Applied Catalysis A: General 382 (2010) 158166

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Applied Catalysis A: General

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

Highly effective MnCeOx catalysts for biodiesel production by

transesterication of vegetable oils with methanol
C. Cannilla b , G. Bonura a , E. Rombi c , F. Arena a,b , F. Frusteri a,b,
a
b
c

CNR-ITAE Nicola Giordano, Salita S. Lucia sopra Contesse, 5, I-98126, Messina, Italy
Dip. di Chimica Industriale ed Ing. Materiali, Universit di Messina, Salita Sperone 31, I-98166, Messina, Italy
Dip. di Scienze Chimiche, Universit di Cagliari-CSGI, Cittadella Universitaria, S.S. 554 bivio Sestu, 09042 Monserrato, Cagliari, Italy

a r t i c l e

i n f o

Article history:
Received 25 February 2010
Received in revised form 14 April 2010
Accepted 15 April 2010
Available online 4 May 2010
Keywords:
Biodiesel
Transesterication reaction
Heterogeneous (liquidsolid) catalysis
Ceriamanganese catalysts

a b s t r a c t
This paper reports the results obtained using a novel MnCeOx system in the transesterication reaction
of rened sunower oil with methanol. The performance of such catalysts has been compared with that
of common acid supported catalysts. Results obtained revealed that MnCeOx system possesses a superior
activity especially by operating at low temperatures (120 C). Independently of Mn loading, the redoxprecipitation method for the preparation of Mn-based systems allowed to obtain always high dispersed
catalysts and, as a consequence, a linear relationship between reaction rate and Mn loading was obtained.
NH3 -TPD and CO2 -TPD measurements indicate that MnCeOx systems are characterized by a prevalent
nature of basic sites. However, the catalyst performance is the result of a synergic role played by both
the surface acid/base character and textural porosity.
2010 Elsevier B.V. All rights reserved.

1. Introduction
Biodiesel is an environmentally friendly, non-toxic, biodegradable mixture, which can be used either as alternative pure fuel
or for blending with conventional oil-derived fractions [1]. Since
biodiesel is produced from renewable vegetable sources, overall well-to-wheel CO2 emissions are lower, thus reducing the
contribution to the greenhouse effect [2]. The physico-chemical
characteristics of biodiesel are similar to those of the fossil diesel
fuel in terms of energy density, cetane number and phase change,
while it is characterized by a higher ash point value. Moreover, a
superior oxygen content (1011%) improves the combustion efciency and the lubricant properties, the last contributing to reduce
the engine stress and maintenance [1,3].
Biodiesel consists of long-chain fatty acid alkyl esters (FAAEs),
obtained by transesterication reaction of triacylglycerides (TGs)
with alcohols. Depending upon the climate and environmental
conditions, several countries are looking for different sources of
vegetable oils [1]; soybean oil in the United States and Brazil [48],
rapeseed [9,10] and sunower [11,12] oil in Europe, palm oil [13]
and coconut oil [14] in the Asian countries. Cotton oil [15], safower
[16], canola [17], jatropha [18], brassica carinata oil [19] and waste
grease [3,20] are also considered as potential biodiesel feedstock.

Corresponding author at: CNR-ITAE Nicola Giordano, Salita S. Lucia sopra Contesse, 5, I-9816, Messina, Italy.
E-mail address: Francesco.Frusteri@itae.cnr.it (F. Frusteri).
0926-860X/$ see front matter 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.apcata.2010.04.031

The structural composition, such as chain length and branching or

degree of unsaturation, affects the physico-chemical properties of
a fatty ester molecule, thus determining the overall properties of
the biodiesel. Saturated compounds (myristic acid, C14:0; palmitic
acid, C16:0; stearic acid, C18:0) exhibit high heat of combustion
values, high cetane numbers and are less ready to oxidation than
unsaturated compounds, however they crystallize at high temperature [3,18]. Biodiesel from sunower oil is a highly unsaturated
mixture, being more prone to oxidation, but its cold ow properties
are acceptable. Although simple linear alcohols, such as methanol,
ethanol, propanol and butanol, are generally used for the oil transesterication, methanol is widely used for its lower cost and its
physico-chemical characteristics (polarity and the shortest chain
alcohol) [21].
Biodiesel production involves three consecutive reactions, with
diglycerides (DGs) and monoglycerides (MGs) as intermediates and
glycerol as a valuable by-product [22]:
TG + CH3 OH  diglyceride + R 1 COOCH3

(1)

DG + CH3 OH  monoglyceride + R 2 COOCH3

(2)

MG + CH3 OH  glycerol + R 3 COOCH3

(3)

