Applied Catalysis A: General 378 (2010) 160168

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Applied Catalysis A: General

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

Biodiesel production process by homogeneous/heterogeneous catalytic system

using an acidbase catalyst
Anastasia Macario a, , Girolamo Giordano a , Barbara Onida b , Donato Cocina b ,
Antonio Tagarelli c , Angelo Maria Giuffr d
a
Department of Chemical Engineering & Materials, Universit della Calabria, Rende (CS), Italy
b
Department of Materials Science & Chemical Engineering, Politecnico di Torino, Torino, Italy
c
Department of Chemistry, Universit della Calabria, Rende (CS), Italy
d
Department of Biotechnology, M.A.A., Universit Mediterranea di Reggio Calabria, Reggio Calabria, Italy

a r t i c l e i n f o a b s t r a c t

Article history: The transesterication of triglycerides contained in waste oilseed fruits with methanol has been studied
Received 1 January 2010 in heterogeneous/homogeneous systems using acid and base catalysts. The acid catalysts (strong acid
Received in revised form 9 February 2010 catalysts: USY, BEA, FAU-X, and weak acid catalysts: MCM-41 and ITQ-6 with Si/Al = ) were prepared
Accepted 10 February 2010
by hydrothermal synthesis procedures. In order to obtain acidbase catalysts, potassium was loaded
Available online 18 February 2010
on different materials by ionic exchange (obtaining K-MCM-41, K-ITQ-6,). XRD, ICP-MS, IR after CO and
CO2 adsorption, thermal analyses and N2 adsorption/desorption techniques have been used for catalysts
Keywords:
characterization. The highest triglycerides conversion and biodiesel yield values were achieved by K-ITQ-
Biodiesel
Transesterication
6 catalysts, after 24 h of reaction at 180 C. Deactivation of this catalyst occurs for potassium leaching, but
Esterication its regeneration and reuse are feasible and easy to perform. A possible continuous biodiesel production
Zeolites process has been proposed.
Acidbase catalysis 2010 Elsevier B.V. All rights reserved.

1. Introduction with methanol, using sodium hydroxide, potassium hydroxide

or potassium methoxide as catalyst [1]. The homogeneous basic
The transestrication of vegetable oils, catalyzed by either acids transesterication shows a very fast kinetic of reaction but also a
or bases, consists in three consecutive and reversible reactions collateral saponication reaction that reduces the biodiesel pro-
in which triglycerides are converted rst to diglycerides, then to duction efciency. To prevent the biodiesel yield loss due to the
monoglyceride and nally to glycerin. In each steps, one ester is saponication reaction, oil and alcohol must be dry and the oil
formed. In the overall reaction, using methanol as alcohol, 3 mol of should have a minimum amount of free fatty acids (less than
methyl esters are produced for each mole of triglyceride. 0.1 wt%). Biodiesel is nally recovered by repeated washing with
Industrial processes use 6 mol of methanol for each mole water to remove glycerol, soap and the excess of methanol. By
of triglyceride obtaining methyl esters as biodiesel mixture contrary, the acid transesterication allows to obtain a biodiesel
(FAME = Fatty Acid Methyl Esters). This large excess of methanol production without formation of by-products. The drawbacks of
ensures that the reaction is driven in the direction of methyl esters. an acid homogeneous transesterication are the corrosive catalyst
The methyl esters mixture (or Biodiesel fuel) has similar proper- (H2 SO4 , H3 PO4 , and HCl) and the slow reaction rate. This may be
ties of fossil diesel fuel (cetane number, kinematic viscosity) but it increased at high temperature and pressure, involving larger costs
does not contain petroleum products and sulfur compounds. Fur- [2]. Methanol and oil are poorly soluble, so the reaction mixture
thermore, it possesses a higher ash point (>130 C) with respect contains two liquid phases. Others alcohols can be used, but being
the conventional diesel. For these reasons biodiesel is recognized more expensive. Moreover, an acid pre-treatment is often carried
as green fuel. Finally, it is almost neutral towards CO2 emission out in the homogeneous alkaline-transesterication of oils having
because its renewable sources (vegetable oils and biomass). more than the 5 wt% of free fatty acids, in order to improve the
Industrial current production of biodiesel is carried out by biodiesel efciency production [13]. Recent works, also, demon-
homogeneous alkali-catalyzed transesterication of vegetable oils strate as a heterogeneous enzymatic catalyst represents a potential
solution to produce biodiesel from very low-quality triglycerides
source [4,5], but in these cases the cost of the enzymes has to
Corresponding author. Tel.: +39 0984 49 66 67; fax: +39 0984 49 66 55. be considered. All these aspects suggest that an environmental-
E-mail address: macario@unical.it (A. Macario). friendly and cheaper biodiesel production process could be carried

