineral
acids and lipases [12]. In this catalytic method, the base catalysts are
unrecyclable after the reaction and suffer from separation problems.
Additionally, the current aqueous quenching practice, which is
performed by acid quenching, results in saponication and emulsion
formation. This process also results in an alkaline wastewater stream,
which leads to the corrosion of equipment and high operating costs.
Moreover, the recovered glycerol is normally impure due to the
presence of salts, soaps, monoglycerides and diglycerides, and the glycerol purication process consequently adds an additional cost. Therefore, for both environmental and economic reasons, there is increasing
interest in the possibility of replacing homogeneous bases by heterogeneous solid catalysts for triglyceride transesterication [2,5,9,1519].
Different heterogeneous base catalysts have been investigated for
the production of biodiesel [10]. Some of these solid catalysts include
alkali-metal and alkaline earth metal carbonates and oxides (MgO,
CaO, BaO and SrO [1923]), lithium base ceramics (Li4SiO4 and Li2SiO3
[24,25]), Na2SiO3 [26], transition metal oxides (ZnO, PbOx, ZrO2 etc.
[27,28]), basic ion-exchange resins [29], layered double hydroxides
[3033], supported bases (basic alumina, [34]), salts impregnated on
Al2O3 and ZnO [3537] and zeolites [38]. CaO has been one of the
most widely used alkaline earth metal oxides as a catalyst for the
transesterication reaction, as the transesterication reaction yields a
98% FAME efciency during the rst cycle [39]. Modications of ZnO
or CaO with lanthanum [40] and lithium [41] have attracted considerable attention for the production of biodiesel due to their high basicity,
low solubility and low preparation cost [1,10].

N. Santiago-Torres et al. / Fuel Processing Technology 120 (2014) 3439

(200)

30

50

(260)

(013)
(531)

(331)

40

(531)
(060)

(331)
(400)
(131)
(131)

(311)

(320)

20

(220)

Sodium zirconate (Na2ZrO3) was prepared via a solid state reaction.

Stoichiometric amounts of zirconium oxide (ZrO2, Sigma-Aldrich) and
sodium carbonate (Na2CO3, Aldrich) were mixed and heat-treated
at 900 C for 4 h. The sample was then characterized using X-ray
diffraction (XRD), scanning electron microscopy (SEM) and nitrogen
adsorption. X-ray diffraction patterns were obtained on a Bruker AXS
D8 Advance diffractometer coupled to a copper anode X-ray tube. The
resulting compounds were identied according to their corresponding
JCPDS les (Joint Committee Powder Diffraction Standards). The
microstructural characteristics of Na2ZrO3 were determined via N2
adsorptiondesorption and scanning electron microscopy (SEM) measurements. For the N2 adsorptiondesorption experiments, isotherms
were acquired on a Bel-Japan Minisorp II at 77 K using the multi-point
technique. The samples were degassed at room temperature for 24 h
under vacuum before analysis. SEM experiments were performed on a
JEOL JMS-7600F SEM.
Transesterication reactions catalyzed by Na2ZrO3 were performed
in a 25 mL three-neck round-bottomed glass ask equipped with a
mechanical stirrer, a reux condenser and a thermometer. The batch
reactions were performed with various stoichiometric methanol/soybean
oil molar ratios. Analytical grade methanol (Sigma-Aldrich, 99.9% purity)
was used along with pure Soybean oil, Nutrioli brand NOM-051SCFI-SSA12010, that was purchased at a local food store (Mexico, D.F.).
The fatty acid composition of the soybean oil was determined by gas
chromatography (GC) analysis and is reported in the Results and
discussion section. Various catalyst concentrations between 1 and 10%
sodium zirconate under vigorous magnetic stirring at 65 C were considered. Additional experiments were performed at different temperatures
(45, 65 and 85 C). A reux condenser was employed to prevent the
evaporation of alcohol. The progress of the transesterication reaction
was monitored at various reaction times between 0.5 and 8 h. After the
corresponding reaction times, the samples were immediately quenched
in an ice bath (~4 C) to control the conversion rate, and the different
phases were separated for analysis. The top liquid layer was the FAME
(fatty acid methyl ester) phase, whereas the bottom liquid phase
was glycerol. Both liquid layers were separated, and the catalyst was
recovered and washed several times with methanol.
The components of the FAME and liquid samples as well as the purity of the biodiesel product were determined using infrared spectroscopy (ATR-FTIR), proton nuclear magnetic resonance (1H NMR) and gas
chromatography coupled with mass spectrometry. For ATR-FTIR spectroscopy measurements, the samples were analyzed using a Nicolet
6700-FTIR spectrometer. Several 1H NMR analyses were performed
using a Bruker Advance II spectrometer (200 MHz) with CDCl3 (99.8%,
Aldrich) as the solvent. A Hewlett Packard-5973 GCMS was used
to evaluate the conversion and selectivity of the product over the
transesterication reactions. The mobile phase was hexane (HPLC
grade, Sigma-Aldrich). The nal ow rate was 0.9 mL/min, and the sample injection volume was 1 L. The temperature of the detector was
250 C, and the temperature analyses were initially performed from
150 to 300 C at a rate of 20 C/min. All analyses were performed at
room temperature. Finally, the catalyst was re-characterized by XRD
after several transesterication cycles to evaluate the structural stability
of the catalyst.