All the above reactions are reversible and then an excess of alcohol
is used to obtain high yields (>99%) of methyl esters (MEs) that also
allow an easier separation of ME from glycerol [2]. Reaction temperature, pressure, alcoholoil molar ratio, water and free fatty acids
(FFAs) content are the main parameters affecting the efciency of
the process. However, a limited solubility of TGs in the alcoholic

C. Cannilla et al. / Applied Catalysis A: General 382 (2010) 158166

Table 1
Composition of the sunower oil.
Acidity indexa

Composition (wt.%)

Palmitic (C16:0)
Stearic (18:0)
Oleic (C18:1)
Linoleic (C18:2)
Linolenic (C18:3)
Arachidate (C20:2)

6.8
3.8
27.1
61.1
0.2
0.3

159

unsaturated (63%) esters, and methanol (MeOH, HPLC-grade, 99.8%)

were used. Pure GC standard chemicals, including fatty acid
methyl esters mix and methyl eptadecanoate, were supplied by
SigmaAldrich. The typical composition of a commercial sunower oil with a low content of FFAs (0.07 wt.%) is reported in
Table 1.
2.2. Catalysts preparation

Numbers in parenthesis show the number of carbon atoms and

the unsaturated centres.

phase and the presence of the solid catalyst require an efcient

mixing to improve the interphase mass transfer rate [21].
Kinetics of the transesterication reactions can be efciently
promoted by either basic or acid catalysts, while high temperature (350400 C) and pressure (100250 bar) are required to
get reasonable yields in supercritical methanol [23]. However,
the nature of the catalyst depends upon feedstock composition,
reaction conditions and post-separation steps. Although low-cost
basic catalysts, such as potassium or sodium hydroxide, can be
used, more than half of the current production processes are
catalyzed by sodium methoxide [5,19]. Basic catalysts are active
under mild conditions (80 C), though their suitability is limited
to rened oils with low FFAs concentration (<0.5 wt.%) and anhydrous (H2 O content < 0.06 wt.%) alcohol [9,24], as side reactions can
produce soaps and gels requiring additional separation steps to
produce commercial-grade biodiesel. On the contrary, acid catalysts can simultaneously promote the TGs transesterication and
FFAs esterication of low-cost feedstock [20,25] even if several
drawbacks exist: longer reaction time, higher operating temperature and the requirement of acid-resistant reactors. Then, many
heterogeneous basic [7] and acidic systems [26], as well as enzymatic catalysts [23,27], have been proposed in the last decade
for the transesterication process. In particular, alkali [9], such
as Na/NaOH/-Al2 O3 [28], alkaline-earth compounds, such as CaO
[13], Li/CaO [29] and SrO [4], rare-earth metal-loaded inorganic
oxides [5,10], Amberlyst-15 [30], FeZn double-metal cyanide
[31], vanadyl phosphate [32], zirconia-supported isopoly- and
heteropoly-tungstate [12], Cs-doped heteropolyacid [33], modied
zeolites [8,34], sulphated metal oxides [14,25,35] and hydrotalcites
[8,36] ensure the best catalytic performances. Recently, a heterogeneous system, based on a mixture of ZnO, Al2 O3 and ZnAl2 O4 for
transesterication of vegetable oils with methanol at 230 C and
50 atm, has been also proposed [37].
This work is aimed at investigating the catalytic performance
of a new class of manganeseceria mixed oxides in the transesterication of sunower oil with methanol, in comparison to
representative acid and basic solid catalysts.
2. Experimental
2.1. Chemicals
Commercial-grade sunower oil (density, 0.85 g mL1 ), containing saturated (10%), mono-unsaturated (27%) and poly-

