Journal of Catalysis 290 (2012) 202–209

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Journal of Catalysis
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Boosted selectivity toward high glycerol tertiary butyl ethers by

microwave-assisted sulfonic acid-functionalization of SBA-15 and beta zeolite
María Dolores González a, Yolanda Cesteros a,⇑, Jordi Llorca b, Pilar Salagre a
a
Departament de Química Física i Inorgànica, Universitat Rovira i Virgili, C/ Marcel
lí Domingo s/n, 43007 Tarragona, Spain
b
Institute of Energy Technologies and Centre for Research in Nanoengineering, Universitat Politècnica de Catalunya, Avda. Diagonal 647, ed. ETSEIB, 08028 Barcelona, Spain

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

Article history: We report for the first time the post-synthesis sulfonic acid-functionalization of commercial beta zeolite
Received 17 February 2012 in one step, by conventional heating as well as with microwaves, and the introduction of higher amounts
Revised 16 March 2012 of sulfonic acid groups in SBA-15 with microwaves. In beta zeolite, dealumination occurred due to the
Accepted 20 March 2012
acidic medium used during sulfonation that favored the generation of new silanols groups, which in turn
Available online 20 April 2012
reacted with the organosulfonating agent resulting in the incorporation of the sulfonic acid groups.
Microwave-assisted sulfonated catalysts showed higher selectivity toward di- and triethers of glycerol
Keywords:
(83–91%) than those sulfonated by conventional heating and much more than a commercial acid macro-
Beta zeolite
SBA-15
porous resin type Amberlyst (35%) after 4 h of reaction. It is remarkable the high selectivity to the bulkier
Sulfonic acid-functionalization triether achieved with functionalized beta samples (32–36%) demonstrating that microporosity is not a
Microwaves barrier for the formation of triether when having appropriate amount and strength of Brønsted acidity.
h-GTBE Ó 2012 Elsevier Inc. All rights reserved.
Glycerol etherification
Dealumination

1. Introduction
During biodiesel production, by transesterification of vegetable
oils with methanol, glycerol (glycerine or 1,2,3-propanotriol) is
formed as by-product in high amounts (10 wt% of the total prod-
uct). The price of glycerol is falling as fast as biodiesel plants are
being built. Research is currently starting to find new outlets to
convert the surplus of glycerol into high-added value products that
improve the economy of the whole process [1,2].
One challenging option is the catalytic etherification of glycerol
with isobutene to obtain di- and tri-tertiary butyl ethers of glyc-
erol, the so-called high ethers (h-GTBE), which can be used as oxy-
genated fuels replacing the highly toxic to the environment methyl
tertiary butyl ether (MTBE). Besides, when h-GTBE was incorpo-
rated in standard 30–40% aromatic-containing diesel fuel, emis-
sions of particulate matter, hydrocarbons, CO and unregulated
aldehydes in the exhaust gases decreased significantly [3]. Regard-
ing heterogeneous catalysis, the best activity results were achieved
for this reaction with acid ion-exchange resins of Amberlyst type
(Amberlyst 15 and 35) [4–7] and with silicas functionalized with
organosulfonic acid groups introduced by conventional heating
[8,9]. When H-Beta and H-Y zeolites were tested for this reaction,
H-Beta showed less conversion but higher selectivity to glycerol
⇑ Corresponding author. Fax: +34 977559563.
E-mail address: yolanda.cesteros@urv.cat (Y. Cesteros).
diethers than Amberlyst 15. However, the formation of the triether
was not observed for this zeolite [7]. This was attributed to steric
hindrance effects due to its microporosity.
The organic tailoring of the surface of materials has received
great attention in the last decade in terms of their application in
the fields of catalysis, sensing and adsorption. Specifically, the
incorporation of organosulfonic acid groups in mesoporous or
microporous materials can generate effective solid acid catalysts
with enhanced catalytic properties. Functionalization of mesopor-
ous silicas with organosulfonic acid groups can be performed by
post-synthesis grafting, in which the material is prepared and then
functionalized [10,11], and co-condensation, where the functional-
ized silane is included in the mesoporous molecular sieve synthesis
sol–gel mixture so that it is incorporated in the structure as the
molecular sieve forms [12,13]. 3-Mercaptopropyltrimethoxysilane
(MPTMS) and phenethyltrimetoxysilane (PETMS), which require a
subsequent treatment to led to the sulfonic acid groups, and 2-
(4-chlorosulfonylphenyl)ethyltrimethoxysilane (CSPTMS) are the
most usual compounds used to introduce the sulfonic acid groups
in mesoporous materials. In the case of zeolites, it is difficult to
introduce bulky organic species due to their microporosity. There
are only few studies about the preparation of zeolites containing
sulfonic acid groups within their pores by direct synthesis through
the incorporation of phenethyl groups (PETMS) covalently tethered
to silicon atoms and subsequent sulfonation of the phenyl rings
[14,15]. However, there are no studies about the incorporation of

