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Applied Catalysis A: General 339 (2008) 45–52

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Comparative study of triglyceride transesterification in the presence

of catalytic amounts of sodium, magnesium, and calcium methoxides
Igor N. Martyanov, Abdelhamid Sayari *
Department of Chemistry, University of Ottawa, Ottawa, Canada K1N 6N5
Received 18 September 2007; received in revised form 2 January 2008; accepted 12 January 2008
Available online 18 January 2008

Abstract
A solution of Mg(OCH3)2 in methanol, in-house prepared solid MgOx(OCH3)22x, and commercial Ca(OCH3)2 were tested at 60 8C in
transesterification of tributyrin with methanol—a model reaction for biodiesel production. The homogeneous magnesium methoxide acts fast at the
beginning of the reaction but quickly forms a suspension/precipitate mixture of much lower catalytic activity. The precipitate was found to be a
complex composition including glycerol and butyric acid derivatives. The reaction over solid MgOx(OCH3)22x is catalytic but sluggish with
deactivation taking place in ca. 4 h. Analysis of the used catalyst revealed surface butyric acid as the most likely species responsible for the catalyst
deactivation. In the presence of Ca(OCH3)2, the yields of the products reach final values in about 4 h. The reaction starts as a heterogeneous process,
however, interaction of Ca(OCH3)2 with reaction products such as glycerol gives rise to catalytically active homogeneous species. Formed in a side
reaction calcium butyric acid derivatives contribute to Ca(OCH3)2 dissolution but do not deactivate the surface of the catalyst.
# 2008 Elsevier B.V. All rights reserved.

Keywords: Biodiesel; Magnesium methoxide; Calcium methoxide; Transesterification; Heterogeneous catalyst