2.2.1. Silica-supported tungstophosphoric (HPW-17) and

molybdophosphoric (HPMo-17) heteropolyacids
Catalysts were prepared by the incipient wetness method using
SiO2 (Cab-O-Sil LM50; SABET , 250 m2 g1 ) as support and two
aqueous solutions containing 17 wt.% of tungstophosphoric heteropolyacid and 17 wt.% of molybdophosphoric heteropolyacid,
respectively. At the end of the impregnation, the samples were
dried at 120 C for 2 h and activated in a stream of dry nitrogen
for 2 h at 300 C.
2.2.2. Cs-exchanged phosphotungstic acid (Cs-HPW)
The sample was prepared by partial neutralization of the
phosphotungstic acid (H3 PW12 O40 ) using an aqueous solution of
Cs2 CO3 , added drop-wise according to the procedure elsewhere
described [38,39]. The Cs0.5 H2.5 PW12 O40 salt obtained was ltered,
dried and activated in a stream of dry nitrogen for 2 h at 300 C.
2.2.3. Naon /SiO2 (NS-20)
A commercial sample of silica (Cab-O-Sil M5, SABET ,
207 m2 g1 ) was dispersed under stirring in an ethanolic solution
containing a known amount of Naon . After ltration, the solid
sample was dried at 80 C overnight. The catalyst so obtained was
pressed, crushed and sieved. The 4070 mesh fraction was used
both for characterization and catalytic measurements.
2.2.4. MnCeOx systems
A series of manganeseceria catalysts, with Mn/Ce atomic
ratio ranging between 0.4 and 3.4, was prepared via the
redox-precipitation route, according to the procedure elsewhere
described [40]. The catalysts were dried at 100 C and calcined in
air at 400 C for 6 h.
2.2.5. Bulk CeO2 , MnO2 , ZnO
A known amount of (NH4 )2 Ce(NO3 )6 was dissolved in hot deionized water and slowly added to a solution of KOH maintained at
60 C, under vigorous stirring, at constant pH (8.0 0.2) by addition of a 0.3 mol L1 KOH solution. After titration, the solid was
digested for 6 h at 60 C and then ltered and repeatedly washed
with hot distilled water. Then, the solid was dried at 110 C for 16 h
and calcined for 6 h in air at 400 C.
A commercial precipitated-activated MnO2 sample (Fluka
product) was selected as a standard sample.
A commercial ZnO sample (Aldrich product) was also used as a
reference system.

Table 2
Physico-chemical properties of the solid acid systems.
Catalyst

Active phase (loading wt.%)

SABET (m2 g1 )

PV (cm3 g1 )

APDa ()

Acidityb (mmolH+ g1 )

HPW-17
HPMo-17
Cs-HPW
NS-20

Phosphotungstic acid (15)

Phosphomolybdic acid (15)
Phosphotungstic acid exchanged with cesium (0.5)
Naon (20)

200
264
207
187

0.62
0.46
0.80
0.52

124
70
155
111

0.74
1.13
0.81
0.92

a
b

Average pore diameter (4 PV/SABET ).

ZPC method.

C. Cannilla et al. / Applied Catalysis A: General 382 (2010) 158166

460
365
360
240
271
237
187
N.D.
36.9
64.0
N.D.
N.D.
68
133
191
314
74
25
0.42
0.59
0.73
0.90
0.2
0.1
a

B/A ratio between surface basicity and acidity.

173
150
143
124
92
89

0.54
1.70
5.20

10.9
19.3
25.4
41.0

0.41
0.87
1.29
3.40

Mn0.3 Ce0.7
Mn0.4 Ce0.6
Mn0.5 Ce0.5
Mn0.7 Ce0.3
MnO2
CeO2

Specic (molNH3 gcat

Acidity
APD ()
PV (cm3 g1 )
SABET (m2 g1 )
K (wt.%)
Mn (wt.%)
Mnat /Ceat

2.3.6. X-ray diffraction

X-ray diffraction analysis of powdered samples was performed
using a Philips X-Pert diffractometer equipped with a Ni -ltered
Cu K radiation at 40 kV and 30 mA. Data were collected over a 2
range of 2085 , with a step size of 0.05 at a speed of 0.05 s1 .

Catalyst

2.3.5. NH3 temperature programmed desorption

NH3 -TPD measurements in the range 100500 C were performed in a ow apparatus, using a heating rate of 12 C min1 and
a He carrier ow rate of 25 STP mL min1 . The desorption process
was monitored by a quadrupole mass spectrometer, acquiring the
signal relative to the mass-to-charge (m/z) ratio 17 (NH3 ). Before
measurements, the samples were treated in situ for 30 min in a 10%
O2 /He ow (25 STP mL min1 ) at 400 C, except for the HPMo-17
sample that was pre-treated at 300 C in helium ow to avoid any
thermal decomposition phenomenon. After the activation treatment, the samples were cooled down to 150 C and then saturated
for 30 min in a 5% NH3 /He stream (25 STP mL min1 ). Thereafter,
the samples were purged in He carrier ow until stabilization of
the signal.

Table 3
Physico-chemical and acidbasic properties of MnCeOx systems along with bulk MnO2 and CeO2 samples.

2.3.4. CO2 temperature programmed desorption

CO2 -TPD measurements in the range of 20350 C were carried out using a linear quartz micro-reactor (dint , 4 mm; l,
200 mm) loaded with ca. 50 mg of catalyst, using a heating rate
of 20 C min1 . After an in situ pre-treatment at 400 C (30 min)
under a 10% O2 /He ow (25 STP mL min1 ), the catalyst was cooled
down to room temperature, switched in the He carrier ow
(30 STP mL min1 ) and saturated with CO2 pulses (0.2 mL). After
saturation, the sample was purged in the carrier ow until stabilization of the baseline. The desorption process was monitored and
quantied by a TCD, preliminarily calibrated by the injection of pure
CO2 pulses.