0021-9517/$ - see front matter Ó 2012 Elsevier Inc. All rights reserved.
http://dx.doi.org/10.1016/j.jcat.2012.03.019
 M.D. González et al. / Journal of Catalysis 290 (2012) 202–209
sulfonic acid groups in zeolites by post-synthesis due to the lack of
reactant silanol groups („SiAOH), which are required to react
with the sulfonating agents [16].
The use of microwaves for the synthesis or modification of
materials is becoming an important tool to reduce the synthesis
time (energy saving) and modify the samples properties [17–20].
Nevertheless, there are no studies about the use of microwaves
for the sulfonation of zeolites or mesoporous silicas.
The aim of this work was the post-synthesis sulfonic acid-
functionalization of commercial beta zeolite in one-step, by con-
ventional heating as well as with microwaves, and the introduction
of sulfonic acid groups during functionalization of SBA-15 with
microwaves. Samples were widely characterized by XRD, N2
physisorption, TGA, XPS, XRF, FTIR and potentiometric titration
techniques. Sulfonated SBA-15 and sulfonated beta materials were
tested as catalysts for the acid-catalyzed etherification of glycerol
with isobutene to obtain selectively h-GTBE.
2. Experimental
2.1. Preparation of the catalysts
SBA-15 sulfonated by conventional heating (SBA-15-CS) was
synthesized with a molar composition of 1.2 SiO2/0.2 chlorosulfo-
nylphenylethyltrimethoxysilane (CSPTMS, Gelest)/6.5 HCl/180
H2O, following the method reported elsewhere [21]. The sulfona-
tion step was made at 40 °C for 24 h by traditional refluxing.
SBA-15 sulfonated with microwaves (SBA-15-MwS) was prepared
at the same conditions than SBA-15-CS, but the sulfonation step
was made at 40 °C for 2 h by refluxing with microwaves (Milestone
ETHOS-TOUCH CONTROL). The reaction mixtures were transferred
to a Teflon-lined autoclave and heated at 100 °C in a conventional
oven for 24 h. The resulting products were filtered, washed repeat-
edly with a large amount of water and dried at 80 °C in an oven
overnight. The surfactant template was removed by extraction
with ethanol under reflux for 24 h and later calcination in air at
200 °C for 24 h. Lastly, one SBA-15 was synthesized following the
same procedure as for preparing sulfonated SBA-15 samples but
omitting the sulfonation step (SBA-15).
Two gram of commercial Na-Beta (Zeochem, Si/Al = 10) was
treated with 1.4 g of CSPTMS in 150 mL of 2 M HCl at 40 °C for
2 h by conventional refluxing (Beta-CS) or by refluxing with micro-
waves (Beta-MwS). Samples were filtered, washed extensively
with deionized water and dried at 80 °C overnight. Amberlyst-15
was supplied by Aldrich (39 m2/g, pore size of 103 Å, acidity of
4.7 meq H+/g).
2.2. Characterization methods
X-ray diffraction (XRD) patterns were obtained with a Siemens
D5000 diffractometer. The patterns of beta zeolite samples were
recorded over a range of 2h angles from 5° to 40°. Crystalline
phases were identified using the Joint Committee on Powder Dif-
fraction Standards (JCPDS) files (48-0074 corresponds to beta).
The integrated intensity of the signal at 2H = 22.4° was used to
evaluate the crystallinity of beta samples. For small-angle powder
XRD patterns of SBA-15 samples, the scanning range was set from
0.5° to 10° with a step of 0.02°.
Textural characterization of the solids was performed by N2
(rN2 = 0.162 nm2) adsorption–desorption at 77 K using a Quadra-
sorb SI surface analyzer. Before measurements, all samples were
outgassed at 573 K for 6 h. The BET-specific surface areas were cal-
culated using adsorption data in the relative pressure range 0 < P/
P0 < 0.1. Micropore and external surface areas were obtained by t-
