Applied Catalysis A: General 367 (2009) 77–83

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Applied Catalysis A: General

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

Catalytic etherification of glycerol by tert-butyl alcohol to produce oxygenated

additives for diesel fuel
F. Frusteri a,*, F. Arena b, G. Bonura a, C. Cannilla b, L. Spadaro a, O. Di Blasi a
a
CNR-ITAE, Istituto di Tecnologie Avanzate per l’Energia ‘‘Nicola Giordano’’, Via S. Lucia 5, 98126 Messina, Italy
b
Dip. Chimica Industriale e Ingegneria dei Materiali, Università di Messina, Salita Sperone 31, 98166 Messina, Italy

A R T I C L E I N F O A B S T R A C T

Article history: The heterogeneous catalytic etherification of glycerol with tert-butyl alcohol was investigated in
Received 5 May 2009 presence of lab-made silica supported acid catalysts. As reference, two commercial acid ion-exchange
Received in revised form 23 July 2009 resins were also used. Experiments were carried out in batch mode at TR ranging from 303 to 363 K. An
Accepted 24 July 2009
increase in reaction temperature favors the formation of di-substituted ethers. The etherification
Available online 3 August 2009
reaction proceeds according to a consecutive path and the surface reaction between adsorbed glycerol
and protonated tert-butanol (tertiary carbocation) can be considered as the rate determining step. Steric
Keywords:
hindrance phenomena and water hinder the formation of tri-substituted ether (TBGE). As expected,
Oxygenated compounds
water removal was necessary to allow the higher ethers formation. The specific activity (turnover
Catalytic conversion
Glycerol ethers frequency, TOF) of A-15 catalyst is significantly higher than that of the other studied acid systems, due to
Biodiesel the wide pore diameter that allows an easier accessibility of the reagent molecules.
ß 2009 Elsevier B.V. All rights reserved.

1. Introduction glycerol could hold a prominent role [7–10]. In particular, tert-butyl

Recently, exhaust gases emitted by internal combustion
engines were considered primarily responsible for environmental
pollution and human diseases [1–5].
Biodiesel is currently used as a valuable fuel for diesel engines.
In spite of a slight power loss, exhausts contain less particulate
matter. Biodiesel is a mixture of methyl esters of fatty acids
(FAMEs) obtained by the transesterification reaction of vegetable
oils with methanol in presence of a basic catalyst [1,2]. Such a
catalytic process converts raw triglycerides into FAMEs, but
produces glycerol as side product.
If biodiesel is produced on a large scale, adequate technologies
capable of converting glycerol into added value chemicals are
necessary [3,4]. In particular, great attention has been already
devoted to the conversion of glycerol into oxygenated additives for
liquid fuels [3,5–7]. In this context, an industrially relevant route
for the conversion of glycerol into oxygenated chemicals involves
the etherification to tert-butyl ethers [5,7–10].
It is well known that the addition of oxygenated additives to
diesel fuels could represent a promising way enhancing the
combustion efficiency in internal combustion engines with a
significant reduction of pollutant emissions. Among several
oxygenated additives proposed to blend with diesel, the ethers of
* Corresponding author.
E-mail address: francesco.frusteri@itae.cnr.it (F. Frusteri).
ethers of glycerol with a high content of di-ethers are considered
promising as oxygenated additives for diesel fuels (diesel, biodiesel
and their mixtures). However, mono-tert-butyl ethers of glycerol
(MBGEs) have a low solubility in diesel fuel; therefore, in order to
avoid an additional separation step, the etherification of glycerol
should address the formation of di- and tri-ethers [5,7–9,11].
The etherification of glycerol can be carried out using
heterogeneous acid catalysts like strong acid ion-exchange resins
[12–18]; however, the utilization of large-pore zeolites has also
been widely investigated [19–22]. Usually, low surface areas and
lack of thermal stability are the major drawbacks of sulfonic resins.
The incorporation of organosulfonic groups over mesostructured
silicas have generated effective solid acid catalysts with enhanced
catalytic properties as compared with conventional homogeneous
and heterogeneous acid catalysts [23]. Moreover, these type of
silica materials functionalized with organosulfonic acid groups
have been used previously for the conversion of biorenewable
molecules [24–27], showing better catalytic performances than
that of the commercial sulfonated resins. Currently, these highly
surface materials characterized by interconnected mesopores and
high accessibility of acid sites represent the best systems for the
etherification reactions [28].
The synthesis of tert-butyl ethers (GTBEs) from isobutene and
glycerol on ion-exchange resins has been already investigated
extensively [8–10]. Isobutene (IB) is produced by catalytic cracking
and steam cracking fractions of petroleum refining and by
isobutane dehydrogenation [5,7]. What appears more attractive