2.3.3. Acid capacity

Acid capacity was determined by potentiometric titrations (zero
point charge method, ZPC). About 0.1 g of each sample was dispersed under stirring in an aqueous solution of NaNO3 0.5 mol L1 .
Acidity, measured by an electrode Orion ROSS, was evaluated considering the pH value at which particles suspended in solution have
zero charge.

1.1

0.3
0.5

Surface (molNH3 m

Basicity

2.3.2. Surface area (SABET ), pore volume (PV) and pore size
distribution (PSD)
Surface area, pore volume and pore size distribution were
determined from the nitrogen adsorption/desorption isotherms
at 196 C, using a Carlo Erba (Sorptomatic Instruments CE Series)
gas adsorption device. Before analysis, all samples were outgassed
at 120 C under vacuum for 2 h. The isotherms were elaborated
according to the BET method for surface area calculation, with
the HorwarthKavazoe (HK) and BarrettJoynerHalenda (BJH)
methods used for the evaluation of micropore and mesopore distributions, respectively.

2.7
2.4
2.5
1.9
2.9
2.6

Surface (molCO2 m

2.3.1. X-ray uorescence (XRF)

The analytical composition of the Mn-based catalysts was determined by X-rays uorescence (XRF) measurements, using a Bruker
AXS-S4 Explorer Spectrometer. The concentration of elements
was determined by the emission value of K1 transitions of Mn
(E = 5.9 keV), Ce (E = 4.8 keV) and K (E = 3.3 keV).

2.4

8.3
3.8

B/Aa ratio

2.3. Catalysts characterization

Specic (molCO2 gcat

160

C. Cannilla et al. / Applied Catalysis A: General 382 (2010) 158166

Fig. 1. PSD of the MnCeOx systems: inuence of the Mn/Ce atomic ratio.

2.4. Catalyst testing

Transesterication reaction of sunower oil with methanol was
carried out in a 300 mL stainless steel AISI 316 autoclave (Parr
Instruments) equipped with a magnetic stirrer, in the temperature
range of 65200 C, according to the following procedure: a known

Fig. 2. NH3 desorption proles as a function of temperature in the range of

100500 C: silica-supported HPMo-17 heteropolyacid and structured MnCeOx systems.

161

Fig. 3. Deconvolution plot of the CO2 -TPD proles in the range of 0350 C.

amount of sunower oil (80 g) was charged into the reactor, adding
44 mL of methanol, which corresponds to a MeOH/oil molar ratio
(Rmet /oil) of 12. Methanol was previously mixed with the catalyst, in
order to operate with a concentration of 1 wt.% of catalyst referred
to the oil. The reactor was preliminarily ushed under a nitrogen
ow to remove the air and heated up to the reaction temperature
(ca. 15 min). At the end of the run, the reactor was cooled down to
room temperature by putting it into an ice-bath, thus allowing all
the gas-phase components to be condensed. Then, the reactor was
opened and the catalyst separated by centrifugation and ltration.
The reaction mixture, after the evaporation of unreacted methanol,
resulted to be composed by a top layer containing oil and methyl
esters products and a bottom layer of glycerol that were further
separated by centrifugation.
According to the EN 14103 method suitable for analysis of
methyl esters C14 C24 , the reaction mixture was analyzed off-line,
by a gas chromatograph HP 7890N, provided with a capillary column HP Innowax (l, 30 m; i.d., 0.32 m; lm thickness, 0.25 m)
and a ame ionization detector (FID), using He as carrier gas. The
following temperature program was adopted for the separation
of the various compounds: 9 min at 210 C; from 210 to 230 C
(with a heating rate of 20 C min1 ) and 230 C for 10 min. The
samples (1 l) were injected in split mode (split ratio of 80:1)
into the GC using an automatic sampler Agilent 7683B Series, each
conversion-selectivity data set being calculated from the average of
three independent measurements with an accuracy of 1%. Methyl
palmitate, methyl stearate, methyl oleate, methyl linoleate, methyl
linolenate and methyl arachidate were used as chemical GC standards for analysis calibration. The biodiesel analysis was carried
out dissolving 50 mg of sample into 1 mL of methyl heptadecanoate
solution (internal standard).
The yield to biodiesel was calculated from the content of methyl
esters analyzed by the following equation:
Yield (%) = 100

molME
3 moloil

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C. Cannilla et al. / Applied Catalysis A: General 382 (2010) 158166