0926-860X/$ see front matter 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.apcata.2010.02.016
 A. Macario et al. / Applied Catalysis A: General 378 (2010) 160168 161

out using acid or basic heterogeneous catalysts or, better, hetero- Waste fruit oilseeds with oleic acid (C18:1, 39 wt%) and linoleic
geneous catalyst with both acid and basic properties. They could acid (C18:2, 30 wt%) as main FFAs content (total free acidity 5.58%)
combine the advantages of the alkaline and acid transesterications is used as triglycerides source.
with those of heterogeneous catalytic process. The suitable catalyst
should possess high activity and selectivity, high water-tolerance, 2.2. Catalysts preparation
high stability, it should be inexpensive and its production process
should be environmental friendly. The activity and selectivity prop- Pure silica MCM-41 type material was prepared starting from a
erties of catalyst generally depend on the amount and the strength gel with the following molar composition:
of acid or basic sites. Towards organic reaction (like transesterica-
tion), catalysts with high hydrophobic surface area are preferable 1SiO2 0.26TMAOH0.12CTABr40H2 O
because otherwise water can interact with active sites preventing
The crystallization time and temperature were, respectively,
the adsorption of organic reactants. As it is well known, zeolites and
24 h at 140 C in autoclave.
related materials are suitable materials for these purposes because
Delaminated zeolite ITQ-6 (Si/Al = ) sample was prepared by
they can be easy synthesized and modied in order to affect the
swelling the laminar pure silica PREFER according to the procedure
acidity, basicity and hydrophobicity of their surface.
described by Corma et al. [22].
In this contest, our work focus on the possibility to use strong
USY zeolite has been supplied by UOP Molecular Sieves. BEA
acid zeolites (USY, BEA, FAU-X), weak acid materials (materials with
catalyst was prepared by hydrothermal synthesis starting from the
high density of silanol groups: pure silica mesoporous materials
following molar gel:
and delaminated zeolites) and materials with acidbase proper-
ties (K-MCM-41, K-ITQ-6) as catalysts for the transesterication of 50SiO2 10TEAOH2Na2 O0.5Al2 O3 350H2 O
waste fruit oilseeds with high amount of free fatty acids (FFAs),
time and temperature of crystallization were, respectively, 5 days
higher than 5 wt% (as low-quality and cheap triglycerides sources),
at 150 C in autoclave.
with methanol to biodiesel. There are many different materials
The molar composition of the gel for hydrothermal synthesis of
developed as catalysts for the transesterication of triglycerides
FAU-X zeolites was the following:
to biodiesel, such as solid acids [611] (Amberlyst-15, H-Zeolites,
Cs-heteropoly acids) or solid basic [9,1119] (KOH-NaX, KI-Al2 O3 , 1SiO2 0.6Na2 O0.1Al2 O3 40H2 O
Na/NaOH/-Al2 O3 , ETS-10, CaO, NaCs-X, KOH-Al2 O3 ). All these
materials show interesting results but only in respect with acid or After the synthesis, the solid phases of all syntheses were recov-
basic catalytic aspect. Moreover, in order to achieve good catalytic ered by ltration and washed with distilled water. The samples
performance, some of them can used only in strong conditions, were calcined in air ow at 550 C for 8 h (heating rate: 5 C/min).
such as high temperature, high methanol content or in presence Finally, samples containing potassium (K-MCM-41, K-ITQ-6) were
of extracting co-solvent, or starting from high quality triglycerides obtained by ionic exchange carried out on correspondent cal-
source. While, the conversion of biological feedstocks to biodiesel cined material at 60 C, for two times, with KCl 1 M solution and