0926-860X/$ – see front matter ß 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.apcata.2009.07.037
78 F. Frusteri et al. / Applied Catalysis A: General 367 (2009) 77–83
is to produce GTBEs by the glycerol etherification reaction in a
solid–liquid catalytic process, by using tert-butyl alcohol (TBA). In
fact, the use of TBA, as both reactant and solvent, instead of gaseous
isobutylene, allows to overcome the technological problems
arising from the need to use solvents able to dissolve glycerol
(i.e., dioxane, dimethyl sulfoxide) and typical drawbacks of a
complex three-phase system (mass transfer phenomena) [9,29].
This study focused on the etherification of glycerol with tert-
butyl alcohol over different solid acid systems. Attention was given
primarily to investigate the main limiting factors for large scale
process development.
2. Experimental
2.1. Catalysts and chemicals
Two solid acid supported catalysts were prepared by the
incipient wetness method using a silica carrier (S.A.BET,
250 m2 g1) and two solutions containing 17 wt.% of Nafion1
ionomer (N-17) and 17 wt.% of tungstophosphoric heteropoly acid
(HPW-17), respectively. An aliquot of the HPW-17 sample was
mixed with a solution containing cesium to exchange a fraction of
H+ protons with Cs+ (Cs-HPW). In addition, two commercial acid
ion-exchange resins, Nafion1 on amorphous silica (SAC-13) and
Amberlyst1 15 dry (A-15), were used as reference catalysts.
Glycerol anhydrous (purity 99.5%) and tert-butyl alcohol
(purity 99.7%), supplied by Fluka (Buchs, Switzerland), were used
as reactants. Standard compounds for GC analysis were supplied
on-demand by Aldrich.
2.2. Catalysts characterization
Surface area (SABET) and pore volume (PV) were determined by
the nitrogen adsorption/desorption isotherms at 77 K using a Carlo
Erba (Sorptomatic Instrument) gas adsorption device. Before
analysis, all the samples were outgassed at 423 K under vacuum
for 2 h. The isotherms were elaborated according to the BET
method for surface area calculation, with the Horwarth–Kavazoe
(HK) and Barrett–Joyner–Halenda (BJH) methods used for micro-
pore and mesopore evaluation, respectively.
The active phase loading and thermal stability were evaluated
by thermo-gravimetric (TG) analyses in the range 293–873 K using
a Netzsch STA409C analyzer, running in air atmosphere with a
heating rate of 10 K/min.
Acid sites were determined by potentiometric titrations with
the zero point charge (ZPC) method. About 0.1 g of each sample
was dispersed in an aqueous solution of NaNO3 0.5 M under
stirring. Acidity, measured by an electrode Orion ROSS, was
calculated on the basis of the pH at which particles suspended in
solution had zero charge.
The list of catalysts used in this study is summarized in Table 1.
2.3. Catalytic testing
The etherification reaction between glycerol and tert-butyl
alcohol was carried out in liquid phase in a 100 cm3 stainless steel
Table 1
List of solid acid catalysts used in this study.
Code Active phase Carrier
HPW-17 Phosphotungstic acid SiO2 (Cabosil LM50; S.A.BET = 250 m2 g1)
Cs-HPW Phosphotungstic acid SiO2 (Cabosil LM50; S.A.BET = 250 m2 g1)
exchanged with cesium
N-17 Nafion1 polymer SiO2 (Cabosil LM50; S.A.BET = 250 m2 g1)
SAC-13 Nafion1 polymer Amorphous silica
A-15 Amberlyst1-15 – a function of the number of acidic sites (see Fig. 2). TOF values were
dry resin
‘‘jacketed-batch reactor’’ (Autoclave Engineers, Inc.) under a stirring
frequency of 1200 min1, in order to limit the influence of external
mass transfer phenomena. Experiments were performed under
different reaction conditions: (i) under pressure; (ii) at reaction
temperatures ranging from 303 to 363 K; (iii) by operating at
different reaction times and (iv) at both different catalyst/glycerol
and alcohol/glycerol ratios.
The experimental procedure was the following: a well defined
amount of glycerol and dry catalyst were loaded into the reactor
and heated up to a prefixed reaction temperature (in 10 min).
