Microporous and Mesoporous Materials 67 (2004) 8794

www.elsevier.com/locate/micromeso

N-alkylation of imidazole by alkaline carbons

J.M. L

opez-Pesta~
na, J. D
az-Ter

an, M.J. Avila-Rey, M.L. Rojas-Cervantes,
R.M. Mart
n-Aranda *
Departamento de Qu
mica Inorg
anica y Qu
mica T
ecnica, Universidad Nacional de Educaci
on a Distancia (UNED),
Paseo Senda del Rey 9, 28040 Madrid, Spain
Received 25 June 2003; received in revised form 15 October 2003; accepted 16 October 2003

Abstract
Several alkaline carbons (exchanged with Na, K, Cs, and their binary combinations) have been tested as basic catalysts in the Nalkylation of imidazole in dry media. The yields of the N-alkylated products, which are key intermediates in the synthesis of
pharmaceutically important anticonvulsant and bactericidal products, were high. The catalysts were characterized by nitrogen
adsorption isotherms, thermal analysis and X-ray photoelectron spectroscopy. The inuence of the alkaline promoter, the reaction
temperature, and the amount of catalyst on the catalytic activity has been studied. The presence of two alkaline promoters on the
carbon surface does not signicantly increase the nal activity of the carbons. The highest values of activity (7075%) are obtained
for the samples containing cesium.

2003 Elsevier Inc. All rights reserved.
Keywords: Alkaline carbons; Catalytic properties; N-alkylation; Imidazole

1. Introduction
The development of solid base catalysts for the
pharmaceutical, food and cosmetic industries is currently a topic of growing interest [13]. Compounds
such as zeolites [4], hydrotalcites [5], alkaline-substituted
sepiolites [6] and modied oxides [7], have shown interesting activities as solid basic catalysts for ne chemical
reactions. Recently, activated carbons have been employed as selective catalysts [8] in this type of reactions,
because of their extended surface area, microporous
structure, and their high degree of surface reactivity [9].
The presence of alkaline metals on the surface of the
carbons results in the generation of basic sites on their
structure [10].
In view of this, the present paper reports the surface
characterization of two series of alkaline carbons and
their catalytic activity in the imidazole alkylation with 1bromobutane (Scheme 1). This reaction has been reported for the preparation of important anticonvulsant

Corresponding author. Tel.: +34-91-3-98-73-51; fax: +34-91-3-9866-97.

E-mail address: rmartin@ccia.uned.es (R.M. Mart
n-Aranda).
1387-1811/$ - see front matter
2003 Elsevier Inc. All rights reserved.
doi:10.1016/j.micromeso.2003.10.008

[11], bactericidal, fungicidal and protozoacidal compounds [12].

2. Experimental
2.1. Catalyst preparation
An activated carbon RX-1 EXTRA Norit has
been employed as pristine carbon. Two series of basic
catalysts were prepared by ionic exchange using the
corresponding solution of the alkaline chlorides for
approximately 60 h at 353 K. In all cases, the liquid-tosolid weight ratio was 10:1. The samples were ltered
and washed with water until no chlorine anions could be
detected. After drying for 16 h at 383 K, the carbons
were pelletized, crushed and sieved to a particle size
ranging from 0.074 to 0.140 mm in diameter. The two
series of catalysts are named MN (Na-Norit, K-Norit,
and Cs-Norit) and MM0 N (NaK-Norit, NaCs-Norit,
and KCs-Norit). The MN series was prepared by using
a 2 M solution of the corresponding alkaline chloride.
The MM0 N series was prepared by using a 1 M solution of the alkaline chlorides of the corresponding
metals in the carbon. Thus, all of the samples should

88

J.M. L
opez-Pesta~na et al. / Microporous and Mesoporous Materials 67 (2004) 8794

2.3. Reaction procedure

Scheme 1. Alkylation of imidazole with 1-bromobutane.