plot analysis of the adsorption data in the 3.5  t  5 Å t range by
203
adopting the de Boer reference isotherm equation, whereas pore
volumes and pore size distributions were determined by the
Barrett–Joyner–Halenda (BJH) method.
Themogravimetric analyses (TGA) were performed with a TA
instruments equipment from 50 °C to 800 °C at 10 °C/min under
airflow.
XP spectra (XPS) were collected at a pressure below 5  10 7 Pa
with a SPECS system using a Al anode XR50 X-ray source (150 W)
and a 9-channel Phoibos 150 MCD detector with pass energy of
25 eV at 0.1 eV steps. Quantification of surface elements was car-
ried out using Shirley baselines and Gaussian–Lorentzian (1:1) line
shapes. Binding energy values were referred to the C1s adventi-
tious signal.
Elemental analyses of the beta samples were obtained with a
Philips PW-2400 sequential XRF analyzer with Phillips Super Q
software. All measures were made in triplicate.
Infrared spectra were recorded on a Bruker-Equinox-55 FTIR
spectrometer with a MCT detector using a DRIFT cell connected
to a temperature controller. Samples were dehydrated at 623 K
for 2 h under nitrogen. The spectra were then acquired at this tem-
perature by accumulating 64 scans at 4 cm 1 resolution in the
range of 400–4000 cm 1.
Acid capacity was measured through the determination of cat-
ion-exchange capacities using aqueous sodium chloride (2 M) solu-
tions as cationic-exchange agent. Released protons were then
potentiometrically titrated [22].
2.3. Catalytic activity
Etherification of glycerol with isobutene (glycerol/isobutene
molar ratio of 0.25) was carried out in a stainless steel stirred auto-
clave (150 mL) equipped with temperature controller and a pres-
sure gauge. Liquid phase pressurized isobutene was injected into
the reactor, previously charged with glycerol and catalyst (0.5 g),
using nitrogen at 10 bar as pushing agent. The temperature was
then raised to 75 °C and the pressure increased accordingly follow-
ing the liquid–vapor equilibrium. Stirring was fixed for all experi-
ments at 1200 rpm to avoid external diffusional limitations.
Catalytic experiments were made at 4 and 24 h. Reaction products
were analyzed by gas chromatography using a SupraWax-280 col-
umn and a FID detector. Glycerol conversion and selectivity to
MTBG were determined from calibration lines obtained from com-
mercial products. For glycerol diethers (DTBG) and triether (TTBG),
which were not available commercially, we isolated them from the
reaction products by column chromatography and identified by 13C
and 1H NMR (see Supplementary data) for proper quantification
[23]. Turnover frequency values (TOF) were calculated as moles
of glycerol converted per mole of active species (H+) per hour.
3. Results and discussion
3.1. Characterization of the catalysts
X-ray diffraction patterns (XRD) of the sulfonated SBA-15 sam-
ples (Fig. 1) showed three peaks corresponding to the 100, 110 and
200 reflections of the ordered 2D hexagonal (P6mm) mesostruc-
ture. After sulfonation of beta, we observed the maintenance of
the zeolite structure although some decrease in crystallinity was
detected for the sulfonated samples (Fig. 2), especially for that sul-
fonated with conventional heating (Table 1).
Fig. 3 shows the N2 adsorption–desorption isotherms of the sul-
fonated samples. N2 adsorption isotherms were Type I for the zeo-
lite samples, attributed to microporous materials, and Type IV for
the SBA-15 samples, associated with mesoporous materials,
according to the Brunauer, Emmett and Teller classification.
204 M.D. González et al. / Journal of Catalysis 290 (2012) 202–209

