J . Chem. Tech. Biotechnol.

1996,65, 186-192

Relationship between Surface Aciditv and

Activity of catalysts in the Transforhation of
Methanol into Hydrocarbons
Ana G. Gayubo,* Pedro L. Benito, Andres T. Aguayo, Martin Olazar &
Javier Bilbao
Departamento de Ingenieria Quimica, Universidad del Pais Vasco, Apartado 644,48080 Bilbao, Spain
(Received 13 April 1995; revised version received 6 September 1995; accepted 7 September 1995)

Abstract: The effect of Si/Al ratio of HZSMS zeolite-based catalysts on surface

acidity and on selectivity in the transformation of methanol into hydrocarbons
has been studied. The acidic strength distribution (measured by combining the
differential scanning calorimetry and the chromatographic analysis) and the total
acidity (measured by calorimetry and temperature programmed desorption),
using ammonia and tert-butylamine, have been studied as acidity measurements.
The nature of the acidic sites has been determined by FTIR analysis of both the
surface OH groups and the interaction of Bronsted and Lewis sites with pyridine.
The increase in light olefin selectivity and the decrease in methanol conversion
with increasing Si/Al ratio are a consequence of the kinetic scheme of the reac-
tion, which has steps in series, and can be explained by the decrease in total
acidity. The same acidic sites are responsible for the formation of light olefins
and for the transformation of these olefins into higher hydrocarbons.

Key words : MTG process, HZSMS zeolite, catalyst acidity, activity.

1 INTRODUCTION The suitability of HZSM5 zeolites for use in the

The conversion of methanol into the hydrocarbons cor-
responding to the range of the boiling point of gasoline
(MTG process) can be schematically represented as a
two-step process.'.' In the first step, alkenes (ethylene,
propylene and, in a smaller proportion, butene) are
formed from oxygenated compounds (methanol and
dimethylether in equilibrium); in the second step
heavier hydrocarbons are formed:
MTG process can be attributed to the shape selectivity
of these zeolites, and not to thermodynamic or chemical
The diffusional restrictions of bulky products
in 5.5 A mean pore diameter zeolites cause a high selec-
tivity towards certain products, which in decreasing
order of preference are :6 normal paraffins, isoparaffins,
monocyclic hydrocarbons, dimethyl-substituted paraf-
fins and aromatic hydrocarbons. The diffusional
restrictions also cause the inhibition of coke precursor

(methanol dimethylether) ~
+ light olefins - parafins
aromatics
cycloparaffins
C , , olefins

* To whom correspondence should be addressed.