have the same total amount of alkaline cations in solution during the interchange process.
2.2. Catalyst characterization
Specic areas of carbon samples were determined by
N2 adsorption isotherms at 77 K, applying the BET
method [13], in a Micromeritics ASAP 2010 Volumetric
System. Volumes adsorbed in the dierent types of pores
were calculated by the DFT (Density Functional Theory) method [14] by means of DFTplus software.
The ash contents of the studied catalysts were obtained by thermogravimetric analysis (TG/DTA Seiko
System 320) of the samples heated up to 923 K. The pH
values of the samples studied were measured following
the method described by Ref. [15], using an Omega
pH-meter, model PHB-62.
X-ray photoelectron spectra (XPS) were acquired
with a VG ESCALAB 200R spectrometer equipped with
a hemispherical electron analyzer and MgKa (hm
1253:6 eV, 1 eV 1.6302 10
19 J) X-ray source. The
powder samples were pressed into aluminum holders
and mounted on a sample rod placed in the pretreatment chamber of the spectrometer. After outgassing at
room temperature for 1 h, they were transferred into the
analysis chamber. The residual pressure in the ionpumped analysis chamber was maintained below
5 10
9 Torr during data acquisition. The intensities of
C 1s, O 1s, and Na 1s, K 2p or Cs 3d5=2 peaks were
estimated by calculating the integral of each peak after
smoothing and subtraction of the S-shaped background and tting the experimental curve to a combination of Gaussian and Lorentzian lines of variable
proportion. The binding energies (BE) were referenced
to the major C 1s component at 284.9 eV, this reference
giving BE values with an accuracy of 0.2 eV.

A mixture of the two reactants, imidazole (5 mmol)

and 1-bromobutane (15 mmol) in absence of solvent, is
contained in a Pyrex ask at the reaction temperature
(293, 313, 333 K) with constant stirring for 5 min.
Subsequently, the catalyst is added and the reaction time
commenced. The volume of reactants was approximately 2.5 ml. Samples of approximately 10 ll are taken
periodically and the evolution of the reaction between
15 and 120 min was followed by Gas Chromatography.
The mass spectra of the products were obtained on a
HewlettPackard HP 5971 A spectrometer. The conversion is expressed in terms of the amount of product 1
obtained in wt.% (Scheme 1).

3. Results and discussion

3.1. Characterization results
The pristine Norit carbon has a high specic area
(1450 m2 /g) and a total adsorbed volume of N2 of 0.571
cm3 g
1 in pores up to 200 nm (Table 1). This carbon is
principally microporous (81.8%), with an important
contribution of mesopores (16.5%), as reected in the
N2 isotherm prole (not shown for brevity), which is
type I in BDDT classication [13]. The hysteresis loop,
classied as type H4, is typical of activated carbons and
is due to the slit-shaped pores present in the carbon.
Although the impregnation with dierent alkaline metals does not signicantly alter the textural characteristics
of the substrate and all the isotherms show the same
prole as that of Norit sample, a decrease in the
Vmicro =Vmeso ratio is observed for impregnated carbons
in the case of bialkaline carbons.
The alkaline cation contents determined by thermal
analysis (Table 2) indicate that the exchange capacity of
Norit decreases when increasing the cation size. Thus,
the exchange capacity for sodium is approximately three
times that for cesium. This is not surprising, taking into
account that the surface of the active carbon has a
measurable density of surface groups with negative
charge, which interact with the M ions by electrostatic

Table 1
Specic area SBET and adsorbed volume data obtained by DFT
Sample

SBET (m2 /g)

Vmicropore (cm3 /g)

Vmesopore (cm3 /g)

Vtotal (cm3 /g)

Norit
Na-N
K-N
Cs-N
NaK-N
NaCs-N
KCs-N

1450
1375
1364
1447
1415
1338
1416

0.467
0.440
0.446
0.460
0.455
0.434
0.463

0.094
0.111
0.046
0.074
0.135
0.104
0.095

0.571
0.570
0.527
0.543
0.608
0.555
0.572

(81.8%)
(77.2%)
(78%)
(84.7%)
(74.8%)
(78.2%)
(80.9%)

(16.5%)
(19.5%)
(8%)
(13.6%)
(22.2%)
(18.7%)
(16.6%)

Values in parenthesis indicate the percentage of each type of pore in carbon sample.
Micropore: width < 2 nm; mesopore: 2 < width < 50 nm. Vtotal : volume adsorbed by pores of width < 200 nm.