500000

400000

Lin (counts)
300000

200000

100000
b

a
0
1 2 3 4 5 6 7 8 9 10
2-Theta - Scale

Fig. 1. XRD patterns of SBA-15-CS (a) and SBA-15-CMwS (b).

1700
1600
1500
1400
1300
1200
1100
Lin (Counts)

1000
900
800
700
600
500 c
400
300 b
200
100
a
0
5 10 20 30
2-Theta - Scale

Fig. 2. XRD patterns of beta (a), Beta-CS (b) and Beta-MwS (c).

Sulfonated SBA-15 and sulfonated beta samples showed lower sur-
face areas and lower total pore volumes than their corresponding
starting material counterparts (Table 1). This could be related to
the incorporation of the organosulfonic acid groups.
In order to confirm and quantify the introduction of the sulfonic
acid groups, X-ray photoelectron spectroscopy (XPS) and thermo-
gravimetric analysis (TGA) techniques were used. XPS is a useful
technique for determining the type of sulfur species and measuring
quantitatively the sulfonic acid groups near the surface region
[13,24], whereas the weight loss observed between 360 and
660 °C in the TGA of organosulfonated samples has been related
in the literature to the loss of organosulfonic acid groups [12,22],
allowing us to calculate the mmol organic sulfonic acid groups/g
sample (Table 1).
The S 2p XP spectra of sulfonated SBA-15 samples only showed
one peak at ca. 168–169 eV with higher intensity for SBA-15-MwS
(Fig. 4a). This peak has been associated with sulfate (S6+) species
due to sulfonic (ASO3H) acid groups [13,24]. Additionally, TGA of
the sulfonated SBA-15 samples (Fig. 5a and b) showed a clear
weight loss between 360 and 660 °C, indicated between bars on
the figures, confirming functionalization. Therefore, the use of
microwaves for the sulfonation of SBA-15 allowed us a faster intro-
duction of higher amounts of sulfonic acid groups in the mesopor-
ous silica, according to the higher S/Si atomic ratio, obtained from
XPS, higher sulfur content due to sulfonic acid groups [12,22]
determined by TGA, lower surface area and higher acidity observed
for SBA-15-MwS (Table 1).
Regarding beta samples, XPS confirmed sulfonation of beta
when using conventional heating as well as microwaves during
the sulfonation step since only one S 2p peak, corresponding to sul-
fonic acid groups, was observed with similar intensity for both
samples (Fig. 4b). This is the first time that the post-synthesis sul-
fonic acid-functionalization of a zeolite is reported. The S/Si atomic
ratio, the sulfur content and the acid capacity values were very
similar for both samples (Table 1). However, Beta-CS showed a
higher decrease in BET, micropore and external surface area than
Beta-MwS with respect to the starting Beta sample (Table 1). This
can be explained by the higher loss of crystallinity suffered by the
conventionally sulfonated sample, as observed by XRD (Fig. 2 and
Table 1). This effect of losing surface area when losing zeolite
 M.D. González et al. / Journal of Catalysis 290 (2012) 202–209 205

Table 1
Characterization of the samples.

Samples Crystallinitya BET area Micropore area External surface Pore volume S/Si surface Sulfur Acid capacity Si/Al surface Si/Al bulk
(%) (m2/g) (m2/g) area (m2/g) (cm3/g) ratiob contentc (meq H+/g)d ratiob ratioe
SBA-15 – 1082 – – 1.68 – – –- – –
SBA-15-CS – 640 – – 0.81 0.03 0.83 0.35 – –
SBA-15-MwS – 575 – – 0.74 0.07 1.01 0.75 – –
Beta 100 584 462 122 0.23 – – – 9 10
Beta-CS 27 330 243 87 0.14 0.06 0.74 0.75 53 55
Beta-MwS 45 505 394 111 0.18 0.06 0.70 0.72 69 71
a
Calculated from XRD patterns.
b
Determined from XPS.
c
(mmol organic sulfonic acid group/g sample) calculated from TGA.
d
Obtained by potentiometric titration.
e
Determined from XRF.

