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);
then, the higher TOF observed for A-15 catalyst could not be due to
the higher specic activity of acidic sites but to the accessibility of
sites which is favored using macro-porous materials like Amber-
lyst. In conclusion, the ethericationof glycerol with TBAshould 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
protable to evaluate the inuence of experimental parameters
using A-15 catalyst characterized by the highest acid capacity.
The inuence 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-etherication reactions, whichbecome important
as the reaction temperature increases [710,28].
In terms of products distribution, it is necessary to consider
that, according to literature evidences [710], the etherication
reaction proceeds according to a consecutive path and the
formation of ve 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 etherication
reaction, only the formation of four ethers was observed: two mono-
substitutedethers (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
Table 2
Physico-chemical properties of the studied samples.
Catalyst Loading (wt.%) of active phase S.A.
BET
(m
2
g
1
) P.V. (cm
3
g
1
) APD (A
) Acidity (mmol
H+
g
1
)
HPW-17 15 200 0.62 124 0.74
Cs-HPW 0.5 (Cs) 207 0.80 155 0.81
N-17 17 81 0.07 35 0.31
SAC-13 13 189 0.52 110 0.15
A-15
a
53 0.40 300 4.70
a
Data supplied by Rohm and Haas.
Fig. 1. Conversion of glycerol on solid acid catalysts: T
R
= 343 K; P
R
= 0.1 MPa; R
A/
G
= 4.0; cat = 1.2 wt.%/glycerol; reaction time = 6 h.
Fig. 2. TOF of glycerol as a function of the catalyst acidity: T
R
= 343 K; P
R
= 0.1 MPa;
R
A/G
= 4.0; reaction time: 2 h.
F. Frusteri et al. / Applied Catalysis A: General 367 (2009) 7783 79
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 etherication reaction occurs at
higher rate under pressure, the reaction mechanismshould involve
the electrophilic attack of a tertiary carbocation, formed through
the protonation of both TBA and isobutene, to the adsorbed
glycerol, to formethers. 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
signicant 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 etherication 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. 3. Glycerol conversion and products distribution vs. reaction temperature: A-15 catalyst; P
R
= 0.1 MPa; R
A/G
= 4.0; cat = 1.2 wt.%/glycerol; reaction time = 6 h.
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; T
R
= 343 K; rpm = 1200 min
1
.
F. Frusteri et al. / Applied Catalysis A: General 367 (2009) 7783 80
isobutylene is used as the reactant [710,28], because the
formation of water should account for hindering the extent of
oligomerisation.
To evaluate how the reaction time affects the evolution of
reaction and catalyst activity, several experiments were carried out
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,
glycerol was almost totally converted and the 1-MBGE was the
main product.
As the reaction proceeded, the concentration of MBGE
decreased and the corresponding concentration of di-ether (DBGE)
increased. This transformation occurred with a low reaction rate;
in fact, after 30 h, MBGEs selectivity was still 50%.
Experimental data obtained by operating at different tert-
butanol/glycerol molar ratios (R
A/G
) are reported in Table 4. It can
be seen that the increase of R
A/G
does not affect the reaction in
terms of products distribution.
As such result was not expected, reaction order with respect to
glycerol (GLY) and tert-butanol (TBA) was determined considering
initial glycerol conversion values (<5%), under the following
reaction conditions: (a) glycerol volume was changed from 5 to
10 ml, while TBA volume was maintained in a large excess; (b) TBA
volume was changed from 5 to 10 ml, while glycerol volume was
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
were established between the reaction rate and molar concentra-
tion of reactants, thus enabling the discovery of the following rate
law:
rate kGLY
0:3
TBA
1:7
(1)
From such an equation, the kinetic constant at each temperature
was calculated and results obtained are summarized in Table 5.
These data are thermodynamically consistent since k increased
with temperature as expected for an endothermic reaction. The
apparent activation energy was close to 70 3 kJ mol
1
, which well
matches the values so far reported in similar kinetic studies [31].
According to the rate Eq. (1), considering that the reaction order
referred to TBA is much higher than one, it can be conrmed that
the etherication reaction occurs with a molecular mechanism
Table 3
Inuence of amount of catalyst on product distribution and yield.
Catalyst (wt.%/glycerol) Product distribution (wt.%) Yield (%)
IB TBA MBGEs DBGEs TBGE GLY H
2
O 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: T
R
=343K; P
R
=0.1MPa; reaction time =6h; rpm=1200min
1
.
Fig. 5. Glycerol conversion and water formation as a function of amount of catalyst
used: A-15 catalyst; P
R
= 0.1 MPa; R
A/G
= 4.0; reaction time = 6 h.
Fig. 6. Glycerol conversion and ethers yield as a function of reaction time: A-15
catalyst; P
R
= 0.1 MPa; R
A/G
= 4.0; catalyst = 7.5 wt.%/glycerol.
Table 4
Effect of tert-butanol-glycerol molar ratio (R
A/G
).
R
A/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: 7.5wt.%/glycerol; T
R
=343K; P
R
=0.1MPa; reaction time =6h; rpm=1200min
1
.
Table 5
Rate constants at different temperature.
Catalyst k10
2
(M
1
min
1
)
303K 323K 343K 363K
A-15 0.5 2.2 13.8 45.0
F. Frusteri et al. / Applied Catalysis A: General 367 (2009) 7783 81
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 etherication, 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
difculty 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 [3236].
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
difculty in obtaining high yields to higher ethers is not
attributable to catalyst deactivation but to the water formation.
However, just to conrm that catalyst does not change during the
reaction, an experiment employing the used catalyst, after its
ltration and regeneration by a drying procedure, was performed.
As Fig. 7 clearly shows, the results obtained with both fresh and
used catalysts are similar, conrming that the A-15 catalyst is
stable and even if it swells during the reaction, its catalytic
properties do not change signicantly.
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
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 [810,28,37], in all the
investigated cases no differences were observed, either in terms of
glycerol conversion or products distribution, thus conrming 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 etherication
reaction.
4. Conclusions
The main ndings of this study can be summarized as follows:
the etherication 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 signicantly 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-
ication 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.
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