1. Introduction batch homogeneously catalyzed processes with continuous

Biodiesel is a renewable fuel that can be produced from
vegetable oils or animal fats via transesterification reaction of
long chain triglycerides with methanol or ethanol [1,2].
Operation on biodiesel can be viewed as an indirect way of
utilization of solar energy harvested by plants. There are
numerous advantages associated with biodiesel including low
to zero net carbon dioxide emission, very low sulfur content,
low toxicity, and high biodegradability. Excellent lubricity
properties [3] make biodiesel an attractive petroleum diesel
extender. Though elevated NOx emission, oxidative stability,
and cold flow properties might pose problems [1,4], modern
diesel engines can, under most circumstances, operate on
biodiesel with no costly modification.
Biodiesel production demonstrates considerable annual
growth. Nevertheless, the relatively high cost of biodiesel
presents a limitation factor. Replacement of refined vegetable
oils with cheaper, lower quality feedstocks, and substitution of
* Corresponding author.
E-mail address: abdel.sayari@uottawa.ca (A. Sayari).
0926-860X/$ – see front matter # 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.apcata.2008.01.007
ones carried out over heterogeneous catalysts would be major
advances with the potential of drastically altering the biodiesel
production routine and lowering its cost.
A number of solid bases, often claimed to be heterogeneous
catalytic systems, have been described in the literature.
Examples include potassium-loaded alumina [5], solid
K2CO3-loaded alumina [6], and strontium oxide [7]. There
have also been a number of publications devoted to the
transesterification activity of magnesium oxide, and magnesia/
alumina mixed oxides. In particular, Leclercq et al. [8] found
that the conversion of rapeseed oil over magnesium oxide at the
refluxing temperature of methanol approaches ca. 69% in 22 h
reaction time. The utilization of a low surface area MgO
resulted in a limited 18% conversion of triacetin after 8 h at
60 8C. The activity of closely related magnesium/aluminum
mixed oxides as well as hydrotalcites has been also limited in
most cases. The oxides prepared by Xie et al. [9] by calcination
of hydrotalcites and tested with soybean oil showed up to 67%
conversion in 9 h at 60 8C. The conversion of tributyrate
measured after 3 h at 60 8C reached 74.8% for the sample of
Mg:Al hydrotalcites with 24 wt% magnesium loading [10].
However, recently studied by Goodwin et al. [11] the Mg–Al
46 I.N. Martyanov, A. Sayari / Applied Catalysis A: General 339 (2008) 45–52
base catalysts were quite active in the reaction of poultry fat
transesterification conducted at 120 8C and elevated pressure.
Calcium oxide and calcium methoxide demonstrated
generally better performance. The transesterification of rape-
seed oil with methanol catalyzed by these two materials was
studied by Gryglewicz [12]. The yield of the methyl ester level
off at 93% after 2 h at the boiling point of methanol. Examined
by Reddy et al. [13], nanocrystalline calcium oxide showed
excellent conversion above 99% of soybean oil after 24 h at
room temperature.
Homogeneous catalysts such as sodium hydroxide, potas-
sium hydroxide, or sodium methoxide exhibit good reaction
rates and are traditionally employed [14,15] to transesterify
high quality feedstock. It is believed that the activity of both
basic homogeneous and heterogeneous catalysts is caused by
alkoxide species generated from alcohol molecules. In this
respect it was deemed instructive to study the catalytic behavior
of various metal alkoxides applied in the form of solution or
solid powder. Taking into consideration the catalytic activity of
magnesium and calcium compounds reported in the literature,
and the low toxicity of alkali earth metals, we undertook a
comparative study of catalytic activities of magnesium and
calcium methoxides in the model reaction of methanol
transesterification of tributyrin.
2. Experimental
2.1. Reagents and materials
Sodium methoxide, calcium methoxide (98%), solution of
magnesium methoxide in methanol (9.8 wt%), anhydrous
methanol (99.8%), tributyrin (98%), calcium acetate mono-
hydrate (99%), and magnesium acetate tetrahydrate (98%)
were purchased from Aldrich and used with no further
purification. Chloroform-d (99.8%) was supplied by Cam-
bridge Isotope Laboratories, Inc. and used in NMR experiments
as received.
A powder of MgOx(OCH3)22x was prepared from the
solution of magnesium methoxide in methanol by vacuum
evaporation in a rotary evaporator for 2 h at 60 8C. The obtained
white powder was sealed in a flask and stored for further use.
2.2. Characterization of catalysts
Infrared spectra of solid catalysts were recorded on a
Magna-FTIR spectrometer 550 from Nicolet. Each spectrum
was an average of 128 scans taken with 4 cm1 resolution in the