186
J. Chem. Tech. Biotechnol. 0268-2575/96/%09.000 1996 SCI. Printed in Great Britain
Catalytic transformation of methanol into hydrocarbons
growing reactions, thus justifying the use of these zeo-
lites in coke deactivation.'
The activity, selectivity and resistance to deactivation
are also a consequence of the composition of the
HZSM5 zeolites. It has been proven that the increase in
aluminium content causes an increase in aromatic selec-
tivity, and a decrease in olefin s e l e ~ t i v i t y . ~ , ~ , ~
Nevertheless, Si/Al ratio is not the sole variable that
can explain the catalyst activity and selectivity. The
kinetic behaviour of the catalyst is a consequence (for a
uniform porous structure) of the surface acidic structure
and this is affected not only by the global %/A1 ratio
but also by different circumstances related to the prep-
aration of the catalyst.
The objective of this paper is to contribute to the
explanation of the different activity and selectivity in the
MTG process, according to the different acidic structure
of the HZSM5 zeolite-based catalysts, when the zeolites
are synthesized with different Si/Al ratios. In order to
isolate the effect of acidity, catalysts with different acidic
structures, but with similar porous structures, have been
used.
2 EXPERIMENTAL
2.1 Catalysts
Five ZSM5 zeolites have been synthesized with different
Si/Al ratios (24, 32, 42, 78 and 154) by following the
method detailed in a previous paper," from sodium
silicate, aluminium sulphate, and tetra-n-propylammon-
ium bromide according to Mobil patents, and have
been cation-exchanged to HZSM5 by using ammonium
nitrate."*'* The physical properties of the HZSM5
zeolite are set out in Table 1. The values of the zeolite
crystal size have been determined in a Mastersizer
instrument from Coulter, and the crystallinity degree
has been measured by IR in a Nicolet 740 FTIR spec-
trophotometer, from the intensity ratio of the bands at
550 and 450cm-'. By means of X-ray diffraction
studies and electron microscopy it has been demon-
strated that the structure of the zeolite crystals is the
one characteristic of HZSM5 zeolites.
TABLE 1
Properties of the Synthesized Zeolites
Zeolite Si/Al BET Vpm
area (cm3 g-')
(mZg - l )
HZSMS-1 24 420 0.65
HZSM5-2 32 405 0.62
HZSM5-3 42 440 0.64
HZSM5-4 78 365 0.62
HZSM5-5 154 395 0.63
187
The final catalyst, as it is used in the reactor, is
obtained by physical mixing, under high humidity con-
ditions, of the zeolite (25 wt%) with a binder (bentonite,
30 wt%) and an inert component (alumina, 45 wt%).
The purpose of the binder is to provide the physical
resistance, while the inert component is used to dilute
the catalyst and provide sufficient mass to absorb the
thermal variations that will occur during the process.
The denomination of the catalysts, based on the Si/Al
ratio of each zeolite used, is: Z1B (Si/Al = 24), Z2B (Si/
A1 = 32), Z3B (Si/Al = 42), Z4B (Si/Al = 78), Z5B (Si/
A1 = 154).
The characterization of the porous structure of the
zeolites has been carried out in nitrogen adsorption
equipment (ASAP 2000 from Micromeritics) for the
measurement of micropores and mesopores, and in a
mercury porosimeter (Autopore 9220 from
Micromeritics) for the measurement of macropores.
The porous structures of all the catalysts synthesized
using different zeolites will be quite similar (see Table 2)
as they will be a consequence of the presence of com-
ponents with the same pore volume distribution.
2.2 Acidity measurement methods
The nature of the acidic sites has been studied by FTIR
analysis of O H groups of the zeolites, and of the ratio of
Bronsted/Lewis sites after pyridine adsorption. The
equipment used is a catalytic chamber, Spectra Tech,
connected in series with an FTIR Nicolet 740 spectro-
photometer.
The surface acidic strength distribution has been
studied by measurement of the differential adsorption
heat of ammonia and tert-butylamine, by combining
differential scanning calorimetry (Setaram DSC 111)
and gas chromatography (Hewlett Packard 5890) in
order to measure the heat of neutralization of the acidic
sites and the amount of base chemically adsorbed,
respectively.' Once the sample is saturated at 423 K,
3 3 1 4
the total acidity measurement is obtained by tem-
perature programmed desorption (TPD) of the base, by
following a ramp of 5 K min-' between 423 K and
873 K, with a helium flow of 20 cm3 min-' and using
Density Crystallinity Crystal
~ m - ~ )
(g ("/.) size
(Pm)
0.94 93 6.3
0.93 91 5.7
0.96 96 4.0
0.97 93 3.8
0.97 92 4.0
188 A . G. Gayubo et al.

TABLE 2
Pore Volume Distribution of the Catalysts (contribution of pores of different diam-
eter, d,)

