Microporous and Mesoporous Materials 29 (1999) 3–48

Review

Methanol-to-hydrocarbons: catalytic materials and their behavior1

Michael Stöcker
SINTEF Applied Chemistry, Department of Hydrocarbon Process Chemistry, P.O.Box 124 Blindern,
N-0314 Oslo, Norway
Received 7 November 1997; accepted 30 January 1998

Abstract

The literature related to methanol-to-hydrocarbons (MTHC ) technology over the past two decades has been
reviewed, covering mainly the methanol-to-olefin (MTO) and methanol-to-gasoline (MTG) reactions. The work
before around 1990 is briefly addressed, and the interested reader’s attention is drawn to review papers published
during the late 1980s summarizing the early work related to the methanol-to-hydrocarbons technology. This review
focuses mainly on the chemistry and mechanism of those reactions including the catalysts involved and their behavior
due to crystal size, pore architecture, acidity and reaction conditions, covering the time since around 1990. In a
second review authored by F. Keil, the process related items of methanol-to-hydrocarbons technology will be
summarized and discussed in the light of kinetic and reaction technology aspects. © 1999 Elsevier Science B.V. All
rights reserved.

Keywords: Methanol-to-hydrocarbons; MTO (methanol-to-olefin); MTG (methanol-to-gasoline); Heterogeneous

catalysis; Review

1. Introduction ogy, one can make almost anything out of coal or

To begin with, the methanol-to-hydrocarbons
technology was primarily regarded as a powerful
method to convert coal into high-octane gasoline.
This concept has been expanded since, not only
with respect to the formation of other fuels, but
also to chemicals in general. Of course, light olefins
are important components for the petrochemical
industry, and the demand for high-quality gasoline
is increasing as well. In fact, with this new technol-
1Dedicated to my wife Wencke Ophaug.
natural gas that can be made out of crude oil.
Methanol is made from synthesis gas (a mixture
of carbon monoxide and hydrogen) which is
formed by steam reforming of natural gas or
gasification of coal. The methanol is then con-
verted to an equilibrium mixture of methanol,
dimethyl ether and water, which can be processed
catalytically to either gasoline (methanol-to-gaso-
line, MTG) or olefins (methanol-to-olefin, MTO),
depending on the catalyst and/or the process oper-
ation conditions. Although methanol itself is a
potential motor fuel or can be blended with gaso-
line, it would require large investments to over-