400–4000 cm1 range. The preparation of KBr pellets contain-
ing solid catalysts consisted of weighting the samples, mixing
them with potassium bromide, grinding with a mortar and
pestle followed by pelletization of 200 mg of the mixture. The
final amount of the catalyst powder in the KBr pellets was ca.
1 wt%.
The in-house prepared MgOx(OCH3)22x and commercial
Ca(OCH3)2 were additionally characterized with thermogravi-
metric analysis (TGA) coupled with mass spectrometric (MS)
identification of gaseous products. In the typical TGA-MS
experiment, the solid samples were fist hold at 40 8C for
20 min, then heated at a rate of 108 min1 in 100 mL/min N2
flow, followed by switching to air at 800 8C and the ramp
continuation till 1000 8C. The TGA recordings were done on a
TGA Q500 form TA Instruments, whereas the leaving gaseous
species were monitored with a Thermostar mass selective
detector from Pfeiffer vacuum.
2.3. Catalytic experiments
The transesterification reactions were conducted in a two-
necked 100 mL round-bottomed flask equipped with a straight
condenser. A heating stirring plate with an oil bath was used to
maintain the reaction temperature of 60 8C and continuous
stirring. A typical experiment with a solid catalyst was carried out
as follows. About 7.9 mL of anhydrous methanol was added to
ca. 10 g of tributyrin. After mixing, 4 mL of the solution
was taken for GC–MS analysis. Later, an appropriate amount of
the catalyst (199 mg for Ca(OCH3)2 or 168 mg for
MgOx(OCH3)22x) was added, and one neck of the flask was
sealed with a septum followed by placing the reactor in the
preheated oil bath. In the case of Ca(OCH3)2, the catalyst used in
the first run was recovered via decantation with a centrifuge
operating at 2000 rpm. The recovered catalyst was subjected to
three cycles of methanol washing and decantation, and then
stored in a sealed container for the following catalytic run.
Experiments with commercially available sodium methox-
ide and solution of magnesium methoxide in methanol were
conducted in a similar way except for different mixing order. In
particular, sodium methoxide was dissolved in ca. 7.9 mL of
methanol to which ca. 10 g of tributyrin was added. A test with
the commercial magnesium methoxide solution was done
through its further dilution with methanol to ca. 7.9 mL
followed by addition of tributyrin. In all experiments with pre-
dissolved sodium methoxide, the commercial solution of
magnesium methoxide and the powdered calcium methoxide,
the molar ratios of tributyrin to sodium, magnesium, or calcium
moieties were close to 17, whereas the molar ratio of methanol
to tributyrin was kept at ca. 6. In the case of in-house prepared
MgOx(OCH3)22x and based on TGA experiment (see Section
3), the molar ratio of tributyrin to magnesium was ca. 16.5,
whereas the tributyrin to methanol ratio was kept the same.
2.4. Analytical procedures for quantification of reaction
products
The course of the reaction was monitored by periodic
collection of 4 mL of the reaction mixture and dissolving it in a
GC–MS sample vial containing 0.8 mL of solution of toluene in
methanol (0.5%, v/v). The diluted reaction mixture with
toluene as an internal standard was later analyzed with a gas
chromatograph (6890N) equipped with a mass selective
detector (5975) both from Agilent Technologies. Separation
of the reaction mixture components was carried out on a 30 m
HP-5MS ((5%-phenyl)-methylpolysiloxane phase) column
with 0.25 mm internal diameter and 0.25 mm film thickness.
During GC runs, the temperature of the column was changed as
 I.N. Martyanov, A. Sayari / Applied Catalysis A: General 339 (2008) 45–52
follows: 208 min1 ramp from 80 to 260 8C, hold at 260 8C for
1 min. The split ratio and the column flow rate were set to 1:100
and 1 mL/min, respectively. To avoid exposure of the filament
and the MS detector to large quantities of methanol, the mass
spectrometer cut off time was set to 1.4 min. Tributyrin, methyl
butyrate and glycerol were available and used for calibration of
the GC–MS for such compounds. The relative concentrations of
monobutyrin and methylbutyrate formed in the presence of
calcium and sodium methoxides were established using 1H
NMR experiments. Analysis of the same sample by GC–MS
taken in combination with the known methyl butyrate
calibration curve made determination of sensitivity of GC–
MS to monobutyrin possible. The calibration coefficient for
dibutyrin was set between its mono and tributyrate counterparts
to deliver good mass balance with respect to glycerol and
butyril moieties. Since only indirect calibration method was
employed, yields of dibutyrin should be treated with caution.
Yields of methyl butyrate, glycerin, monobutyrin, and
dibutyrin as well as conversion of tributyrin were calculated
according to the following formulas:
½MB ½GL
Y MB ¼  100%; Y GL ¼  100%;
3½TB0 ½TB0
½MonoB ½DiB
Y MonoB ¼  100%; Y DiB ¼  100%;
½TB0 ½TB0
 