Catalyst % micropore YOmesopore % macropore

d, < pm lo-' pm < d , < 0.01 pm 0.01 pm < d, < 2 pm

Z1B 8.0 14.7 11.2

Z2B 8.6 15.3 16.0
Z3B 8.8 15.5 15.1
Z4B 1.5 14.0 78.4
Z5B 8.1 14.6 11.2

gas chromatography (Hewlett Packard 5890 connected
with a Perkin Elmer ion trap detector) for measurement
of desorption products.
In Fig. 1, the diagram of heat flow registered in the
calorimeter (lower plot) and the chromatographic signal
(upper plot) in the cycle of adsorption (by pulses) and
desorption of tert-butylamine, for the Z1B catalyst, are
shown as an example of the applications of these
methods. Three peaks can be observed in the TPD: one
peak at low temperature (470 K), corresponding to the
desorption of the physically adsorbed base (carrying out
the adsorption at 473 K no physical adsorption has
been determined); and two peaks at high temperature,
corresponding to the desorption of butene (564 K) and
ammonia (685 K) resulting from the cracking of the
chemically adsorbed base.I3 Thus, the measurement of
the total acidity of the zeolite will be given by the high
temperature peaks (the mmol amount of chemically
adsorbed base is obtained from the area under any of
the high temperature peaks).
s 10'
. base 1-butylamine
- 973
catalyst 216
- 104
m
c purpose, there is a sample-taking loop of 25 cm3
.g 3 10'-
-0
'c 2 l o 4 -
a
0,
iii 1 10'-
2
2.3 Equipment and reaction conditions
The equipment for the reaction and analysis of the pro-
ducts is outlined in Fig. 2. The reaction has been carried
out in Autoclave Engineers BTRS Jr. equipment. The
reactor is a vertical cylinder (6.4 mm internal diameter,
152.4 mm long, with a volume for the catalyst of up to
5 cm3) which is placed in a stainless steel chamber
heated by means of an electric resistance. The bed tem-
perature is controlled and monitored by means of an
Eurotherm 9 1 temperature controller. The furnace tem-
perature, the temperature of the transfer line to the
chromatograph and the temperature of the reactor wall
are controlled by means of three Eurotherm 847 tem-
perature controllers.
In the bottom of the furnace are placed two eight-
port-valves which are driven by compressed air. One of
the valves permits the passage of reactants to the
reactor or sends them through a second line, which
allows a sample of the reactants to be taken for chro-
matographic analysis. The second valve permits a
sample of the products to be taken; this sample is sent
to the on-line chromatograph for analysis. For this
through which the outlet products of the reactor pass.
In addition to the entrances for methanol and inert
gas feeding, the reactor equipment is provided with
three auxiliary gas entrances: for reactor purge with

0 2000 4000 6000 8000 10000 12000

helium; for the helium that carries the sample through
Time (s) the transfer line to the chromatograph; and for the
compressed air that drives the valves. The purge of the
reactor and the feeds are provided with needle valves
for flow control. Each one of the entrances is provided
with a three-port-valve that allows or stops the access
of the feed to the system or sends it to the outlet though
a vent line. The helium flow is measured with a Brooks
5850 mass flow meter.
An IsoChrom LC isocratic pump (Spectra-Physics)
-201 3 7 3 has been used to feed methanol to the reactor through a
0 2000 4000 6000 8000 10000 12000
Time (s)
1.6 mm inner diameter steel pipe.
The analysis on-line of the reaction products has been
Fig. 1. Example of the study carried out by combining calo- carried out in a Hewlett Packard 5890 gas chromato-
rimetry and chromatography measurements of the adsorption
(by pulses)-desorption of bases. Upper plot, chromatographic graph, which is provided with a Hewlett-Packard soft-
measurement. Lower plot, calorimetric measurement. Base, ware, H P 3365 Chemstation. The chromatographic
terr-butylamine. Temperature, 423 K. Catalyst, Z1B. column system consists of a 5 m long HP-1 semi-
Catalytic transformation of methanol into hydrocarbons 189

mass flow
controller

Fig. 2. Reaction equipment.