600 600
a b

Adsorbed volume (cm 3 STP/g)

Adsorbed volume (cm3STP/g)

400 400

200 200

0 0
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
Relative pressure (p/po) Relative pressure (p/po)

200 300
c d
250
Adsorbed volume (cm 3 STP/g)
Adsorbed volume (cm3 STP/g)

150
200

100 150

100
50
50

0 0
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
Relative pressure (p/po) Relative pressure (p/po)

Fig. 3. Nitrogen adsorption–desorption isotherms of SBA-15-CS (a), SBA-15-MwS (b), Beta-CS (c) and Beta-MwS (d).

crystallinity has been previously reported for other beta-modified the zeolite framework, and the accessibility of the aluminum
samples [18,25]. atoms depending on the pores arrangement and sizes [26]. In a
Taking into account that the main difficulty to introduce bulky previous study, we also conclude that the use of microwaves dur-
organic species in a zeolite is the lack of reactant silanol groups ing dealumination in acidic medium led to higher dealumination
(„SiAOH) [16], an important key to understand these good beta than conventional heating for the same treatment conditions
sulfonation results is the beta dealumination occurring under the [18]. We believe that zeolite dealumination during sulfonation
acidic conditions used during sulfonation. The Si/Al atomic surface favors the generation of new silanol groups than can react with
ratio and the Si/Al bulk ratio of Beta-CS and Beta-MwS, calculated the organosulfonating agent resulting in the incorporation of the
from XPS and XRF respectively, confirmed dealumination. It is well sulfonic acid groups (Scheme 1). In order to confirm this proposed
known that zeolite beta is easier to dealuminate than ZSM-5 or mechanism, we compared the FTIR spectra of commercial beta, a
mordenite [17,18,26]. This has been related to the flexibility of partially dealuminated beta sample, which was obtained by
206 M.D. González et al. / Journal of Catalysis 290 (2012) 202–209

3.2. Catalytic activity

19000
(a) SBA-15-CS
SBA-15-MwS
17000 Table 2 shows the catalytic activity of SBA-15 and beta samples
compared with that of a commercial Amberlyst-type catalyst for
15000
CPS

the etherification of glycerol with isobutene. The reaction products

13000 obtained were mono-tert-butyl glycerol ether (MTBG), di-tert-bu-
11000
tyl glycerol ether (DTBG) and tri-tert-butyl glycerol ether (TTBG).
Besides, diisobutylene (DIB) was detected in low amounts for all
9000 the sulfonated samples.
174 172 170 168 166 164 162 160
Pure silica (SBA-15) and commercial beta zeolite showed the
Binding Energy (eV)
lowest conversion values due to their low amount of acid centers.
However, functionalized catalysts were very active due to the pres-
19000
ence of the sulfonic acid groups. Sulfonated SBA-15 and sulfonated
16500
(b) Beta-CS
Beta-MwS
beta catalysts showed higher conversion and higher TOF values
14000 than the commercial Amberlyst-type catalyst at the same reaction
CPS

11500
9000
6500
4000
174 172 170 168 166 164
Binding Energy (eV)
Fig. 4. (a) XP spectra of samples SBA-15-CS (conventional heating) and SBA-15-
MwS (microwaves) in the S 2p core level region; (b) XP spectra of samples Beta-CS
(conventional heating) and Beta-MwS (microwaves) in the S 2p core level region.
treatment of commercial beta in HCl 2 M for 15 min, and the sulfo-
nated beta sample Beta-CS (Fig. 6). As we can observe, there was a
clear increase in the intensity of the silanol band (around
3745 cm 1) for the partially dealuminated sample, whereas after
sulfonation, the silanol band decreased as a consequence of the
reaction of the silanol groups, formed during dealumination, with
the organosulfonating agent. Although the zeolite sulfonated with
microwaves suffered higher dealumination than when sulfonated
by conventional heating, similar amounts of organosulfonic acid
groups were incorporated for both samples (Table 1). This could
be related to the generation of some silanols in Beta-MwS which
were not accessible to the sulfonating agent.
conditions (Table 2). This can be explained by the higher surface
area of the SBA-15 and beta zeolite catalysts that should favor a
better distribution of the acid centers and, therefore, the accessibil-
ity of the reagents to the acid sites. SBA-15 sulfonated by conven-
162 160 tional heating (SBA-15-CS) showed higher TOF than the rest of
sulfonated samples (SBA-15-Mw-S, Beta-Mw-S and Beta-CS),
which exhibited similar TOF values. Taking into account that this
catalyst has the lowest acid capacity (Table 1), this can be related
again to its higher surface area and pore volume (Table 1), which
facilitate the accessibility of the reagents to the acid sites.
With respect to the selectivity results, after 4 h of reaction, cat-
alyst Beta showed higher selectivity toward the diethers than
Amberlyst-15 and SBA-15, in this order (Table 2). This agrees with
the results reported by Klepáčová et al. for one H-Beta catalyst
with respect to the Amberlyst-15 [7]. For our Na-Beta, this behav-
ior can be attributed to the presence of free Brønsted protons, as
observed by 1H NMR for commercial Na-Beta zeolites [18,27]. In
a previous study, we reported that the same commercial Beta used
in this study led high yield to b-phenylacetaldehyde for the isom-
erization of styrene oxide, catalyzed by Brønsted acid sites [18].
The detection of glycerol triether in very low amounts for catalyst
Beta, in contrast to the absence reported by Klepáčová et al. [7] for
one H-Beta catalyst, suggests that microporosity is not a barrier for