½TB
CTB ¼ 1  100%;
½TB0
where [TB]0 is the initial concentration of tributyrin, [MB],
[GL], [MonoB], [DiB], [TB] are in order, the concentrations of
methyl butyrate, glycerol, monobutyrin, dibutyrin, and tribu-
tyrin at the time of sampling.
Proton NMR spectra of products were recorded on a
400 MHz UltraShield NMR spectrometer from Bruker.
Deuterated chloroform was used as a solvent and an internal
standard. The relative concentrations of monobutyrin and
methyl butyrate were obtained in a standard 1H NMR
experiment. In particular, as was established for monobutyrin,
the methylene groups adjacent to the carbonyls gave the
expected triplet centered at 2.31 ppm, whereas the triplet of the
similar group of methyl butyrate was shifted upfield to
2.26 ppm. Partial signal overlapping was easily circumvented
by taking into consideration only the two most downfield peaks
of the monobutyrin triplet and followed by appropriate
corrections.
The precipitate from homogeneous Mg(OCH3)2 as well as
the solid catalysts, MgOx(OCH3)22x, Ca(OCH3)2, were
analyzed after catalytic reactions regarding the presence of
low quantities of butyric acid, glycerol, mono-, dibutyrin and
their derivatives. The typical procedure consisted of three steps.
The first step was the washing of spent catalyst with methanol
(ca. 2  20 mL). The second step consisted of acidification of
the spent catalyst slurry with hydrochloric acid to pH ca. 3 to
protonate captured ionic species, and initiate their desorption
into the surrounding liquid. The final step included sampling of
2 mL of the generated liquid and its analysis on GC–MS.
47
Analogous acidification and GC–MS analysis procedure was
employed for the liquid phase after completion of the catalytic
reaction and separation of the solid catalyst. Application of this
analysis procedure to the liquid phase of the reaction mixture
was particularly informative in regard to the presence of butyric
acid derivatives detected as butyric acid.
3. Results and discussion
3.1. Catalyst characterization
Infrared spectroscopy of MgOx(OCH3)2x revealed the
presence of peaks with maxima at 2931, 2860, 2796 cm1
characteristic of carbon hydrogen stretching vibrations in –CH3
groups, a single peak at 1092 cm1 characteristic of oxygen–
carbon vibration in –OCH3 groups, and a broad peak at
3445 cm1 typical for oxygen–hydrogen vibrations in interact-
ing hydroxyl groups or water molecules. During the pellet
formation MgOx(OCH3)22x was exposed to ambient moisture
and carbon dioxide. The presence of adsorbed water was evident
from a well-developed peak at 1631 cm1, surface carbonates
from overlapping peaks at 1395 and 1466 cm1. For commercial
Ca(OCH3)2, the peak maxima for carbon–hydrogen stretching
vibrations were centered at 2937, 2866, 2817 cm1, and the
carbon–oxygen vibration peak at 1074 cm1. Although less
pronounced than for MgOx(OCH3)2x, oxygen–hydrogen
vibrations in hydroxyl groups and water had two peaks: a sharp
one with maximum at 3645 cm1, and a broad one at 3414 cm1.
The presence of adsorbed water molecules and carbonates that
may lead to catalyst deactivation [16] manifested itself by a peak
at 1609 cm1 and two overlapping peaks centered approximately
at 1421 and 1473 cm1. Comparison of FTIR data for
MgOx(OCH3)22x and Ca(OCH3)2 powders revealed obvious
similarities. Both samples contained –OCH3 group as evident
from the occurrence of carbon–oxygen and carbon–hydrogen
vibrations. For the MgOx(OCH3)2x powder, the frequencies of
carbon hydrogen vibrations were red-shifted, whereas the
carbon–oxygen frequency was blue-shifted in comparison to
Ca(OCH3)2.
The results of TGA-MS analysis are presented in Fig. 1a. It
is worth noting that whereas the observed weight loss provides
information about the total weight of species leaving the solid
sample, mass spectrometry reveals their nature. As many as 43
fragments were followed during TGA-MS analysis, but only
the four most informative ones are shown in Fig. 1. In
particular, the fragment with m/z equal to 15 (typical for CH3+)
was chosen as a representative of organic carbonaceous
molecules, m/z of 18 for water, m/z of 44 for carbon dioxide and
m/z equal to 31 as a fragment typical for methanol. The
abundance the fragment with m/z of 45 was very low ruling out
the formation of dimethyl ether during TGA experiments.
The derivative of the TGA trace observed for
MgOx(OCH3)2x (Fig. 1a) revealed two peaks at 83 and
374 8C at which the rate of weight loss reached local maxima.
At both temperatures the weight loss was accompanied by