capillary column, a 1.83 m long Porapack Q packed groups clearly decreases as the Si/A1 ratio increases,
column, and a SO m long Pona capillary column. which proves that Bronsted acidity of HZSMS zeolites
Because of the great number of compounds analysed in increases with aluminium content (as there are more
each chromatographic run and the complexity required skeletal hydroxyl groups, AIOHSi). It must be pointed
for the mass balance, a program in FORTRAN has out that the spectra studied correspond to the zeolites,
been written. and not to the catalysts, because the bands correspond-
ing to hydroxyl groups are masked by the bands corre-
sponding to the binder (bentonite).
3 RESULTS
3.1.2 BronstedlLewis ratio
3.1 Effect of Si/AI ratio on the surface acidic structure In Fig. 4 the FTIR spectra of adsorbed pyridine are
and on the kinetic behaviour shown for some HZSMS zeolites samples with different
aluminium contents. The spectra have been carried out
3.1 .I Bronsted acidity once the samples have been activated at 673 K for 1 h,
HZSMS zeolites contain two main types of hydroxyl
pyridine has been adsorbed at 423 K and physisorbed
groups: (A) one type is characterized by an IR band
pyridine has been removed by vacuum at 423 K. The
with a wavenumber of approximately 3610 cm-' which spectra that are shown have been obtained by subtrac-
can be assigned to skeletal O H groups, SiOHAl, that ting the corresponding white trial (prior to pyridine
are responsible for the strong Bronsted acidity of the
zeolites. The intensity of the band is related to the alu-
minium content of the zeolites and to the amount of
proton e x ~ h a n g e ; ' ~ .(B)
' ~ a second type of hydroxyl
group, with an IR band at 3740-3720cm-' has been
associated either with silica amorphous impurities' or
with silanol groups, SiOH, that is to say, terminal
hydroxyl groups located at the external surface of the
In the literature there are discrepancies con-
cerning these silanol groups, which are considered to be
non-acidic or weakly
In Fig. 3 the FTIR spectra of the framework hydroxyl
groups of four of the HZSMS zeolites prepared with
different Si/Al ratios and calcined at 803 K are shown.
__ -
The spectra have been registered by diffuse reflectance
in a catalytic chamber, once the samples have been acti- 3900 3800 3700 3600 3500 3400 00

vated at 673 K for 1 h. It can be observed that the peak W a v e n u m b e r ( c m ')

assigned to silanol groups does not depend on the Si/A1 Fig. 3. FTIR analysis of hydroxyl groups of HZSMS zeolites
ratio, while the peak corresponding to skeletal hydroxyl with different Si/AI ratios.
 A . G. Gayubo et al.

t-.butylarnine
200 Si/AI=154 0
70
42
175
24 A
- H 150 ammonia
.125
-3
1
Si/AI=1540
78 0
Y, 420
0
100 24A

75 F
50 * ' . ' . " I *

0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8

;li HZSM5-1
b ) HZSM5-3
C ) HZSM5-3
d ) HZSh15-3
1700 1600 1500 1400
Waveiiurnber (crx-' )
Fig. 4. FTIR analysis of pyridine adsorbed at 423 K on
HZSM5 zeolites with different SiiAl ratios.
adsorption) from the spectrum of each sample. Conse-
quently, the negative absorbance peaks (on the left of
Fig. 4) correspond to species that disappear as adsorp-
tion takes place, and the positive absorbance peaks (on
the right of Fig. 4) correspond to species generated as
pyridine adsorption takes place.
The Bronsted/Lewis sites ratios, determined" from
the intensity of adorption bands at 1550 and 1455 cm-'
of Fig. 4 are set out in Table 3. It can be observed that
the Bronsted/Lewis sites ratio increases with the Si/Al
ratio. This result can be due to a higher stability of the
zeolite and to a lower density of acidic sites as the Si/Al
ratio increases, which hinders the dehydroxylation of
Bronsted sites.22
3.1.3 Acidic strength distribution and total acidity
In Fig. 5 the differential adsorption heats of ammonia
and tert-butylamine for some of the synthesized catalyst
mm0'base/g,eoll,e
Fig. 5. Differential adsorption heat at 423 K of NH, and of
tert-butylamine, for catalysts prepared with zeolites of differ-
ent SiIAl ratios.
are shown. The acidic strength distribution of the cata-
lysts is almost identical to that of the corresponding
zeolite used in its preparation, because the alumina used
as an inert component is non-acidic and the acidity of
the bentonite binder is negligible compared with that of
the zeolite. It can be observed that tert-butylamine can
titrate very strong acidic sites, with adsorption heat
above 200 kJ mol-'. The results of the differential
adsorption heat of ammonia, a stronger base, show that
this base can titrate acidic sites weaker than those
titrated using tert-butylamine.
It is observed in Fig. 5 that as the Si/Al ratio
increases, the total acidity decreases, even though a
small number of stronger acidic sites has been gener-
ated. The relative proportion of weakly acidic sites
noticeably decreases. The values of total amount of
adsorbed base are set out in Table 3.
In Table 4 the results of temperature programmed
desorption (TPD) of ammonia and tert-butylamine are
set out. The temperatures of the chemical desorption
peak and the amount of chemisorbed base, expressed as
mmol of chemisorbed base per g of zeolite in the cata-
lyst, for both bases are shown. The temperatures shown
for tert-butylamine correspond to desorption of the