110 110

100
a 100
b
Weight (%)

Weigth (%)

90 -CH2CH2PhSO3H 90 -CH2CH2PhSO3H

80 80

70 70

60 60
0 200 400 600 800 0 100 200 300 400 500 600 700 800
Temperature (ºC) Temperature (ºC)

110 110
c d
100 100
Weigth (%)

Weigth (%)

90 -CH2CH2PhSO3H 90 -CH2CH2PhSO3H

80 80

70 70

60 60
0 100 200 300 400 500 600 700 800 0 100 200 300 400 500 600 700 800
Temperature (ºC) Temperature (ºC)

Fig. 5. Thermogravimetric weight loss curves of SBA-15-CS (a), SBA-15-MwS (b), Beta-CS (c) and Beta-MwS (d).
 M.D. González et al. / Journal of Catalysis 290 (2012) 202–209 207

Scheme 1. Mechanism of sulfonic acid-functionalization of zeolite beta.

3,5
microwaves (Table 1). However, for Beta catalysts, which had sim-
3 ilar amount of acid centers (Table 1), the higher selectivity to h-
2,5 GTBE of catalyst Beta-MwS could be attributed to a higher accessi-
bility of its acid sites, since this catalyst showed slight higher pore
c
Abs

2 volume (Table 1), slight higher mesoporosity (Fig. 7) and higher

1,5
b
1 a
0,5
4.000 3.900 3.800 3.700 3.600 3.500
cm
-1
Fig. 6. FTIR spectra of commercial beta (a), partially dealuminated beta (b) and
sample Beta-MwS (c).
the formation of the bulkier glycerol triether, since the reaction can
take place with the appropriate amount and strength of Brønsted
acid centers, as later confirmed for sulfonated beta catalysts.
Sulfonated SBA-15 and sulfonated beta catalysts showed higher
selectivity to h-GTBE than the Amberlyst catalyst at the same reac-
tion conditions. It is important to note that Amberlyst-15 produces
diisobutylenes (DIB), the non-desired byproducts which can be
problematic when formulated with fuels, in higher amounts than
the rest of catalysts (Table 2). These acid-based resins seem to be
able to further dimerize the remaining isobutylene to produce
the corresponding DIB. This is in agreement with the results previ-
ously reported by other authors [5,7,8].
Interestingly, the samples sulfonated with microwaves showed
a remarkably higher selectivity to h-GTBE than those functional-
ized by conventional heating, especially after 4 h of reaction. For
SBA-15 catalysts, this can be mainly related to the higher amount
of Brønsted acid sites incorporated in the sample sulfonated with
external surface area after sulfonation than the beta catalyst ob-
tained by sulfonation with conventional heating (Table 1).
The effect of microwaves on sulfonic acid-functionalization, and
therefore on the catalytic activity results, when compared with
conventional heating, can be mainly related to the most homoge-
neous heating achieved with microwaves [28,29], which favors
crystallinity of the synthesized samples [20,28]. In addition, for
modified beta samples, microwaves in acidic medium favored dea-
lumination and therefore the formation of slight higher mesopo-
rosity, as previously reported [18].
All sulfonated catalysts maintained the sulfur content after
reaction, as determined by TGA. This confirms that there was no
leaching of the sulfonic acid groups during reaction. However, from
N2 adsorption–desorption results, we observed a decrease in sur-
face area after reaction for all of them, especially after longer reac-
tion time. In order to evaluate the nature of the products remaining
in the catalytic pores after reaction, several used catalysts, after fil-
tration, were submitted to extraction by refluxing with 50 mL of
ethanol for 1 h. After rotary evaporation of the solvent, the result-
ing solution was analyzed by gas chromatography. All chromato-
grams showed the presence of several peaks corresponding to
glycerol and products of reaction (mainly monoethers, diethers
and triether in less proportion). Additionally, from 4 h to 24 h of
reaction, we observed a considerably decrease in TOF (Table 2).
This confirms that some deactivation occurred for all catalysts (in-
cluded Amberlyst-15). From all these results, we can conclude that
the deactivation process can be explained by the presence of
208 M.D. González et al. / Journal of Catalysis 290 (2012) 202–209