desorption of water, methanol and perhaps some other organic
compounds. The relative amount of methanol to water was
48 I.N. Martyanov, A. Sayari / Applied Catalysis A: General 339 (2008) 45–52
Fig. 1. (a) Thermogravimetric analysis of the MgOx(OCH3)22x powder. (b)
Thermogravimetric analysis of the Ca(OCH3)2 powder.
noticeably higher at 374 8C than at 83 8C. The shoulder of the
374 8C peak on the derivative curve (Fig. 1a), is mainly due to
water desorption. An analogous experiment carried out for
commercial Ca(OCH3)2 (Fig. 1b) revealed only a high
temperature peak centered at 535 8C, which was apparent
from the derivative of the weight loss curve. The most
pronounced was a signal with m/z = 18 characteristic of water.
Less intense but well developed was a signal at m/z = 15, the
fragment characteristic of organic moieties. It should be noted
that the relative intensities of the signals for m/z = 18 and 15
cannot be considered proportional to the relative molar amounts
of water and organic species desorbed. Indeed, the low
abundance of m/z = 15 fragment maybe due to a particular
fragmentation pattern of an organic molecule entering the
mass-spectrometer, or low ionization probability of this
molecule in comparison to water. Additionally, assuming that
CaO is the final product, the material balance imposes some
obvious limitation on how much water and carbon (as organic
molecules) can be formed upon calcination of Ca(OCH3)2. For
a TGA run carried out in nitrogen, some residues of carbon on
the sample can be present even at 800 8C. Switching the carrier
gas from nitrogen to air at 800 8C should lead, however, to
complete carbon burn-out. The weight loss observed upon
switching at 800 8C form nitrogen to air was significant yet well
below the weight loss at around 535 8C.
The total weight loss for calcium methoxide in the
temperature interval from 40 to 1000 8C was 43.3 wt% and
consistent with CaOx(OCH3)22x mixture, where x is equal to
0.07. Though the CaO0.07(OCH3)1.86 formula seems to better
reflect the actual composition of the sample, throughout
this paper, the commercial identification Ca(OCH3)2 will be
used. The total weight loss of 47.9 wt% observed for
MgOx(OCH3)2x in the temperature range from 40 to
1000 8C would be consistent with x equal to 0.2. Assuming
magnesium oxide as the final compound of high temperature
treatment, 168 mg of the MgOx(OCH3)2x used later for
catalytic experiments contains ca. 0.002 mol of Mg ions. The
absence of a low temperature weight loss in the TGA profile for
calcium methoxide is consistent with the presence of loosely
bound methanol on the surface of the solid MgOx(OCH3)2x.
Ignoring the low temperature weight reduction around 83 8C
would give x equal to 0.44. Summarizing the results of FTIR
and TGA experiments, the in-house prepared magnesium-
based solid catalyst can be best characterized as a
MgOx(OCH3)2x mixture with x close to 0.44 and some
methanol adsorbed on it.
3.2. General consideration of tributyrin transesterification
Scheme 1 depicts the major steps in transesterification of
tributyrin. The reaction consists of three reversible steps
[15,17], propagating from tributyrin, through dibutyrin and
monobutyrin, to glycerol. Each step involves reaction with one
molecule of methanol and produces one molecule of methyl
butyrate as the target product. The stoichiometry of the
complete transesterification process requires three molecules of
methanol for each molecule of tributyrin. The equilibrium
nature of the process creates the necessity for methanol excess
to achieve higher yields of the target product.
It is worth noting, that two isomers of dibutyrin and
monobutyrin are possible and actually observed in the
experiment. Though isomers of dibutyrin/monobutyrin can
be partially/completely separated with the employed GC–MS
method, only the total amounts of dibutyrin and monobutyrin
are shown in all figures.
With the basic catalysts in use, the driving force is believed
to be the deprotonation of methanol resulting in the formation
of nucleophilic methoxide ions that attacks the carbon moiety
of the carbonyl group (Scheme 2).
3.3. Catalytic activity of sodium methoxide
As methoxide ions are expected to be an active species in the
process and sodium, potassium hydroxides as well as sodium
methoxide are classic base catalysts used for biodiesel
production, it was of interest to run the reaction in the presence
 I.N. Martyanov, A. Sayari / Applied Catalysis A: General 339 (2008) 45–52 49