The purity of Na2ZrO3 was analyzed by XRD. Fig. 1 shows the XRD
pattern of the sample after thermal treatment at 900 C for 4 h. The diffraction pattern was tted to the JCPDS le 35-0770, which corresponds
to Na2ZrO3 with a monoclinic structure. Therefore, Na2ZrO3 was obtained without the presence of any impurities at the XRD detection level
(N 3%). The Na2ZrO3 microstructural characteristics were determined
using SEM and N2 adsorption. The morphology and particle size of the
sample were analyzed by SEM (Fig. 2). The Na2ZrO3 particles exhibited
a dense polyhedral morphology, with an average particle size of ~1 m.
These particles produced large agglomerates with sizes greater than
1520 m. The dense morphology was corroborated by the textural
analysis performed using nitrogen adsorptiondesorption experiments,
in which a surface area of 1.3 m2/g was determined using the BET
model [45]. All microstructural results are in good agreement with the
solid-state reaction synthesis method.
Once the Na2ZrO3 was characterized, the material was used as a
catalyst in the transesterication reaction of soybean oil and methanol.
Initially, the objective was to investigate the inuence of the amount
of catalyst used on the conversion. The amount of catalyst was
varied between 1 and 10 wt.% (catalyst/oil weight ratio), and the
transesterication reactions were performed at 65 C for 3 h.
These experimental conditions were established based on different
references reporting that some alkaline ceramics show the best
conversion under similar conditions [24,25]. As shown in Fig. 3,
the conversion increased as the amount of catalyst increased from
1 to 3 wt.%. In this range, the conversion varied from 84.5 to
98.3%, with the best conversion ratio at 3 wt.% catalyst. The conversion tended to decrease for higher catalyst concentrations. With
10 wt.% catalyst, the conversion ratio decreased to 93.3%. Note
that in heterogeneous catalysis, mass transfer and reactant adsorption on the catalyst are extremely crucial. Therefore, a molar ratio
that is greater than the stoichiometric molar ratio of methanol is
required to shift the equilibrium of the reaction [46]. Because the
oil/methanol ratio was not varied, but the catalyst content was
increased, it may have partially decreased the nal conversion
observed at catalyst concentrations greater than 3 wt.%.
After the optimal catalyst amount was determined to be 3 wt.%, the
temperature conditions were optimized for this amount of catalyst. As
shown in Fig. 3, varying the temperature to greater than or less than
65 C resulted in decreased reaction conversion efciencies. At 45 C,
the conversion ratio decreased to 78.4%, indicating a decrease in the
kinetic properties of the reaction. Increasing the temperature to 85 C
strongly favored the conversion to glycerol, and the nal conversion
ratio was a modest 83.3%.

(020)
(011)
(211)

2. Experimental section

3. Results and discussion

Intensity (a.u.)

Sodium zirconate (Na2ZrO3) has recently been examined for high

temperature CO2 capture and has shown some interesting behavior
[4244]. It has been found that Na2ZrO3 is able to trap CO2 due to its
lamellar crystal structure and because of its high surface basicity [42].
Therefore, the aim of the present work is to determine the inuence of
sodium zirconate as a catalyst in the transesterication reaction of
soybean oil, where the parameters of temperature, time and reagent:
catalyst molar ratios were examined.

35

60

2
Fig. 1. XRD pattern of the Na2ZrO3 catalyst synthesized by solid-state reaction.

36

N. Santiago-Torres et al. / Fuel Processing Technology 120 (2014) 3439

FAME conversion efficiency (%)

100

3 wt% of catalyst
5 wt% of catalyst
10 wt% of catalyst

98
96
94
92
90
88
86
84
0

time (hours)
Fig. 4. Kinetic curves of the FAME conversion efciency of the soybean oil and methanol
transesterication reaction, varying the Na2ZrO3 amount as catalyst.

100

1480 -1100

720

1748

3330

Fig. 4 shows three different kinetic curves for the FAME conversion
as a function of time and with varying amounts of catalyst (3, 5 and
10 wt.%). This gure shows that the experiments performed with
3 wt.% catalyst resulted in the highest FAME conversion for each time
examined relative to the other kinetic series. This result is in good agreement with the previous results presented in Fig. 3. Additionally, the
three kinetic curves show important increases in efciency during the
rst three hours, which correspond to the highest FAME conversion.