J.M. L
opez-Pesta~na et al. / Microporous and Mesoporous Materials 67 (2004) 8794

Table 2
Some characterization data of the catalysts
Catalyst

pH

Ash (%)

M2 O (%)

Cation
(mol/100 g
cat.)

Norit
Na-N
K-N
Cs-N
NaK-N
NaCs-N
KCs-N

8.0
8.4
9.6
10.4
9.8
10.0
10.4

3.1
4.8
4.0
5.5
5.2
5.3
4.4

1.7
0.055
0.9
0.019
2.4

0.017
2.1
0.054
2.2
0.024
1.3
0.014

Values estimated assuming that a single ion of average molecular

weight is present.

forces during the adsorptionimpregnation process. For

reasons of steric hindrance, and principally in the micropores of the substrate, it is obvious that the Na ions
(ionic radius 0.095 nm) can easily access the centers
located in micropores, whereas the Cs ions (ionic
radius 0.169 nm) have to overcome a diusional barrier.
The pH values are also given in Table 2. The pristine
carbon, RX-1 EXTRA Norit, exhibits a basic pH (8.0)

89

that increases only slightly in the sample exchanged with

sodium, but considerably in the Cs-Norit sample. In
spite of the exchange capacity for the cesium (determined by thermal analysis), approximately three times
less than the capacity of the sodium, the highest basicity
of the rst cation could be the cause of the increase
observed in the pH of the sample (10.4). The basicity of
the carbon catalysts was evaluated by the Knoevenagel
condensation probe reaction, which has been applied to
estimate the basicity of a wide range of microporous
solid materials [6]. It was found that most of the basic
sites of alkaline carbons have pKa values in the range
10:7 6 pKa 6 13:3, but they also contain sites with
13:3 6 pKa 6 16:5. Subsequently, they could be used as
appropriate catalysts for the alkylation of imidazole
pKa 14:5.
In order to get a more precise idea about the chemical
state and the relative dispersion of the alkaline metals on
the surface of the carbon, a study of the dierent samples by X-ray photoelectron spectroscopy was carried
out. The binding energies of C 1s and O 1s core levels,
and the characteristic inner levels of the alkaline elements are given in Table 3, together with the M/C

Table 3
Binding energies (eV) of core electrons and atomic ratios calculated by XPS
Catalyst

C 1s

Norit

284.9
286.4
288.9
290.6
292.5

O 1s

M (BE)

M/C atomic ratio

Na

Cs

530.9 (44)
532.7 (56)

1072.5a

0.0050

531.0 (24)
532.8 (51)
534.5 (25)

293.0b

(59)
(20)
(10)
(11)

530.9 (47)
532.6 (53)

723.9c

NaK-N

284.9 (74)
286.6 (20)
288.3 (6)

531.4 (25)
533.0 (44)
534.8 (31)

1071.2a ; 292.9b

0.0002

NaCs-N

284.9 (73)
286.6 (18)
288.3 (9)

531.4 (27)
533.0 (45)
534.8 (28)

1071.2a ; 723.9c

0.0001

KCs-N

284.9 (74)
286.6 (18)
288.3 (8)

531.4 (25)
533.0 (47)
534.8 (28)

292.8b ; 723.9c

Na-N

K-N

Cs-N

(57)
(23)
(7)
(6)
(7)

284.9 (57)
286.2 (25)
287.5 (18)
284.9 (60)
286.8 (30)
289.4 (10)
284.9
286.5
288.1
289.7

531.2
532.5
533.9
535.2

(29)
(41)
(19)
(11)

0.0030

0.0027

Values in parenthesis indicate the percentage of each peak.

a
Na 1s.
b
K 2p3=2 .
c
Cs 3d5=2 .