1387-1811/99/$ – see front matter © 1999 Elsevier Science B.V. All rights reserved.
PII: S1 3 8 7 -1 8 1 1 ( 9 8 ) 0 0 31 9 - 9
4 M. Stöcker / Microporous and Mesoporous Materials 29 (1999) 3–48
come the technical problems connected with the
direct use of methanol as a motor fuel. The com-
mercial MTG reaction runs at temperatures
around 400°C and a methanol partial pressure of
several bars and uses a ZSM-5 catalyst. These are
the optimal conditions for converting the olefins
that form within the catalyst into paraffins and
aromatics. However, at one point in the MTG
reaction, the product mixture consists of about
40% light olefins. The importance of light olefins
as intermediates in the conversion of methanol to
gasoline was recognized early. Consequently, a
number of attempts were made to selectively form
light olefins from methanol, not only on medium-
pore zeolites but also on small-pore zeolites, SAPO
type molecular sieves and large-pore zeolites (to a
much lesser extent). If one interrupted the reaction
at the point of about 40% light olefin formation,
one could harvest these C –C olefins. By adjusting
2 4
the reaction conditions (such as, for example,
raising the temperature to 500°C ) as well as the
catalyst applied, one can increase dramatically the
olefin yield. This discovery led to the development
of the MTO process, which generates mostly pro-
pylene and butylene, with high-octane gasoline as
a byproduct. However, the catalyst can be modified
in such a way that even more ethylene is pro-
duced [1].
1973 marked the beginning of the energy crisis,
and new interest in synfuels and other chemicals
favored the continuation of the methanol-to-
hydrocarbon research [2]. Already the MTG and
MTO processes represent a sort of chemical
factory, to be brought on stream as the technologi-
cal and/or economic demands arise. One can go
one step further and convert the olefins to an
entire spectrum of products, through another
ZSM-5 based process: Mobil’s olefin-to-gasoline
and distillate process (MOGD), originally devel-
oped as a refinery process, which works well
coupled with the MTO process. In the MOGD
reaction, ZSM-5 oligomerizes light olefins,
from either refinery streams or MTO, into higher-
molecular-weight olefins that fall into the gasoline,
distillate and lubricant range (see also Fig. 1)
[1].
In 1979 the New Zealand government selected
the MTG process over the Fischer–Tropsch
(SASOL process) for converting natural gas from
their extensive Maui field to gasoline. At that time,
Mobil’s fixed-bed MTG process was unproven
commercially, whereas the SASOL technology was
already commercialized [1]. The New Zealand
plant started to produce about 600 000
ton year−1 gasoline from April 1986, supplying
one-third of the nation’s gasoline demand [2].
The gasoline production part of the factory was
later closed down, due to the price available for
gasoline versus the price of methanol, however,
the methanol production part is still in
operation.
The MTO technology seems now to be ready
for commercial use. The MTO process of Mobil
has been demonstrated in the same experimental
4000 ton year−1 plant at Wesseling (Germany)
used to prove the fluid-bed MTG process, applying
ZSM-5 as catalyst [2]. In cooperation with Norsk
Hydro, UOP announced in 1996 that their
SAPO-34 based MTO process was to be realized
in the construction of a 250 000 ton year−1 plant
using a natural gas feedstock for production of
ethylene. A 0.5 ton year−1 demonstration unit
operated by Norsk Hydro has verified the olefin
yields and catalyst performance. SAPO-34 is
extremely selective towards ethylene and propylene
formation with the flexibility of altering the ratio
between the two olefins by varying the reactor
conditions [3].
The discovery of the MTG reaction happened
by accident. One group at Mobil was trying to
convert methanol to other oxygen-containing com-
pounds over a ZSM-5 catalyst. Instead, they
received unwanted hydrocarbons. Somewhat later,
another Mobil group, working independently, was
trying to alkylate isobutane with methanol over
ZSM-5 and identified a mixture of paraffins and
aromatics boiling in the gasoline range – all coming
from methanol. Although the discovery of MTG
was accidental, it occurred due to a balanced effort
in catalysis over many years. The MTO reaction
seems to benefit from this development, although
independent research has been performed since.
The evolution of the methanol-to-hydrocarbons
(MTHC ) technology, from its discovery until its
realization on a demonstration and/or commercial
 M. Stöcker / Microporous and Mesoporous Materials 29 (1999) 3–48
Fig. 1. Gasoline and distillate production via methanol and Mobil’s ZSM-5 technology (reproduced by permission of Elsevier Science
B.V., Amsterdam).
scale, has been accompanied by extensive research
related to the basic question of the mechanism of
formation of the initial C–C bond [1,2]. This
review tries to highlight the milestones of this
development during the past decade.
A number of reviews exist dealing with the
methanol-to-hydrocarbons technology, mainly
covering the MTG reaction, and the summaries
by Chang and others should be particularly men-
tioned here [4–11]. I recommend the interested
reader to consult these reviews for the R&D work
performed during the 1980s and earlier. This
review will focus on the MTO reaction, however,
recent results covering the MTG reaction will be
addressed as well.
2. The chemistry of methanol-to-hydrocarbons:
mechanistic and kinetic considerations
The main reaction steps of the methanol conver-
sion to hydrocarbons can be summarized as fol-
lows:
5
Methanol is first dehydrated to dimethyl ether
(DME ). The equilibrium mixture formed, con-
sisting of methanol, dimethyl ether and water, is
then converted to light olefins. In the last step of
this scheme, the light olefins react to form paraffins,
aromatics, naphthenes and higher olefins by
hydrogen transfer, alkylation and polycondensa-
tion (see Fig. 2).
There is general consensus that the intermediate
in the dehydration of methanol to dimethyl ether
[step 1 in Eq. (1)] over solid acid catalysts is a
protonated surface methoxyl, which is subject to
a nucleophilic attack by methanol [12]. The subse-
quent conversion of light olefins to paraffins, aro-
matics, naphthenes and higher olefins [step 3 in
Eq. (1)], which proceeds via classical carbenium
ion mechanisms with concurrent hydrogen
transfer, is well known from hydrocarbon chemis-
try in acid media [11]. However, the second step
in Eq. (1), which represents the initial C–C bond
formation from the C reactants, has been the
1
topic of an extensive discussion throughout the
(1)
6 M. Stöcker / Microporous and Mesoporous Materials 29 (1999) 3–48
Fig. 2. Methanol-to-hydrocarbons reaction path (reproduced by permission of Elsevier Science B.V., Amsterdam).
years. A large number of papers is available pre-
senting more than 20 possible mechanistic propos-
als for the formation of the first C–C bond. The
most discussed and/or relevant of these mecha-
nisms can be broadly classified and briefly summa-
rized as follows [11–13]:
The oxonium ylide mechanism has without doubt
received strong attention. Van den Berg et al. [14]
postulated that dimethyl ether interacts with a
Brønsted acid site of the solid catalyst to form a
dimethyl oxonium ion, which reacts further with
another dimethyl ether to form a trimethyl oxo-
nium ion. This trimethyl oxonium ion is subse-
quently deprotonated by a basic site to form a
surface associated dimethyl oxonium methyl ylide
species [11,12]. The next step is either an intramo-
lecular Stevens rearrangement [14], leading to the
formation of methylethyl ether, or an intermolecu-
lar methylation [15], leading to the formation of
the ethyldimethyl oxonium ion. In both cases
ethylene is formed via b-elimination (see Scheme 1)
[11]. A bifunctional acid–base catalyzed condensa-
tion was suggested by Olah [16 ]. Methanol and
dimethyl ether form a trimethyl oxonium ion
(using for example WO on alumina), which is
3
deprotonated to dimethyl oxonium methyl ylide.
However, Olah concluded (based on labelling
experiments) that the ylide undergoes bimolecular
methylation to form the ethyldimethyl oxonium
ion, rather than an intramolecular Stevens
rearrangement [12,17].
Much research has been concentrated on the
questions about the existence of the oxonium
ylides, their ability to rearrange according to
Stevens and the zeolite’s ability to abstract a
proton from the oxonium ions to form the desired
ylides. Again, Olah and coworkers performed a
number of experiments in an endeavor to answer
these questions by attempting the synthesis of the
ylide directly via three different approaches: (1)
reaction of photochemically formed methyl car-
bene with dimethyl ether; (2) deprotonation of the
trimethyloxonium ion; and (3) desilylation of the
dimethyl [(trimethylsilyl ) methyl ] oxonium ion
[17,18]. No ylide species were isolated in these
experiments, however, their existence was inferred
from the product isotope distributions by using
13C or 2H labelled compounds. The observed iso-
tope distributions of methylethyl ether appeared
to rule out the Stevens rearrangement [12].
Furthermore, Olah et al. investigated the photo-
chemical reaction of diazomethane with dialkyl
ethers, using labelled and unlabelled CH N [18].
2 2
Based on the analysis of the product isotope
distribution, they proposed the transmethylation
process yielding dimethyl ether via the formation
of methylethyloxonium methyl ylide, which either
decomposes to ethylene and dimethyl ether or is
 M. Stöcker / Microporous and Mesoporous Materials 29 (1999) 3–48
Scheme 1
protonated by methanol (or water) impurities to
give an oxonium salt, which then undergoes rapid
methyl transfer to form dimethyl ether [18]. These
observations were taken as an evidence against the
Stevens rearrangement as the predominant path-
way [12]. According to Huisgen, the reaction of
diazomethane with dialkyl ethers proceeds via an
initial ylide formation, followed by a Stevens
rearrangement [19]. However, this was questioned
by Franzen and Fikentscher [20], who concluded
that the formation of methylethyl ether and ethy-
lene could be rationalized by b-elimination from a
methyleneoxonium ylide intermediate.
A lot of suitable information was obtained by
running those experiments, however, they did not
give a definitive answer with respect to the ylide
question as a result of their shortcomings.
Nevertheless, if those oxonium ylides do exist and
7
are involved in the C–C bond formation, their is
still the question about the zeolite’s ability to
abstract a proton from the oxonium ions to form
the desired ylides. Hunter and Hutchings [21,22]
investigated this topic closely, concluding with the
suggestion that a surface-bound methoxyl is initially
formed, which is deprotonated to a surface-bound
ylide. This ylide is isoelectronic with surface-bound
carbene [23,24], which in turn engages in a C–C
bond formation by C–H attack. However, the
nature of the basic site for deprotonation was not
specified [12]. Another group investigated the ques-
tion of basicity by preparing the trimethyloxonium
ion bound to ZSM-5 and following its decomposi-
tion by means of 13C MAS NMR spectroscopy.
Upon warming to room temperature, the sample
slowly decomposed to methyl-ZSM-5 and phy-
sisorbed dimethyl ether, confirming that the conju-
8 M. Stöcker / Microporous and Mesoporous Materials 29 (1999) 3–48
gate base of H-ZSM-5 is nucleophilic rather than
basic towards the methylating agent [12,25]. Similar
results (formation of methyl-ZSM-5) were moni-
tored by Forester et al. [26 ] applying in situ Fourier
transform infrared (FTIR) spectroscopy.
Chao et al. studied the conversion of methanol
to hydrocarbons over ZSM-5 with mixtures of
labelled and unlabelled methanol and dimethyl
ether at elevated temperatures. Their results indi-
cate that ethylene was the primary hydrocarbon
product through bimolecular reactions of dimethyl
ether with or without methanol on the catalysts
surface. The C–C bond was formed following an
acidic mechanism via oxonium ions with intermo-
lecular transfer of H and D. An isotope distribu-
tion analysis of the products showed that
propylene was most likely produced by the reaction
of ethylene and C species from methanol adsorbed
1
on the ZSM-5 surface [27].
In addition, a number of other investigators
favor the ‘oxonium proposal’ as the most likely
mechanism as a result of the linear dependence of
hydrocarbon formation activity on zeolite
Brønsted acidity [28–33].
In summary, the oxonium ylide mechanism
involves the formation of a surface-bound interme-
diate as the initial reaction step. The zeolitic
surface OH-group is methylated to form the
methyloxonium intermediate, which gives rise to a
surface-bound methylene-oxoniumylide due to
deprotonation. The surface-bound methylene oxo-
niumylide is isoelectronic with a surface-associated
carbene, as outlined in Scheme 2 [34,35]. Further
methylation results in the initial C–C bond forma-
tion [11].
Scheme 2
The carbene mechanism involves the a-elimination
of water from methanol followed by either poly-
merization of the resultant carbene to olefins or
by concurrent sp3 insertion of the carbene into
methanol or dimethyl ether [36–38]. The forma-
tion of the carbene by the cooperative action of
acid and basic sites in mordenite was suggested by
Swabb and Gates [38] and can be summarized as
follows:
[Zeo−O−÷H–CH –OHH–O–Zeo]
2
H O+:CH (2)
2 2
According to Salvador and Kladnig [39], carbenes
are generated through decomposition of surface
methoxyls formed originally upon chemisorption
of methanol on the zeolite (zeolite Y ) [12].
Venuto and Landis [37] addressed for the first
time the subject of mechanism of methanol conver-
sion to hydrocarbons over zeolites (zeolite X ),
whereas Chang and Silvestri [36 ] reported the
conversion of methanol to hydrocarbons over
ZSM-5, favoring the carbene mechanism for the
initial C–C bond formation as well. Later, the
possibility of a sequential mechanism was consid-
ered by Chang [40].
Up to now, experimental evidence with respect
to the intermediate carbene formation has been
indirect, for example by trapping the reactive C
1
intermediate from 13C labelled methanol decompo-
sition over ZSM-5 using unlabelled propane. The
analysis of the product isomer and isotope distribu-
tions gave indications that the reactive C interme-
1
diate was carbenic and the mode of attack on
propane was sp3 insertion into H–C bonds [41].
 M. Stöcker / Microporous and Mesoporous Materials 29 (1999) 3–48
Such carbene insertions are indiscriminate in selec-
tivity [42], resulting in a statistical distribution of
the butane isomers (i:n=1:3). Methylation by a
carbocationic C intermediate would, by contrast,
1
result in high isobutane selectivity [43]. However,
this interpretation was questioned by van Hooff
[44] who suggested that low i/n-butane ratios could
be explained by hydride transfer between propane
and butyl cations. If hydride transfer were slower
to t-butyl cation than to the secondary cation, low
i/n-butane ratios would result. Hydride transfer
would also activate propane for C–C scission,
leading to doubly labelled butanes [12]. Chang
and Chu [45] replied by showing that once propane
enters into the main reaction path, the i/n-butane
ratios will be constant due to complete isotope
scrambling, and independent of the degree of 13C
substitution, contrary to the experimental observa-
tion. Van Hooff ’s proposal also failed to account
for the high i/n ratios observed in the reaction of
methanol alone [12].
Evidence in favor of carbene intermediacy in
the conversion of methanol to gasoline over
H-ZSM-5 was reported by Dass et al. [46 ]. The
authors observed a decrease in the abundance ratio
of isobutane to that of n-butane, observed on
addition of propane to the feed. The lowering of
the i/n-butane ratio may be accounted for in part
by conversion of propane yielding butanes, pre-
dominantly n-butane. An additional effect is the
raise of the i/n-butane ratio on adding helium as
diluent in the control sample. At least the greater
part of the i/n-butane ratio lowering effect may be
attributed to these two causes.
Lee and Wu [23] conducted a model study using
diazomethane, which was reacted over various
catalysts including ZSM-5, with the aim of observ-
ing a possible surface-stabilization of carbene.
Although olefins were formed even with ‘inert’
materials, hydrocarbon yields were seen to increase
substantially in the presence of acidic surfaces.
They proposed the formation of a methyloxonium
species via interaction with an acid site. This
species reacts with excess diazomethane, forming
an ethyloxonium species by C–H insertion, and
final b-elimination affords ethylene [12]. The inter-
pretation of Lee and Wu was challenged by Olah
et al. [47] who were not able to induce the insertion
9
of singlet methylene into trimethyloxonium tetra-
fluoroborate. On the other hand, the alkylation of
diazomethane by alkyl cations is known.
Consequently, Olah et al. suggested an alternate
interpretation where a stabilized ‘incipient methyl
cation’ on the acid site reacted with diazomethane
to form ethylene. The carbene mechanism was
further debated by Olah et al. [47] based on
thermochemical arguments, however, calculated
stabilization energies in the range of 285–
314 kJ mol−1 showed that surface-stabilized diazo-
methane is not an unreasonable intermediate for
hydrocarbon formation from methanol [12,48].
Nováková et al. [49] assumed the formation of
the first C–C bond in ethylene and propylene
during methanol transformation over zeolites to
occur via the reaction of gaseous methanol (or
dimethyl ether) with C species whose C–H bonds
1
are strongly weakened. These species are probably
polarized methoxyls or protonated formaldehyde
which could also yield species of carbene-like char-
acter. The authors observed, that on H-ZSM-5,
the lack of methanol in the gas phase led to a
disproportionation of methoxyls to methane and
formaldehyde. This was not observed on dealumi-
nated H–Y, probably due to the supply of metha-
nol by the decomposed surface species [49].
Hutchings et al. [50] contributed with a number
of papers dealing with the mechanistic aspects of
the methanol to hydrocarbons reaction, among
them the reaction of methanol with added
hydrogen using WO on alumina and H-ZSM-5
3
catalysts which did not significantly alter the pro-
duct distribution from that of normal methanol
conversion. The authors considered their results
as a clear evidence against the involvement of a
gas phase carbene intermediate. In addition, the
behavior of the methoxylmethyl radical in the gas
phase has been studied and the results demonstrate
that this species is not involved either as an inter-
mediate in initial C–C bond formation in the
methanol to hydrocarbons reaction [50].
Whereas the oxonium ylide mechanism essen-
tially involves the formation of a surface-bound
intermediate as the initial reaction step, the carbene
mechanism involves only surface associated inter-
mediates [11], see Scheme 2.
Other authors/groups favored the carbocationic
10 M. Stöcker / Microporous and Mesoporous Materials 29 (1999) 3–48
mechanism [50–55]. According to Ono and Mori
[51] surface methoxyls may function as free methyl
cations, which adds to the C–H bond of dimethyl
ether to form a pentavalent carbonium transition
state. Abstraction of a proton completes the reac-
tion, analogous to the proposed ‘superacid mecha-
nism’ by Olah et al. [43]. However, one may argue
whether the C–H bond of methanol or dimethyl
ether is sufficiently nucleophilic to undergo substi-
tution as proposed by Ono and Mori. This item
was investigated by Smith and Futrell [56 ] who
reacted methylcarbenium ion with methanol.
Hydride abstraction to form methane and
CH OH+ was the superior reaction (85–90%),
2
however, proton transfer from the methyl cation
to methanol (forming methylene) happened to a
certain extent (7%). C species were not observed.
2
These results give rise to some doubt about the
suggested mechanism, attacking directly the C–H
bond of the methoxyl group by a methyl cation
[12].
As an alternative for the formation of methylox-
onium intermediates, the free radical mechanism
has been introduced [57]. The participation of free
radicals in the conversion of methanol to hydro-
carbons over natural mordenite has been suggested
by Zatorski and Krzyzanowski [58], however,
without experimental evidence documented in their
report. Later, Clarke et al. [59] recognized that
dimethyl ether could be the source of methylradi-
cals when they identified free radicals in the reac-
tion of dimethyl ether over H-ZSM-5 monitored
by ESR spectroscopy. Clarke et al. proposed that
radicals are formed initially by interaction of
dimethyl ether with paramagnetic centers (solid-
state defects) in the zeolite and that C–C bond
formation results from direct coupling of radicals
[12,59]. The suggestion of Clarke et al. eliminates
the requirement of strongly basic sites for proton
removal from C–H, a major drawback of a number
of introduced mechanisms [12]. However, this
concept was considered as unlikely because of the
probability of radical interaction with the zeolite
surface [11,57], Therefore, Chang et al. suggested
the following reaction path (Scheme 3).
Choukroun et al. [60] observed that radical
dimerization of dimethyl ether gave dimethoxye-
thane exclusively (in fluorosulfonic acid ), however,
Scheme 3
this product has never been observed in the
dimethyl ether reaction over zeolites [12].
The free radical pathway has been discussed by
several other authors concluding with experimental
evidence against a radical mechanism, like Hunter
et al. [61] who studied the behavior of the
methoxymethyl radical in the gas phase conversion
of methanol to hydrocarbons over ZSM-5. The
same authors ended up with the same conclusion
when investigating the reactions of dimethyl ether
and methanol over H-ZSM-5 with added NO and
O [62]. In continuation of this work, Hutchings
2
compared the inhibition of the methanol conver-
sion to hydrocarbons over H-ZSM-5 induced by
co-feeding NO with the inhibition by NH and
3
NH OH [63]. It was considered that NO does not
2
act as a radical scavenger during this reaction, nor
does NO co-feeding lead to the generation of
NH as a catalyst poison. It was observed that
3
inhibition induced by NH OH closely simulates
2
that observed by NO co-feeding [63].
Free radical signals have been detected during
ESR measurements carried out on the conversion
of methanol to hydrocarbons over H-ZSM-5 in a
flow reactor at temperatures between 200°C and
280°C [64]. However, the signals were quenched
by the presence of C oxygenates. Thus in the
presence of methanol no change in the ESR signal
was observed when the system transformed from
being nonactive to being active for forming C–C
bonds. When the methanol feed was stopped a
clearly observable ESR signal due to organic free
radicals appeared, which means that free radicals
are present in the C–C active catalyst, but it is
unclear (doubtful ) whether they are essential for
the reaction or not [64].
Most of the mechanistic studies related to the
methanol to hydrocarbons reaction were carried
 M. Stöcker / Microporous and Mesoporous Materials 29 (1999) 3–48
out using ZSM-5 as catalyst. The mechanisms
proposed so far may broadly be classified into
two groups:
The consecutive type mechanism with one carbon
from methanol adding during each step. Addition
and cracking reactions of the alkene molecules
may take place as illustrated as follows [65]:
2C C H +H O
1 2 4 2 be consistent with the ‘hydrocarbon-pool’ type
C H +C C H
2 4 1 3 6
C H +C C H …
3 6 1 4 8
A parallel type mechanism, known as ‘hydrocarbon-
pool mechanism’ was suggested by Dahl and
Kolboe [65,66 ], who studied the methanol to
hydrocarbons conversion applying SAPO-34 as
catalyst and 13C-labelled methanol as feed [and
(12C) ethene (made in situ from ethanol ) ] (see
Scheme 4).
Scheme 4
The ‘hydrocarbon-pool’=(CH ) represents an
2n
adsorbate which may have many characteristics in
common with ordinary coke, and which might
easily contain less hydrogen than indicated. It
would perhaps be better represented by (CH )
xn
with 0<x<2 [66 ].
When using SAPO-34 in the title reaction, the
product pattern is thus simpler than, e.g. ZSM-5,
where a much wider range of products was found.
Therefore, it might be easier to obtain a picture of
the reaction pathway using SAPO-34, and the
authors showed that the consecutive mechanism,
in as far as propene formation was concerned, did
not turn out to be valid. They concluded, that
only a minor part of the propene molecules may
have been formed by addition of methanol to
11
ethene since this would imply a 12C/13C ratio larger
than one. The majority of the propene molecules
were formed directly from methanol [65,66 ].
The nature of the ‘hydrocarbon-pool’ mecha-
nism was not discussed by Dahl and Kolboe. The
methanol to hydrocarbons reaction could proceed
via a ‘rake mechanism’ as first proposed by
Cormerais et al. [67]. Their mechanism may also
mechanism. In the case of Cormerais et al. [67],
the hydrocarbon pool would rather consist of
ethoxy, propoxy, butoxy groups etc., formed by
methylation of the next lower member. From
results obtained in studies of methanol conversion
on H-ZSM-5 [54,68,69] the authors believe rather
that the reaction proceeds via an adsorbate which
is continually adding and splitting off reactants
and products. Their results were in agreement with
a ‘hydrocarbon-pool’ type mechanism, and ethene
was observed as an inert primary product. In the
co-reaction of ethene and methanol over SAPO-34,
most of the product was made from methanol,
and there was about 90% unconverted ethene
remaining at the time when methanol was fully
converted. The propene and the butenes made
during the reaction exhibit distributions of 12C
and 13C which are nearly random at all times. This
observation supports the ‘hydrocarbon-pool’
mechanism, too. Randomness will, however, also
result if propene and butenes were adsorbed, isoto-
pically isomerized, and desorbed at a much faster
rate than ethene [65]. Methane was mainly formed
from methanol–dimethyl ether, and only to a
minor extent by fragmentation of higher hydro-
carbons. As would be expected, the same applies
to CO and CO . Some mechanistic details using
2
SAPO-34 may differ from those obtained over
H-ZSM-5, due to the unusual high selectivity for
the formation of ethene (and propene) [66 ].
The distribution of olefins formed in the
H-ZSM-5 catalyzed conversions of methanol were
examined at low partial pressures as a function of
contact time by Dessau [70]. The results clearly
indicated that ethylene was only obtained at long
contact times, and then via secondary reequilibra-
tion of the primary kinetic olefinic products, pro-
pylene and butenes [70]. Theoretical (NDO)
calculations suggest that the (secondarily) formed
12 M. Stöcker / Microporous and Mesoporous Materials 29 (1999) 3–48
ethoxyl fragment may be alkylated by methanol
to a higher fragment or decompose with the
desorption of ethylene [71].
The complexity of the methanol to hydro-
carbons reaction as a result of rapid secondary
reactions as well as limitations of suitable tech-
niques to follow this reaction has always been a
problem to get conclusive evidence for the chemis-
try of the methanol conversion. Besides the topic
of formation of the first C–C bond, the number
and nature of intermediates have been a matter of
large interest. 13C MAS NMR spectroscopy turned
out to be a powerful tool with respect to the
identification of the intermediates formed, and a
number of investigations has been conducted
mainly applying ZSM-5 and SAPO-34 catalysts.
Anderson and Klinowski [72,73] monitored the
catalytic conversion of methanol to hydrocarbons
over ZSM-5 at temperatures up to 370°C and
identified 29 different organic species in the
adsorbed phase using 13C MAS NMR spectro-
scopy. The authors were able to observe the fate
of those species during the course of the reaction.
This technique allowed them to follow different
kinds of shape selectivity in the zeolite host, to
identify CO as an intermediate in the reaction, and
to distinguish between mobile and attached species.
Only methanol was present at room temperature.
In samples treated at 150°C dimethyl ether was
found. At 250°C and above a new signal, due to
CO intermediates, appeared. A number of aliphatic
and aromatic compounds were formed at 300°C
and above (see Fig. 3 and Table 1) [72,73].
However, the role of CO in the conversion of
methanol to gasoline on zeolite H-ZSM-5 has been
debated by Munson et al. [74], based on their in
situ 13C MAS NMR investigations. In contradic-
tion to Anderson and Klinowski, Munson and
coworkers concluded that CO is neither an inter-
mediate nor a catalyst in MTG chemistry on
zeolite H-ZSM-5 [74].
The combination of 13C NMR spectroscopy and
gas chromatography allowed Derouane and
coworkers to support the carbenium ion mecha-
nism for the conversion of methanol to hydro-
carbons over H-ZSM-5 since carbenium ions are
very strongly stabilized on the acidic and highly
polarizing surface of this zeolite [75].
Salehirad and Anderson [76 ] reported on the
use of 13C MAS NMR spectroscopy to monitor
the course of methanol conversion over
H-SAPO-34 applying sealed capsules containing
the catalyst with different loadings of 13C enriched
methanol. Being isostructural with the mineral
chabazite, SAPO-34 has a cage structure rather
than a channel structure as in ZSM-5. The acidity
of H-SAPO-34 is lower than that of H-ZSM-5.
These two features have consequences with respect
to the catalytic performance of SAPO-34 such that
this catalyst is selective for the synthesis of light
olefins, i.e. C –C hydrocarbons. The lower acidity
2 4
and high selectivity of H-SAPO-34 in contrast to
H-ZSM-5 enable a better understanding of the
conversion reaction mechanism using 13C MAS
NMR spectroscopy. The authors stated experi-
mental evidence for a stepwise methylation reac-
tion via surface-bound species derived from: (a)
the treatment of several samples with different
loadings of methanol at 250–290°C and; (b) when
either 13C-methanol is coadsorbed with 12C-ethy-
lene over the catalyst or 12C-ethylene is reacted
with pre-13C methylated SAPO-34. The hydro-
carbon products in these experiments were mainly
isobutane and isopentane as well as methane,
ethylene and propane [76 ]. The presence of
branched C and C saturated hydrocarbons in
4 5
the intracrystalline space causes an additional
steric constraint on the diffusion of linear hydro-
carbons since isobutane and isopentane are too
large to leave the intracrystalline pore system. This
favors the diffusion of C and C species out of
1 2
the crystallites and is responsible for the apparent
overall selectivity of SAPO-34 for ethylene [77].
Hydrocarbon formation from methanol on
H-SAPO-34 was monitored in a closed static
system by 13C MAS NMR and in an open flow
system by gas chromatography by Xu et al. [78].
Methanol was shown to be converted via the same
pathway in either the static or the flow systems
but with steady state and non-steady state modes,
respectively. The medium acid strength of
H-SAPO-34 is thought to be decisive for its good
selectivity towards the formation of light olefins
[78]. Similar in situ solid-state 13C MAS NMR
investigations have been performed by other
authors as well [79–82]. Finally, tritium NMR
 M. Stöcker / Microporous and Mesoporous Materials 29 (1999) 3–48 13

Fig. 3. 13C MAS NMR spectra of a ZSM-5 sample heated to 300°C for 35 min and recorded with proton decoupling only: (a)
aliphatic region; and (b) aromatic and CO region. Intensities in (a) and (b) are not on the same scale. The insert shows J-coupling
of methane and cyclopropane carbons (recorded without decoupling). Spectral assignments are given in Table 1 (reproduced by
permission of the American Chemical Society, Washington DC ).

investigations were carried out in order to monitor
routes to the ethylene production on the conver-
sion of methanol to hydrocarbons applying
H-ZSM-5 as catalyst [83].
Besides solid-state NMR spectroscopy, a variety
of other techniques like in situ FTIR spectroscopy
[26,84,85], flow reactor/GC-MS spectrometry
[13,86–88], temperature programmed desorption
( TPD) [49,85,89] as well as differential scanning
calorimetry (DSC ) [69,90] have been used to
follow the complexity of the methanol to hydro-
carbons reaction. Again a review exists covering
the use of spectroscopic techniques to investigate
the MTG process [91]. Examples are quoted of
catalyst characterization, investigation of the first
C–C bond formation, alkene oligomerization and
catalyst deactivation through coke formation.
Obviously, a large number of experiments have
been done to resolve the question of C–C bond
formation from methanol. Although the answer
still remains elusive, these experiments tell us at
least what is probably not involved in the bond
14 M. Stöcker / Microporous and Mesoporous Materials 29 (1999) 3–48

Table 1
Assignment of 13C MAS NMR signals for the ZSM-5 sample treated at 300°C for 35 min (according to Ref. [73])