Table 4
Basic sites distribution evaluated on the basis of CO2 -TPD proles.
Catalyst

Basic strength (molCO2 m2 )

Mn0.3 Ce0.7
Mn0.4 Ce0.6
Mn0.5 Ce0.5
Mn0.7 Ce0.3

Contribution (%) of medium and strong basic sites

Weak (T1 , 93 C)

Medium (T2 , 165 C)

Strong (T3 , 289 C)

0.85
0.83
0.38
0.35

0.90
0.93
0.96
0.78

0.90
0.93
1.17
0.81

The factor 3 takes into account that each triglyceride molecule

yields three methyl esters molecules, while the molecular weight of
biodiesel was calculated from the composition of a representative
of sunower oil (see Table 1).
3. Results and discussion
3.1. Structural and morphological properties
The list of the studied catalysts along with their main physicochemical properties are reported in Tables 2 and 3.
In spite of different surface area (187264 m2 g1 ) and pore volume (0.50.8 cm3 g1 ), the solid acid catalysts are characterized by
a similar proton-exchange capacity (1.0 mmolH+ gcat 1 ), while the
partial neutralization of the HPW-17 sample with Cs+ ions does not
yield any signicant changes neither in terms of surface area nor in
the proton-exchange capacity (Table 2) [33].
The MnCeOx catalysts are characterized by SA values decreasing
monotonically with the Mn/Ce atomic ratio from 173 to 124 m2 g1 ,
while a PV growing from 0.42 to 0.90 cm3 g1 accounts for a progressive broadening of the APD from 68 to 314 (Table 3). Such
regular trends points out as the textural properties are tightly
dependent on the MnOx loading [40]. Indeed, the pore size distribution (see Fig. 1) shows for all the systems a Gaussian-shaped
prole, whose maximum shifts from ca. 8 to 4050 nm as the Mn/Ce
atomic ratio rises from 0.41 to 3.40. This is related to the formation
of large clusters at higher MnOx loading, giving rise to a comparable
inter-particle porosity [43].
As the transesterication reaction can be catalyzed by either
acidic or basic systems, NH3 and CO2 chemisorption/desorption
measurements were carried out to determine the surface acidbase
properties; namely, NH3 desorption data probe strength and concentration of acidic sites irrespective of their nature [39,41], while
the chemisorption of the acidic CO2 molecule monitors both
Brnsted and Lewis basicity.
The ammonia desorption proles in Fig. 2 shown that the HPMo17 sample has a broad peak spanned in the range 150400 C, with a
maximum at ca. 200 C and markedly tailed at higher temperatures;
that is diagnostic of a rather large strength distribution, accounting for a concentration of surface acid sites of 1.16 mmol g1 well
comparing with data obtained by titration method (1.13 mmol g1 )
(see Table 2). Still in agreement with potentiometric data, the
MnCeOx systems feature a much poorer surface afnity towards
ammonia, with some slight inuence of the Mn loading. In particular, Mn0.3 Ce0.7 shows a higher acid character since absorbs
186 mol NH3 gcat 1 , while Mn0.5 Ce0.5 and Mn0.7 Ce0.3 have a much
lower acidity, as they adsorb an amount of NH3 which is close to one
order of magnitude lower (37 and 64 mol NH3 gcat 1 respectively).
The maximum of desorption peak of Mn0.3 Ce0.7 and Mn0.5 Ce0.5 is
around 150200 C, whereas the broad signal of Mn0.7 Ce0.3 has a
maximum at around 320 C. The highest acidity of Mn0.3 Ce0.7 could
be related to a higher availability of weak acid sites of ceria [42].
As regards the bulk oxides (see Table 3), the commercial
MnO2 results to be characterized by signicant basic properties,
even more pronounced than CeO2 under the same surface area
(2.9 mol m2 ). Moreover, differently from ceria, MnO2 exhibits