using mesoporous calcium silicate mixed oxides, as heterogeneous a ratio solid/solution equal to 0.01 g/ml. After ionic exchange, the
catalysts with acids and basics, is recently published and patented dried samples were activated at 300 C for 8 h. Commercial anhy-
by Lin et al. [20,21]. drous potassium silicate in powder was supplied by Alfa Aesar
Besides the usual zeolites characterization techniques (XRD, Co.
TG-DTA, ICP-MS, N2 adsorption), the study of the adsorption of
CO and CO2 on the catalysts has been carried out by IR spec- 2.3. Catalysts characterization
troscopy, in order to identify the nature and the strength of the
catalytic active sites. The reaction conditions were not optimized Powder X-ray diffraction (XRD) data were recorded using a
for the highest reaction yield: all catalytic tests provided to com- Phillips PW 1710 diffractometer with CuK radiation. The samples
pare the activities of different catalysts. The catalyst showing the were scanned in the range of 2 from 1 to 8 (for mesoporous
best catalytic performances (triglycerides and FFAs conversion and materials) or from 5 to 45 (for microporous materials) in steps
biodiesel yield) was regenerated and used for more than one reac- of 0.005 with a count time of 1 s at each point. XRD analyses of all
tion cycle. The efciency of catalyst regeneration procedure has synthesized samples show the characteristic diffraction peaks (pat-
been evaluated in order to perform a possible continuous biodiesel terns not reported), conrming that the expected phases have been
production process. Chemical composition (free fatty acids, mono- obtained for all materials. BET surface area and physical properties
glycerides, diglycerides and triglycerides content) and total acidity of samples were evaluated by N2 adsorption/desorption isotherms
of the biodiesel nal product have been measured. carried out at 77 K on a Micromeritics ASAP 2020 sorption ana-
lyzer. Thermal decompositions of as-synthesized samples were
investigated by SHIMADZU DTG-60 instrument, between 20 C and
2. Materials and methods 850 C, at a ramp of 5 C/min in air with a ow rate of 5 ml/min.
Chemical composition of samples was evaluated by an Elan DRC-e
2.1. Materials ICP-MS instrument (PerkinElmer SCIEX). Samples were introduced
by means of a quartz nebulizer. The ICP torch was a standard torch
The silica sources used for catalysts preparation were: pre- (Fassel type torch) with a platinum injector. For the quantitative
cipitated silica (BDH) and silica fumed (Aerosil 200 (Degussa) or analysis, calibration curves were built on six different concentra-
silica fumed (Aldrich)). The structure directing agents used were: tions in a calibration range of 15000 g/l and having composition
cetyltrimethylammonium bromide (CTABr, Aldrich) for meso- similar to that of solution samples. Standard solutions were pre-
porous materials. The mineralizing agents were: sodium hydroxide pared by diluting a solution of Na and K (1000 mg/l).
(Carlo Erba), tetramethylammonium hydroxide (TMAOH, 25%, For IR measurements, self-supporting wafers were prepared and
Fluka) and tetraethylammonium hydroxide (TEAOH, 40%, Fluka). activated under dynamic vacuum (104 Torr) for 1 h at 573 K, in
Aluminum hydroxide (98%, Aldrich) was used as metal sources for an IR cell allowing in situ thermal treatments, gas dosage and IR
AlBEA catalyst preparation, while sodium aluminate (NaAlO2 , 99%, measurements to be carried out both at room temperature and at
Carlo Erba) was used as aluminum source for FAU-X preparation. a nominal temperature of 77 K, presumably in fact around 100 K.
162 A. Macario et al. / Applied Catalysis A: General 378 (2010) 160168