3004
2853
2926

Fig. 2. SEM images of the Na2ZrO3 catalyst synthesized by solid-state reaction.

Nevertheless, at prolonged reaction times, the FAME conversion

decreases, with nal FAME efciencies of approximately 8790%.
Similar effects have been previously observed [47]. Amin and coworkers have reported that high quantities of methanol (30:1) in
transesterication reaction systems, as in the present case, tend to
decrease the FAME conversion over long periods of time [47].
Alkaline-modied zirconias were used as the catalyst materials in
that report; therefore, similar effects may be produced in this
study. In our case, the decrease in FAME conversion was associated
with further glycerol production.
The biodiesel was characterized using ATR-FTIR, 1H NMR and GC
MS. Fig. 5 shows the ATR-FTIR spectra of the biodiesel produced over
different reaction times at 65 C with 3 wt.% Na2ZrO3 as a catalyst.
Although the spectra do not exhibit any major changes, there are
some specic vibration bands that must be analyzed. At approximately
3330 cm1, there is a wide vibration band associated with O\H bonds
that corresponds to the presence of methanol [48]. As expected, this
O\H vibration band can be clearly observed in the biodiesel sample

0.5 h

FAME conversion efficiency (%)

98
96

1h

94

1015

92

3h

90
88

4h

86
84

(85 C)

82

8h

80

(45 C)

78
76
0

10

Catalyst amount (wt%)

Fig. 3. FAME conversion efciency of the soybean oil and methanol transesterication
reaction, using Na2ZrO3 as catalyst and varying temperature and the catalyst amount.

4000

3000

2000

1000

Wavenumber (cm-1)
Fig. 5. ATR-FTIR spectra of the biodiesel produced at different reaction times at 65 C with
3 wt.% of Na2ZrO3 as catalyst.

N. Santiago-Torres et al. / Fuel Processing Technology 120 (2014) 3439

9000
8000
7000
6000

Abundance

prepared over 0.5 h, indicating an incomplete reaction. In this case,

the FAME conversion was 86.7%. This band disappeared over longer
reaction times, showing good progress of the transesterication reaction. Aside from this band, the ATR-FTIR spectra were in very good
agreement with previous reports [4951]. The three well-dened vibration bands located at 3004, 2926 and 2853 cm1 correspond to carboxylic acid compounds. The presence of a strong C_O double bond band
at ~ 1748 cm 1 corresponds to the ester group, which conrms the
transesterication of the oil [50]. In addition to the previous vibration
bands, other vibration bands were observed between 1480 and
1100 cm1, which correspond to the \CH2 scissor and \CH3 antisymmetric vibrations. These spectra also exhibited a specic vibration band
at approximately 720 cm1, corresponding to the cis isomers of \CH.
Finally, the rst (0.5 h) and last (8 h) ATR-FTIR spectra exhibited a vibration band located at 1015 cm 1, which can be associated with
C\(OH) vibrations. In the rst case, this band can be attributed to the
presence of methanol, whereas in the second case, this vibration band
may be associated to the partial dissolution of glycerol because the
formation of glycerol is favored for long reaction times. A closer analysis
of the 8 h spectrum shows an O\H vibration band between 3100 and
3400 cm1. This result is in good agreement with the decrease
in FAME conversion observed over long reaction times, which was
previously associated with a higher glycerol conversion.
The soybean oil and aliquots of different biodiesel products were
characterized by NMR. Fig. 6 shows the 1H NMR spectra of the initial
soybean oil and biodiesel produced with 3, 5 and 10 wt.% of the Na2ZrO3
catalyst during 3 h at 65 C. Initially, the pure soybean oil spectrum ts
very well with previously reported 1H NMR spectra [11]. The transformation of soybean oil into biodiesel (FAME) could then be determined
by the appearance of a signal at ~3.5 ppm (9H), corresponding to the
metylenic \CH3 protons. Additionally, some specic differences were
observed among the spectra. The 3 wt.% spectrum shows three very
small peaks located at 0.9, 4.1 and 4.2 ppm. These peaks were observed
in the spectrum for the soybean oil and correspond to the \CH2 and
\CH3 protons of the palmitic and linoleic chains. The presence of
these peaks indicates incomplete FAME conversion, which corroborates
the gravimetric quantication. The presence of these peaks was not
observed in the other 1H NMR spectra. Residual methanol was also
observed in all transesterication reaction samples at 3.4 ppm. Integration of the signals showed that the methanol concentration increased as
a function of the catalyst content, from 0.16 to 1.14. The presence and
increase in methanol concentration can be correlated to the incomplete
FAME conversion observed when the amount of catalyst was increased
from 3 to 10 wt.%. It must be mentioned that glycerol is insoluble in
CDCl3; therefore, it was not detected.