Scheme 1. Reaction steps in transesterification of tributyrin.

of homogeneous (pre-dissolved) sodium methoxide. The
results of this experiment are shown in Fig. 2. The reaction
proceeded very fast, starting immediately upon mixing the
reagents, but the yields leveled off within 20 min. Under the
present conditions, considerable yields of glycerol and
monobutyrin were detected, though the dibutyrin yield was
negligible, and conversion of tributyrin was close to 100%. The
final yield of methyl butyrate upon reaching final stage was ca.
91% of the stoichiometrically possible value.
3.4. Catalytic activity of the solution of Mg(OCH3)2 and
solid MgOx(OCH3)22x
started, the homogeneous solution became translucent indicat-
ing the formation of particulate matter suspension, which
partially converted into a bulk white precipitate in 20 min.
It is reasonable to suggest that the abrupt change in the rate
of transesterification process is associated with a change of its
nature from homogeneous to heterogeneous catalysis. The
heterogeneously catalyzed reaction is expected to be slower as
only sites on the surface of the catalyst particles can be involved
in the process. Rough estimate for 20 nm MgO particles shows
that only 8% of MgO units are actually on the surface and can

Interestingly enough, the reaction catalyzed by homoge-

neous Mg(OCH3)2 taken in the same molar amounts as sodium
methoxide also started right during mixing of the compounds,
but slowed down drastically thereafter (Fig. 3). About 24
methyl butyrate molecules per Mg2+ were formed during the
first 2 min of the reaction, whereas during the following 6 h of
the reaction, only 12 turnovers took place. As the reaction

Scheme 2. The mechanism of ester transesterification in the presence of a base Fig. 2. Transesterification of tributyrine in the presence of pre-dissolved
catalyst. sodium methoxide.
50 I.N. Martyanov, A. Sayari / Applied Catalysis A: General 339 (2008) 45–52
Fig. 3. Transesterification of tributyrine in the presence of magnesium meth-
oxide solution.
potentially participate in a catalytic process. Moreover,
agglomeration of the particles into larger aggregates may
create mass transfer limitations that would further reduce the
apparent rate of the reaction.
As for the chemical process involved in suspension/
precipitation formation, analysis of the composition of the
precipitate was proven to be quite informative. Even washing
with methanol resulted in partial loss of precipitate integrity.
The GC–MS analysis of the surrounding liquid after precipitate
washing showed high concentrations of glycerol, mono- and
dibutyrin. Further disintegration of the precipitate upon its
acidification with hydrochloric acid resulted in the appearance
of large amounts of butyric acid. This finding suggests that the
derivatives of the reaction products such as glycerol, mono and
dibutyrin, as well as the reaction by-product butyric acid are all
ingredients of the precipitate. Direct mixing of glycerol/
methanol mixture with the solution of magnesium methoxide
gave rise to a white gel in about 6 min. Similar chemistry,
though less pronounced, can be expected from mono and
dibutyrin. During a catalytic run, the formation of any of these
products is expected to contribute to the suspension/precipitate
formation abruptly slowing the reaction process.
The catalytic activity data for the in-house prepared
MgOx(OCH3)22x are presented in Fig. 4. The behavior of
this material was quite different from homogeneous magne-
sium methoxide. The reaction was much more sluggish and
essentially stopped within 3 h. The turnover number calculated
as a molar ratio of methyl butyrate produced in 3 h to the total
number of magnesium ions in the solid was about 4.5.
Consideration of the basic sites located only at the surface of
MgOx(OCH3)22x would significantly increase the calculated
turnover number leaving no doubt that the reaction is catalytic
in nature.
The lower activity of the MgOx(OCH3)22x solid catalyst in
comparison to homogeneous magnesium methoxide can at least
in part be explained by the lower number of basic sites available
for the reaction. As for the catalyst deactivation, formation of
Fig. 4. Transesterification of tributyrine in the presence of the magnesium
methoxide-based solid catalyst.
the reaction products such as di- and monobutyrin and glycerol
should definitely slow the process down due to their
competition for basic sites and reverse reactions that would
take place. However, as evident from the experiment with
magnesium methoxide solution (Fig. 3), formation of di- and
monobutyrin as well as glycerol in the amounts far exceeding
the number of potential catalytic sites does not shut the reaction
down. Therefore, the presence of the main reaction products
though detrimental, cannot be the sole factor for catalyst
deactivation.
The situation with the potential side product butyric acid is
completely different. Indeed, the dissociation constants (pKa)
of butyric acid, glycerol, methanol are 4.75 [18], 14.15 [18] and
15.5 [19], respectively. The dissociation constants for di- and
monobutyrin are not available but are expected to be of the
same order as for glycerol. As can be seen, the difference in the
ionization constants of butyric acid and methanol is so large
that for all practical purposes deprotonation of butyric acid and
deactivation of surface basic sites is much more thermo-
dynamically favorable than deprotonation of methanol.
Formation of species resembling the structure of butyric acid
salts on the surface of a solid catalyst in the amounts
comparable with the number of catalytic sites can be very
detrimental to the catalyst activity. Indeed, once formed these
species would prevent methanol deprotonation thus making the
catalyst inactive.
Further experiments provided support to this hypothesis.
Addition of a fresh portion of MgOx(OCH3)22x to the reaction
mixture after 6 h run resumes the reaction, which, however,
comes to a halt after 3–4 h as with the initial portion of the
catalyst. This experiment shows that the deactivation of
the catalyst is unlikely to be due to chemicals accumulated in
the solution, but rather related to chemicals that mainly are
generated and reside on the surface of the catalyst.
Washing the used MgOx(OCH3)22x with methanol, reactive
dissolution of the solid with hydrochloric acid combined with
comparative GC–MS analysis showed a considerable amount
 I.N. Martyanov, A. Sayari / Applied Catalysis A: General 339 (2008) 45–52 51