Spectra were collected on a Bruker IFS 55 Equinox instrument

equipped with a MCT cryodetector working with 2 cm1 resolution.
Difference spectra are obtained after subtraction of the spectrum
of the naked sample.

2.4. Transesterication reaction

The alcoholysis of triglycerides with anhydrous methanol

(99.9%, SigmaAldrich) performed in batch Teon-steel autoclaves
immersed in a temperature-controlled bath. The reaction temper-
ature was varied from 100 C to 180 C. In a typical experiment
5.0 g of oil were mixed with 2.74 ml of methanol (molar ration
oil:methanol equal 1:20) and 0.15 g of catalyst (5 wt% respect to
oil). Then the mixture was transferred in the autoclave and stirred
(650 rpm). The autoclave was close and heated in the bath until the
desired temperature. The reaction was been carried out under auto-
geneous pressure in the batch-autoclave system for the required Fig. 1. Catalytic performance (triglycerides conversion and biodiesel yield) obtained
by all catalysts tested at 100 C, at 5 wt% respect to the oil, for 24 h and with a molar
time. To analyze the reaction progress, products and reactant were
ratio between oil:methanol equal to 1:20.
separated from catalyst and glycerin by centrifugation in hexane
(95%, SigmaAldrich). To analyze the chemical composition of the
biodiesel produced we used the ASTM D-6584-00 method. Through 100 C, 24 h of reaction, 650 rpm, 5 wt% of catalyst respect to the
this method, it is possible to quantify triglycerides (TG), diglyc- triolein, molar ratio equal to 1:20 between oil and methanol.
erides (DG), monoglycerides (MG), free fatty acids and methyl ester As observed from Fig. 1, the strong acid catalysts (USY, BEA
by unique chromatogram. The Rtx -Biodiesel fused silica capil- and FAU-X) do not reach an appreciable triglycerides conversion
lary column (10 m 0.32 mm 0.10 m) was used in an Agilent in the reaction conditions. Commercial potassium silicate, appears
6890 GC instrument equipped with FID detector. Before analysis, as the best catalysts showing a triglycerides conversion of the 82%
trimethylsilyl-triuoroacetamide (98%+ Acros Organics) was added and biodiesel yield of the 79%. Among the synthesized catalysts
to the mixture as silyating agent. Tricaprin (SigmaAldrich, puriss. reported in Fig. 1, the most promising are K-MCM-41 and K-ITQ-6.
p.a. standard for GC) was added as external standard. 1 l of sample Their triglycerides conversion is similar, 58% and 64% respectively,
was injected and analyzed by the following oven temperature pro- whereas the biodiesel yield differs signicantly, being 56% for K-
gram: 1 min at 140 C, 10 C/min to 360, 8 min at 360 C. To correct ITQ-6 and only 3% for K-MCM-41.
the area obtained from the GC, in order to calculate the exact triglyc- The pure silica mesoporous material, Si-MCM-41, has not been
erides conversion and biodiesel yield, the response factors for each used as catalyst in the mentioned reaction due to very weak acidity
compounds have been calculated using the correspondent standard of its surface. While, concerning the pure silica delaminated zeolite
compound (puriss. p.a. standard for GC): oleic acid, methyl oleate, ITQ-6, due to its high weak acid silanols groups density, its catalytic
monoglycerides, diglycerides and triolein. The biodiesel yield (in activity at 100 C until 24 h of reaction can be detected but, in any
percentage) was calculated according to the following equation: case, has been low: the triglycerides conversion was closed to 20%.
  Starting from these results, in order to improve the catalysts per-
ABio /RBio formance, time and temperature of reaction have been increased.
By =
[(ABio /RBio ) + (AFFA /RFFA ) + 2(ADG /RDG ) + 3(ATG /RTG )] Operating at 180 C and following the reaction for 72 h, for acid
100 catalysts (FAU-X, BEA, USY) an increasing of triglycerides conver-
sion has not been observed. Finally, large increase of triglycerides
where Ai is the area of the peak correspondents to each compounds conversion and biodiesel yield have been observed for K-MCM-41
and Ri is the related response factor. Total acidity value of nal and K-ITQ-6 catalysts, maintaining the temperature at 100 C and
biodiesel mixture was calculated by the Standard European Method increasing the reaction time until 72 h (see Fig. 2(a)). In particu-
EN14104 and compared with the European Quality Standard Spec- lar, K-ITQ-6 catalyst gave a triglycerides conversion of 98% and a
ication of Biodiesel EN14214-UNI10946. biodiesel yield of 74% (Fig. 2(b)). The triglycerides conversion of
K-MCM-41 reached a value of 90%, but the main products were
2.5. Recovery and regeneration of catalyst the free fatty acids (32%) and monoglycerides (42%) whereas the
biodiesel yield grew only up to the 15%. Instead for K2 SiO3 catalyst a
At the end of each reaction cycle, two centrifugation processes faster reaction kinetic has been observed: after 17 h of reaction, the
were carried out in order to separate the catalyst from the reaction triglycerides conversion was 73% (Fig. 2(a)) and the biodiesel yield
mixture and the glycerol to biodiesel mixture. The recovered cata- was the 68% (Fig. 2(b)). After almost 30 h of reaction, the potassium
lyst has been washed with ethanol, in order to remove all organic silicate shows its best catalytic performance (83% of triglycerides
compounds (triglycerides and esters tracks), and then with water, conversion and 80% of biodiesel yield) and they do not change for
in order to remove ethanol. After drying at 120 C for 1 night, the longer reaction time. A further increase of the reaction temperature
catalyst was reused for another reaction cycle. In order to check (up to 180 C) for K-ITQ-6 caused a faster kinetic of transesteri-
the presence of organic compounds, a thermal analysis has been cation (Fig. 3). At 180 C, the K-ITQ-6 catalyst gave the 97% of
carried out on the regenerated catalysts. triglycerides conversion and the 80% of biodiesel yield after 24 h
of reaction. Following the reaction until 96 h, the triglycerides con-
3. Results and discussion version was observed to grow up to 99%, the biodiesel yield and
the FFAs conversion to increases up to 90%. The composition of the
3.1. Catalytic test results: screening of all tested catalysts biodiesel mixture at different reaction time is reported in Table 1.
At 180 C, the amount of free fatty acids, tri-, di- and monoglyc-
For a rst comparison among all catalysts tested, the same erides decreases and simultaneously the amount of methyl esters
reaction conditions were employed for the starting experiments: increases when reaction time increases up to 48 h. In these con-
 A. Macario et al. / Applied Catalysis A: General 378 (2010) 160168 163