Table 2
Catalytic results for the glycerol etherification with isobutene.

Catalysts Reaction time (h) Conversion (%) TOFa 10 (h 1

) Selectivity to MTBGb (%) Selectivity to h-GTBEc (%) DIBd (wt%)
Amberlyst-15 4 73 0.76 65 35 (3) 33.0
24 99 0.17 23 77 (19) 36.2
SBA-15 4 41 – 87 13 (0) 3.3
24 62 – 86 14 (2) 10.0
SBA-15-CS 4 98 7.60 39 61 (5) 0.7
24 99 1.28 15 85 (28) 2.2
SBA-15-MwS 4 99 3.58 9 91 (36) 1.7
24 100 0.60 9 91 (39) 6.8
Beta 4 44 – 32 68 (1) 5.3
24 49 – 39 61 (2) 6.1
Beta-CS 4 93 3.37 49 51(5) 2.3
24 100 0.60 12 88 (32) 10.4
Beta-MwS 4 100 3.77 17 83 (15) 2.0
24 100 0.63 9 91 (36) 9.4
a
TOF: turnover frequency.
b
MTBG: glycerol monoethers.
c
h-GTBE: glycerol diethers + glycerol triether. In parenthesis, selectivity to glycerol triether (%).
d
DIB: diisobutylene.

with isobutene. It is important to note the higher selectivity to

h-GTBE achieved for the microwaved-sulfonated samples after
4 h of reaction (83–91%). This has been related to the higher
amounts of Brønsted acid sites incorporated in SBA-15 sulfonated
under microwaves whereas for beta acid-functionalized with
microwaves, this could be associated with a slight higher accessi-
bility of its Brønsted acid sites. The excellent catalytic result
achieved with functionalized beta samples revealed the great
importance of acidity in front of porosity for this etherification
reaction.

Acknowledgments

The authors are grateful for the financial support of the Ministe-
rio de Ciencia e Innovación and FEDER funds (CTQ2008-04433/PPQ
Fig. 7. BJH pore size distribution of sulfonated zeolites.
and CTQ2009-12520). M.D.G. acknowledges FPU Grant AP2007-
03789. J.L. is grateful to ICREA Academia program. We thank
reagents and reaction products in the pores. This decreases the Ms. Irene Marín for her help in the performance and interpretation
accessibility of the reagents to the acid sites. of 13C and 1H NMR spectra.
The selectivity to the triether obtained for Beta-MwS after 24 h
Appendix A. Supplementary material
of reaction (36%) is the best result achieved for this reaction up to
now using a zeolite as catalyst. Additionally, this result was com-
Supplementary data associated with this article can be found, in
parable to that obtained with SBA-15-MwS and much higher than
the online version, at http://dx.doi.org/10.1016/j.jcat.2012.03.019.
that obtained with the Amberlyst catalyst, which is a macroporous
acid ion-exchange resin.
References

4. Conclusions
Commercial beta zeolite was successfully sulfonated in one
step, for the first time, by a post-synthesis simple method using
microwaves as well as conventional heating. The zeolite dealumi-
nation occurring due to the acidic medium used during acid-
functionalization appears to be a key factor in the generation of
new silanol groups that can react with the organosulfonating
agent. Although the two samples had similar acidity, the sample
sulfonated with microwaves presented higher surface area (micro-
pore and external), slight higher pore volume, slight higher meso-
porosity and a less decrease in zeolite crystallinity than the
conventional sulfonated sample. Additionally, SBA-15 was sulfo-
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achieving a faster incorporation of higher amount of sulfonic acid
groups than by conventional heating.
Acid-functionalized samples resulted in outstanding activity
and selectivity to h-GTBE catalysts for the etherification of glycerol
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