Before the addition of tert-butanol, the reactor was fluxed with
nitrogen to remove the air; then, tert-butanol was injected into the
reactor by a syringe: this was taken as the starting point of the
reaction. At the end of the experiments, the reactor was cooled
down (at 298 K) by an ice-bath until the vapour pressure of the
mixture turned down to the atmospheric one, thus allowing all the
gas phase compounds to condense. After the opening of the
autoclave, we collected a completely liquid mixture, without any
solidification of TBA on the reactor walls. The liquid reaction
mixture was analyzed off-line by a gas chromatograph, HP 6890N,
provided with a capillary column HP Innowax (l, 30 m; i.d.,
0.53 mm; film thickness, 1.0 mm) under the following oven
temperature program: from 40 to 220 8C (with a heating rate of
20 8C min1) and at 220 8C for 3 min. An automatic sampler Agilent
7683B Series was used (0.2 ml of samples were injected), each data
set being obtained, with an accuracy of 1%, from an average of
three independent measurements using the external standard
method (n-heptane, 8 wt.% in respect to the reaction mixture). The
samples were not collected at different reaction times for avoiding to
spill out a not representative sample of the reaction system due to the
different density of the mixture compounds. Water content was
calculated by considering the reaction stoichiometry and confirming
the result by a quantitative TCD analysis. In each experiment, carbon
balance was close to 98%.
3. Results and discussion
Physico-chemical properties of catalysts are summarized in
Table 2.
Catalysts are characterized by different surface area ranging
from 53 to 207 m2 g1 and porosity comprised between 0.07 and
0.80 cm3 g1. In terms of SA and porosity, the data obtained with
SAC-13 sample are similar to that provided by the supplier.
Furthermore, all the catalytic systems show an average pore
diameter (APD) increasing with the porosity, apart from A-15 that
is characterized by a wide pore texture (300 Å), although it has the
lowest SA (53 m2 g1). The acid capacity of A-15 sample was
significantly higher than the other investigated samples.
In order to collect quantitative data approaching the equili-
brium composition and to obtain a reliable comparison of the
catalytic functionality at a prefixed time (6 h), preliminary
experiments using different solid acid catalysts were carried out
at 0.1 MPa, 343 K, with a tert-butanol-to-glycerol molar ratio (RA/G)
equal to 4. The results shown in Fig. 1 demonstrate that a low
catalyst/glycerol ratio equivalent to 1.2 wt.% (much lower than
that so far reported in literature [7–10]) is adequate to guarantee
high glycerol conversion. Indeed, after 6 h of reaction, low glycerol
conversion levels were reached using SAC-13, N-17 and HPW-17
catalysts (8–15 mol.%), while by the Cs-HPW and A-15 samples,
characterized by higher acid capacity (Table 2), the reaction takes
place at higher rates, reaching at the end of the reaction a glycerol
conversion of 54 and 82 mol.%, respectively.
Considering that catalysts are characterized by different acid
capacity, the turnover frequency (TOF) of glycerol was reported as
determined from the initial reaction rate (glycerol conversion <5%)
 F. Frusteri et al. / Applied Catalysis A: General 367 (2009) 77–83
Table 2
Physico-chemical properties of the studied samples.
Catalyst Loading (wt.%) of active phase S.A.BET (m2 g1)
HPW-17 15 200
Cs-HPW 0.5 (Cs) 207
N-17 17 81
SAC-13 13 189
A-15a – 53
a
Data supplied by Rohm and Haas.
and normalized to the number of acid sites. As it can be seen, the
TOF appears to be comparable on all the systems, except for the A-
15 sample that exhibits a TOF value about 3 times higher. At first
glance, this result could indicate that the glycerol etherification is a
structure sensitive reaction; however, what should be considered in
a reaction involving encumbered molecules is also the accessibility
of active sites. As reported in Table 2, it can be seen that A-15