0.0005

0.0001

0.0006

0.0001

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J.M. L
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atomic ratios, determined from the peak intensities and

the tabulated sensibility atomic factors [16]. The C 1s
core level is complex. Applying peak synthesis procedures, several components can be revealed. A major
peak at 284.9 eV and other two/three (four in the case of
the Norit pristine) more peaks centered at high binding
energies can be discerned. The peak located at 284.9 eV
can be assigned to carbon atoms in the CAC bonds of
graphitic-like structure of the carbon, and even to Hcontaining carbon species (ACHA), the small chemical
shift of the latter species with respect to the former ones
makes it dicult to distinguish them. A second peak
with a 1530% ratio of the total area is observed around
286.4 eV, which can be associated with CAO bonds in
alcohol groups. The third component close to 288 eV, in
general less intense than the former, is attributed to
carbon atoms in ketonic species (C@O) and the last one,
above 289 eV, to more oxidized (ACOOA) or carbonate
species. In the Norit sample, besides this peak, which is
observed at 290.6 eV, another component at 292.5 eV is
detected. This last peak, due to a shake-up satellite
p ! p produced in graphitic structures, is observed in
some cases. It appears that surface graphitic layers of
carbon become amorphous upon treatments in basic
solutions.
Similarly, the O 1s line prole is quite complex,
especially in the Norit sample. The rst component
centered at 531 eV, is due to oxygen atoms in CAO and/
or COO species of the carbonaceous support. The second one, at 532 eV, is attributed to oxygen atoms
in hydroxides (and carbonates) of the corresponding
alkaline metals. In the Norit sample, two more components above 533 eV are observed, which could be assigned to molecular oxygen atoms in water, probably
with dierent interaction degree with the surface or
dierent localization, for example, at the external surface and at micropores. In all cases, the predominant
oxygen species is that of hydroxide (and carbonate).
Although present in the pristine Norit, it increases in the
impregnated carbons.
The Na 1s, C 1s + K 2p, and Cs 3d core level spectra
of the MAN series are shown in Fig. 1. The binding
energies of the inner electrons of the alkaline elements
t well with hydroxide species, although carbonates
species cannot be discarded, due to the proximity of the
binding energies of these last species. Nevertheless, it
does not mean that Na , K and Cs are not ion exchanged on surface negative groups. As it is known, the
surface of carbon materials presents negative groups
that easily interact with alkaline cations when the corresponding ion exchange treatment is carried out. This
ion exchange generates the active sites. Nevertheless, the
exposure to ambient condition can generate a partial
carbonation of the surface by reaction with CO2 , as
detected by XPS. This is a common process in basic
solid materials.

Fig. 1. XPS spectra of the MN series of catalysts.

The M/C atomic ratio at the surface, determined by

XPS, diminishes when the size of the alkaline cation
increases as a consequence of a lower exchange in the
case of cesium than in the case of sodium, as determined
by thermogravimetric analysis. However, the XPS results show a slight cesium enrichment at the surface,
because the M/C ratio is around 1.8 times less for cesium
than for sodium, whereas the content in metallic cation
(mol M/100 g carbon) determined by thermogravimetric
analysis is 3 times higher for the Na-Norit than for the
Cs-Norit (Table 2).
3.2. Synthesis of N-alkyl imidazoles
For liquid phase reactions catalyzed by solid catalysts, special care should be taken to avoid diusion
limitations. To check the external and internal diusion
a series of experiments using imidazole and 1-bromobutane, and Na and Cs carbons as catalysts, were car-

J.M. L
opez-Pesta~na et al. / Microporous and Mesoporous Materials 67 (2004) 8794

91

Table 4
Conversion values (%) at dierent stirring speeds
Carbon

Stirring
speed
(rpm)

Temperature (K)
293

313

333

Na-N

1000
3500

24
25

37
40

47
49

NaCs-N

1000
3500

42
43

57
57

65
66

Reaction time: 2 h; amount of catalyst: 0.025 g; particle size:

0:140 < d < 0:250 mm.