of butyric acid released. Analogous acidification experiment

with the liquid part of the reaction mixture separated from used
MgOx(OCH3)22x revealed only traces of butyric acid perhaps
due to unremoved catalyst particles. It should be noted that
when no dilution was used for trace GC–MS analysis, the
presence of glycerin and monobutyrin in the liquid became also
apparent.
At elevated temperatures, magnesium salts can by them-
selves serve as catalysts in reactions of transesterification [20].
However, direct examination of catalytic activity of magnesium
acetate used as a substitution for magnesium butyrate showed
no activity under the current experimental conditions.
The low pKa for butyric acid, negligible activity of
magnesium acetate salt under the current experimental
conditions, preferential accumulation of butyric acid anions
on the surface of solid MgOx(OCH3)22x, all point to formation
of butyric acid salts as the most likely species deactivating the
catalyst.

3.5. Catalytic activity of solid Ca(OCH3)2

The results of a catalyst activity test of commercial

Ca(OCH3)2 are presented in Fig. 5a. The observed kinetic
curves are consistent with classical examples of sequential
reaction process. The reaction started significantly slower than
with homogeneous sodium and magnesium methoxides, but
easily surpassed the magnesium methoxide and leveled off in
4 h. The final concentrations of methyl butyrate, monobutyrin
and glycerol were quite similar to those observed for NaOCH3,
which, however, are reached after much longer reaction time.
At first glance, the reaction in the presence of Ca(OCH3)2 is
a purely heterogeneous process. It started with no delay and did
not noticeably accelerate with time at initial stages, which
would be the case if catalytically active species quickly
accumulated in the liquid. Further investigation, however,
revealed some inconsistencies. The recovered catalyst was
washed with methanol, and tested again under the same
conditions (Fig. 5b). Though the final concentrations of methyl
butyrate, glycerol and monobutyrin were the same as in the first
run, the concentration of methyl butyrate underwent a
significant jump upon mixing of the reagents. The jump in
the concentration of methyl butyrate cannot be attributed to
residual methyl butyrate left in the slurry after washing. Indeed,
attempts to wash the used catalyst more thoroughly produced
quantitatively similar results. Secondly, a decrease in the
concentration of tributyrin and an increase in the concentration
of dibutyrin are so obvious that cannot be neglected. The
presence of considerable amounts of a dissolved catalytic
species seems to be a more likely case, which would also be
consistent with the observed behavior of homogeneous
Mg(OCH3)2.
There are a few other observations pointing at the fact that in
the presence of solid Ca(OCH3)2, the contribution of
homogeneous catalytically active species at the late reaction
stages cannot be ignored. First, the loss of calcium methoxide
during the reaction followed by its washing and drying was
close to 35 wt%. Secondly, the pH of the liquid surrounding
Fig. 5. (a) Transesterification of tributyrine in the presence of calcium meth-
oxide solid catalyst, first run. (b) Transesterification of tributyrine in the
presence of calcium methoxide solid catalyst, second run.
Ca(OCH3)2 at the end of the first run was in the 12–13 range,
indicating the presence of bases in the solution. Thirdly, most
importantly, the liquid part of the reaction mixture recovered
after the first run was by itself catalytically active for tributyrin
transesterification.
A few chemicals were examined in regard to their ability to
interact with solid Ca(OCH3)2 producing homogeneous
catalysts. First, ca. 7.9 mL of methanol was agitated at
60 8C with a typical amount of Ca(OCH3)2 followed by
Ca(OCH3)2 separation with the centrifuge. The recovered
methanolic solution showed no catalytic activity in transester-
ification reaction most likely due to low solubility of calcium
methoxide in methanol [12]. The same experiment with
tributyrin created some ambiguity: though some catalytic
activity was detected, the reaction proceeded slowly with no
initial jump. Moreover, the tributyrin is a substance that is much