Compound Aliphatic Aliphatic Aromatic

signal no.a signal intensityb signal no.a

Isobutane 3 s
Propane 7 s
CO s
n-Butane 3, 9 m
n-Hexane 1, 4, 8 m
Isopentane 1, 2, 4, 10 m
n-Heptane 1, 2, 4, 8 m
Methane 13 m
Ethane 11 w
Cyclopropane 12 w
o-Xylene 5 s 4, 12, 17
1,2,4,5-Tetramethylbenzene 6 s 8, 11
p-Xylene 6 s 7, 13
1,2,4-Trimethylbenzene 5, 6 m 4, 6, 8, 11, 13, 16
1,2,3,5-Tetramethylbenzene 5, 8 m 5, 7, 10, 13
Toluene 5 w 2, 13, 14, 18
m-Xylene 5 w 2, 12, 15, 17
1,3,5-Trimethylbenzene 5 w 3, 16
1,2,3-Trimethylbenzene 5, 8 w 5, 7, 16, 19
1,2,3,4-Tetramethylbenzene 5, 8 w 7, 9, 16

aRefers to Fig. 3.
bs=strong, m=medium, w=weak. Owing to the nuclear Overhauser effect (NOE) these intensities give only a rough guide to the
concentration of each species.

formation, particularly in the presence of zeolite
catalysts [12]. So far, the surface-bound species,
that means the carbene and oxonium ylide propos-
als have received significant experimental support,
especially with respect to the methanol conversion
over ZSM-5 catalysts. The common feature of
both approaches, which is the involvement of the
zeolite conjugate base which acts as a base towards
a non-bonded reactant species, has been ques-
tioned [35]. Especially for the methanol conversion
to hydrocarbons over H-ZSM-5, evidence for a
mechanism based on the intermediacy of surface-
bound species (methoxy groups) has been obtained
spectroscopically [26,39,84,92–94]. The authors
concluded that the surface-bound species is depro-
tonated via a nearby zeolite basic site (‘adjacent
Al–O site’) to a surface-bound carbene which in
turn engages in C–C bond formation [76 ].
Kinetic investigations related to the methanol to
hydrocarbons conversion normally consider the
methanol–dimethyl ether mixture as a single
species. This seems to be justified, since the
dimethyl ether formation is much faster than the
subsequent reactions, so that the oxygenates are
at equilibrium [11,36 ]. Based on the autocatalytic
nature of the methanol conversion over ZSM-5,
Chen and coworkers applied a kinetic model,
which takes into account that the rate of disappear-
ance of oxygenates is accelerated by their reaction
with olefins. At low conversions (<50%) the con-
version of olefins into aromatics can be neglected
and a reasonable fit was obtained, meaning that
the autocatalytic step is much faster than the
formation of the first olefin from the oxygenates.
Fitting experimental data obtained on H-ZSM-5
with varying concentrations of acid sites showed
a linear correlation between the rate constant of
the reaction of oxygenates with olefins and the
intrinsic acid activity of the catalyst [11,95].
Ono and Mori [51] proposed the first step in
the model of Chen and Reagan [95] to be bimolec-
ular. Assuming this reaction to be of second order
with respect to the concentration of the oxygenates
and the autocatalytic reaction to be of first order
 M. Stöcker / Microporous and Mesoporous Materials 29 (1999) 3–48
with respect to both the oxygenates and the olefins,
reasonable fits of the kinetic model were obtained
at 219 and 239°C, indicating that the autocatalytic
effect decreases with increasing temperature
[11,51].
The model of Chen and Reagan [95] was modi-
fied by Chang through adding a bimolecular step
accounting for the carbene insertion in the primary
olefins [96 ]. By assuming all reactions to be first
order and the carbenes to be in steady state, his
model predicts a lower rate constant for the reac-
tion of the oxygenates with the olefins than for
the carbene insertion. This was found to be in line
with the observation that carbene insertion into a
C–H bond is slower than carbene addition to
double bonds. The comparison with experimental
data was acceptable. Chang’s description of the
carbene insertion in olefins predicts a redistribution
of the olefinic species, but not a net increase in the
production of olefins [96 ]. This was corrected for
by Anthony [97] and Ref. [11].
A revision of Chang’s modified model [96 ] was
suggested by Sedran et al. [98] who were able to
predict the product distribution at various conver-
sion levels and temperatures. Anthony and Singh
[99] concluded from a kinetic analysis of the
methanol conversion to lower olefins on chabazite
type zeolites that propylene, methane and propane
are formed through primary reactions and do not
participate in any secondary reactions. However,
dimethyl ether, CO and ethane do. Ethylene and
CO appeared to be produced by secondary reac-
2
tions. Furthermore, the product selectivities could
be correlated to the methanol conversion even
though the selectivity and the conversion changed
with increasing time on stream due to deactivation
by coke formation [11,99].
Based on the carbene mechanism, Mihail et al.
[100] developed a kinetic model for the MTO
reaction up to C H containing 33 reactions. The
5 10
formation of carbene from dimethyl ether turned
out to be the rate determining step among the
kinetic parameters evaluated. This is in line with
the findings of Chen and Reagan [95] and Ono
and Mori [51]. After all, the model was extended
to comprise 53 reactions, including the formation
of aromatics and C+ aliphatic compounds
5
[11,101].
15
A kinetic model for the methanol conversion to
olefins with respect to methane formation at low
conversions was discussed in the literature [102].
The study of Hutchings et al. revealed that, at low
conversion, hydrogen formation from methanol
decomposition and the water gas shift reaction
were significant over the zeolite ZSM-5, and, there-
fore, these reactions should not be included in the
derivation of kinetic models for this reaction. In
view if this, the authors considered it unlikely that
methane formation predominantly proceeds via
the reaction of carbene intermediates with molecu-
lar hydrogen [102].
The effect of axial gas dispersion on the light
olefin yield during the MTO reaction was investi-
gated by Tshabalala and Squires [103] using
pulsed-tracer experiments conducted for a hori-
zontal gas flow through a microreactor. At a given
WHSV, a large variation in axial Peclet numbers
was achieved, with values between 2 and 20 [103].
A kinetic model was used by Luk’yanov [104]
as the basis of a computer simulation, establishing
the influence of the correlations among the rates
of the fundamental reaction steps on the composi-
tion of the products formed. Conditions for opti-
mized activity of the catalysts for the conversion
of methanol were formulated. The influence of the
Si–Al ratio in ZSM-5 zeolites on their activity in
each major reaction step was established [104].
3. Summary of the early studies (before about
1990)
As already mentioned, a number of reviews exist
dealing with the methanol-to-hydrocarbons tech-
nology, especially covering the research and devel-
opment work performed during the 1980s and
earlier [4–6,11]. The interested reader should con-
sult these reviews, however, a brief summary of
the earlier work is given in the following.
3.1. Microporous/zeolitic materials
3.1.1. Large-pore microporous/zeolitic materials
Differently modified Y zeolites have been
applied by Salvador and Kladnig [39] in the MTO
reaction. Light olefins, mainly propylene, were
16 M. Stöcker / Microporous and Mesoporous Materials 29 (1999) 3–48
observed at 250°C. The activity of H–Y was high
compared with Na–Y, which was not active in the
temperature range studied, i.e. up to 350°C. Ion-
exchanged Y zeolite samples with less than 16.4
Na+ and K+ ions per unit cell are active for the
dimethyl ether conversion, according to Cormerais
et al. [105]. Catalytic activity in the methanol-to-
hydrocarbon reaction of NaH–Y zeolite samples
was observed at lower temperatures as the degree
of proton exchange increased [106 ] and at higher
temperatures (350°C ) as the dealumination degree
increased [107]. The temperature dependence indi-
cates that increasing proton exchange leads to
more active sites on Na–Y zeolite, in line with
findings by other authors [105]. MTO reactions
using dealuminated cubic faujasite (Si–Al ratio of
5.7) were studied at about 400°C by Kubelková
et al. [108], who detected mainly C –C olefins
3 7
besides aromatics up to C . Furthermore, NaH–Y
9
(76% ammonium exchange degree) with Si/Al
ratios between 2.5 and 8.9 were used as methanol
conversion catalysts at 300°C, however, mainly
aromatization products were detected under the
experimental conditions applied [109].
A selectivity control to olefins was aimed at by
Davidova et al. applying Ni, Cr and Pb exchanged
Ca–Y zeolites [110]. Ni exchanged Ca–Y produced
mainly C –C olefins when precalcined in a He
2 4
stream. The incorporation of Cr and Pb into
NiCa–Y zeolites changed dramatically the selectiv-
ity to olefins, due to a preferred formation of
highly dispersed nickel particles which favor the
formation of paraffins. A second group prepared
Y zeolites modified by Pt2+, Pd2+, Zn2+ or Ni2+
cations [111]. A predominant formation of C -C
2 5
paraffins was found only for catalysts having a
low metal hydrogenation activity.
Schwartz and Ciric [112] applied rare-earth and
Zn-exchanged X-type zeolite in the MTO reaction.
In the range of 330–390°C, the MeOH conversion
and the molar selectivity towards C –C olefins on
2 4
RE–X zeolite reached 51% and 43.3 mol%, respec-
tively. Zn–X zeolite was less active.
A methanol-rich feed was converted over a
ZSM-12 zeolite-containing catalyst which con-
tained, in addition, magnesium and/or manganese
into an olefin-rich hydrocarbon mixture, especially
enriched in propylene [113]. ZSM-45 was used in
the MTO reaction in the presence of a diluent
selected from water, hydrogen-containing gas,
nitrogen, He, CO and CO or mixtures of these
2
diluents [114].
Mordenite is a highly active catalyst for the
conversion of methanol to hydrocarbons, prefera-
bly in the temperature range of 300–500°C
[11,115]. However, mordenite deactivates rapidly
[116,117]. The selectivity to olefins and the resis-
tance to deactivation can be improved by alumi-
nation, however, this treatment reduces the acidic
character. Propylene is the main olefin produced
on dealuminated mordenite. Stable modified mor-
denite catalysts were obtained when the dealumina-
tion was carried out at about 100°C with 8 M HCl
or by Ba2+ exchange and chemical vapor
deposition of Si from Si(OCH ) [117–119].
34
Ba2+-exchanged dealuminated mordenites are
more resistant to deactivation by coke than the
parent dealuminated mordenites. As the degree of
Ba2+-exchange increased, the selectivity to propyl-
ene and butenes was enhanced, while the selectivity
to aromatics dropped [119]. Some technical
aspects related to the methanol-to-hydrocarbons
technology are covered by patents using dealumi-
nated mordenite (Si/Al ratio higher than 80) as
catalyst [120,121]. Isomorphously substituted erio-
nite ( ERI ) and mordenites (MOR) were prepared
and tested in the MTO reaction at 350–450°C
using the pulse method in a fluidized catalyst bed
microreactor. The yield of olefins formed decreased
in the following order:
B−ERI>ERI>Ga−ERI>Fe−ERI and
B−MOR>MOR>Ga−MOR>Fe−MOR
The olefin yields were highest for the boron-
containing zeolites and lowest for the ferrozeolites
[122]. The catalyst lifetime of mordenite in the
MTG reaction was improved by dealumination,
and the activity of highly improved dealuminated
MOR was maintained at least for eight hours. As
a result, the long-life dealuminated mordenite was
obtained by the preferential removal of strong
acidic sites in the internal framework without
removing the aluminum atoms on the external
surface [123].
AlPO -5, SAPO-5 and MeAPO-5 molecular
4
 M. Stöcker / Microporous and Mesoporous Materials 29 (1999) 3–48
sieves were used in the methanol-to-hydrocarbons
reaction as well [124]. AlPO -5 showed very low
4
activity compared with SAPO-5. Very high metha-
nol conversions (almost 100%) were obtained with
SAPO-5 between 380 and 500°C, however, the
olefin selectivity decreased with increasing temper-
ature, whereas the selectivity towards aromatics
increased. The highest selectivity to hydrocarbons
was obtained with BeAPO-5 [124]. Tapp et al.
[125] applied SAPO-5 and CoAPO-5 in the metha-
nol-to-hydrocarbons reaction at 360°C. The typical
hydrocarbon fraction contained 45% light olefins,
15% higher aliphatics and 40% aromatics. IR and
TPD experiments demonstrate that AlPO s possess
4
a very low acidity. The introduction of bivalent
and tetravalent cations into the framework of
aluminophosphates results in the generation of
Brønsted acid sites, which enhance the catalytic
activity for methanol conversion to hydrocarbons
[125–127].
3.1.2. Medium-pore microporous/zeolitic materials
The pentasil-type zeolite ZSM-5 has been the
candidate among the medium-pore zeolites to be
investigated as catalyst for the methanol-to-hydro-
carbons reaction. A very large number of papers
exist dealing with this microporous material as
MTO or MTG catalyst. A systematic literature
survey has been prepared by Froment et al. [11],
especially with respect to this zeolite type, where
certain aspects related to the catalytic test condi-
tions (space time, temperature, partial pressure,
etc.) as well as to the catalyst preparation (ion
exchange method, isomorphous substitution, Si/Al
ratio of the material, etc.) have been investigated.
The effect of space time on the methanol conver-
sion and the hydrocarbon distribution clearly
demonstrates that C -C olefins are intermediates
2 4
in the MTG reaction [36,128,129]. The yield of
light olefins increases with space time and reaches
a maximum, indicating the intermediate character
of the light olefins formed. An important feature
of the methanol to hydrocarbons reaction on
ZSM-5 is that a further increase of space time
results in a continuing change of the hydrocarbon
distribution, although the conversion is complete
[11]. The sudden increase in the conversion of
methanol to hydrocarbons with space time was
17
related to the required concentration of the inter-
mediate dimethyl ether [130]. In a batch reactor,
the methanol conversion also showed an induction
period, whereas this was not the case with dimethyl
ether as feed [131]. The influence of the size and
shape of ZSM-5 catalyst particles, the operation
conditions and the internal recycle on olefin yield
was investigated for a fixed bed reactor system
[132]. The zeolite was agglomerated by extrusion
to cylinders, rings and monoliths. The use of
monoliths as catalysts was not advantageous, due
to problems of heat transfer.
The effect of increasing the temperature on the
product distribution in the methanol-to-hydro-
carbons reaction using H-ZSM-5 is similar to
increasing the space time at a constant temperature
[36 ]. At higher temperatures, the olefin formation
is favored with respect to the formation of aro-
matics [128,129]. Thermodynamically, the effect
of increasing the temperature over the same range
of partial pressures of olefins is to shift the distribu-
tion towards the lower olefins [24]. This equilib-
rium distribution is only approached at low
conversions of methanol to hydrocarbons [11].
Whereas ethylene is most abundant at low temper-
atures, butene and especially propylene become
more important at higher temperatures [133]. Ono
et al. [134] monitored an abrupt jump in the
conversion of methanol to hydrocarbons applying
H-ZSM-5 at constant space time when increasing
the temperature from 280 to 300°C. It was con-
cluded, that the reason for this jump was the onset
of cracking of oligomers which were formed from
small olefins and remain in the ZSM-5 pores at
low temperatures [11,130]. Jansen van Rensburg
et al. [135] concluded that at low conversion
and/or low temperature, ethylene is mainly a resid-
ual primary reaction product. At higher temper-
atures, however, ethylene is a product resulting
from secondary cracking [11].
The partial pressure of methanol or dimethyl
ether has been shown to have a strong influence
on the olefin selectivity. A decrease of the partial
pressure tends to enhance the olefin formation and
suppress the aromatization reactions [136 ]. Chang
and Lang [137] observed an eight-fold increase in
selectivity towards light olefins when the partial
pressure of methanol was changed from 1 to
18 M. Stöcker / Microporous and Mesoporous Materials 29 (1999) 3–48
0.07 bar and keeping the space time constant. All
the results of the experiments at low partial pres-
sures of methanol indicate that ethylene is not the
initial olefin formed from methanol, but is formed
by the secondary re-equilibration of the primary
olefins, i.e. propylene and butenes. The ethylene
formation at higher partial pressures of methanol
is mainly the result of a thermodynamic control
[11]. This is in fact in contradiction to Haag et al.
[138] who applied a high-silica H-ZSM-5 catalyst
(Si/Al ratio of 800) at atmospheric pressure and
low methanol conversion and concluded that ethy-
lene is the primary olefin from methanol. Increased
selectivities towards the formation of ethylene by
decreasing the methanol partial pressure were
observed by several authors [139–141].
Investigations related to the conversion of meth-
anol as a function of space time on H-ZSM-5
catalysts with varying Si/Al ratios showed that the
maximum in the yield of the intermediate light
olefins shifted towards higher methanol conver-
sions with increasing Si/Al ratio [128,133]. Wu
and Kaeding [142] correlated the product distribu-
tion of the methanol to hydrocarbons reaction on
ZSM-5 with the conversion of the alcohol.
Ethylene was the major primary hydrocarbon pro-
duced from methanol at low conversion. At higher
conversion, the olefins undergo scrambling or
thermodynamic equilibration reactions also pro-
ducing olefin mixtures with good correlation
coefficients for the Flory equation.
Several authors report on the influence of the
synthesis conditions of H-ZSM-5 on the selectivity
towards light olefins, including the effect of
sodium-free gels (higher selectivity towards light
olefins) and the crystallization time (decrease in
selectivity at longer crystallization times) [143–
146 ]. The crystal size of ZSM-5 zeolites has been
found to be an important factor influencing the
methanol conversion to light olefins. Applying
crystals with a size of less than 2 mm, a higher
selectivity for the production of light olefins and
particularly ethylene has been reported
[139,147,148].
The effects of the water content of the reaction
mixture on the physicochemical properties and the
performance of ZSM-5 type zeolite catalysts in
methanol conversion reactions were investigated
by Suzuki et al. [149]. The average diameter of
the zeolite crystallites increased as the water
content in the reaction mixture increased. The
authors concluded that lowering the aluminum
content at the outer shell of the crystallites by
lowering the water content of the reaction mixture
depressed the coke deposition and improved the
catalyst stability [149]. Other modifications of
ZSM-5 zeolites ( like ion exchange [150,151] and
others) are reported as well:
Following Inui et al. [152], acidification of
ZSM-5 should be done by ammonium chloride or
HCl in order to obtain higher olefin selectivities,
because less strongly acid sites are formed in this
way than by ion exchange with ammonium nitrate.
Similar investigations were performed by other
groups, partly arriving at the same conclusions
[153–155].
Several modifications of the Mobil type ZSM-5
zeolite were suggested in order to improve the
selectivity towards light olefins in the MTO reac-
tion, especially with respect to ion exchange and
impregnation methods: Cs+ and Ba2+ exchange
[133,147,150,151], phosphorus impregnation
[133,156–161], Mg modification [146,160,161],
Mo modification [159], Sb O impregnation [162]
2 3
and adsorption of Si-containing compounds
[163,164].
Isomorphous substitution of Si by Al or other
metals results usually in the generation of catalyti-
cally active sites. Especially B-ZSM-5 type catalysts
have attracted a lot of attention with respect to
the conversion of methanol [165–174]. It was
concluded that B-ZSM-5 is more suitable for the
production of propylene, while ethylene is more
selectively formed on Al-ZSM-5 as well as on
fluorinated aluminosilicate pentasiles [11,175].
ZSM-5 catalysts containing Zr, Hf and Ti are also
more selective in the conversion of methanol to
olefins [176–178]. Inui et al. [179] introduced a
procedure for preparing various high-silica ZSM-5
zeolites by replacing Al at the stage of gel forma-
tion by transition metals. Ti and Zr containing
zeolites were the most selective ones towards light
olefins. V-ZSM-5 with a high vanadium content
(Si/V ratio of 90) revealed a high selectivity
towards light olefins [180].
Isomorphously substituted ZSM-5 catalysts
 M. Stöcker / Microporous and Mesoporous Materials 29 (1999) 3–48
were investigated in detail by Inui et al. [181,182]
in order to optimize the selectivity of metal con-
taining zeolites in the MTO reaction towards ligh-
ter olefins. At complete conversion of methanol,
the selectivity towards olefins on the various metal
substituted ZSM-5 zeolites varied as followed:
Ga=Cr<V<Ge<Mn<La=Al<Ni<Zr
=Ti<Fe<Co=Pt
It was clear that ZSM-5 substituted with Fe, Co
and Pt revealed the highest selectivity in the forma-