ried out changing the stirring speed (1000 and 3500 rpm)
and the particle size (<0.074, 0:074 < d < 0:140, and
0:140 < d < 0:250 mm in diameter). As an example, the
results obtained for two of the catalysts are shown in
Tables 4 and 5. These results indicate that, in this range
of conditions, the reaction is not controlled by either
external or internal diusion. Thus, we can safely compare the activity of dierent carbon catalysts under
these reaction conditions.
In this study some reaction parameters such as the
type of alkaline promoter, the temperature, the catalyst
amount and the type of alkyl halide were investigated.
The alkylation of N-heterocycles can aord C-alkylated
products or N-alkylated products, depending on whether the acid or the basic properties are, respectively,
predominant in the catalyst [17]. Under our experimental conditions, we have found that N-alkyl imidazoles of type 1 (Scheme 1) are exclusively obtained,
which conrms the basic nature of the active centers of
the catalyst used. The mass spectra of the reaction
products conrm that 1 (m/s: 124 (M ), 97, 81, 55 (100),
41), is selectively formed. The mechanism of alkylation
of N-heterocycles with alkyl halides is well known. As
an example, the mechanism for imidazole is represented
in Scheme 2. According to this mechanism, 1 mol of
imidazole stoichiometrically consumes another mole of
the alkyl halide. The rst reaction step is the abstraction,
by the solid basic carbon, of the hydrogen at the Nposition of the imidazole. In the second step, the
resulting anionic molecule attacks the alkyl halide at the
1-position and a new nitrogencarbon bond is formed
Table 5
Conversion values (%) at dierent particle sizes
Carbon

Particle size (rpm)

Temperature (K)
293

313

333

Na-N

< 0.074
0:074 < d < 0:150
0:150 < d < 0:250

25
24
25

40
38
39

49
50
49

NaCs-N

< 0.074
0:074 < d < 0:150
0:150 < d < 0:250

42
43
42

57
57
56

65
66
66

Reaction time: 2 h; amount of catalyst: 0.025 g; stirring speed: 3500

rpm.

Scheme 2. Mechanism of the alkylation of imidazole with 1-bromobutane.

with the elimination of Br
ion. In the third step bromide anion reacts with the proton abstracted by the
carbon catalyst to generate HBr, while the N-alkylimidazole is released into the reaction media and the
carbon catalyst is regenerated.
3.3. Inuence of the alkaline promoter
The alkylation of imidazole with 1-bromobutane was
carried out with both series, MN and MM0 N, of exchanged Norit carbons at dierent temperatures. As an
example the results obtained at 333 K are given in Fig. 2.
From the results, it can be said that for the monoalkaline series, the order of activity is: Na-N < K-N < Cs-N,
being the Cs-N around 1.5 times more active than NaN. The order of activity observed in the bialkaline series
is: NaK-N < NaCs-NKCs-N. The same trends in the
activity were observed at 293 and 313 K for both series.
Conversions of 75% are reached in only 120 min of
reaction when Cs-N is used as catalyst. Similar conversion values (70%) are obtained in 120 min when using
KCs-N and NaCs-N. Lower conversion values (around
55%) are obtained with the NaK-N. The KCs-N activity
is almost the same as the observed for the Cs-N sample.
A similar trend is observed when NaK-N and Na-N are
compared. So, the presence of two alkaline cations on
the surface of the catalyst does not appear to have any
positive eect on the activity of the carbon, and similar
conversion values are obtained at long reaction times.
Furthermore, for shorter reaction times, the conversion
values for the bialkaline carbons are slightly lower than
for the monoalkaline ones, and a pseudo-plateau is
observed in the conversion curves around 2030 min in
the former case. Additionally, the activity of NaCs-N is
much higher than that of Na-N, the higher basicity of
cesium may account for the higher activity. Therefore,
the most active samples (Cs-N, NaCs-N and KCs-N) are
those containing cesium. For the bialkaline catalysts

92

J.M. L
opez-Pesta~na et al. / Microporous and Mesoporous Materials 67 (2004) 8794

Fig. 2. Alkylation of imidazole (5 mmol) with 1-bromobutane (15 mmol) at 333 K using 0.05 g of alkaline carbon as catalyst: (A) MN series and (B)
MM0 N series.

containing this cation, the cesium amount on the surface

(determined by XPS, see Table 3) is the same and so is
the catalytic activity. This result agrees with the fact that
the most active sample is the Cs-N, which is the one
containing the highest amount of cesium on the surface,
as detected by XPS.
By conclusion, if both series are compared, the order
of activity of the catalysts is: Na-N < K-N < NaKN < NaCs-N  KCs-N  Cs-N. Therefore, the presence
of two alkaline cations in the catalyst does not enhance
the catalytic activity with respect to the Cs-N sample.

equation [18]). In general, the NaCs-N is 1.52 times

more active than the Na-N at any temperature. The
plateau reached in the conversion values at around 60
min for the NaCs-N sample could be explained by the
generation of a signicant amount of HBr in the reaction media, which may neutralize the basicity of the
active sites. Maybe this eect occurs at longer reaction
times for the Na-N sample, less active, not being
observed at the reaction time studied.