catalyst is characterized by an average pore diameter (APD) much
higher (300 Å) in respect to the other catalysts (APD, 35–155 Å);
then, the higher TOF observed for A-15 catalyst could not be due to
the higher specific activity of acidic sites but to the accessibility of
sites which is favored using macro-porous materials like Amber-
lyst. In conclusion, the etherification of glycerol with TBA should be
considered as an unstructured sensitive reaction.
On the basis of such results and considering that the aim of this
study was to explore the feasibility of the process based on the
conversion of glycerol with TBA, we have considered more
profitable to evaluate the influence of experimental parameters
using A-15 catalyst characterized by the highest acid capacity.
The influence of reaction temperature on glycerol conversion
and products distribution is shown in Fig. 3. Glycerol conversion
linearly increased with reaction temperature growing from 10% at
303 K up to 85% at 343 K. It can be observed that, at high
temperatures (363 K), glycerol was not totally converted due to the
occurrence of de-etherification reactions, which become important
as the reaction temperature increases [7–10,28].
In terms of products distribution, it is necessary to consider
that, according to literature evidences [7–10], the etherification
reaction proceeds according to a consecutive path and the
Fig. 1. Conversion of glycerol on solid acid catalysts: TR = 343 K; PR = 0.1 MPa; RA/
G = 4.0; cat = 1.2 wt.%/glycerol; reaction time = 6 h.
79
P.V. (cm3 g1) APD (Å) Acidity (mmolH+ g1)
0.62 124 0.74
0.80 155 0.81
0.07 35 0.31
0.52 110 0.15
0.40 300 4.70
formation of five different alkyl glycerol ethers could be expected:
3-tert-butoxy-1,2-propandiol (1-MBGE), 2-tert-butoxy-1,3-pro-
pandiol (2-MBGE), 1,3-di-tert-butoxy-2-propanol (1,3-DBGE),
1,2-di-tert-butoxy-3-propanol (1,2-DBGE) and tri-tert-butoxy-
propane (TBGE).
Taking into account the results reported in Fig. 3B, when glycerol
reacts with TBA, depending on the extent of the etherification
reaction, only the formation of four ethers was observed: two mono-
substituted ethers (1-MBGE and/or 2-MBGE) and two di-substituted
ethers (1,3-DBGE and/or 1,2-DBGE). Tri-substituted ether never
formed in the whole range of temperature investigated.
3-Butoxy-1,2-propandiol (1-MBGE) was the main mono-ether
formed and, depending on the reaction temperature, even to
different extent, its concentration was always much higher than
the correspective 2-tert-butoxy-1,3-propandiol (2-MBGE).
Indeed, since the reaction takes place between the tert-butyl
cation (tertiary carbocation) and glycerol [10,30], it is probable
that initially the electrophilic attack occurs on the primary carbon
of glycerol due to steric hindrance and electrostatic effects exerted
by –OH groups of glycerol. As regards the formation of di-ethers,
1,3-di-tert-butoxy-2-propanol (1,3-DBGE) was the main com-
pound formed (its concentration linearly increased with reaction
temperature) while the concentration of 1,2-di-tert-butoxy-3-
propanol (1,2-DBGE) reached a maximum value of 7% at 343 K,
after which it remained almost constant. Then, the formation of
1,3-DBGE is favored for the same reasons noted above (steric
encumbrance and electrostatic effect).
Besides, it is also important to consider that, by dehydration of
TBA, isobutene could be formed. To eventually increase the
concentration of isobutene in liquid phase, experiments, under
pressure as a function of the reaction time, were carried out. The
results obtained by operating at 0.1 and 1.0 MPa are reported in
Fig. 4, in terms of glycerol conversion (A) and selectivity to GTBEs
(B).
It can be seen that, as the reaction proceeds, the glycerol
conversion is always higher by operating at 1.0 MPa. The most
Fig. 2. TOF of glycerol as a function of the catalyst acidity: TR = 343 K; PR = 0.1 MPa;
RA/G = 4.0; reaction time: 2 h.
80 F. Frusteri et al. / Applied Catalysis A: General 367 (2009) 77–83