tion of light olefins. The catalytic properties of
isomorphously substituted Be-ZSM-5 were studied
for the methanol to hydrocarbons reaction by
Romannikov et al. [183], concluding with the
preferred formation of olefins for this type of
catalyst compared with Al-ZSM-5, which pro-
duced mainly paraffins and aromatics [183].
However, the methanol conversion was consider-
ably higher with Al-ZSM-5 than on the Be-ZSM-5,
except for one example.
Fleckenstein et al. [184] compared the conver-
sion of methanol to olefins between H-ZSM-5 and
H-ERI, concluding with a preferred formation of
lower olefins using H-ERI, whereas H-ZSM-5 pro-
duced larger amounts of aromatics. Faster deacti-
vation was observed for the small-pore erionite
zeolite [185].
A number of patents exist and has been reviewed
with respect to the improvement of the ZSM-5
catalyst and/or the process conditions in the meth-
anol to hydrocarbon reaction since this zeolite has
attracted a lot of interest during the last decades.
The available information is quite tremendous,
and the results of this search have been summa-
rized in Table 2 (covering the time before 1989).
However, details should be followed up in the
original patent literature.
An examination of published experimental data
for a wide range of concentrations of strong acid
centers of zeolite ZSM-5 made it possible to estab-
lish the ultimate nature of dependences of the yield
of individual products of methanol transformation
into gasoline [209]. Regression equations describ-
ing the relationships between the concentration of
acid centers, the Si/Al ratio, and the composition
of synthesis products were formulated. The depen-
19
Table 2
Patent literature covering the improvement of the ZSM-5 cata-
lyst and/or process conditions in the methanol-to-hydrocarbon
reaction (time period before 1989)
Improvement/process attempt Refs.
Fluidized bed reactor technology [186–189]
Interstage sorption fractionator technology [190–192]
Adiabatic reactor technology [193]
Different reaction zones with recycling [194]
Presence of diluent [195,196 ]
Aromatics-rich hydrocarbon mixtures [197–200]
Large catalyst particles [201]
Reactivated zeolite [202]
Zeolite catalyst in a silica binder [203]
Zeolite catalyst modified by metal inclusion [204]
Ga-ZSM-5 [205]
Pentasil LZ 40 [206,207]
Temperature and pH variations [208]
dences obtained can be used to predict the hydro-
carbon composition of gasoline with account taken
for monitoring and control of the necessary degree
of acidity of the high-silica zeolites both at the
stage of preparation of the catalysts and during
their use [209].
Besides ZSM-5, other medium-pore type zeolites
have been investigated with respect to the catalytic
conversion of methanol to hydrocarbons, however,
much less attention has been paid to the other
end-member of the pentasil series, i.e. ZSM-11,
probably because it was soon recognized that the
shape-selective properties of ZSM-5 were superior
to those of ZSM-11 [11,210,211]. In the conver-
sion of methanol to gasoline on ZSM-11, much
less C –C products were observed than with
1 2
ZSM-5 while C+-aliphatics are more abundant.
6
Whereas on ZSM-5 the aromatics fraction is
mainly composed of xylenes, on ZSM-11 more
C –C aromatics are produced [11]. The differ-
9 10
ence in shape-selectivity is attributed to the relative
dimensions of the channel intersections and to the
difference in the relative length of the straight
( ZSM-5, ZSM-11) and tortuous channels
( ZSM-5). Furthermore, since ZSM-11 contains
only one type of channel, the molecular traffic
control shape-selectivity should, in principle, not
occur in this catalyst. This provides a possible
explanation for the higher yield of polysubstituted
20 M. Stöcker / Microporous and Mesoporous Materials 29 (1999) 3–48
aromatics when using ZSM-11: the methanol reac-
tant and aromatic products cannot avoid counter-
diffusion as in ZSM-5, and this increases the
probability of alkylation of the aromatics [11].
Ione et al. [165] studied the properties of
ZSM-11 type metallosilicates in the conversion of
methanol to olefins: Al-ZSM-11 proved to be the
most active and selective catalyst in this reaction
compared to other metal-substituted ZSM-11 sys-
tems. Chang et al. [212] patented the application
of ZSM-48 (high silica medium-pore zeolite) for
the production of olefins from methanol or
dimethyl ether. At high conversion and at temper-
atures lower than those needed to obtain compara-
ble product distributions with ZSM-5, the reactor
effluent consisted mainly of olefins. The higher
olefin selectivity obtained with ZSM-48 are proba-
bly taken as conditions optimal for olefin pro-
duction on ZSM-48 and for gasoline production
on ZSM-5. Yet, from the product distribution it
can be deduced that ZSM-5 is far more active than
ZSM-48. The major difference is found in the
production of higher molecular weight olefins,
which is significantly higher on ZSM-48. In addi-
tion, fewer aromatics are formed on ZSM-48. The
high yield of paraffins in conjunction with the low
yield of aromatics is indicative of severe coke
laydown. Indeed, the deactivation of ZSM-48 with
its one-dimensional pore structure was much faster
than that of ZSM-5 [11,212].
Zeolite EU-2, patented by Casci et al. [213], is
another medium-pore high silica zeolite. When
synthesized with a Si/Al ratio of at least 120,
ZSM-48 is isostructural with zeolite EU-2 [214].
A high selectivity towards propylene and butene
and a low selectivity towards aromatics were
reported in the conversion of methanol to hydro-
carbons on zeolite EU-2 [11,213].
3.1.3. Small-pore microporous/zeolitic materials
Chang et al. [215] claimed in a patent the
discovery of chabazite, erionite, zeolite T and
zeolite ZK-5 as active catalysts for the conversion
of methanol to light olefins. The light olefin con-
centration in the hydrocarbon fraction was always
less than 60 wt% at 100% methanol conversion.
The hydrocarbon fraction became richer in light
olefins as the conversion of methanol decreased.
Hydrocarbon fractions with more than 80 wt% of
light olefins were obtained with a dealuminated
H-erionite [4,11,215,216 ]. Dealuminated chaba-
zite-type catalysts (Si/Al ratio of about 10) gave
molar selectivities towards light olefins of up to
94% at 100% methanol conversion, according to a
study performed by Cartlidge and Patel [217].
Wunder and Leupold [218] applied a mixture of
Mn-exchanged chabazite and erionite zeolites,
obtaining a hydrocarbon fraction containing
37.1% ethylene, 26.5% propylene and 2.7% butene
at 90% conversion of methanol (feedstock —
70:30 vol% mixture of methanol–water; reaction
temperature, 400°C ). The selectivity towards ethy-
lene and propylene was higher than when normal
H-forms of these zeolites were applied. The same
group compared the chabazite type zeolites with
pentasils, concluding with a smaller tendency of
the latter zeolites to form coke, whereas the small-
pore zeolites revealed a higher olefin selectivity
[219]. Cation exchanged chabazites were used by
Singh and Anthony [220], who obtained yields of
ethylene, propylene and propane in the range of
about 35, 30 and 25%, respectively, in the metha-
nol-to-hydrocarbons reaction. The deactivation by
coke was fast [221].
Kljueva et al. [122] evaluated the acidic and
catalytic properties of isomorphously substituted
erionite implementing B, Ga and Fe atoms. The
creation of new acid centers led to catalysts with
a lower hydrogen transfer capacity, resulting in
enhanced selectivities towards lighter olefins due
to a lower olefin conversion into paraffins. TMA
and H-offretite calcined at 450°C have been
reported with a certain activity to mainly form
propylene, propane, n-butane and n-butene in the
conversion of methanol into hydrocarbons [222].
The methanol conversion on zeolite H–T
(intergrowth of erionite–offretite) was monitored
by Ceckiewicz at 400°C: the products were mainly
ethylene, propylene, propane, C -C hydrocarbons
4 5
and dimethyl ether with a methanol conversion of
84.5% [85,223,224]. Corresponding results were
obtained by Gubish and Bandermann [225], using
the same type of zeolite.
A number of patents exist dealing with the
manufacture of light olefins from methanol con-
taining feedstocks, applying erionite, TMA-offret-
 M. Stöcker / Microporous and Mesoporous Materials 29 (1999) 3–48
ite, zeolite T, clinoptilolite or ZSM-34 as catalysts
[226–231]. Givens et al. [226,227] claim that the
use of steam as diluent enhanced the selectivity for
ethylene. Hydrocarbon fractions containing up to
90 wt% of light olefins were reported for ZSM-34.
Inui and Takegami [232] and Inui et al.
[233,234] have studied the influence of the crystal-
lization conditions of ZSM-34 as catalyst for the
MTO reaction. They found that an optimum selec-
tivity was obtained with ZSM-34 crystallized for
25–39 days at 100°C.
Modified clinoptilolite zeolites were applied by
several authors, both ion-exchanged and natural
samples, which showed lower activity than the
former ones [235,236 ]. Hydrocarbon fractions
containing up to 84.6 wt% of lower olefins were
observed at almost 100% methanol conversion.
FU-1 zeolite was used both in its sodium and
H-forms. Moderate light olefin selectivities were
obtained for H-FU-1 zeolite at 450°C: 10 wt%
ethylene, 26 wt% propylene and 38 wt% butenes,
besides paraffins. However, the sodium form of
FU-1 showed negligible activity in the methanol-
to-hydrocarbons reaction [237].
Sigma-1 possesses a high activity for methanol
conversion and a high selectivity for light olefins
at 400°C: the main products obtained were ethy-
lene and propylene. The hydrocarbon fraction
consisted of up to 78% of lower olefins (19%
ethylene, 46% propylene and 13% butenes) whereas
no aromatic compounds were detected in the pro-
duct [238].
Highly selective conversion of light olefins has
been reported by Kaiser [239–243] using SAPO
molecular sieves. Especially SAPO-17 and
SAPO-34 have shown a very high selectivity for
light olefins at almost 100% methanol conversion
[239,243–246 ]. The high activity is related to the
Al-OH group with a vibration frequency at about
3600 cm−1 [247]. With SAPO-34 combined molar
selectivities to light olefins up to about 96% at
complete methanol conversion to hydrocarbons
were observed [temperature 375°C–450°C, atmo-
spheric pressure, WHSV (methanol ) 0.83–
0.87 h−1]. Very low yields of methane and other
saturated hydrocarbons were found. Increasing the
temperature results in a smooth increase in selectiv-
ity to ethylene (as high as 61%). The catalysts are
21
further characterized by improved life time before
deactivation through coke formation. Deactivated
catalysts are fully restored through air regenera-
tion. The crystallinity of the molecular sieve is
retained during methanol conversion and regenera-
tion [239,248]. SAPO-16 and SAPO-44 have been
used as catalysts for the conversion of methanol
to hydrocarbons as well [240,243,249]. However,
the methanol conversion was only 51% at 425°C
in the case of SAPO-16. Furthermore, Kaiser
applied metalloaluminophosphates (MeAPO) and
metallosilicoaluminophosphates (MeAPSO) as
well in order to form light olefins from a 70:30 wt%
water–methanol mixture [250,251]. MgAPO-34,
CoAPSO-34 and MnAPO-34 can completely con-
vert methanol, but methane and carbon dioxide
selectivities were high, indicating that sintering
occurred during pretreatment of the samples [11].
CoAPO-34 showed the following product distribu-
tion (in mol%) at 425°C [ WHSV (methanol ):
0.94 h−1, reaction time: 4.8 h]: ethylene 45.3%,
ethane 0.8%, propylene 27.1%, butenes 8.3%,
methane 6.2%, CO 10.0%, traces of propane and
2
C –C hydrocarbons (olefin selectivity: 80.7%)
5 6
[251].
3.2. Non-microporous/non-zeolitic materials
Most of the work concerning the conversion of
methanol to hydrocarbons has been done on
microporous/zeolitic materials. However, the con-
version of dimethyl ether and methanol was inves-
tigated over several salts of 12-tungstophosphoric
acid, H PW O , at 290°C [252]. For acid salts
3 12 40
of Na, the catalytic activity decreased in parallel
with the acidity as the Na content increased.
However, the carbon number distribution and the
olefin/alkane ratio of the resulting hydrocarbon
mixture were almost independent of the Na
content. These results indicate that the acidity
determines the activity, but its effect on the selectiv-
ity is not significant. Light olefin selectivities in the
range of up to 65% have been reported by the
authors [252].
Moffat [253] studied the methanol conversion
to hydrocarbons on 12-tungstophosphoric acid
compounds (H PW O ) as well. The selectivity
3 12 40
to hydrocarbons other than methane was found
22 M. Stöcker / Microporous and Mesoporous Materials 29 (1999) 3–48
to depend on the reaction temperature and the
residence time as well as on the pretreatment
conditions. It turned out that at low residence
times the predominant product was dimethyl ether
while at high residence times hydrocarbons larger
than methane were evident [253]. The conversion
of methanol to hydrocarbons on Aerosil sup-
ported Ag (SiW O ) catalysts were followed by
4 12 40
Ehwald et al. [254] who showed that the support
had a stabilizing effect on the catalytic activity.
Best results with respect to the production of
olefins and other hydrocarbons were obtained in
the medium range of surface concentrations of the
active component. Their results indicated that the
deposition of coke causing catalytic deactivation
took place predominantly at the exterior surface
of the catalyst, whereas active sites within the pore
system remained untouched by deactivation [254].
The same group reported on the investigation
of methanol to hydrocarbons using alumina –
supported H (SiW O ) catalysts [255]. Two
4 12 40
different types of (SiW O )4− anions exist on the
12 40
surface of the catalysts, depending on the concen-
tration of the heteropoly compound. Increasing
the H (SiW O ) concentration from 5 to 40 wt%
4 12 40
of W results mainly in an increase in the surface
density of Brønsted acid sites, whereas the distribu-
tion of their acid strength is only slightly shifted
towards higher values. From the dependence of
the yield of the hydrocarbon on the H
4
(SiW O ) content of the catalysts, it was con-
12 40
cluded that under the conditions applied hydro-
carbon formation from methanol occurred only
on adjacent acid groups, the density of which was
evaluated to be approximately 1 mmol m−2 [255].
However, in both publications the formation of
ethylene and propylene under these conditions
(reaction temperature 300°C, LHSV 0.1 h−1, feeds-
tock: methanol–nitrogen in a molar ratio of 1:1,
methanol conversion higher than 76%) was only
minor compared with the production of C+ com-
4
pounds including at large part of aromatics
[254,255].
H PW O catalysts have been patented both
3 12 40
as neat as well as lanthanide metal modified sys-
tems, and typical olefin selectivities for ethylene,
propylene and butenes were 18.1, 21.9 and 11.0%,
respectively (catalyst: H PW O , reaction condi-
3 12 40
tions: temperature 300°C, LHSV 0.2 h−1, feed:
methanol–helium containing 26.2 mol% methanol,
methanol conversion of 77%) [256 ].
4. Recent studies of the methanol-to-hydrocarbons
reaction
The work published in the present decade is
reviewed in this section, which covers the more
recent developments related to the topic of this
review. However, the ‘border line’ between the
literature covered in Section 3 (Summary of the
early studies) and the present section is not strictly
a certain year rather than the content of suitable
publications and their relations to each other.
Nevertheless, a rough distribution in earlier and
recent studies should help the reader to follow the
main lines of the development. The same splitting
has been chosen as in Section 3.
4.1. Microporous/zeolitic materials
4.1.1. Large-pore microporous/zeolitic materials
Following the recent literature there is no doubt
that the focus concerning investigations of cata-
lysts suitable for the methanol conversion to
hydrocarbons has been on the small- and medium-
pore-type microporous/zeolitic materials. How-
ever, a few studies have been published dealing
with large-pore type zeolites or other microporous
materials.
A process for converting a feedstock consisting
of a mixture of methanol–water (molar ratio of
1:4) to light olefins using ECR-1 (complex syn-
thetic zeolite having structural similarities to both
naturally occurring mordenite and mazzite),
mazmorite (consisting of complex intergrown syn-
thetic permutations of ECR-1) and/or ECR-18
(synthetic paulingite-type zeolite) has been pat-
ented by Janssen and Vaughan [257]. However, at
450°C and a WHSV of 1.0 h−1, the obtained olefin
selectivities were in the range of 27 wt% for ethy-
lene and 11 wt% for propylene ( ECR-1) as well as
38 wt% for ethylene and 30 wt% for propylene
( ECR-18).
Higher selectivities to light olefins were obtained
by applying dealuminated mordenite (Si/Al ratio
 M. Stöcker / Microporous and Mesoporous Materials 29 (1999) 3–48
of 80) in the conversion of methanol to hydro-
carbons at 480°C using a water–methanol mixture
(feed ratio – 70:30 wt%): up to 81% with a metha-
nol conversion of 97% [258]. The durable activity
of the dealuminated mordenites and the selectivity
to light alkenes can also be improved by decreasing
the partial pressure of methanol and adding more
water to the feed. The decrease of the partial
pressure of methanol leads to a higher yield of
light alkenes and a lower yield of alkanes, oligo-
mers and aromatics. Water competes with light
olefins for the Brønsted and Lewis acid sites. The
adsorption of water on these acid centers reduces
their strength and concentration and, thereby, the
probability of their interaction with hydrocarbons.
As a consequence, the initial conversion of light
olefins, mainly propylene, into oligomers, aro-
matics and coke decreases. Both the lower yield of
coke precursors and the weaker interaction
between coke precursors and acid sites reduces the
deactivation by coke. At the early stages of the
reaction, the gradual reduction of the number of
acid sites decreases the probability of their inter-
action with light alkene molecules. Thereby, the
conversion of light alkenes into alkanes and aro-
matics decreases and the selectivity to light alkenes
increases [258].
The acid strength and catalytic activity of
SAPO-44 and the isomorphously substituted
MeAPSO-44 (Me=Co, Mn, Cr, Zn, Mg) molecu-
lar sieves in the methanol to hydrocarbons reaction
were measured by Hočevar et al. [259]. In addition,
the results were compared with those of AlPO -5
4
and AlPO -14 samples. The acidity strength of the
4
samples has been determined qualitatively from
the temperatures of dimethyl ether desorption
peaks, and the following sequence has been
obtained:
MnAPSO−44>CoAPSO−44~ZnAPSO−44
>MgAPSO−44>CrAPSO−44
>SAPO−44>AlPO −5
4
~AlPO −14
4 mechanisms with respect to the formation of
The highest selectivity to ethylene formation
among these catalysts has been found for
CoAPSO-44. The selectivities to ethylene of
23
SAPO-44 and MeAPSO-44 (Me=Co, Mn, Cr)
samples are about three times higher than the
selectivities of SAPO-34 and MeAPSO-34 (Me=
Co, Mn, Cr) [259].
4.1.2. Medium-pore microporous/zeolitic materials
The methanol to gasoline conversion over
H-ZSM-5 has been studied by using the ‘temper-
ature programmed surface reaction ( TPSR)’ tech-
nique [260,261]. This technique is able to delineate
the two steps in the process: the dehydration of
methanol to dimethyl ether and the subsequent
conversion of dimethyl ether to hydrocarbons. The
activation barriers associated with each step were
evaluated from the TPSR profiles and are 108 and
195 kJ mol−1, respectively. The methanol desorp-
tion profiles showed considerable changes with the
amount of methanol molecules adsorbed per
Brønsted site of zeolite (see Fig. 4 which shows a
typical TPSR of three methanol molecules
adsorbed per Brønsted site of H-ZSM-5).
Furthermore, the authors compared this metha-
nol to hydrocarbons reaction (over H-ZSM-5)
with the corresponding gas phase reaction, and
the results are shown in Fig. 5.
Fig. 5 shows that, once the protonated cluster is
formed, the activation energies for the formation
of dimethyl ether as calculated for the gas phase
and as measured for H-ZSM-5 are comparable in
magnitude, viz. 111 and 107.5 kJ mol−1, respec-
tively. The main difference between the gas phase
and the catalytic processes lies in the energetics of
the formation of the protonated methanol cluster:
while the heat of formation of the active catalytic
species [(CH OH ) H+-ZSM-5−] is exothermic, the
3 n
gas phase heat of formation of (CH OH ) H+ is
3 n
strongly endothermic [260,261].
Density functional theory calculations have been
used to determine the transition states and adsorp-
tion complexes of reactants, intermediates and
products as well as the corresponding activation
barriers and adsorption energies of the numerous
steps involved in the methanol to hydrocarbons
reaction on an acidic zeolite [262]. Two different
dimethyl ether from methanol have been consid-
ered: the first proceeds via an associative inter-
action between two methanol molecules,
24 M. Stöcker / Microporous and Mesoporous Materials 29 (1999) 3–48