67
69
85
82

two desorption peaks centred at around 107 and 270 C, accounting

for weak and strong basic strength sites (see Fig. 3).
The CO2 -TPD proles of Mn-based catalysts show for all the
samples a desorption prole spanned in the range 20350 C, monitoring the presence of surface basic sites with a broad strength
distribution, the specic (molCO2 gcat 1 ) and intrinsic basicity
(molCO2 m2 ) values being summarized in Table 3. Interestingly,
in all the MnCeOx systems a dominant basic character is observable
(B/A > 1). Really, CO2 strongly interacts with surface basic centers of
Mn-based systems, but, from a quantitative point of view, it is not
easy to state a well dened trend with the Mn loading. Indeed, by
increasing the Mn/Ce ratio, several reactive surface oxygen species
can be involved in CO2 adsorption, leading to different distribution proles [40,48]. Then, in order to discriminate the contribution
of basic sites of different strength, a deconvolution analysis of the
MnCeOx proles obtained by CO2 chemisorption has been done. By
an iterative data treatment, it was found that all TPD proles can
be described by a linear combination of three Gaussian peaks with
maxima at 93, 165 and 289 C respectively (see Table 4). For all the
systems, this deconvolution analysis provides a very accurate tting (r2 > 0.99) of the experimental curves, as shown in Fig. 3. On the
basis of literature evidences [7], the desorption peak at low temperature (T1 ) was attributed to the interaction of CO2 with sites
of weak basic strength, mostly corresponding to OH groups on
the catalyst surface. Instead, the peaks at higher temperature (T2
and T3 ) were attributed to both medium and strong sites, related
respectively to the oxygen of Men+ O2 ion pairs and isolated O2
anions (250350 C), that can be expected to possess Lewis base
character.
Taking into account such considerations, it is possible to state
that by increasing the Mn loading, the concentration of weak
sites progressively decreases from 0.85 until 0.35 mol m2 (see
Table 4), while medium and strong sites do not follow a progressive
trend with the Mn/Ce ratio.
The highest basicity of Mn0.3 Ce0.7 (either specic or surface)
could be justied considering that the contribution of weak basic
sites of ceria in such sample is signicant [42]. On the contrary,

Fig. 4. XRD patterns of MnCeOx systems.

C. Cannilla et al. / Applied Catalysis A: General 382 (2010) 158166

Fig. 5. ME yield (%) with differently functionalized solid catalysts: sunower oil
weight, 80 g; Rmet/oil , 12 mol/mol; Rcat/oil , 1 wt.% (3 wt.% for ZnO); TR , 200 C; reaction
time, 5 h.

although Mn0.7 Ce0.3 exhibits the lowest value of both specic

(240 mol gcat 1 ) and surface basicity (1.9 mol m2 ), it shows a
wider population of medium and strong basic sites (82%).
In order to attain further information on the structural properties of the MnCeOx systems, samples were analyzed by XRD
measurements. As shown in Fig. 4, irrespective of the composition, the redox precipitated samples show diffraction patterns
with a main broad and smoothed signal spanned in the 2
range 2040 and a less intense component between 40 and 60 .
These diffraction patterns are diagnostic of the lack of a longrange crystalline order which, according to the characteristics of
the redox-precipitation process, can be attributed to an intimate
interaction of MnOx and CeOx species at a (quasi)molecular level,
hindering the growth of large crystalline domains [4345] and
allowing the formation of nanosized MnCeOx oxide particles.
3.2. Catalytic activity
The results of a preliminary screening of different catalysts in the
sunower oil transesterication with methanol at 200 C, including
silica-supported heteropolyacids, the commercial bulk ZnO and one
MnCeOx catalyst, are shown in Fig. 5. Such data refer to the oil conversion values taken after 5 h of reaction using a Rmet/oil of 12 and
a catalyst/oil mass ratio (Rcat/oil ) of 1 wt.%. In addition, considering
that at 200 C the uncatalyzed reaction could occur [32], a blank
test was carried out. The result of the blank test reveals that the
transesterication reaction proceeds, but with a rate much lower

163

Fig. 6. Oil conversion and ME yield as a function of reaction temperature: Mn0.5 Ce0.5
catalyst; sunower oil weight, 80 g; Rmet/oil , 12 mol/mol; Rcat/oil , 1 wt.%; reaction time,
5 h.

(ME yield of about 10%) than that observed in presence of catalyst. The methyl esters yield of the commercial ZnO sample (Rcat/oil ,
3 wt.%) is comparable with literature data (75%) under analogous
reaction conditions [44], while the activity scale of the supported
and precipitated systems, in terms of ME yield, resulted to be the
following:
Mn0.5 Ce0.5 > HPMo-17 > HPW-17 > NS-20 > Cs-HPW
indicating that the Mn0.5 Ce0.5 sample ensured the best catalytic
performance. It is important also to underline that with such a catalyst, an easier separation of the reaction products at the end of run
(clean solution) was allowed. However, the results conrmed that
the typical solid acidic systems (HPW-17 and HPMo-17 samples)
also exhibit a considerable transesterication activity due to the
presence of surface Brnsted acid sites [46,47].
The preliminary screening of the different catalytic systems
prompted us to shed light into the behaviour pattern of the novel
MnCeOx systems and factors affecting a potential process development based on their use.
The effect of the reaction temperature on biodiesel yield in the
range of 120200 C, using Mn0.5 Ce0.5 , catalyst is shown in Fig. 6.
As expected, the ME yield increases with reaction temperature. In
addition the higher temperature mitigated the interphase diffusion
phenomena favouring a better mixing of the two phases, alcohol
and oil [17]. It is important to observe that, the reaction proceeds
with a signicant rate even at 120 C obtaining an oil conversion of
ca. 40% and a ME yield of 37%. Considering the low Rcat/oil (1 wt.%)
used, in comparison to higher ratios normally used in similar exper-

Fig. 7. Inuence of reaction time on oil conversion and methyl esters yield [A]; reaction kinetics for Mn0.5 Ce0.5 catalyst [B]. Sunower oil weight, 80 g; Rmet/oil , 12 mol/mol;
Rcat/oil , 1 wt.%; TR , 140 C.