Fig. 3. Glycerol conversion and products distribution vs. reaction temperature: A-15 catalyst; PR = 0.1 MPa; RA/G = 4.0; cat = 1.2 wt.%/glycerol; reaction time = 6 h.

evident pressure effect was observed after 2 h of reaction: the
glycerol conversion values increases from 53% (at 0.1 MPa) to 72%
(at 1.0 MPa).
Furthermore, after 6 h, no differences were seen in terms of
glycerol conversion, since the reacting system reaches the
equilibrium. In terms of selectivity to ethers, apart from the
reaction pressure, a progressive decreasing in MBGEs concentra-
tion can be observed as a function of the reaction time. In any case,
no TBGE forms due to steric hindrance.
Therefore, considering that the etherification reaction occurs at
higher rate under pressure, the reaction mechanism should involve
the electrophilic attack of a tertiary carbocation, formed through
the protonation of both TBA and isobutene, to the adsorbed
glycerol, to form ethers. Indeed, the tert-butyl cation concentration
in liquid phase is ruled out by a dynamic equilibrium existing
between TBA and isobutene. Naturally, the concentration of
isobutene in liquid phase is higher by operating under pressure.
To assess how the products distribution and yield to higher
ethers could be affected by the amount of catalyst used, several
experiments were carried out with different catalyst/glycerol
weight ratios. Results reported in Table 3 clearly point out that
without catalysts the reaction does not take place, while a
significant rise in the glycerol ether formation can be observed as
the amount of catalyst increases. In particular, the highest
cumulative yield (28%) to higher ethers of glycerol (DBGEs + TBGE)
was obtained with an amount of catalyst equivalent to 7.5 wt.%
with respect to the glycerol weight.
Moreover, it is noteworthy that increasing the catalyst weight,
the conversion of glycerol becomes strongly limited by the
growing formation of water (see Fig. 5), which negatively affects
the etherification equilibrium. It is also important to consider that,
under the reaction conditions, a certain amount of isobutene (<5%)
forms due to tert-butanol dehydration. However, we did not
observe the formation of oligomers that normally form when