Fig. 4. Temperature programmed surface reaction (TPSR) of methanol over H-ZSM-5. The profiles are for methanol (m/e 31) (Ω),
dimethylether (m/e 45) (–––), water (m/e 18) (#), C -C aliphatic hydrocarbons (m/e 43) ($) and aromatic hydrocarbons (m/e 91)
3 5
(%). The solid line is the fitted profile for water evolution (reproduced by permission of Chemie, Weinheim).

generating directly dimethyl ether, while the other
proceeds via a methoxy surface species intermedi-
ate. The presence of water lowers the activation
barrier of the last mechanism by more than
50 kJ mol−1 [262]. Furthermore, the effect of
making the zeolitic cluster slightly more acidic (by
lengthening the Si–H bond distances) over the
activation barriers of dimethyl ether formation has
been studied using density functional theory calcu-
lations. Changes in the order of 5 kJ mol−1 were
observed [263].
The adsorption structures and thermally induced
surface chemistry of methanol adsorbed on
H-ZSM-5 was studied by means of IR spectro-
scopy, mass spectrometry and thermogravimetry
conducted by Mirth and Lercher [264]. At low
equilibrium pressures (up to 10−3 mbar) methanol
interacts selectively with the Brønsted acid sites of
the zeolite by forming a methoxonium ion which
can be oriented in two different forms. The meth-
oxonium ion points either with its methyl or with
its OH+ group to the SiO-Al site of the zeolite.
2
Upon increasing the alcohol pressure up to 1 mbar,
protonized clusters of about three strongly
hydrogen bonded molecules were observed. During
temperature desorption most of the protonated
methanol desorbed without reaction below 250°C.
Subsequently, two types of methoxy groups were
present, which were generated by reaction of meth-
anol with Si-OH-Al and with terminal silanol
groups, respectively. Above 200°C, dimethyl ether
was produced from reactions of desorbing metha-
nol with methoxonium ions or methoxy groups
[264].
Chinese researchers suggested that lower olefins
mainly originated from the cracking of higher
olefins (or their precursors) formed through an
autocatalytic homologation reaction when apply-
ing H-ZSM-5 in the MTO reaction [265], whereas
a ‘new zeolite’ developed at the Nanjing University
showed high activity, good selectivity and stability
in the MTG reaction [266 ]. However, the structure
of the ‘new zeolite’ was not disclosed by the
authors!
 M. Stöcker / Microporous and Mesoporous Materials 29 (1999) 3–48
Fig. 5. One-dimensional potential energy diagram for the pri-
mary step of the MTG process (methanol to dimethylether and
water). The top part of the figure is for the gas phase reaction,
whereas the bottom half is the reaction over H-ZSM-5. All
figures are in kJ mol−1 (reproduced by permission of Chemie,
Weinheim).
The catalyst life and performance of calcium
containing aluminoborosilicates with various crys-
tal sizes for methanol conversion to light olefins
were studied by Kawamura et al. [267–269]. The
crystal size was controlled by adding boric acid.
For the zeolites with similar Si/Al and Ca/Al ratios,
the initial catalyst activity was independent of the
crystal size and was the same as that of the calcium
containing aluminosilicates synthesized in the
absence of boric acid which exhibited the best
catalyst performance for production of light olefins
from methanol. However, the catalyst life of the
calcium containing aluminoborosilicates, defined
as the time during which methanol conversion is
100% with no residual dimethyl ether and with
light olefin yields of >50%, was extended by a
decrease of the crystal size. The amount of coke
deposited on the zeolite after the reaction increased
with decreasing crystal sizes. The rate of coke
formation was independent of the crystal size. As
the decrease in the crystal size corresponds to the
increase in the outer surface per gram of zeolite,
25
these results indicate that deactivation of the zeo-
lites is attributable to the poisoning of the outer
surface by coke deposition. From the fact that the
rate of coke formation is independent of the zeolite
crystal size, it was concluded that coke or its
precursors are formed in the zeolite crystal and
migrate to the outer surface of the zeolite crystal.
Finally, the acidic properties (investigated by
means of ammonia-TPD and diffuse reflectance
FT IR spectroscopy) of the calcium containing
aluminoborosilicates synthesized in the presence
of boric acid were similar to those of calcium
containing aluminosilicates synthesized in the
absence of boric acid [267,269].
ZSM-5 type zeolites containing alkaline earth
metals were hydrothermally prepared from synthe-
sis mixtures containing alkaline earth metal salts.
By this method, the amount of alkaline earth
metals occluded in ZSM-5 was more than that of
the alkaline earth introduced by the conventional
ion exchange method [270]. The chemical state of
the alkaline earth metals in these systems were
studied by diffuse reflectance FT IR spectroscopy,
and the spectra of the OH regions are shown
in Fig. 6.
The IR spectrum of H-ZSM-5 was characterized
by two well-defined signals at 3605 and
3740 cm−1, assigned to the acidic bridged OH of
Si(OH )Al and to the terminal SiOH, respectively.
The broad peak at near 3500 cm−1 is attributed to
hydrogen bonding between adjacent hydroxyl
groups. Except for Mg-ZSM-5, intensities of all of
these signals for alkaline earth metal containing
ZSM-5 were very weak as compared with those of
H-ZSM-5. It was found that these alkaline earth
metal containing ZSM-5 zeolites revealed a high
selectivity to light olefins at temperatures above
500°C, where ethylene and propylene were formed
in yields greater than 50%. The catalyst life of
these systems could be greatly extended by modifi-
cation with alkaline earth carbonates to suppress
coking and dealumination. Furthermore, it was
found that calcium phosphate modified micro-
crystalline H-ZSM-5 synthesized from the synthe-
sis mixtures with low H O/SiO ratios showed an
2 2
excellent catalyst performance [270].
Howden et al. investigated a number of factors
influencing the light olefin selectivity during the
26 M. Stöcker / Microporous and Mesoporous Materials 29 (1999) 3–48

Table 3
Methanol-to-gasoline hydrocarbon yields for different reactor
designs (according to Ref. [272])

Fixed bed Fluidized bed

reactor reactor

Hydrocarbon product [wt %]

Light gas 1.3 4.3
Propane 4.6 4.4
Propylene 0.2 4.3
i-Butane 8.8 11.0
n-Butane 2.7 2.0
Butenes 1.1 5.8
C+ Gasoline 81.3 68.2
5
C+ Gasoline 83.9 91.2
5
(including alkylate)

Gasoline octane numbers

RON 93 95
MON 83 85

in a cost advantage over fixed bed MTG of at

Fig. 6. FT IR Spectra of various zeolites (SiO /Al O =200)
2 2 3
(reproduced by permission of The Japan Petroleum Institute,
Tokyo).
conversion of methanol over ZSM-5 [271]. The
authors found that the most important factors
influencing olefin selectivity are the temperature of
the reaction and the Si/Al ratio of the ZSM-5. For
small laboratory scale experiments, they found it
feasible to achieve a light olefin selectivity around
65%, of which about 15% would be ethylene, by
adopting the following parameters (approximate
values):
Partial pressure of methanol 0.2 bar
Reaction temperature 450°C
SiO /Al O mol ratio of ZSM-5 250:1
2 2 3
Crystallite size <5 mm
Mobil published a comparison of their fixed bed
versus fluid bed operation results based on the
MTG demonstration plant (4000 t year−1) using
ZSM-5 as catalyst. The MTG hydrocarbon yields
are summarized in Table 3 [6,272].
As shown in Table 3, fluid bed MTG gives
higher yields of higher quality gasoline than fixed
bed MTG. This yield and quality advantage cou-
pled with the improved energy utilization results
least 10% [272].
Catalytic conversion of methanol to light olefins
was monitored using high silica zeolite of the
pentasil type MFI structure by Al-Jarallah et al.
[273]. The reaction was carried out in a fixed bed
reaction set-up at 400°C, WHSV=4 h−1, pressure
of 1 bar and a methanol–nitrogen weight ratio of
2.78. The silicalite zeolite was modified by impreg-
nation with metal nitrates of Ag, Ca, Cd, Cu, Ga,
In, La and Sr to study their effects on the activity
and selectivity of the catalysts to light olefins.
Incorporation of La and Ag led to an improvement
in light alkene selectivity of the silicalite by 18%
and 14%, respectively (see Fig. 7). This was attrib-
uted to enhanced shape selectivity of the silicalite
resulting from reduction of the apparent pore size
of the zeolite channels. The active life-on-stream
was slightly decreased due to coke deposition
[273].
Again a number of recent patents exist covering
the improvement of the ZSM-5 catalyst and/or
process conditions in the methanol-to-hydro-
carbons reaction. The results of this search have
been briefly summarized in Table 4, however,
details can be found in the original patent
literature.
 M. Stöcker / Microporous and Mesoporous Materials 29 (1999) 3–48 27

Fig. 7. Product distribution for various modifications of silicalite (ZSM-5) at 400°C, WHSV 4 h−1 and 2.78 (wt/wt) methanol-to-
nitrogen ratio (reproduced by permission of Elsevier Science B.V., Amsterdam).