more viscous than methanol. Agitation with Ca(OCH3)2
resulted in some fine particles dispersed in the liquid that
could not be entirely removed by centrifugation. These fine
particles of the solid catalyst whose presence was obvious from
52 I.N. Martyanov, A. Sayari / Applied Catalysis A: General 339 (2008) 45–52
Scheme 3. Surface salts of butyric acids as catalytically inactive species.
the translucent appearance of the centrifuged tributyrin, are
likely to be responsible for the limited catalytic activity
observed.
GC–MS analysis of the liquid part of the recovered and
washed Ca(OCH3)2 slurry before the second run revealed
methyl butyrate and glycerol as the main compounds.
Acidification did not change this qualitative observation. The
butyric acid concentration was below the detection limit before
and after acidification. The presence of glycerol prompted us to
explore its reactivity with solid calcium methoxide. The
standard amount of Ca(OCH3)2 was agitated with 2 mL of
glycerol pre-diluted with 2 mL of methanol to lower glycerol
viscosity. The process was continued at 60 8C for 6 h. About
2 mL of methanol was added and the transparent yellow liquid
was separated with the centrifuge. Later, it was established that
the solution generated through Ca(OCH3)2/glycerol interaction
did catalyze the transesterification reaction. The nature of the
liquid phase compounds and time of interaction with calcium
methoxide are major factors governing the formation of
homogeneous catalytically active species. Indeed, interruption
of the first run after 2 h, where concentration of glycerol is
limited, and conducting a second run right after repeated
washing of the catalyst with methanol essentially eliminates the
initial jump in methyl butyrate concentration.
Contrary to MgOx(OCH3)22x, butyric acid could not be
detected in the washed slurry of Ca(OCH3)2 before or after its
acidification, but could be easily detected by GC–MS upon
acidification of the liquid part of the mixture after reaction
completion. To check for possible catalytic activity of calcium
butyrate, calcium acetate was tested instead. Though some
activity was detected earlier by Serio et al. [20] for calcium
acetate and stearate at 200 8C, our experiments showed no
activity for calcium acetate under the current conditions. The
observations put Scheme 3 in new perspective. Though like for
MgOx(OCH3)22x the main transesterification reactions
(Scheme 1) seem to be accompanied by a minor process
leading to the surface butyric salt species, the faith of these
species is different. Calcium salts of butyric acid go into the
liquid phase thus exposing new surface catalytic sites of
Ca(OCH3)2 rather than deactivating the catalyst by residing on
its surface.
4. Conclusions
The most important results of this study can be briefly
summarized as follows:
Pre-dissolved in methanol, magnesium methoxide is a
powerful homogeneous catalyst for tributyrin transesterifica-
tion. The formation of products such as glycerin renders
homogeneous magnesium methoxide unstable and leads to a
precipitate of complex composition containing derivatives of
glycerol, mono-, dibutyrin and butyric acid.
The in-house prepared MgOx(OCH3)22x possesses a weak
heterogeneous catalytic activity. The fast catalyst deactivation
is most likely due to accumulation of the butyric salt species on
the surface of the catalyst.
With solid Ca(OCH3)2, transesterification of tributyrin
begins as a heterogeneous process. Later, however, the
interaction of calcium methoxide with the reaction products,
such as glycerin, results in the formation of soluble species that
are catalytically active. Forming in a side process, calcium salts
of butyric acid are soluble in the reaction mixture though
catalytically inactive. They should contribute to the catalyst
dissolution, however, unlike for MgOx(OCH3)22x, cannot
deactivate the surface of the calcium methoxide.
Acknowledgements
We thank the Natural Sciences and Engineering Research
Council of Canada (NSERC), the Ontario Research &
Development Challenge Fund (ORDCF) and the Canada
Foundation for Innovation (CFI) for financial support. A.S. is
the Government of Canada Research Chair in Catalysis by
Nanostructured Materials (2001–2008).
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