Fig. 4. Glycerol conversion (A) and selectivity to ethers (B) at different reaction pressure as a function of time: A-15 = 1.2 wt.%/glycerol; TR = 343 K; rpm = 1200 min1.
 F. Frusteri et al. / Applied Catalysis A: General 367 (2009) 77–83 81

Table 3
Influence of amount of catalyst on product distribution and yield.

Catalyst (wt.%/glycerol) Product distribution (wt.%) Yield (%)

IB TBA MBGEs DBGEs TBGE GLY H2O DBGEs + TBGEs

0.0 0.0 76.0 0.0 0.0 0.0 23.4 0.1 –

0.3 2.8 52.4 18.7 7.1 0.0 13.4 4.0 10.7
1.2 4.9 28.6 36.6 13.7 0.0 6.4 7.5 16.7
7.5 4.2 16.6 41.4 25.0 0.4 2.6 8.7 28.2

A-15: TR = 343 K; PR = 0.1 MPa; reaction time = 6 h; rpm = 1200 min1.

Fig. 6. Glycerol conversion and ethers yield as a function of reaction time: A-15
catalyst; PR = 0.1 MPa; RA/G = 4.0; catalyst = 7.5 wt.%/glycerol.

Fig. 5. Glycerol conversion and water formation as a function of amount of catalyst volume was changed from 5 to 10 ml, while glycerol volume was
used: A-15 catalyst; PR = 0.1 MPa; RA/G = 4.0; reaction time = 6 h. maintained in a large excess. In these conditions, the concentration
of the exceeding reactant can be considered almost invariant.
On the basis of the results obtained, logarithmic relationships
isobutylene is used as the reactant [7–10,28], because the were established between the reaction rate and molar concentra-
formation of water should account for hindering the extent of tion of reactants, thus enabling the discovery of the following rate
oligomerisation. law:
To evaluate how the reaction time affects the evolution of
reaction and catalyst activity, several experiments were carried out rate ¼ k½GLY0:3 ½TBA1:7 (1)
at 1, 2, 6, 24 and 30 h, using a catalyst-to-glycerol weight ratio of
7.5%. The results obtained are shown in Fig. 6. After 2 h of reaction, From such an equation, the kinetic constant at each temperature
glycerol was almost totally converted and the 1-MBGE was the was calculated and results obtained are summarized in Table 5.
main product. These data are thermodynamically consistent since ‘‘k’’ increased
As the reaction proceeded, the concentration of MBGE with temperature as expected for an endothermic reaction. The
decreased and the corresponding concentration of di-ether (DBGE) apparent activation energy was close to 70  3 kJ mol1, which well
increased. This transformation occurred with a low reaction rate; matches the values so far reported in similar kinetic studies [31].
in fact, after 30 h, MBGEs selectivity was still 50%. According to the rate Eq. (1), considering that the reaction order
Experimental data obtained by operating at different tert- referred to TBA is much higher than one, it can be confirmed that
butanol/glycerol molar ratios (RA/G) are reported in Table 4. It can the etherification reaction occurs with a molecular mechanism
be seen that the increase of RA/G does not affect the reaction in
terms of products distribution. Table 5
Rate constants at different temperature.
As such result was not expected, reaction order with respect to
glycerol (GLY) and tert-butanol (TBA) was determined considering Catalyst k  102 (M1 min1)
initial glycerol conversion values (<5%), under the following 303 K 323 K 343 K 363 K
reaction conditions: (a) glycerol volume was changed from 5 to
A-15 0.5 2.2 13.8 45.0
10 ml, while TBA volume was maintained in a large excess; (b) TBA

Table 4
Effect of tert-butanol-glycerol molar ratio (RA/G).

RA/G Conv. (%) Selectivity (%) Yield (%)