Fig. 2. Triglycerides conversion and biodiesel yield, as function of time, obtained at 100 C, with the 5 wt% of catalyst respect to the oil and with a molar ratio between
oil:methanol equal to 1:20.

Fig. 4. Comparison between K-ITQ-6 and commercial KOH catalysts. Conditions for
KOH: 24 h at 70 C, methanol:oil molar ratio 10:1catalyst amount: 5 wt%; condition
for K-ITQ-6: 48 h at 180 C, methanol:oil molar ratio 20:1catalyst amount: 5 wt%.

Fig. 3. Triglycerides conversion, biodiesel yield and FFAs conversion, as function of

Further investigations have not been applied to this catalyst due to
time, obtained using K-ITQ-6 catalyst at 180 C, at 5 wt% respect to the oil and 1:20
molar ratio between oil:methanol. its low catalytic performance.
Due to the promising results obtained by K-ITQ-6 catalyst, a
comparison of its catalytic performance with those of commercial
ditions, the triglycerides conversion is almost complete, whereas KOH homogeneous basic catalyst could be interesting. For this pur-
the biodiesel yield only slightly increases, because the reaction pose, in the Fig. 4 the biodiesel yield, the FFAs and the triglycerides
proceeds with the conversion of mono- and diglycerides to free conversion obtained for K-ITQ-6 and KOH catalysts are reported.
fatty acids (see Table 1). The temperature increasing does not affect The main result noticeable by this comparison is, even if the time
appreciably the catalytic performance of pure silica ITQ-6 material: and temperature of reaction is different for two catalysts, when
the triglycerides conversion grew to 38% but the biodiesel yield was the triglycerides conversion is complete, K-ITQ-6 permits to obtain
closed to 3%. This means, most probably, that the weak acid silanol higher biodiesel yield and higher FFAs conversion than KOH cat-
groups of the ITQ-6 surface are able to estericate the free fatty alyst. Moreover, no soap products are detectable in the reaction
acids but they are not able to transestericate the triglycerides. mixture using K-ITQ-6 catalysts by GC analysis (results not showed)

Table 1
Triolein conversion, biodiesel yield and chemical composition of biodiesel mixture obtained using 5 wt% of K-ITQ-6 catalyst at 180 C and with triolein:methanol molar ratio
1:20.

Time [h] Triglycerides conversion [%] Biodiesel yielda [%] Methyl estersb [%] Free fatty acids [%] MGc [%] DGc [%] TGc [%]

17 94 65 67.2 12.5 15.6 2.1 2.6

24 96.7 79.7 82.4 6.08 9.23 1.14 1.13
48 98 87 88.7 2.41 7.97 0.32 0.63
a
By = {(ABio /RBio )/[(ABio /RBio ) + (AFFA /RFFA ) + 2(ADG /RDG ) + 3(ATG /RTG )]} 100.
b
Weight percentage of methyl esters, obtained directly by GC, after correction with response factors.
c
EN14214-UNI10946 values [wt%]: MG = 0.8; DG = 0.20; TG = 0.20.
164 A. Macario et al. / Applied Catalysis A: General 378 (2010) 160168

Fig. 5. N2 adsorption isotherms of mesoporous (a) and delaminated ITQ-6 (b) catalysts, before and after ionic exchange.