TABLE 3
Ratio of Bronsted/Lewis Sites Obtained from the Intensity of the IR Bands, and Total
Acidity Measurements Carried out by Calorimetry

Zeolite Bands ratio Total acidity

1550 cm-'/1455 em-'
(rnrnol N H , g - I ) (mmol tert-butylamine g-')

HZSM5-1 2.86 0.58 0.54

HZSM5-2 3.10 0.5 1 0.46
HZSM5-3 3.40 0.41 0.40
HZSMS-4 3.63 0.28 0.26
HZSMS-5 4.42 0.13 0.16
Catalytic transformation of methanol into hydrocarbons 191

TABLE 4 MeOH
TPD Results of Ammonia and tert-Butylamine (desorption at
30
5 K min-') rest of tIC A

~~ ~ ~~~~~ ~

!20/
Zeolite TPD of NH, TPD of tert-butylamine ,@,

10
T (K) (mmol g - ' ) T (K) (mmol g - ' )
0
HZSMS-1 700 0.50 583 0.38 0 01 02 03 04 05 ( 6
HZSMS-2 695 0.36 577 0.30
HZSM5-3 691 0.27 514 0.25
HZSMS-4 685 0.19 570 0.19
HZSM5-5 667 0.10 560 0.10 30
E
P
g 20

alkene resulting from tert-butylamine cracking. The

small discrepancy between total acidity titrated by T P D
0
and that titrated by calorimetry (Table 3) corresponds 0 002 004 006 008 01 012
to the amount of physisorbed base (which shows a Contact time [h)

separate peak at low temperature in TPD).
It is observed that the maximum of the chemical
desorption peak displaces towards lower temperatures
with increasing Si/AI ratio. However, conclusions con-
cerning differences in acidic strength distribution cannot
be drawn from this result, because this displacement is
not only affected by acidic strength of the catalyst but
also by other factors such as total amount of adsorbed
base (or total acidity) and the conditions of the analysis,
that is to say, carrier gas flow and amount of catalyst
o ample.^
From the results of Table 4 it can be definitely stated
that there is a great decrease in total acidity as the Si/A1
ratio increases, but the variation in Si/Al ratio only
slightly affects the acidic strength distribution (Fig. 5).
Fig. 6. Product distribution in the conversion of methanol at
623 K. Upper plot, against total acidity of the catalysts. Lower
plot, against contact time over Z l B catalyst.
through a maximum. This kinetic behaviour of catalysts
with different Si/Al ratios is similar to that previously
observed by other a ~ t h o r s .From
~ . ~ the results shown in
the lower plot of Fig. 6 it can be concluded that the
effect of contact time on selectivity is quite similar to the
effect of total acidity of the catalyst.
Thus, it can be stated that both activity and selec-
tivity of catalysts are functions, mainly, of the total
acidity of catalysts.