GLY 1-MBGE 2-MBGE 1,3-DBGE 1,2-DBGE TBGE DBGE + TBGE

2.0 93.1 67.8 1.6 22.4 7.6 0.6 28.5

4.0 93.6 68.0 1.8 20.8 8.9 0.4 28.2
5.0 95.3 70.3 2.0 18.7 9.1 0.0 26.5

A-15: 7.5 wt.%/glycerol; TR = 343 K; PR = 0.1 MPa; reaction time = 6 h; rpm = 1200 min1.
82 F. Frusteri et al. / Applied Catalysis A: General 367 (2009) 77–83
Table 6
Reaction advancement after catalyst replacing.
Reaction time (h) Conv. (%) Yield (%)
GLY MBGEs DBGEs TBGE
24.00 95.9 54.0 41.0 1.0
50.00a 93.6 47.5 44.2 1.8
A-15: 7.5 wt.%/glycerol; TR = 343 K; PR = 0.1 MPa; rpm = 1200 min1.
a
After 24 h, the ‘‘used’’ catalyst was unloaded from the reactor and replaced by ‘‘fresh’’ catalyst.
Fig. 7. Products distribution recorded by using ‘‘fresh’’ and ‘‘re-used’’ A-15 catalysts.
wherein TBA is quickly protonated on the acid sites forming a
tertiary carbocation able to react with the glycerol strongly
adsorbed (partial order 0.3) on the catalyst surface.
In order to shift the reaction equilibrium and favor the
consecutive path of glycerol etherification, some experiments
were carried out to better assess how water affects catalytic
activity. On this account, an experiment was stopped at a reaction
time of 6 h and, after dehydration of the reaction mixture by
zeolites, the run was continued for further 6 hours, thus obtaining
a net increase in the yield of DBGEs from 28.5% (before water
removal) to 41.5%. This result clearly demonstrates that the
difficulty in obtaining higher ethers is due to the presence of water,
as previously inferred. Indeed, it is noteworthy that water also
competes with tert-butanol and glycerol on the active site
adsorption. Really, the higher water acidity in relation to tert-
butanol results in a lowering of catalyst activity due to the
formation of solvated sites, as reported in the literature [32–36].
Since the A-15 resin could swell during reaction due to the
inclusion of water in its polymeric structure, we decided to stop the
run after 24 h of reaction, substituting the ‘‘used’’ catalyst with a
same amount of ‘‘fresh’’ catalyst and continuing the experiment for
25 more hours. Results obtained are summarized in Table 6.
It is possible to observe that the replacement of the catalyst only
slightly favored the formation of higher ethers; therefore, the
difficulty in obtaining high yields to higher ethers is not
attributable to catalyst deactivation but to the water formation.
However, just to confirm that catalyst does not change during the
reaction, an experiment employing the ‘‘used’’ catalyst, after its
filtration and regeneration by a drying procedure, was performed.
As Fig. 7 clearly shows, the results obtained with both ‘‘fresh’’ and
‘‘used’’ catalysts are similar, confirming that the A-15 catalyst is
stable and even if it swells during the reaction, its catalytic
properties do not change significantly.
Further attempts to elucidate how experimental procedures
could affect catalyst performance and to investigate if, during the
reactor heating, experimental conditions could change due to the
occurrence of thermal and catalytic reactions, different runs were
carried out under the following conditions: (i) after the mixing of
Products distribution (wt.%)
IB TBA MBGEs DBGEs TBGE GLY H2O
3.0 12.3 35.1 37.7 1.1 1.7 8.5
2.9 13.3 31.6 39.8 2.0 2.5 7.3
glycerol with the catalyst, the reactor was heated up to reaction
temperature and then alcohol was added; (ii) after the mixing of
alcohol with the catalyst, the reactor was heated up to reaction
temperature and then glycerol was added; (iii) after the heating of
the reactor, alcohol, glycerol and the catalyst were added at same
time.
Even if the alkylation agent is usually injected into the reactor
after mixing of glycerol and catalyst [8–10,28,37], in all the
investigated cases no differences were observed, either in terms of
glycerol conversion or products distribution, thus confirming that
the formation of ethers is strictly dependent upon the surface
reaction between adsorbed glycerol and tert-butyl cation, which
can be considered as the rate limiting step of the etherification
reaction.
4. Conclusions
The main findings of this study can be summarized as follows:
 the etherification of glycerol with tert-butyl alcohol effectively