Finally, H-Theta-1 zeolite ( TON ) has been pat-
ented as a catalyst for the methanol-to-hydro-
carbons reaction, converting a methanol/1-butene
mixture (82:18 mol% ratio) at 400°C preferentially
to isopentenes [281,282].
In conclusion, an increase in olefin selectivity of
Table 4
Recent patent literature covering the improvement of the
ZSM-5 catalyst and/or process conditions in the methanol-to-
hydrocarbon reaction (1989 or later)
medium-pore zeolites was tried through modera-
tion of their strong acid sites by incorporation of
basic materials like Ca, Mg, Zn, Sr, B and P. As
the selectivity to olefins increased but the activity
decreased, the reaction temperature was raised up
to 600°C from around 400°C. Unfortunately, on
these catalysts and at those higher temperatures,
the major olefin in the products was propylene,
and the most valuable ethylene was formed fairly
little.

Improvement/process attempt Refs. 4.1.3. Small-pore microporous/zeolitic materials

Fe, Al containing ZSM-5
Formulated pentasil type zeolite
Olefinic gasoline and distillate range liquids
Ether-rich fuel production
Conversion of olefins to diesel
Reactivated MTG catalyst
Hydrocarbon dewaxing utilizing a reacti-
vated spent MTG zeolite catalyst
Since the beginning of the 1990s, the main focus
[274]
concerning the catalytic system to be investigated
[275]
[276 ] mostly has been concentrated around the silico-
[277] alumino-phosphate molecular sieve SAPO-34 with
[278] different modifications. Inui in Kyoto has been
[279] involved strongly in this research [283–289].
[280]
Characteristics of various zeolite catalysts for the
light olefin production ( like ZKU-4, Ca-ZSM-5,
28 M. Stöcker / Microporous and Mesoporous Materials 29 (1999) 3–48
Fe-silicate, SAPO-34 and Ni-SAPO-34) were
investigated and summarized (see Fig. 8).
ZKU-4 zeolite has an offretite–erionite
intergrowth structure, and is regarded as a kind
of small-pore zeolite. While narrow pore zeolites
such as chabazite and ZSM-34 were effective for
the methanol to hydrocarbons reaction, these two
catalysts had short lifetimes due to rapid coke
deposition. Inui and coworkers have considerably
improved ZSM-34 type catalysts in both olefin
selectivity and catalyst lifetime by arranging crys-
talline size and uniformity and adding quinoline
in the feed gas, however, the coke formation could
not be prevented completely [284]. Medium pore
size zeolite ZSM-5 had a too strong acidity to
produce light olefins with high selectivity [283].
H-ZSM-5 catalysts, modified with basic materials
( like Ca) are effectively used at higher reaction
temperatures such as 600°C and yield propylene
as the major product by obeying b-scission [284].
However, a certain amount of aromatics was
formed as well. A pentasil Fe-silicate yielded ethy-
lene and propylene almost exclusively, at an equiv-
alent ratio at lower temperatures around 300°C,
Fig. 8. Comparison of hydrocarbon distribution from methanol conversion on various zeolite catalysts (reproduced by permission of
Prof. T. Inui, Kyoto University, Japan).
whereas aromatic compounds were not formed at
all (see Fig. 8).
SAPO-34 has a chabazite structure, but much
weaker acidity than chabazite, and exhibits activity
for methanol to light olefins conversion at a
medium range temperature of around 450°C. Ni
containing SAPO-34 produced ethylene with a
selectivity of 90 at 100% methanol conversion
without significant deactivation. This indicates that
proper acidity control prevents the formation of
aromatics and allows highly selective conversion
of methanol to light olefins [283,284]. The Ni
containing SAPO-34 catalysts were prepared by
adding nickel nitrate to the solution for mixed gel
preparation according to the rapid crystallization
method (4 h). By controlling the uniformity of the
gel mixture, Ni-SAPO-34 crystals with Si/Ni ratios
of 100 and 40 were prepared having a sharp crystal
size distribution around 0.8–0.9 mm. As shown in
Fig. 9, with increasing of Ni-incorporation the acid
strength measured by ammonia-TPD profiles
decreases not only for the strong acid sites but
also for the weak acid sites [289].
The corresponding results for the methanol con-
 M. Stöcker / Microporous and Mesoporous Materials 29 (1999) 3–48
Fig. 9. Ammonia-TPD profiles for SAPO-34 and Ni-SAPO-34
catalysts (reproduced by permission of Elsevier Science B.V.,
Amsterdam).
version to olefins on SAPO-34 and different
Ni-containing SAPO-34 molecular sieves are sum-
marized in Fig. 10.
Ni-SAPO-34 having a Si/Al ratio of 40 exhibited
an extraordinary high ethylene selectivity as high
as 90% at total methanol conversion conditions
[289]. From the extrapolation of the relationship
between the internal acid density of various
Ni-SAPO-34 catalysts prepared by different meth-
ods and the ethylene selectivity at total methanol
conversion, it was concluded that the ethylene
selectivity could arrive at 100% if the internal acid
Fig. 10. Catalytic performance of SAPO-34 and Ni-SAPO-34s in methanol conversion. Reactions conditions: 20% MeOH–80%
nitrogen, GHSV 2000 h−1, temperature: 450°C (reproduced by permission of Elsevier Science B.V., Amsterdam).
29
density could be controlled to be 3.0 mmol m−2
[289].
In the early period of the investigations of MTO
catalysts, small-pore zeolites such as chabazite,
erionite, ZSM-34 and offretite were selected as the
target of the catalysts for this purpose, because
pore openings consisting of eight T-membered
rings were regarded as just fitting the size of small
olefin molecules. Indeed, those small-pore zeolites
gave considerably higher selectivities to ethylene
and propylene, however, rapid deactivation of the
catalyst performance, as a result of coke formation
in the cavities involving the pore channels, could
not be avoided. In order to mitigate the coke
deposition, the acid sites of those materials were
modified by basic materials, but those kinds of
post-modifications were not successful as desired.
It turned out to be quite difficult to neutralize the
acid sites uniformly and adjusting the proper acid
strength for selective olefin formation [289].
Although Ni-SAPO-34 is a small-pore micro-
porous material like chabazite, its acidity was
considerably weaker than that of chabazite and
even SAPO-34. Obviously, this property just fits
for exclusive ethylene formation from methanol
via dimethyl ether, and the consecutive reactions
do not occur. As the oligomerization of ethylene
and aromatization cannot happen on this catalyst,
no coke formation is observed. This provides not
only a large potential to develop a novel ethylene
30 M. Stöcker / Microporous and Mesoporous Materials 29 (1999) 3–48

synthesis process, but also a guiding principle for

the synthesis of other highly shape selective cata-
lysts [287].
Pop et al. [290] investigated the influence of
different operating parameters on the product dis-
tribution of the MTO process in a fixed-bed labora-
tory scale reactor using SAPO-34 as catalyst. They
observed 90% total olefin selectivity and a 61%
ethylene selectivity (435°C and LHSV 1.95 h−1).
Recirculation of dimethyl ether and unreacted
methanol was applied to improve the selectivities
by about 1%. Due to the high catalyst deactivation
rate, the continuous recirculation of the catalyst
in a fluidized bed reactor–regenerator system is
advisable. The proposed reduced kinetic model
could satisfactorily correlate the data at 400°C.
Further data and kinetic parameter calculations
could validate the model versus different operating
conditions [290].
A quantitative description of the active sites in
the dehydrated acid catalyst H-SAPO-34 for the
Fig. 11. IR spectra of Brønsted-OH in H-SAPO-34 at 77 K
conversion of methanol to olefins has been before (curve a) and after (curve b) the adsorption of CO. It is
reported by Smith et al. [291]. Their neutron revealed, using a fitting procedure, that both bands are consti-
diffraction study of the deuterated form of tuted of three components (A, B and C ). The overall fitted
SAPO-34 (D-SAPO-34) revealed two different spectrum is reported on top of the Figure (see also Table 5,
reproduced by permission of J.C. Baltzer Science Publishers,
bridging hydroxyl Brønsted sites. These sites are
Amsterdam).
also identified by IR spectroscopy which distingu-
ishes their acid strength from the shift in O-H
frequencies following adsorption of CO at 77 K scopy were used to characterize Ni-SAPO-34
(see Table 5 and Fig. 11). molecular sieves to be applied in the MTO reac-
Both their powder refinement results of tion. It was established that the Ni ions were all
D-SAPO-34 and the IR study of CO adsorption in tetrahedral, framework sites, and the loosely
of H-SAPO-34 point to a nearly equal occupancy bound extra-framework protons were thought to
of the two acidic protons [291]. be the key components of the catalyst for the
X-ray absorption (near-edge and extended fine highly selective conversion of methanol to ethylene
structure) along with diffuse reflectance IR spectro- [292]. The reported catalytic test results demon-

Table 5
IR spectroscopic features of the Brønsted OH groups in H-SAPO-34 before and after CO adsorption (according to Ref. [291])a

OH group n (cm−1) Areab OH,CO n (cm−1) Areab

OH OH-CO
A 3630 7.8 A∞ 3343 57.6
B 3625 3.1 B∞ 3276 10.2
C 3601 10.6 C∞ 3411 26.7
Fit A + B + C — 21.5 Fit A+B+C — 94.5
Curve aa — 20.8 Curve ba — 97.1

aRefers to Fig. 11.