and three clear phases are visible after centrifugation: catalyst, erides conversion. In fact, the pore dimension of acid microporous
glycerol and biodiesel, and their separation is easy. materials used (FAU-X, USY and BEA) does not exceed 6 (see
Finally, the total acidity of biodiesel mixture, measured by Table 2) while the spherical molecular diameter of triolein (triglyc-
the European Standard method (EN14104), is equal to 0.23 mg eride of oleic acid C18), calculated by empirical correlation [23], is
KOH/g after 48 h of reaction, when the amount of free fatty 14 . This aspect is also conrmed by a previous study [9] where
acids is 2.42 wt%. This is a good value of biodiesel nal acidity, the activity of a strong acid zeolites (BEA) has been increased (of
considering that the maximum value accepted by the European the 10%) by lantanium ionic exchange, due to the fact that the
Quality Standard Specication of Biodiesel (EN14214-UNI10946) La species are able to increase the presence of external basic
is 0.5 mgKOH/g (0.8 mgKOH/g for the American ones ASTM6751). sites. In any case, the more acid La-BEA catalyst are not able to
Moreover, also the maximum amount of diglycerides and triglyc- reach a triglycerides conversion upper to 50%, meaning that the
erides are respected, while only the amount of monoglycerides is strong acid zeolites are not suitable as heterogeneous catalyst for
higher (see legend in Table 1). biodiesel production. Moreover, the high hydrophilicity of the sur-
face of these acid catalysts can be another reason of their inactivity
3.2. Catalysts characterization towards the transesterication reaction. The Si/Al molar ratio of
these catalysts, in fact, ranging between Si/Al = 550 in the start-
Main physico-chemical properties of tested catalysts are sum- ing synthesis gel. Then, the surface of nal catalyst can be very
marized in Table 2. For the microporous materials (USY, FAU-X hydrophilic, due to presence of aluminum and the water can covers
and BEA) the low triglycerides conversion may be ascribed to the the surface of the acid solid, preventing the adsorption of organic
fact that the higher density of active acid sites is inside to the substrate. Further investigations have been carried out only on
catalyst structure. Then, the big molecule of triglycerides can- the samples that have showed the best or an appreciable catalytic
not enter inside the microporous channels of the catalysts and performance, that is the mesoporous materials and delaminated
the very low concentration of acid sites on the external surface zeolites.
of these catalysts is not enough to obtain an appreciable triglyc- Therefore, textural properties of these catalysts have been ana-
lyzed by ICP-MS, N2 adsorption/desorption and thermogravimetric
thermal analyses. After ionic-exchange with K+ the amount of
potassium loaded is 0.22 wt% and 1.59 wt% for MCM-41 and ITQ-6,
respectively (Table 2).
The N2 adsorption/desorption isotherm, BET surface area and
pore diameter of the mesoporous sample after potassium loading
by ionic exchange, has been reported in Fig. 5(a). Both BET value
and pore size of mesoporous structures decrease after K+ loading,
indicating the presence of the cation. For ITQ-6 delaminated zeolite,
the ionic exchange, carried out to load potassium cation on the
highly hydroxilated surface of this material, strongly reduces the
nal BET value (Fig. 5(b)), indicating a great amount of potassium
loaded (as conrmed by ICP elemental analysis).
The hydrophobicity of mesoporous samples and delaminated
zeolites were estimated from the weight loss of physisorbed water
at 200 C. The K-MCM-41 loses the 6.80% and the K-ITQ-6 loses
only the 3.21% (Fig. 6). These results indicate that the delaminated
zeolite containing potassium is more hydrophobic than K-MCM-41
(thermogravimetric analysis results). This can be one explanation
why K-MCM-41 shows a lower catalytic activity towards the trans-
Fig. 6. TG curves of K-ITQ-6 and K-MCM-41 catalysts. esterication reaction, respect to the K-ITQ-6 catalyst.
 A. Macario et al. / Applied Catalysis A: General 378 (2010) 160168 165

Fig. 7. IR spectra related to the adsorption of CO at 77 K on K-ITQ-6 outgassed at 573 K. Section (a) OH stretching region; section (b) CO stretching region.