37

5000
4000
3000
2000
1000

1.0

2.0

3.0

4.0

5.0

6.0

7.0

8.0

9.0

time (min)
Fig. 7. Typical gas chromatogram obtained from the different biodiesel products. In this
case the chromatogram corresponds to the biodiesel produced after 3 h of reaction at
65 C, using 3 wt.% of Na2ZrO3 as catalyst.

The average degree of FAME unsaturation (DU) was calculated by

comparing the 1H NMR integration values for the methyl group
(3.67 ppm) and the olen protons (5.35 ppm) in the methyl ester
products [11,38]. The DU values from soybean oil obtained in this
manner were 0.89, 1.09 and 1.07 for the 3, 5 and 10 wt.% of catalyst,
respectively. These values are similar to previous reports, where values
between 0.96 and 1.06 were obtained [11,38,52,53].
The biodiesels were nally characterized by GCMS to more
precisely elucidate their chemical compositions. Fig. 7 shows a typical
chromatogram obtained from the different biodiesel products. At low
retention times, the GC curves showed an incomplete peak, which
may be associated with the methanol originally present in the samples
(see RMN results). The rst well-dened peak, which was observed
after 1.7 min, corresponds to the hexane used as a solvent in these
experiments. After the hexane peak, three peaks appeared at 5.4, 6.1
and 6.4 min, and the chemical compositions of these peaks were identied by mass spectrometry, which showed that these were a typical
mixture of biodiesel esters. The rst peak (5.4 min) was associated

FAME conversion efficiency (%)

100

(D)
(C)
(B)

(A)

98
96
94
92

Na 2ZrO3 catalyst was

washed with methanol

90
88
86
84
82
80

Chemical shift (ppm)

Fig. 6. 1H NMR spectra of the initial soybean oil (A) and biodiesels produced with 3 (B),
5 (C) and 10 wt.% (D) of Na2ZrO3 as catalyst during 3 h at 65 C.

Cycle number
Fig. 8. Na2ZrO3 reutilization analysis of ve transesterication reactions performed with
3 wt.% of catalyst, at 65 C for 3 h.

38

N. Santiago-Torres et al. / Fuel Processing Technology 120 (2014) 3439

with hexadecanoic acid methyl ester (CH3-O-CO-(CH2)14-CH3), the

second peak (6.1 min) corresponded to 9-, 12-, octadecadienoic acid,
methyl ester (CH3-O-CO-(CH2)7-CH = CH-CH2-CH = CH-(CH2)4-CH3),
and the third peak (6.4 min) was determined to be octadecanoic acid
methyl ester (CH3-O-CO-(CH2)16-CH3).
Finally, to evaluate the cyclability performance of the Na2ZrO3, the
transesterication process was repeated ve times using the same
catalyst. Fig. 8 shows that the FAME conversion was diminished as a
function of the cycle number, from 98.3% in the rst cycle to 81.3% in
the fourth cycle. The catalyst was then washed after the fourth cycle,
and it exhibited some recovery in the FAME conversion (84.0%) in the
following cycle. The reduction in FAME conversion observed during
the cycles may be attributed to several factors, as follows: 1) After
each cycle, the catalyst was recovered by decantation, and part of the
catalyst was lost (~ 5% after ve cycles). 2) Although the crystalline
structure of Na2ZrO3 did not change (XRD analysis not shown), the
particle surface must suffer inactivation, as it was evidenced during
the washing process.
4. Conclusions
Na2ZrO3 was synthesized, characterized and evaluated as a basic
catalyst for the production of biodiesel. The biodiesel produced through
a transesterication reaction was characterized. Qualitative and quantitative results showed that Na2ZrO3 has excellent catalytic activity and
good stability due to its basic strength and because it is stable during
transesterication reactions. The FAME conversion reached an excellent
efciency of 98.3% after 3 h at 65 C. Additionally, the biodiesel characterization corroborated the FAME conversion and other parameters,
such as its high purity, composition (typically 9, 12, octadecadienoic,
hexadecanoic and octadecanoic acid methyl esters) and degree of
unsaturation (between 0.89 and 1.09). The biodiesel produced with
Na2ZrO3 showed similar conversions relative to other basic heterogeneous and homogeneous systems, and the obtained biodiesel had
good properties. Finally, the cyclic behavior revealed that the catalyst
had a relatively stability. Nevertheless, Na2ZrO3 should be further analyzed and improved upon to maintain its high initial FAME conversion.
All of these results suggest that Na2ZrO3 could become an alternative
solid base catalyst for scalable and cost-effective production of biodiesel.
Acknowledgments
The present work was nancially supported by the project
IN102313-PAPIIT-UNAM. The authors thank A. Tejeda and O. Novelo
for technical help.
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