3.2 Kinetic behaviour of the catalysts 4 CONCLUSIONS

In Fig. 6 the evolution of reaction products as a func-
tion of total acidity of different catalysts (upper plot)
and as a function of contact time for catalyst Z1B
(lower plot) are shown. The compositions (in wt%) of
the following fractions : light olefins (C, -), the other
hydrocarbons, and non-converted oxygenated
(methanol and dimethylether), have been plotted. The
kinetic results of both plots correspond to runs at
623 K. The kinetic results of the upper plot in Fig. 6
correspond to a contact time of 0.052 h. In order to
avoid erroneous conclusions due to deactivation (more
noticeable with increasing temperature),', the results
shown in Fig. 6 have been obtained by extrapolating to
zero time the evolution of each fraction from experi-
ments of 12 h duration.
In the upper plot of Fig. 6 it is observed that as total
acidity increases (that is to say, with decreasing Si/A1
ratio) selectivity towards heavier hydrocarbon forma-
tion increases, while light olefin selectivity passes
Taking into account the effect of Si/Al ratio on total
acidity and on acidic strength distribution, clear evi-
dence of total acidity being the variable most affected
by %/A1 ratio has been observed. This result leads us to
postulate that the important effect of Si/Al ratio on
MTG process selectivity can be attributed to the varia-
tion in total acidity as aluminium content changes, and
cannot be attributed to the slight variation observed in
acidic strength distribution with aluminium content.
There is no clear evidence of the intervention of sites
of different acidic strength in either of the two steps in
series of the kinetic scheme, eqn. (1): conversion to light
olefins from oxygenated, and transformation of olefins
into hydrocarbons in the range of gasoline. The effect of
Si/Al ratio can be considered similar to the effect of
contact time for a process with steps in series, such as
the one studied in this paper. The increase in selectivity
to light olefins (intermediate product in eqn. (1))
observed in the literature as Si/Al ratio increases, is
192
explained on the basis of the decrease observed in total
acidity (or amount of active sites of the catalyst), which
attenuates the second step (formation of heavy
hydrocarbons) of the kinetic scheme, eqn. (1).
ACKNOWLEDGEMENTS
This research was carried out with the financial support
from the University of the Basque Country/Euskal
Herriko Unibertsitatea (Project UPV 069.310-EB035/
94) and from DGICYT (Project PB90-0655).
REFERENCES
1. Chang, C. D. & Silvestri, A. J., The conversion of meth-
anol and other 0-compounds to hydrocarbons over
zeolite catalysts. J. Catal., 47 (1977) 249-59.
2. Chang, C. D., Chu, C. T. W. & Socha, R. F., Methanol
conversion to olefins over ZSM-5. I. Effect of temperature
and zeolite SiO,/Al,O, . J. Catal., 86 (1984) 289-96.
3. Chen, N. Y. & Garwood, W. E., Some catalytic properties
of ZSM-5, a new shape selective zeolite. J . Catal., 52
(1978)453-8.
4. Ducarme, V. & Vedrine, J. C., ZSM-5 and ZSM-11 zeo-
lites: Influence of morphological and chemical parameters
on catalytic selectivity and deactivation. Appl. Catal., 17
(1985) 175-84.
5. Csicsery, S. M., Catalysis by shape selective zeolites-
science and technology. Pure & Appl. Chem., 58 (1986)
841-56.