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C. Cannilla et al. / Applied Catalysis A: General 382 (2010) 158166

Fig. 8. ME yield as a function of Mn loading: sunower oil weight, 80 g; Rmet/oil ,

12 mol/mol; Rcat/oil , 1 wt.%; TR , 140 C; reaction time, 1 h.

Fig. 9. Rate of ME formation under kinetic regime: sunower oil weight, 80 g;

Rmet/oil , 12 mol/mol; TR , 140 C; reaction time, 1 h.

iments (i.e., 35 wt.%) [5,12,31] and the low process temperature

investigated, it is evident that the result obtained appears very
interesting in view of potential practical exploitation.
Indeed, the data in Fig. 6 show that the catalytic transesterication of sunower oil with methanol can be effectively run at 140 C
using the MnCeOx system. Therefore the attention was focused to
investigate the inuence of reaction time on oil conversion and
ME yield. Results obtained at 140 C (see Fig. 7A), using Mn0.5 Ce0.5
sample show that oil conversion trend satisfactorily obeys to rstorder reaction kinetics (see Fig. 7 B). Such result, contrarily to what
observed by other authors [17,49], points out the absence of any
induction time due to interphase diffusional resistances. In addition, results reveal that, by operating with Rcat/oil 1 wt.%, to obtain
oil conversion close to 100%, long reaction time is requested.
As the physico-chemical properties can affect the functionality of the MnCeOx system, the inuence of the manganese loading on the catalytic activity was investigated at 140 C. Experiments
were stopped after 1 h of reaction time to obtain data far away from
equilibrium conditions. A blank test was also carried out, indicating that the contribution of the thermal conversion is very low (oil
conversion < 1%) whereas a marked inuence of MnOx loading on
catalyst performance is evident. As shown in Fig. 8, ME yield regularly increases with Mn loading up to a maximum value of ca.
50% obtained with Mn0.7 Ce0.3 catalyst, characterized by the highest
Mn/Ce atomic ratio (3.4).
Taking into account the results obtained in kinetic regime, the
reaction rate was plotted as a function of the Mn loading (see
Fig. 9). Referring the rate to both catalyst and manganese mass,
two straight-line relationships with a different slope were found.
Notably, this nding would signal a constant intrinsic activity of the
surface active sites due to a constant dispersion of the active phase
in the whole range of the Mn loading (941 wt.%). These evidences
well match with previous characterization results of similar systems [43], since it was shown that the redox-precipitation method
effectively enables a uniform molecular-like dispersion of the
MnOx species across the ceria matrix, irrespective of the Mn/Ce
ratio, due to the selective co-generation of the MnOx and CeOx
phases [4345].
Then, to disclose the inuence of the main physico-chemical
properties on the catalytic activity of the MnCeOx system, the
values of the reaction rate have been plotted as a function of
both average pore diameter (APD) and intrinsic basic capacity
(see Fig. 10). It is evident that the surface chemical proper-

ties of the systems do not allow a proper rationalization of the

catalyst performance, as the reaction rate decreases with the concentration of surface basic sites, resulting the highest for the
Mn0.7 Ce0.3 sample characterized by the lower intrinsic basic capacity (1.9 molCO2 m2 ). In spite of this, the largest population of
medium and strong basic sites per surface unit on the Mn0.7 Ce0.3
and Mn0.5 Ce0.5 (see Table 4) reects a lower concentration of weak
sites. That evidence could explain their superior activity in respect
to the Mn0.4 Ce0.6 and Mn0.3 Ce0.7 catalysts. However, the different
reactivity of Mn0.7 Ce0.3 and Mn0.5 Ce0.5 points out that the basic
strength controls the reaction but, evidently, other factors could
play an important role, like the porosity. Really, the main differences between the two systems are represented by PV and APD
values, being respectively 0.73 cm3 g1 and 191 for Mn0.5 Ce0.5
and 0.90 cm3 g1 and 314 for Mn0.7 Ce0.3 . The reaction rate signicantly increased with APD (see Fig. 10), thus highlighting that
catalyst porosity strictly inuences the active sites accessibility
that, in case of big molecules involved in the transesterication
reaction, like TGs, could be limited by the catalyst pore diameter.
Considering that the redox-precipitation method employed to
prepare the MnCeOx catalysts foresees the use of potassium (KOH)
that could remain in the structure (mostly in the form of carbonate
species) and that K also could play a catalytic role in the transesteri-

Fig. 10. Correlation among textural or surface properties with catalytic data (TR ,
140 C; reaction time, 1 h) of the Mn-based systems.