takes place on solid acids catalysts, hence providing a promising
way to transform glycerol into value added products to be used
as oxygenated additives blended with diesel fuels;
 the accessibility of acid sites plays a fundamental role in
promoting catalyst activity and the systems with large pores are
more indicate to perform reaction at high rate;
 a low catalyst/glycerol ratio equivalent to 1.2 wt.%, much lower
than that so far reported in literature, is adequate to guarantee
high glycerol conversion;
 the reaction pressure significantly affects the reaction kinetic,
the tert-butyl cation concentration in liquid phase being ruled
out by a dynamic equilibrium existing between TBA and
isobutene;
 no oligomers form during reaction since, under the reaction
conditions, the formation of water limits the extent of
oligomerisation reaction;
 water formed during the reaction inhibits the glycerol ether-
ification and its removal from the reaction medium is necessary
for the formation of di- and tri-ethers. On this account, the design
of a ‘‘water-separating’’ reaction medium could increase the
formation of higher ethers.
References
[1] G. Knothe, J. Van Gerpen, J. Krahl (Eds.), The Biodiesel Handbook, AOCS Press,
Champaign, IL, 2005.
[2] M. Mittelbach, C. Remschmidt, Biodiesel—The Comprehensive Handbook, M.
Mittelbach, Graz, Austria, 2004.
[3] S. Fernando, S. Adhikari, K. Kota, R. Bandi, Fuel 86 (2007) 2806–2809.
[4] J.M. Marchetti, V.U. Miguel, A.F. Errazu, Renew. Sust. Energy Rev. 11 (2007) 1300–
1311.
[5] F. Ancillotti, V. Fattore, Fuel Process. Technol. 57 (1998) 163.
[6] P. Satgé de Caro, Z. Mouloungui, G. Vaitilingom, J.Ch. Berge, Fuel 80 (2001) 565–
574.
[7] R.S. Karinen, A.O.I. Krause, Appl. Catal. A: Gen. 306 (2006) 128–133.
[8] K. Klepáčová, D. Mravec, E. Hájeková, M. Bajus, Petrol. Coal 45 (2003) 54–57.
[9] K. Klepáčová, D. Mravec, M. Bajus, Appl. Catal. A: Gen. 294 (2005) 141–147.
[10] K. Klepáčová, D. Mravec, A. Kaszonyi, M. Bajus, Appl. Catal. A: Gen. 328 (2007)
1–13.
[11] J. Deutsch, A. Martin, H. Lieske, J. Catal. 245 (2007) 428–435.
 F. Frusteri et al. / Applied Catalysis A: General 367 (2009) 77–83
[12] A. Juha, A. Linnekoski, O.I. Krause, L.K. Struckmann, Appl. Catal. A: Gen. 170 (1998)
117–126.
[13] J.F. Knifton, J.C. Edwards, Appl. Catal. A: Gen. 183 (1999) 1–13.
[14] Y. Pouilloux, S. Abro, C. Vanhove, J. Barrault, J. Mol. Catal. A: Chem. 149 (1999)
243–254.
[15] B.-L. Yang, S.-B. Yang, R.-Q. Yao, React. Funct. Polym. 44 (2000) 167–175.
[16] R. Alcántara, L. Canoira, C. Fernandez-Martin, M.J. Franco, J.I. Martinez-Silva, A.
Navarro, React. Funct. Polym. 43 (2000) 97–104.
[17] C. Park, M.A. Keane, J. Mol. Catal. A: Chem. 166 (2001) 303–322.
[18] J.M. Adams, D.E. Clement, S.H. Graham, J. Chem. Res. (1981) S254.
[19] A.A. Chin, S.S.F. Wong, Zeolites 17 (5–6) (1996) 524.
[20] I. Hoek, et al. Appl. Catal. A: Gen. 266 (2004) 109–116.
[21] K.J. Won, K.D. Jung, H.J. Uk, K. Min, K.J. Man, Y.J. Eui, Catal. Today 87 (1–4) (2003)
195–203.
[22] P.S.E. Dai, J.F. Knifton, Zeolites 18 (5–6) (1997) 417–418.
[23] J.A. Melero, R. van Grieken, G. Morales, Chem. Rev. 106 (2006) 3790.
[24] I.K. Mbaraka, D.R. Radu, V.S.-Y. Lin, B.H. Shanks, J. Catal. 219 (2003) 329.
83
[25] I.K. Mbaraka, B.H. Shanks, J. Catal. 229 (2005) 365.
[26] P.L. Dhepe, M. Ohashi, S. Inagaki, M. Ichikawa, A. Fukuoka, Catal. Lett. 102 (2005)
163.
[27] J.A. Bootsma, B.H. Shanks, Appl. Catal. A: Gen. 327 (2007) 44.
[28] J.A. Melero, G. Vicente, G. Morales, M. Paniagua, J.M. Moreno, R. Roldán, A.
Ezquerro, C. Pérez, Appl. Catal. A: Gen. 346 (2008) 44–51.
[29] P.M. Słomkiewicz, Appl. Catal. A: Gen. 313 (2006) 74–85.
[30] R.A. Van Santen, P.V.N.M. Van Leeuwen, J.A. Moulijn, B.A. Averill, Stud. Surf. Sci.
Catal. 123 (1999).
[31] F. Cunill, M. Iborra, C. Fité, J. Tejero, J.F. Izquierdo, Ind. Eng. Chem. Res. 39 (2000)
1235–1241.
[32] F. Ancillotti, F. Mauri, E. Pescarollo, J. Catal. 46 (1977) 49–57.
[33] F. Ancillotti, F. Mauri, E. Pescarollo, L. Romagnoni, J. Mol. Catal. 4 (1978) 37–48.
[34] A. Gicquel, B. Torck, J. Catal. 83 (1983) 9–18.
[35] P. Rys, W.J. Steinegger, J. Am. Chem. Soc. 101 (1979) 4801–4806.
[36] W.J. Casey, D.J. Pietrzyk, Anal. Chem. 45 (1973) 1404–1407.
[37] D.E. López, J.G. Goodwin Jr., D.A. Bruce, J. Catal. 245 (2007) 381–391.