6. Derouane, E. G. & Vedrine, J. C., On the role of shape
selectivity in the catalytic conversion of alcohols and
simple hydrocarbon molecules on zeolite ZSM-5. J.
Molec. Catal., 8 (1980) 479-83.
7. Guisnet, M. & Magnoux, P., Fundamental description of
deactivation and regeneration of acid zeolites. Stud. Surf
Sci. Catal., 88 (1994) 53-68.
8. Chang, C. D., Methanol conversion to light olefins. Cataf.
Rev.-Sci. Eng., 26 (1984) 323-45.
9. Luk’yanov, D. B., Effect of SiO,/Al,O, ratio on the activ-
ity of HZSM-5 zeolites in the different steps of methanol
conversion to hydrocarbons. Zeolites, 12 (1992) 287-91.
10. Benito, P. L., Gayubo, A. G., Aguayo, A. T. & Bilbao, J.,
Evolucion de la estructura de la zeolita H-ZSM-5 con las
etapas de tratamiento termico de su preparacion. Ajinidad,
51 (1994) 375-8.
A. G. Gayubo et al.
11. Argauer, R. J. & Landolt, G. R., Crystalline zeolite
HZSM-5 and method of preparing the same. US Patent,
3,702,886, 1972.
12. Chen, N. Y., Miale, J. N. & Reagan, W. J., Preparation of
zeolite, example 5. US Patent, 4,112,056, 1973.
13. Aguayo, A. T., Gayubo, A. G., Ereiia, J., Olazar, M.,
Arandes, J. M. & Bilbao, J., Isotherms of chemical adsorp-
tion of bases on solid catalysts for acidity measurement. J.
Chem. Tech. & Biotechnof.,60 (1994) 141-6.
14. Aguayo, A. T., Gayubo, A. G., Ereiia, J., Olazar, M.,
Arandes, J. M. & Bilbao, J., Measurement of acidity
strength distribution of solids by chemical adsorption of
bases. Ajinidad, 51 (1994) 122-4.
15. Jacobs, P. A. & von Ballmoos, R., Framework hydroxyl
groups of H-ZSM-5 zeolites. J. Phys. Chem., 86 (1982)
3050-2.
16. Datka, J. & Piwowarska, Z., Acid properties of
NaHZSM-5 zeolites of various Si/AI ratios and of
NaHZSM-11 zeolite studied by I.R. spectroscopy. Zeo-
lites, 8 (1988) 30-4.
17. Qin, G., Zheng, L., Xie, Y. & Wu, C., On the framework
hydroxyl groups of H-ZSM-5 zeolites. J. Catal., 95 (1985)
609-12.
18. Forester, T. R. & Howe, R. F., In situ FTIR studies of
methanol and dimethyl ether in ZSM-5. J. Am. Chem.
SOC.,109 (1987) 5076-82.
19. Dessau, R. M., Schmitt, K. D., Kerr, G. T., Woolery, G. L.
& Alemany, L. B., On the presence of internal silanol
groups in ZSM-5 and the annealing of these sites by
steaming. J. Catal., 104 (1987)484-9.
20. Ghosh, A. K. & Kydd, R. A,, Infrared study of the effect of
H F treatment on the acidity of ZSM-5, Zeolites, 10 (1990)
766-71.
21. Vedrine, J. C., Auroux, A., Bolis, V., Dejaifve, P., Nac-
cache, C., Wierzchowski, E. G., Hagy, J. B., Gilson, J. P.,
van Hooff, J. H. C., Van der Berg, J. B. & Wolhuizen, J.,
Infrared microcalorimetric, and electron spin resonance
investigations of the acidic properties of the H-ZSM-5
zeolite. J. Catal., 59 (1979) 248-62.
22. Datka, J. & Tuznik, E., Infrared spectroscopic studies of
acidic properties of NaHZSM-5 zeolites. J. Catal., 102
(1986)43-51.
23. Kapustin, G. I., Brueva, T. R., Klyachko, A. L., Beran, S.
& Wichterlova, B., Determination of the number and acid
strength of acid sites in zeolites by ammonia adsorption.
Comparison of calorimetry and temperature-programmed
desorption of ammonia. Appl. Catal., 42 (1988) 239-46.
24. Aguayo, A. T., Benito, P. L., Gayubo, A. G., Olazar, M. &
Bilbao, J., Acidity deterioration and coke deposition in a
H-ZSM-5 zeolite in the MTG process. Stud. Surf Sci.
Catal., 88 (1994) 567-72.