3.3. Infrared spectroscopy analyses results Upon adsorption of CO, the band at 3698 cm1 is not perturbed
(section (a), body of the gure). The band due to isolated silanols,
Due to the good catalytic performance showed by K-ITQ-6, we instead, decreases and that due to H-bonded silanols increases
have characterized the catalyst by FT-IR analysis, in order to have at 3660 cm1 . The measured shift is some 90 cm1 , revealing
additional information on the nature of the acid and basic catalytic the same Brnsted acidity of silanols as in the case of K-ITQ-6.
sites. The stretching mode of CO molecules interacting with silanols is
observed at 2156 cm1 (section (b)), as in the case of K-ITQ-6. At
3.4. Adsorption of CO at 77 K low coverage, a shoulder is hardly discernible at 2162 cm1 , due
to CO interacting with K+ ions [25]. The band due to physisorbed
Fig. 7 reports IR spectra related to increasing coverage of CO liquid-like CO is observed at 2138 cm1 and its relative intensity
adsorbed at 77 K onto K-ITQ-6, previously outgassed at 573 K. In the with respect to the band at 2156 cm1 is weaker than in the case
OH stretching region (section (a)), the decrease of the isolated SiOH of K-ITQ-6. This is ascribed to the absence of microporosity in the
stretching mode at 3750 cm1 is observed, accompanied by the MCM-41 sample, at variance with K-ITQ-6.
increase of the broad band at 3660 cm1 , due to the same species
interacting via H-bonding with CO. The shift, which is an indirect 3.5. Adsorption of CO2 at room temperature
measure of the Brnsted acidity, is about 90 cm1 , i.e. the value
measured for isolated silanols in all silica ITQ-2 and amorphous sil- Fig. 9 reports the IR spectra related to the adsorption of CO2 at
ica Aerosil [24]. The stretching mode of CO molecules interacting room temperature on K-ITQ-6 (section (a)) and K-MCM-41 (sec-
with silanols is observed at 2156 cm1 (section (b)), as expected tion (b)), previously outgassed at 573 K. In the case of K-ITQ-6, a
[24]. Another band increases at 2138 cm1 , due to liquid-like CO, composite band between 1600 cm1 and 1700 cm1 is observed,
probably mainly physisorbed in ITQ-6 microporosity. Fig. 8 reports accompanied by a second one at 1349 cm1 . These bands are not
the IR spectra related to increasing coverage of CO adsorbed at 77 K depleted by outgassing at RT and they are ascribed to carbonate
onto K-MCM-41. The inset in section (a), which refers to the OH species, formed by interaction of CO2 with basic oxygen sites. They
stretching region, reports the spectrum of the sample outgassed at are not formed upon adsorption of CO2 on K-MCM-41 (section (b)).
573 K before adsorption of CO. Besides the band at 3748 cm1 , due In conclusion, only on the surface of ITQ-6 exchanged with
to isolated silanols, a broader band is observed at 3698 cm1 , which potassium, both acids and basics sites are present, which are
is ascribed to silanols perturbed by hydrocarbon moieties, due to responsible of its higher catalytic activity, with respect to the K-
templates residues. MCM-41.

Table 2
Main physico-chemical properties of catalysts tested.

Catalyst type Si/Al gel molar ratio BET surface area [m2 /g] Pore diameter [] K+ loaded [wt%]

USYa 15 720 6
AlBEA 50 545 5.6
H-FAU-X 5 764 5.9
Si-MCM-41 969 47
K-MCM-41 677 42 0.22
ITQ-6 900
K-ITQ-6 288 1.59
a
Si/Al content measured in the crystals.
166 A. Macario et al. / Applied Catalysis A: General 378 (2010) 160168

Fig. 8. IR spectra related to the adsorption of CO at 77 K on K-MCM-41 outgassed at 573 K. Section (a) OH stretching region; section (b) CO stretching region.

3.6. Proposed reaction mechanism

In the Fig. 10 the reaction mechanism proposed for the reaction

catalyzed by acidbasic K-ITQ-6 catalyst is reported.
As it is possible to notice, the presence of potassium loaded
by ionic exchange to the silanol groups of the pure silica delam-
inated zeolite allows the formation of homogeneous methoxide
(Fig. 10(a)) that promotes the carbonyl carbon atom attack of
triglycerides, and the homogeneous Brnsted basic catalysis takes
place [26].
Simultaneously, the free weak Brnsted acid silanol groups
of the catalyst can protonate the carbonyl group of TG and
FFAs, increasing their electrophilicity and rendering they more
susceptible to the alcohol nucleophilic attack, allowing the
transesterication and esterication reaction by a well known
homogeneous Brnsted acid catalysis mechanism [27]. The acid
esterication of free fatty acid by weak acid Brnsted silanol groups
of catalyst prevents the saponication reaction and the biodiesel
separation and purication can be carried out more easily. For this
reason the FFAs conversion is higher than the value obtained by
commercial KOH (as showed in the Fig. 4). Moreover, the simul-
taneous presence of basic and acidic sites on the K-ITQ-6 catalyst
surface could also explain why for an interesting heterogeneous
basic catalyst (the ETS-10), reported by a Suppes et al. [16], the
high free fatty acids concentration (about the 30 wt%) inhibit the
basic solid catalyst.