C. Cannilla et al. / Applied Catalysis A: General 382 (2010) 158166

165

Table 5
Inuence of K content on the catalyst performance.
Catalyst

K (wt.%)
a

Mn0.5 Ce0.5 m
Mn0.5 Ce0.5
Mn0.7 Ce0.3 eb
Mn0.7 Ce0.3 wc
Mn0.7 Ce0.3
a
b
c

1.7
1.7
4.3
5.2

Reaction rate (molME gcat 1 min1 )

Mn (wt.%)

5.5 10
7.9 104
1.1 103
2.3 103
2.9 103

25
25
41
41
41

ME yield (%)
10
15
20
40
50

Precipitation with NH4 OH .

Washing with a 103 M solution of HNO3 .
Washing with deionized water repeatedly.

cation reaction, some experiments were performed with samples

previously treated to reduce or eliminate K from the catalyst composition. On this account, a MnCeOx sample (Mn0.7 Ce0.3 w) was
prepared by using the redox-precipitation method, washing it for
a long time with deionized water. An amount of such sample was
further washed in an acid solution (103 mol L1 , HNO3 ) to eliminate K (Mn0.7 Ce0.3 e). In addition, a new MnCeOx sample without
K (Mn0.5 Ce0.5 m) was prepared by using NH4 OH as the precipitant
reactant.
The results obtained using such catalysts are reported in Table 5.
It can be seen that, in terms of reaction rate and ME yield,
data obtained are compared with that of two representative
MnCeOx samples prepared by redox-precipitation route with KOH,
Mn0.5 Ce0.5 and Mn0.7 Ce0.3 . Using the Mn0.5 Ce0.5 m catalyst without
K, it is possible to attain a ME yield of 10% in comparison to a ME
yield of 15% obtained with Mn0.5 Ce0.5 containing 1.7% of K. At high
Mn/Ce ratio the ME yield signicantly increases, with a maximum
value of 50% on the Mn0.7 Ce0.3 sample. Such a catalyst, characterized by Mn loading of 41 wt.%, exhibits the best performance in term
of reaction rate as well. Indeed, on similar but timely washed samples, like Mn0.7 Ce0.3 w and Mn0.7 Ce0.3 e, a lower conversion rate
was obtained in correspondence of the sample containing a lower
amount of K. This result has forced us to investigate the leaching
phenomena that could occur during reaction. Then, the Mn0.7 Ce0.3
sample was soaked with pure methanol for 1 h at 140 C and then
the methanol solution was analyzed by X-ray uorescence (XRF).
The XRF analysis revealed that only trace of both Mn and K goes in
solution. However, to exclude that such low amount of Mn and K
in liquid phase could affect the reaction, the recovered methanol
solution was used as medium reaction for a new experiment. Same
result of the uncatalyzed run was obtained, demonstrating so that
the low amount of Mn and K dissolved in liquid phase does not
signicantly contribute to alter the catalytic activity of Mn-based
systems and therefore the homogeneous catalytic route could be
considered not very signicant. As a rst hypothesis, it could be considered that potassium act as a simple structural promoter (not
completely removable by washing) or rather as an electronic promoter able to improve the functionality of manganese. At moment,
this is only a mere speculation and additional investigations are
necessary to conrm the assumption.

than 140 C in 5 h of reaction, by operating at low catalyst/oil ratio

(1 wt.%), without evident catalyst deactivation phenomena;
- The obtainment of a linear relationship between reaction rate and
Mn loading conrms that the redox-precipitation method allows
to obtain highly dispersed catalysts even at high Mn loading;
- Correlations between catalytic activity of MnCeOx catalysts and
physico-chemical properties highlight that the basic strength
controls the reaction but, owing to the large dimension of the
molecules involved in the transesterication reaction, the accessibility of active sites has also to be taken into account. The activity
does not depend only on the acidbase capacity, but it is the result
of a synergic role played by both the surface properties and the
textural porosity;
- K, incorporated in the catalyst structure during the preparation
procedure, could contribute to enhance the catalytic performance
of MnCeOx system. Further investigations are necessary to clarify
its role.
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