bIntegrated intensity of the adsorption bands.
 M. Stöcker / Microporous and Mesoporous Materials 29 (1999) 3–48
strate a clear effect of the temperature on the
product distribution of the methanol conversion
over Ni-SAPO-34 (Al/Ni ratio of 58.7) after 2 h
on stream: temperature increase from 250 to 450°C
increases the methanol conversion (from 90.5 to
95.5%), whereas the selectivity to ethylene
decreases dramatically from 94.5 to 60.5% [292].
The catalytic activity and selectivity of
as-synthesized and modified samples of SAPO-34
and Me-APSO-34 (MeNCo, Ni) for the conver-
sion of methanol to olefins have been investigated
by van Niekerk et al. [293]. The catalytic perfor-
mance for the conversion of methanol to light
olefins of all the catalyst samples prepared was
found to be closely related to the number of strong
acid sites present as determined through ammonia-
TPD. Mild steaming, encountered during deep-
bed calcination, increased the relative crystallinity
and the lifetime of SAPO-34 due to the formation
of stronger acid sites probably on the external
surface of the crystallites as well as the catalytic
performance. Selectivities to light olefins were typi-
cal of those previously reported (up to 92 wt%)
and essentially constant for all the samples investi-
gated. The almost complete absence of C+ olefins
5
was ascribed to the so-called ‘cage-effect’ which
imposes a restriction on the formation of those
compounds. Dilution of the methanol with water
as opposed to nitrogen increased the catalyst utili-
zation value three-fold and reduced the rate of
coke formation during reaction. Treatments such
as steaming, silanization and poisoning of strong
sites by ammonia all reduced the number of strong
acid sites and, thus, reduced catalytic perfor-
mance [293].
The selectivity and stability of the H-SAPO-34
catalyst for the methanol to olefins reaction was
much better than those of erionite and erionite–
offretite intergrowth type zeolites as reported by
Liang et al. [249]. These authors found that after
55 regenerations, H-SAPO-34 retains its catalytic
performance (under the reaction conditions of
450°C, WHSV of 6.9 h−1 and methanol/water
ratio of 20:80) for the methanol conversion, the
total hydrocarbon yield, the content of light olefins
and the ethylene formation level in the hydro-
carbon products at values of 100, 98.6, 91.7 and
56.6%, respectively [249].
31
The hydrothermal treatment of SAPO-34 at
temperatures in excess of 700°C for periods suffi-
cient to destroy a large portion of their acid sites
while retaining at least 80% of their crystallinity,
was found to result in a catalyst for converting
methanol to lower olefins having an increased
catalyst lifetime, increased selectivity for light ole-
fins formation and decreased selectivity for paraffin
production compared with the untreated SAPO-34
starting material [294].
The methanol conversion to light olefins was
investigated using different SAPO type molecular
sieves by Chen et al. [295]. At a temperature of
500°C and a WHSV of 1.5 h−1 SAPO-34 showed
the highest selectivity towards formation of ethy-
lene and propylene (almost 90%), followed by
SAPO-18 (ca. 80%), SAPO-17 (around 72%) and
finally SAPO-5 (about 53%). The bridging
Si-OH-Al groups in these SAPOs were monitored
by means of diffuse reflectance IR spectroscopy
(DRIFT ), and the strength of the Brønsted acid
sites was measured by ammonia-TPD resulting in
the following order of Brønsted acid site strength:
SAPO-5<SAPO-17<SAPO-18<SAPO-34, the
last one having cages smaller than those of SAPO-5
and SAPO-17. The deactivation rate decreased
in the order SAPO-17>SAPO-34>SAPO-18>
SAPO-5 [295]. Yang et al. [296 ] compared the
catalytic behavior of the small-, medium- and
large-pore SAPO-type materials in the methanol
conversion to hydrocarbons. They concluded that
SAPO-34 favors the formation of lower olefins,
SAPO-11 the production of C and C hydro-
5 6
carbons and SAPO-5 the formation of C+ hydro-
7
carbons [296 ]. The selectivities towards lower
olefins increased with increasing temperature over
SAPO-34 and SAPO-5. The effect of contact time
was not significant on SAPO-34 and SAPO-11
under the reaction conditions studied (reaction
temperatures, 350–400°C; WHSV, 0.4–0.9 h−1).
The selectivity towards lower olefins increased with
increasing silicon content of SAPO-11. Lowering
the partial pressure of methanol increased the
selectivity towards lower olefins over SAPO-5
[296 ].
The reaction products of the methanol conver-
sion to olefins over H-SAPO-34, H-chabazite and
H-ZSM-5 was compared by Nawaz et al. [297]. A
32 M. Stöcker / Microporous and Mesoporous Materials 29 (1999) 3–48
strongly shape-selective eight-membered ring
microporous material was needed to suppress the
formation of aromatics, and thereby get the highest
olefins selectivity. An olefin yield slightly above
80 mol% at close to 100% conversion of methanol
could be obtained with the H-SAPO-34 catalyst
(reaction conditions: temperature 400°C, WHSV:
1 h−1, feed consisting of 40 mol% methanol ). Fast
deactivation was the main limitation in the MTO
reaction. The deactivation rate, which was much
smaller in the case of H-ZSM-5, appears partly
structure dependent, but a large difference in deac-
tivation rate between the isostructural catalysts
H-SAPO-34 and H-chabazite was observed
(H-chabazite deactivated much faster than
H-SAPO-34) due to the higher acid site content
of H-chabazite compared with H-SAPO-34 [297].
The same group investigated SAPO-17 and its
isostructural zeolite erionite with respect to the
catalytic behavior in the methanol to olefins reac-
tion [298]. SAPO-17 proved superior to erionite
both concerning the olefin selectivity and the cata-
lyst lifetime. Ethylene constituted almost 70 mol%
and propylene almost 20 mol% of the product,
compared with a maximum of 40 mol% ethylene
and 30 mol% propylene with erionite (at 425°C
reaction temperature and 0.5 h−1 WHSV ).
SAPO-17 was active for up to 20 h, whereas erio-
nite only for less than 2 h. Experiments with
SAPO-17 in the reaction temperature range of
350–475°C showed an optimum behavior around
425°C. Outside this temperature, the lifetime and
selectivity towards lower olefins deteriorated
rapidly. A deactivated sample of SAPO-17 could
be restored to full activity by calcination in air at
500–550°C [298]. A number of catalytic test
experiments at 400°C were performed on SAPO-17
where the partial pressure of methanol was varied.
From the plots of methanol conversion versus time
on stream ( Fig. 12), it is apparent that the catalyst
lifetime increased when the methanol pressure was
lowered. The yield of hydrocarbons before regener-
ation became necessary was, however, essentially
constant. This may suggest that the coke formation
is mechanistically connected with the hydrocarbon
formation [298].
In spite of the fact that SAPO-34 has a higher
acid strength than SAPO-17, the latter converts
Fig. 12. Methanol conversion over SAPO-17 at various partial
pressures at 400°C.
methanol more deeply than SAPO-34. This must
be attributed to their different pore structures.
SAPO-17 contains partly the SAPO-5 structure
that is similar to the mordenite structure. This
permits formation of fused-ring aromatics, and
furthermore, it contains a one-dimensional pore
structure and therefore, effective diffusion is very
low [285]. These facts might be the reason for the
higher deactivation rate of SAPO-17 compared
with SAPO-34.
The activity, selectivity and coke formation on
SAPO-34 and H-ZSM-5 at 425°C in the conversion
of methanol to hydrocarbons have been studied
using a microbalance reactor [299]. A selectivity
to light olefins of 91 mol% at 100% conversion of
methanol into hydrocarbons was observed over
SAPO-34, but the catalyst suffered from rapid
deactivation. H-ZSM-5 showed a lower activity,
lower selectivity to light olefins and a lower rate
of deactivation. Co-feeding methanol and ethylene
or propylene showed that methanol is responsible
for the formation of methane and ethylene, and
that added ethylene and propylene participate in
secondary reactions [299].
SAPO-18 and its MeAPO analogues (MeNMg,
Zn), which are isostructural with AlPO -18, are
4
structurally closely related to chabazite/SAPO-34.
Those AEI compounds have been investigated in
the methanol to olefins reaction, and SAPO-18
revealed catalytic properties comparable to
SAPO-34: 47 wt% selectivity towards ethylene and
40 wt% selectivity towards propylene at t
DME
(breakthrough of dimethyl ether defined as the
time span with more than 99% conversion of
 M. Stöcker / Microporous and Mesoporous Materials 29 (1999) 3–48
methanol and dimethyl ether). The catalytic test
conditions were as follows: temperature 420°C,
WHSV of 1 h−1, feed: methanol diluted with 60%
nitrogen [300]. MgAPO-18 and ZnAPO-18
showed much higher selectivities to propylene and
butenes and shorter catalyst lifetimes than
SAPO-18. AlPO -18 was inactive as MTO catalyst.
4
The SAPO- and MeAPO-18 systems formed thin
plates of the same dimensions (crystal size
0.1–2.0 mm) which was fortunate for the study and
comparison of catalytic activity, since diffusion
induced effects should be equal [300].
MeAPSO molecular sieves (MeNTi, Fe, Zn,
Mg, Mn, Co and others) were patented by UOP
for a fluidized-bed-based methanol to olefins reac-
tion, providing mainly high propylene selectivities
(up to 53 wt%) at 480°C and a WHSV of around
1.85 h−1 using a methanol/nitrogen feed consisting
of about 78.5 mol% nitrogen [301].
4.2. Composite materials
Only limited and uncomplete information has
been available concerning the published material
related to the application of composite catalysts
for the methanol-to-hydrocarbons process technol-
ogy. A Soviet high-silica zeolite TsVM (pentasil-
type structure) was modified by Rostanin et al.
[302] with respect to the removal of undercrystal-
lized silicate fragments present at the surface of
the zeolite crystals. This catalyst was used for the
manufacture of high-octane gasoline at 370–380°C
applying a methanol–water feedstock with various
compositions and recirculation of the hydro-
carbon gases.
The surface acidity, surface structure and metha-
nol to olefins catalytic activity of Fe O /ACDM
2 3
zeolite catalysts were monitored by Qinghua et al.
[303], however, without describing the ACDM
zeolite system. Their results showed that calcina-
tion treatment did not influence the crystallinity
of the H-ACDM zeolite, and impregnation treat-
ment did not destroy the supporting zeolite. With
increasing Fe content and higher calcination tem-
peratures, the number of acid sites and the amount
ratio of Brønsted/Lewis sites on the zeolite surface
decreased as shown by ammonia-TPD and
pyridine-IR. In addition, the conversion rate of
33
methanol and the selectivity to light olefins
decreased as well, however, both of them were
higher than those for H-ACDM. Besides, the
results of the Mössbauer spectra revealed that
Fe O took part in the MTO reaction and was
2 3
partly reduced to FeO [303].
Finally, a fluid catalytic cracking process for the
conversion of a hydrocarbonaceous feedstock has
been disclosed. The process results in an increased
yield of lower olefins, and methanol is typically
co-processed with the feedstock to obtain a proper
feed dispersion prior to injection into the FCC
reactor. During cracking of the feedstock,
co-cracking of the methanol dispersant to lower
olefins occurs, resulting in an increased yield of
light alkenes, typically ethylene and propylene.
Suitably, an amount of methanol of up to 10 wt%
on feed is used, preferably 3.5–7.5 wt% on feed.
The temperature employed in the FCC unit is
greater than 400°C, suitably from 500 to 800°C.
The catalyst comprises a zeolite with a pore diame-
ter of 0.3–0.7 nm commonly used for FCC, for
instance ZSM-5. The zeolite catalyst is optionally
present as a physical mixture with a second sepa-
rate zeolite with a pore diameter above 0.7 nm,
for instance a physical mixture of ZSM-5 and
zeolite Y [304].
5. Catalyst deactivation, coke formation and
regeneration
The porous structure of large-pore molecular
sieves can easily host carbonaceous residues which
usually cause catalyst deactivation. This loss of
activity by coke formation is rather rapid with
mordenite [116 ] due to the blockage of the uniform
non-interconnecting channels by coke. Zeolites X
and Y can initially accommodate some coke in the
supercages without blockage of the pore structure,
whereas SAPO-5, MAPO-5 and MeAPO-5 (one-
dimensional pore structure) deactivate in a similar
manner as mordenite [11]. Swabb and Gates
studied the deactivation of H-mordenite in the
conversion of methanol in the range of 100–240°C
[38]. Olefin polymerization occurred on the strong
acid sites, and these oligomers were strongly
adsorbed. Traces of lower olefins were only
34 M. Stöcker / Microporous and Mesoporous Materials 29 (1999) 3–48
detected at 240°C. The deactivation of H-
mordenite seemed to be more related to coverage
of acid sites than to pore-blockage [11].
H-mordenite and H-ZSM-5 catalysts used in the
conversion of 13C-enriched methanol (90%) were
investigated by in situ 13C CP MAS NMR spectro-
scopy in order to monitor the formation of carbo-
naceous residues [305]. Depending on the zeolite,
differences in the nature of the carbonaceous resi-
dues were detected: organic residues on H-ZSM-5
showed a broad aliphatic product distribution, and
the aromatic–olefinic region revealed the presence
of BTX compounds. However, a different situation
was observed for H-mordenite: a much narrower
distribution of paraffinic products was encoun-
tered, and only propylene, propane and n-butane
were properly detected. By contrast, the broader
aromatic region indicates the formation of a great
variety of aromatic compounds, including fused
aromatic ring systems. The absence of palpable
amounts of isoparaffins and C -aliphatics for
5
H-mordenite results from its large pore size which
renders easier the conversion of lower olefins into
aromatics by mechanisms resembling conjunct
polymerization. The formation of fused ring aro-
matics is also possible in the mordenite structure
and explains the broader aromatic resonance which
has been observed [305].
The rate of coke formation is lower when dea-
luminated mordenite is exchanged with Ba cations,
according to Sawa et al. [119]. After 8 h on stream
the amount of coke deposited per mol of reacted
methanol diminished as the degree of Ba exchange
increased. This was explained by the weakening of
the Brønsted acid sites due to the Ba exchange [11].
Froment et al. observed that on dealuminated
mordenite the selectivity changed with time on
stream. The yield of light olefins increased, while
the yields of paraffins and aromatics dropped, even
when the methanol conversion was maintained at
100% (see Fig. 13).
Coke would already be formed at early stages
of the methanol conversion and would cover the
strong acid sites, thus reducing the conversion of
olefins to paraffins and aromatics. In conclusion,
coke deposition can vary the selectivity on large-
pore molecular sieves by coverage of acid sites and
pore blockage. The effect of blockage is more
pronounced for molecular sieves with one-dimen-
sional non-interconnecting channels [11].
A gradientless method has been used to study
the deactivation of high-silica zeolite ZVM for the
synthesis of hydrocarbons from methanol [306 ].
It was shown that olefins were responsible for the
coke formation and that the coke formed affected
the rates of different reaction pathways for chemi-
cally converting methanol and the reaction pro-
ducts in different ways. Furthermore, the authors
demonstrated that the conversion of methanol to
hydrocarbons proceeds in a quasi steady-state pro-
cess with respect to the state of the catalyst chang-
ing throughout the course of the deactivation. A
kinetic model was proposed for the deactivation
of the catalysts [306 ].
Review papers exist dealing with the coke forma-
tion and regeneration of medium-pore type zeolites
(mainly ZSM-5) applied in the methanol conver-
sion reaction [307,308], and a few highlights are
summarized in the following:
During the MTG process the ZSM-5 catalyst
becomes less effective due to three forms of
deactivation:
(1) the deposition of a carbonaceous residue on
and in the ZSM-5 catalyst;
(2) an irreversible loss of activity due to the effect
of steam on the zeolite structure;
(3) during regeneration, when coke is removed by
oxidation, the high temperatures involved may
affect the zeolite structure.
These processes can be controlled by minimizing
the regeneration temperature, the reaction temper-
ature and partial pressure of steam and adjusting
operating procedures to minimize coke formation.
The total number of cycles before a new ZSM-5
catalyst charge is required for the MTG process
has not yet been reported, but catalyst life appears
to be longer than 2 years, the period once antici-
pated [307].
In a review on the influence of the pore structure
on the coking and deactivation of zeolites, Guisnet
and Magnoux [308] concluded that both the rate
of coke formation and the nature and/or distribu-
tion of the coke components depend on the pore
structure. The rate of coke formation also depends
on the operation conditions, of course, although
sometimes it is difficult to discriminate between
 M. Stöcker / Microporous and Mesoporous Materials 29 (1999) 3–48
Fig. 13. Methanol conversion into hydrocarbons on mordenite ( Temperature: 480°C, Si/Al=80, feed: 30–70 wt% methanol/water)
(reproduced by permission of The Royal Society of Chemistry, Cambridge).
the effects of the pore structure and the acidity
[308].
One of the major advantages of ZSM-5 when
compared with other zeolites is its high resistance
to deactivation by coke formation [11]. It was
early recognized that intracrystalline coke forma-
tion on zeolites is a shape-selective reaction,
directly related to the pore structure [309,310]. By
comparing coke formation on ZSM-5 and morde-
nite in the methanol conversion it was clearly
demonstrated that the low selectivity towards coke
formation on ZSM-5 must arise from structural
constraints on the reaction of the same intermedi-
ates of coke [11]. Dejaifve et al. [116 ] showed that
the deposition of carbonaceous residues on ZSM-5
occurs essentially on its external surface and that
the active sites are not covered by coke. This
finding was supported by Schulz et al. [311] and
Slinkin et al. [312] who studied the oligomerization
of olefins on ZSM-5 and proposed that the coke
precursors were formed inside the catalysts, but
have a high mobility, due to the low density of
acid sites, so that they are readily desorbed to
form coke on the outer surface. In this scheme,
the density of the acid sites inside the channels
may be a more important factor for the resistance
to coke formation than the shape selectivity [11].
Magnoux et al. [313] attribute the low coking rate
on ZSM-5 to a large extent to the low density of
35
its acid sites. Time-on-stream experiments revealed
that ZSM-5, although considered to be highly
resistant to deactivation by coke formation, could
also deactivate significantly due to the formation
of substantial amounts of coke. This was rational-
ized by either a limited access of the reactant by
blockage of the pore openings or by formation of
non-desorbable polymerization products inside the
pores [11,314].
Ione et al. [315] studied the effect of the Si/Al
ratio on the coke formation on ZSM-5 type zeolites
in the methanol reaction. An increase in the pro-
duction of aromatics, which, in turn resulted in a
faster deactivation, was observed with decreasing
Si/Al ratio. This was confirmed by Bibby et al.
[316 ] who noticed that the overall rate of coke
formation was related to the aluminum content of
ZSM-5, but not the initial rate of coke formation
and the ultimate amount of coke formed. It was
also shown that coke formation continued, even
after complete deactivation, due to thermal crack-
ing of methanol. Suzuki et al. [145] monitored the
effect of the crystallization time on the properties
of ZSM-5. The Al content at the external surface
increased with crystallization time, while the cata-
lyst stability in the methanol conversion
decreased [11].
Bibby et al. [316,317] presented experimental
evidence that part of the coke formed during the
36 M. Stöcker / Microporous and Mesoporous Materials 29 (1999) 3–48
methanol conversion must be inside the channel
system. They found a linear relationship between
the sorption capacity (expressed as void volume)
and the coke formation (expressed as a volume
fraction of the zeolite volume). McLellan et al.
[318] monitored the acidity of the ZSM-5 catalyst
as a function of the coke content and concluded
that coke formation occurs initially at the channel
intersections. In a second stage, external coke was
formed and topological blocking of the zeolite
channels was observed. This was confirmed by
means of an XPS study of the coke formation
during the methanol conversion on ZSM-5 [319].
Internal coke formation occurred predominantly
during the conversion of methanol until the cata-
lyst was essentially deactivated. Only then, after
8 wt% coke had already been deposited inside the
catalyst, was external coke formed, probably due
to thermal cracking of methanol [11]. This was
confirmed by Behrsing et al. [320] who investigated
carbonaceous deposits on ZSM-5 during methanol
conversion at 460°C with TEM and observed
external coke at approximately 6 wt% coke.
According to Schulz et al. [311], the initial coke
formation during methanol conversion probably
proceeds relatively slowly via carbenium ions, ole-
fins or aromatics as precursors. Further coke for-
mation is fast and results mainly from direct
reaction of methanol with the coke [11].
The coke formation and deactivation on ZSM-5,
ZSM-11 and ZSM-48 was followed by Froment
et al. [321] using a microbalance in conjunction
with on-line GC. In this way it was possible to
obtain evidence about the effect of coke on both
the main and the coking reaction. For ZSM-5 and
ZSM-11, but not for ZSM-48, the effect of coke
was more pronounced on its own formation than
on the rate of the main reaction [11].
Chen et al. [322] found that the yield of methane
was closely related to the extent of coking in their
investigation of the deactivation of modified
ZSM-5 catalysts in the MTO reaction at high
temperature. Since methane and the C+ fraction
5
gradually increased with time on stream, it was
suggested that the coke deposition on the acid sites