3.7. Reusability of catalyst

The reusability was studied only for K-ITQ-6 and K2 SiO3 , due
to the fact that these catalysts having best performance. For K-
ITQ-6 catalysts the amount of recovered material was about 80% of
the initial quantity (calculated weighting the dried sample before
and after reaction). While, concerning commercial K2 SiO3 , even if
during the rst reaction cycle the catalytic performance are better
that that of K-ITQ-6, the solid is partially dissolved in the reaction
media and only less than the 40 wt% can be recovered. Moreover,
Fig. 9. Difference IR spectra related to the adsorption of CO2 at RT on K-ITQ-6 (sec- the biodiesel yield after the second cycle strongly decreases to 63%.
tion (a)) and K-MCM-41 (section (b)) outgassed at 573 K. Curve 1: in contact with Triglycerides conversion achieved during the second reaction
CO2 (p = 47 mbar); curve 2: outgassed at RT after contact with CO2 . cycle by K-ITQ-6 was only the 56%, whereas the biodiesel yield was
 A. Macario et al. / Applied Catalysis A: General 378 (2010) 160168 167

Fig. 10. (a) Proposed potassium methoxide mechanism formation. (b) Proposed transesterication Brnsted acid mechanism.

35%, after 24 h of reaction at 180 C (5 wt% of catalyst and molar ratio transestericationesterication process and the second one for
oil:methanol equal to 1:20). Comparing these results with those catalyst regeneration. Each xed-bed reactor is supplied by catalyst
obtained after the rst reaction cycle, a clear potassium leaching regeneration lines, consisting of hexane feed for organic com-
has been taken. Moreover, the results of ICP analysis carried out pound removing, water feed for hexane removing and, nally,
on the used catalyst show that, after the rst use, the amount of KCl 1 M solution feed for potassium exchange and fresh catalyst
potassium on K-ITQ-6 zeolite decreases from 1.59 wt% to 0.51 wt%, preparation. When the catalyst is exhaust, the reactor stops to
with a leaching of potassium of the 78%. work and the catalyst regeneration process starts, simultaneously,
This means that the maximum amount of potassium in the nal the second reactor, terminated the catalyst regeneration, starts to
biodiesel does not reach the 0.1 wt% (result obtained by mass bal- work for a new biodiesel production process with the fresh cata-
ance on potassium presents on K-ITQ-6 catalyst before and after lyst.
reaction). However this metal content can be easily reduced by a
bland washing of biodiesel with distilled water.

3.8. Regeneration of catalyst

The thermal analysis carried out on the regenerated catalyst,

after one reaction cycle, shows that the regeneration procedure
allows to obtain a free catalyst surface: no mass loss is detected
(Fig. 11) a part of physisorbed water. By 29 Si NMR analysis car-
ried out on regenerated catalyst the amount of terminal silanol
groups measured are quite the same of the amount detected on
the fresh ITQ-6: 27 3% and 28 5%, respectively. This result sug-
gested to use the regenerated catalyst for a new ionic exchange
cycle in order to prepare new catalyst (K-ITQ-6) for biodiesel pro-
duction. After this ionic exchange, the same amount of potassium
was loaded (1.62 4 wt%) and the same catalytic performance of
new K-ITQ-6 catalyst has been obtained: 92% of biodiesel yield and
complete triglycerides conversion after 48 h at 180 C.
A possible ow-sheet of continuous process for biodiesel
production using heterogeneous acidbasic K-ITQ-6 catalyst is
reported in the Fig. 12. Two reactors are need: the rst one for Fig. 11. TG and DTA curves of regenerated ITQ-6 catalysts.
168 A. Macario et al. / Applied Catalysis A: General 378 (2010) 160168

Fig. 12. Flow-sheet of proposed continuous process for biodiesel production.

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