3.4. Inuence of the reaction temperature

In order to study the eect of the amount of catalyst,

imidazole has been alkylated with 1-bromobutane using
two dierent amounts of catalyst (0.025 and 0.05 g). The
Na-N and NaCs-N carbons have been selected for this
study. Fig. 4 represents the conversion values obtained
at 333 K. A conversion level around 50% is obtained in
120 min using 0.05 g of Na-N. However, when a
quantity of 0.025 g of catalyst is employed, the conversion value at the same reaction time is around 35%,
which is 1.4 times lower. When NaCs-N is employed,
these values are around 70% and 60% respectively. It
would be expected that conversion would increase proportionally to the amount of catalyst. However, this

The eect of the reaction temperature has been

studied during the alkylation of imidazole with 1-Brbutane in a batch reactor system using 0.025 g of each
catalyst (Na-N and NaCs-N). Fig. 3 illustrates the results.
It can be observed that, as expected, an increase in
reaction temperature increases the reaction rate and,
consequently, the yield of the reaction, the selectivity
being 100% in all cases (the eect of reaction temperature is an expected result since the conversion increases
with the reaction temperature following the Arrhenius

3.5. Inuence of the amount of catalyst

Fig. 3. Alkylation of imidazole (5 mmol) with 1-bromobutane (15 mmol) using Na-N (0.025 g) (A) and NaCs-N (0.025 g) (B), as catalysts.

J.M. L
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93

Fig. 4. Alkylation of imidazole (5 mmol) with 1-bromobutane (15 mmol) at 333 K using dierent amounts of catalysts (0.025 and 0.050 g). (A), Na-N
and (B), NaCs-N.

eect is not observed during the reaction, probably because in the reactions in the absence of solvent an
optimum amount of catalyst exists and an excess of it
does not aord any benecial eect on the conversion
of the reactions.
3.6. Inuence of the nature of the alkyl halide
Alkylation of imidazole with 1-bromobutane, 2-bromobutane and 1-bromohexane were carried out on Cs-Norit
exchanged sample, which is the most basic catalyst of
both series. From the results showed in Fig. 5, it can be
stated that the order of activity is: 1-bromobutane >
2-bromobutane1-bromohexane, indicating that the
nature of the alkyl halide aects the evolution of the
reaction. The ramication and the length of the chain in
the alkyl halide decrease the yield of the reaction. It is
reasonable to assume that the size of the hydrocarbon
would have an eect on conversion values through steric
hindrance.

4. Conclusions
Alkaline-promoted Norit carbons are active catalysts
for the liquid phase preparation of N-substituted imi-

dazoles. The activity tends to increase with the size of

alkaline promoter (Na-N < K-Cs < Cs-N). The presence
of two alkaline promoters (NaK-N, NaCs-N, or KCsN) on the carbon surface does not signicantly increase
the nal activity of the carbons when compared to the
samples that present only one type of alkaline cation on
their surface. The highest values of activity are obtained
for the samples containing cesium. This may be due to
the highest basicity and the slight enrichment of this
cation on the surface, as conrmed by XPS, if compared
with those obtained for the bulk by thermal analysis. An
increase in reaction temperature exerts a positive eect
on the reaction rate and, consequently, increases the
yield of the reaction. The N-alkylation of imidazole can
be extended to prepare other N-substituted heterocycles,
which could serve as precursors in the primary route
to pharmaceutical compounds of interest.

Acknowledgements
Financial support of this work by Spanish CICYT
(project MAT2001-0319) is gratefully acknowledged.
Norit pristine carbon has been kindly supplied by Norit
Company. The authors wish to express their gratitude to
Professor J.L.G. Fierro for the fruitful XPS discussion
and to Professor E. Teso-Vilar for the mass spectra
analysis.

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Fig. 5. Alkylation of imidazole (5 mmol) with dierent alkyl halides (15

mmol) at 333 K using Cs-N catalyst (0.05 g).

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