enhanced the secondary cracking reaction through
a non-ionic mechanism [11]. Langner [323] and
Schulz et al. [311] also believe significant amounts
of methane to be symptomatic for coke laydown.
The main mechanism of methane formation from
methanol would be a non-ionic methylation of the
coke deposits, followed by elimination of meth-
ane [11].
In situ NMR spectroscopy has been applied to
investigate reaction pathways leading to coke for-
mation during the methanol conversion over
ZSM-5 by Anderson and Klinowski [72,73]. These
authors recorded 13C NMR spectra of zeolite
samples in sealed tubes after heating in methanol
to successively higher temperatures. The spectra
of adsorbed products showed the initial hydro-
carbon species to be aliphatic in nature, with
aromatics first detected at 300°C [72,73,307].
The influence of water formed during the metha-
nol conversion on the coke formation chemistry
has not yet been clearly established. Water at high
temperatures can modify the acidity of high-silica
zeolites by hydrolyzing aluminum from the zeolite
lattice, which may in turn affect the coking beha-
vior of the zeolite [307].
Pentasil type zeolite catalysts with different Si/Al
ratios and carbonized during the methanol conver-
sion at 380–420°C have been studied by ESR
spectroscopy [324]. The appearance of condensed
coke structures, which provided a narrow ESR
signal, took place at low temperatures (about
400°C ) and was determined by the time of coke
formation and the distribution density of active
sites in the pentasil type zeolite.
Pop et al. [325] investigated the kinetics of the
coke deposits formation and their influence on the
product selectivities by running experiments in a
demonstration scale fluidized bed reactor for the
MTG process. New reaction indices were advanced
for on-line monitoring of the catalyst activity.
Computer simulated deactivation of a ZSM-5
zeolite during methanol conversion to gasoline
with randomly distributed catalytic sites was per-
formed by Nelson and Bibby [326 ]. Data from
this ‘random lattice’ simulation was in qualitative
agreement with available experimental results,
whereas simulated deactivation with periodically
distributed catalytic sites was not. The main
difference between the ‘random lattice’ simulation
data and experimental results was that the number
of accessible intersections in the simulation was
 M. Stöcker / Microporous and Mesoporous Materials 29 (1999) 3–48
larger than that expected from experimental acces-
sible volumes in deactivated zeolites. This differ-
ence may be explained if the ‘coke molecule’
covering an active site ‘grows’ to exclude a volume
greater than that of a single intersection (see
Fig. 14).
The influence of the carrier gas on the deactiva-
tion rate and on the nature of coke on an H-ZSM-5
catalyst during methanol conversion was studied
by Bauer et al. [327]. Recycling hydrogen-contain-
ing light gases was found to prolong the time on
stream and to enable partial reactivation of spent
zeolite catalysts. In spite of significant dealumina-
tion of H-ZSM-5 during methanol conversion at
temperatures of about 415°C no loss of activity
was observed over several reaction cycles indicat-
ing that the MTG reaction occurs on relatively
few sites [327].
The nature, deposition and the role of coke
characteristics in the regeneration of H-ZSM-5 as
catalyst for the MTG process have been investi-
gated [328–330]. The coke deposited on the
H-ZSM-5 catalyst in the MTG process in the
250–450°C range was basically soluble in pyridine
and had a structure constituted by methyl-substi-
tuted polycyclic aromatics. The molecular weight
of the coke components and their C/H ratio
increased with time on stream and temperature.
The acidity deterioration occurred simultaneously
with the increase in content of coke deposited (up
to 1.6 wt% with respect to the catalyst at 350°C )
and was attributable to the irreversible occupation
of acid sites. The coke components preferably
Fig. 14. Schematic representation of the volume (black area) in
zeolite ZSM-5 excluded by a ‘coke molecule’: (a) excluded
volume is one intersection; and (b) excluded volume is more
than one intersection — assumes coke growing into adjacent
channels (reproduced by permission of Elsevier Science B.V.,
Amsterdam).
37
occupy strongly acidic sites [328]. According to
Benito et al. [329], coke deposition takes place
almost exclusively in the internal channels of
H-ZSM-5 (deposition of paraffins, oligomers and
alkylated monoaromatics) and in the intersections
between these channels (deposition of alkylated
mono- and biaromatics) until the catalyst becomes
totally deactivated for hydrocarbon production.
The high branching of the H-ZSM-5 zeolite micro-
porous structure explains why, in spite of the
progressive blockage of internal channels, active
sites remain accessible from lateral channels and
deactivation by pore blockage is avoided. This
interpretation coincides with the kinetic results of
deactivation, which follow an equation dependent
on the concentration of the reaction components,
and corresponds to active-site blockage mecha-
nisms. Furthermore, the acidity as well as the
activity decreased almost linearly with the coke
content. It was proven that deposited coke is very
unstable [329] and undergoes severe aging (with a
H/C ratio decrease) during the thermal treatment
at regeneration temperature. Coke instability will
have a strong influence on regeneration kinetic
studies and on catalyst regeneration in the reactor.
On the basis of their results, Ortega et al. [330]
concluded that aging treatment by sweeping with
an inert gas was needed in both cases in order to
obtain reproducible and well-controlled results
under conditions in which coke was equilibrated.
In spite of the high selectivity for linear light
hydrocarbons, the small-pore molecular sieves gen-
erally suffer from relatively rapid deactivation
during the methanol conversion reaction [11]. The
large cavities are responsible for this rapid deacti-
vation. For example, the fast deactivation of zeolite
T (erionite–offretite intergrowth) was attributed to
the blockage of the cavities by coke at 400°C and
by methoxy groups at 200–300°C. Aromatics and
heavy branched compounds can be formed inside
the large cages at temperatures above 300°C. These
molecules cannot diffuse through the porous struc-
ture because their kinetic diameter is larger than
the pore-opening size of the small-pore molecular
sieves. Thus, they remain inside the large cages
where they can form carbonaceous deposits block-
ing the pore openings and preventing the access
of reagent molecules to the active sites. The rate
38 M. Stöcker / Microporous and Mesoporous Materials 29 (1999) 3–48
of deactivation depends on the acidity: the higher
the catalyst acid strength, the faster the deactiva-
tion by coke formation [11]. To minimize the
deactivation of HT zeolite by coke formation, Ni-
and Pt-exchanged samples have been used, and
the reaction was followed in the presence of
hydrogen. The deactivation of Pt-HT was much
slower than that of HT but only paraffinic hydro-
carbons were produced [331]. The H-form of
chabazite, erionite and T-type zeolites deactivate
faster than dealuminated H-chabazite or
H-SAPO-34 and H-SAPO-17 [11].
As mentioned earlier, deactivation by coke may
be due to both covering of acid sites and blockage
of the pore structure [11, 332–334]. The intercon-
necting three-dimensional network of pores with
supercages existing in small-pore molecular sieves
provides room for accommodating some coke
without immediately blocking the pores [332]. It
has been suggested that the deactivation by coke
and its effect on the product distribution depend
on the way the coke is deposited on the catalyst
[247]. Initially, aromatics and branched isomers
formed inside the cavities are adsorbed irreversibly
on the strong acid sites. As a consequence, the
concentration of strong acid sites decreases and so
does the olefin conversion to paraffins, as
illustrated in Fig. 15.
Fig. 15. Methanol conversion into hydrocarbons on SAPO-34 (temperature: 480°C, Si/Al=0.15, feed: 30–70 wt% methanol/water)
(reproduced by permission of Elsevier Science B.V., Amsterdam).
Subsequently, the pores are blocked and the
concentration of acid sites decays abruptly. The
methanol conversion then drops from 100% to a
final value, which depends on the temperature and
the water concentration in the feed. In this final
stage the principal products are dimethyl ether,
methane and small amounts of light olefins (see
Fig. 15) which are formed by reactions requiring
only weak acid sites [11,247].
Controversial debates have been conducted in
connection with the irreversible deactivation of
clinoptilolite samples. Sakoh et al. [236 ] claim that
the activity of clinoptilolite can be completely
restored by recalcination in air, Hutchings et al.
[235] observed the opposite in their study of
deactivation and regeneration of clinoptilolite cat-
alysts modified by either ammonium ion exchange
or hydrochloric acid treatment [11]. Gubisch and
Bandermann monitored the behavior of HCl-
exchanged zeolite Na–T as a function of the
number of regeneration cycles [225]. Regeneration
was carried out between 420 and 520°C, and they
found that the catalyst activity decreased slowly
from cycle to cycle, regardless of the regeneration
temperature. After 16 regeneration cycles the con-
version of methanol dropped from 100 to 80% [11].
Liang et al. [249] regenerated SAPO-34, erionite
and erionite–offretite zeolite samples at 530°C in
 M. Stöcker / Microporous and Mesoporous Materials 29 (1999) 3–48
air after methanol conversion at 450°C and 5 h−1
WHSV. With SAPO-34 the initial conversion of
methanol after 55 regeneration cycles was still
100%, while the total hydrocarbon yield and the
level of light olefins in the hydrocarbon mixture
were constant, too. The offretite–erionite type
samples suffered from an appreciable deterioration
after repeated regenerations [11].
Selective deactivation was demonstrated for the
MTO reaction over SAPO-34 by Chen et al. [335].
The reason for this selective deactivation can be
quite complex. The coke deposition resulted in
changes not only in intrinsic selectivity but also in
shape selectivity. The coke formation during MTO
was found to be a transition-state shape selective
reaction [335]. The effect of coke formation during
the methanol to olefins reaction over SAPO-34 at
425°C was further studied by the same group,
which made the following important observations.
(1) Methanol was converted to dimethyl ether
both externally and internally over SAPO-34. The
dimethyl ether formation at the external surface
was not significant, probably due to the relatively
weak external acidity of the catalyst. The forma-
tion of dimethyl ether at the external surface gave
a slightly lower rate for olefins formation. The
methanol to dimethyl ether ratio found from the
experiments was far from equilibrium. (2)
The coke recorded as the total mass increase in
the ‘tapered element oscillating microbalance
( TEOM )’ reactor, could be divided into active
coke formed from oxygenates and inactive coke
formed from olefins. The active coke promoted
the conversion to olefins and could in fact represent
the true surface intermediate of the reaction. (3)
Coke reduced the dimethyl ether diffusivity, which
enhanced the formation of olefins. (4) The coke
formation enhanced the ethylene formation. The
ethylene to propylene ratio increased with
intracrystalline coke content, regardless of the
nature of the coke [336 ].
Chen et al. [337] continued their work by study-
ing the adsorption of the reactant, the reaction,
the desorption of the products and the coke forma-
tion as a function of the coke content in the
TEOM reactor under conditions of the MTO
reaction over SAPO-34. The adsorption of metha-
nol changed only slightly with coke formation,
39
while the conversion of methanol changed with
coke formation significantly, which was most likely
caused by the decrease in the diffusion rate due to
coke formation on the catalyst. Furthermore, the
authors observed that the MTO reaction was
clearly influenced by the methanol diffusion.
Finally, the operation conditions are very impor-
tant with respect to the stability of small-pore
molecular sieves. Marchi and Froment [247]
demonstrated that it is possible to suppress the
steps that involve coke formation on SAPO-34 by
increasing the temperature and the water content
in the feed. Obviously, water weakens the strong
acid sites responsible for hydrocarbon trans-
fer reactions. With H-T zeolite, Gubisch and
Bandermann [225] found that increasing methanol
partial pressure and WHSV favor the yield of coke
due to an increasing influence of hydrogen transfer
reactions [11].
6. Commercial implications
Mobil’s methanol to gasoline (MTG) process
has attracted worldwide attention. Its discovery
has been hailed as the first new route in more than
40 years for the production of gasoline from coal.
The commercial development effort has been cen-
tered on two versions of reactor design, the fixed-
bed and the fluidized-bed concepts. The control
and dissipation of the heat generated by the exo-
thermic conversion reaction is the major concern
in reactor design [338,339]. The first commercial
fixed-bed unit, located in New Zealand, used steam
generation and reactor effluent gas recycle to con-
trol the reactor temperature. The fluidized-bed
version has been operated in a 4000 ton year−1
scale in Wesseling (Germany). The advantage of
that pilot plant was the desired selectivity of hydro-
carbons in the product mixture (cf. Table 3).
Besides producing high quality gasoline (MTG
operation) process conditions can be varied to
produce olefins (MTO operation), which can be
converted to gasoline and diesel. The fluid-bed
technology provided all advantages in terms of
increased product yield, better quality and a very
efficient heat recovery. Depending on the world
marked situation (price, demand, etc.) the fluid-
40 M. Stöcker / Microporous and Mesoporous Materials 29 (1999) 3–48
ized-bed technology is available to produce liquid
fuels via methanol [340].
Nowak et al. [341] and Martin et al. [342,343]
combined the exothermic MTO reaction with the
endothermic steam cracking of hydrocarbons by
adjusting the operation conditions in such a way
that the overall process was nearly thermoneutral.
This was favorable from an engineering point of
view since the problems associated with heat
removal in MTO and heat generation in steam
cracking were avoided. The appropriate temper-
ature for a balanced operation of this coupled
methanol–hydrocarbon cracking (CMHC ) is in
the range of 600–700°C using ZSM-5 type zeo-
lites [344].
It is likely that future commercialization of the
methanol-to-olefins (MTO) process will take place
in a fluidized-bed reactor for many of the same
reasons which encouraged fluidized-bed MTG
development, including better temperature control
and constant product composition. The olefins
produced by this process can be readily converted
to gasoline, distillate and/or aviation fuels by
commercially available technologies ( like Mobil’s
MOGD process) [345].
UOP and Norsk Hydro introduced a selective
and economical route for converting natural gas
to olefins, the GTO process. The first step in this
process is natural gas conversion to methanol
followed by the UOP–Hydro MTO process using
UOP’s unique SAPO-34 catalyst. The primary
products are ethylene and propylene, two large-
volume base petrochemicals [3,346,347]. SAPO-34
was found to be catalytically very selective for
methanol conversion to ethylene and propylene.
The UOP–Hydro MTO process has the advantage
of high selectivity to ethylene due to this catalyst.
Ethylene has been shown to be the primary product
of this reaction. Ethylene subsequently oligo-
merizes to higher compounds, which are thermo-
dynamically favored but are produced at substan-
tially lower levels with the SAPO-34 catalysts than
with the ZSM-5 catalysts. Although these com-
pounds may exist within the SAPO-34 cavities,
only small linear olefins and paraffins readily pass
through the <4 Å diameter pores of the molecular
sieve. This high selectivity to ethylene gives
SAPO-34 a significant advantage over other types
of catalyst systems.
The need to remove the high exothermic heat
of the MTO reaction as well as the need for
frequent regeneration led to a fluidized-bed reactor
and regenerator design. This design also required
development of a fluidized-bed MTO catalyst with
the strength and integrity to last in fluidized-bed
conditions. UOP has commercially manufactured
the MTO SAPO-34 catalyst that has shown the
type of attrition resistance and stability that
enables it to handle multiple regenerations and
fluidized-bed conditions. Multiple regeneration
studies in a small-scale as well as in a larger
reactor-regeneration demonstration unit (process-
ing methanol feed of 0.5 MTD) have been per-
formed by UOP–Hydro. Fig. 16 shows the results
of 50 h of continuous methanol-to-olefins opera-
tion performed in the large demonstration plant
and using SAPO-34.
The spent catalyst is circulated to the regenera-
tor, where coke is burned off, and then returned
to the reactor to achieve a steady state. Steam is
also generated in the regenerator to remove the
exothermic heat from coke burning. The
UOP–Hydro MTO process can increase total ole-
fins by more than 60% on a per pass basis and
offers a flexible ethylene/propylene ratio between
0.75:1 and 1.5:1 [347]. Finally, since the MTO
process for the production of ethylene and propyl-
ene requires a large quantity of methanol feed, the
methanol production should be at the same site as
the MTO process. Both the UOP–Hydro MTO
process and the SAPO-34 catalyst are currently
available for licence from UOP and Hydro [3,346 ].
7. Conclusions
Over the last few decades, methanol-to-hydro-
carbons technologies have been the focus for a
large number of researchers dealing with the
upgrading of natural resources beneficial both for
the petrochemistry and fuel industries. The strong
emphasis on the R&D efforts resulted in the build-
ing of an MTG plant in New Zealand by Mobil
and a licence offer by UOP–Hydro for the MTO
process. However, the changing marked situation
 M. Stöcker / Microporous and Mesoporous Materials 29 (1999) 3–48
Fig. 16. Continuous test results of the UOP/Hydro SAPO-34 catalyst in the MTO demonstration plant (reproduced by permission
of Elsevier Science B.V., Amsterdam).
worldwide with respect to the demand and price
for the final and/or intermediate products governs
the present and future development with respect
to the application of all parts of those technologies.
Besides the process engineering aspects, a huge
knowledge concerning the involved microporous
materials has been gathered during this research,
especially with respect to ZSM-5 (MTG directed )
and SAPO-34 (MTO directed ) which is of benefit
for the ‘zeolite’ community in general. While the
FCC research promoted the insight into the field
of large-pore zeolites/microporous materials, the
methanol to hydrocarbons research contributed
strongly to the enhancement of the knowledge
directed towards the medium- and small-pore
molecular sieves.
It follows from the results reviewed that
medium-pore zeolites/microporous materials yield
generally C –C hydrocarbons, whereas small-
5 11
pore molecular sieves usually generate C –C
2 4
hydrocarbons. This may be related to diffusion
constraints and cavity dimensions. However, the
porous structure is not the only factor which must
be taken into account in order to reach, for
example, a high selectivity to C –C olefins. High
2 4
selectivities for light paraffins, principally propane,
can be observed on small-pore zeolites. The reduc-
tion of the concentration of acid sites, responsible
for hydrogen transfer reactions, decreases the con-
41
version of olefins to paraffins. The methods applied
to reduce the concentration of strong acid sites in
zeolites/microporous materials are dealumination,
cation exchange and isomorphous substitution of
Al by polyvalent cations [11].
SAPO molecular sieves, with their mild acidity,
are very interesting alternatives to obtain high
selectivities for light olefins. The conditions of
synthesis, dealumination and cation exchange seem
to be very important for obtaining a catalyst with
a good performance for methanol conversion into
light olefins. Furthermore, the ratio of acid sites
on the external surface to acid sites in the porous
structure also plays an important role. The
smaller the crystallite size, the higher this ratio.
Finally, the presence of certain OH groups
(n =3600 cm−1, which correspond to Al-OH
OH
bonds) were found to be the most active ones for
the methanol conversion into hydrocarbons.
Consequently, it is very important that the access
to these acid sites is not blocked [11].
The research directed towards methanol-to-
hydrocarbons is still in progress and new concepts
are under development and will contribute to an
enhanced knowledge within this field, like the
application of ‘Zebedee’ (acronym for zeolites by
evolutionary de novo design) to prepare catalysts
for the production of ethylene and propylene [348].
The author is aware of the fact that not all
42 M. Stöcker / Microporous and Mesoporous Materials 29 (1999) 3–48
contributions published so far could be taken into
account in connection with the preparation of this
review. However, he hopes that this paper can
contribute to provide an overview within this topic
of heterogeneous catalysis, which plays an impor-
tant role from a technological and (at least for
certain countries) industrial point of view.
8. Note added in proof
Inui and Kong [349] have reported a reliable
synthetic procedure for Ni-SAPO-34 crystals
(0.85 mm in size) having the catalytic performance
of methanol to ethylene with a selectivity as high
as 88%. Goguen et al. [350] have revealed a
hydrocarbon-pool mechanism in MT6 chemistry
on H-ZSM-5 using a pulse–quench catalytic reac-
tor monitored by in-situ NMR spectroscopy.
Acknowledgements
The author is indebted to Prof. Jens Weitkamp
( University of Stuttgart, Germany) for his kind
encouragement during the preparation of this
review. Thanks are due to Tordis Whist for techni-
cal assistance in connection with the preparation
of the figures, and the relevant publishers/authors
are gratefully acknowledged for their permission
to reproduce the figures as cited in the text.
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