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SINTEF Materials and Chemistry, Department of Hydrocarbon Process Chemistry, P.O. Box 124 Blindern, N-0314 Oslo, Norway
Received 25 April 2004; received in revised form 15 November 2004; accepted 20 November 2004
Available online 8 April 2005
Dedicated to Diplom-Chemiker Ulf Blindheim on the occasion of his 70th birthday
Abstract
This paper provides an overview about todays use of zeolites and related microporous materials as catalysts within the elds of
rening, petrochemistry and commodity chemicals. The content of this presentation is devoted to gas phase catalysiswith focus on
acid catalysis, hydrocarbon conversion and formation, oil and natural gas upgrading as well as catalytic probe reactions for the
characterisation of zeolites and related microporous materials. The review is primarily meant for beginners who intend to get
acquainted with this eld. However, for more detailed information the interested reader is invited to consult the dedicated papers
cited throughout this overview.
2005 Elsevier Inc. All rights reserved.
Keywords: Zeolites; Microporous materials; Gas phase catalysis; Crude oil upgrading; Natural gas conversion
1. Introduction
Catalysis by zeoliteswith focus on hydrocarbon
conversion and formationcovers nowadays a broad
range of processes related to the upgrading of crude oil
and natural gas. This includes, among others, uid catalytic cracking (FCC), hydrocracking, dewaxing, aliphate
alkylation, isomerisation, oligomerisation, transformation of aromatics, transalkylation, hydrodecyclisation
as well as the conversion of methanol to hydrocarbons.
All these conversions are catalysed by zeolites or related
microporous materials, based both on the acid properties and shape-selective behaviour of this type of
materials.
The rst part of this chapter deals with the understanding of the chemistry of acid catalysis using zeolites
or related microporous materials, including the formation of acid sites, carbocation chemistry and their
*
1387-1811/$ - see front matter 2005 Elsevier Inc. All rights reserved.
doi:10.1016/j.micromeso.2005.01.039
258
tons associated with negatively charged framework oxygens linked into alumina tetrahedra, are the Brnsted
acid sites, as demonstrated in Fig. 1 [2].
The protons are quite mobile at higher temperatures,
and at 550 C they are lost as water molecules followed
by the formation of Lewis acid sites, as shown in Fig. 2
[2].
For zeolites, it can be stated that the concentration of
aluminum in the lattice is directly proportional to the
concentration of acid sites. However, for other microporous solids, corresponding correlations are not straightforward [3].
2.2. Carbocations
In general, the nature of acid sites in zeolites is well
understood, however, there is much less consensus on
the reaction mechanisms for hydrocarbon conversion
or formation over microporous materials. It is generally
accepted that the reaction mechanisms of hydrocarbon
conversion and formation on acid zeolites and related
catalysts involve the formation of carbocations. However, whether these carbocations act as transition states
or as intermediates is still under discussion, and is, in
addition, depending on the type of hydrocarbon. The
behaviour of carbocations and their reaction pathways
259
Fig. 3. Representation of alkylcarbenium (a) and alkylcarbonium ions (bc). R represents either hydrogen or alkyl group [4]. Reproduced by
permission of Elsevier, Amsterdam.
260
Fig. 5. b-Scission mechanism for secondary and tertiary alkylcarbenium ions [1,8]. Reproduced by permission of Wiley-VCH, Weinheim.
261
Fig. 7. Schematic reaction pathways for carbonium ion decay (protolytic cracking) of a protonated 3-methylpentane together with principle
transition states for dehydrogenation and cracking [1]. Reproduced by permission of Wiley-VCH, Weinheim.
A simplied reaction network for the catalytic cracking of alkanes using zeolites is shown in Fig. 8 [11].
At higher reactant partial pressure the classical cracking mechanism is gradually replaced by oligomerisation
cracking, where we observe substantial oligomerisation
preceding the cracking process. Experimental evidence
for such a route has been demonstrated by Werst et al.
[12] using labeling investigations, and revealing entire
scrambling of carbon-labeled olenic cracking products.
The importance of this mechanism increases with higher
conversion and higher partial pressure as well as lower
reaction temperatures. However, the fundamental chemistry related to this cracking mechanism is basically the
same as observed for the classical cracking mechanism
[1].
2.4. Mechanistic pathway for the alkylation of isobutane
with n-butene on zeolites (CC bond formation)
Zeolites and related microporous materials are also
used as catalysts for the formation of carboncarbon
Fig. 8. Simplied reaction network for the cracking of alkanes on zeolites [11]. Reproduced by permission of Imperial College Press, London.
262
transfer and n-butene addition. The latter is usually controlled by using back-mixed reactors operating at
high conversions and low alkene concentrations. The
hydride transfer rate is depending on the stability of
the carbenium ion and the space limitations given by
the microporous framework of the zeolite. The slower
the hydride transfer the more multiple alkylation takes
place, forming C12 and C16 units, which block the active
sites as well as the micropores and deactivate the catalyst [1].
Typical side reactions are classical cracking and oligomerisations over weak Brnsted acid sites, producing
larger olens, which participate in alkylation and lead to
the formation of larger alkylate molecules, which again
contribute to increased deactivation of the catalyst [1].
The coke is formed through a combination of hydride
transfers, inter- and intra-molecular alkylation reactions
and oligomerisations leading to heavy, unsaturated cyclic and acyclic compounds [4].
2.5. Shape selectivity of acid zeolites and related
microporous materials
In 1960, Weisz and Frilette [19] introduced the
expression Shape-Selective Catalysis by demonstrating that Ca A zeolite dehydrated 1-butanol at 260 C
but not isobutanol. This observation showed that the
conversion took place inside the microporous structure
of the Ca A zeolite (0.5 nm pore diameter), not available
for the branched isobutanol due to its large kinetic
diameter. This size exclusion model has since then been
used to remove linear hydrocarbons from mixtures containing both branched and linear hydrocarbons.
The mechanisms of molecular shape-selective catalysis can be described and summarised as follows:
Reactant selectivity describes the phenomenon of
microporous catalysts acting as molecular sieves and
excluding bulky molecules from entering the intra-crystalline void-structure while allowing smaller molecules
to enter. The critical exclusion limit can be varied over
a wide range of dierent zeolites and related microporous solids [4].
Product selectivity refers to discrete diusivities of the
reaction products formed with respect to the microporous pore architecture and crystal size of the catalyst
particles. Sterically less hindered product molecules
may easily leave the microporous framework, whereas
bulky product molecules may stay much longer in the
cavities of the zeolites. The term molecular trac control
has been coined by Derouane and Gabelica in 1980
describing qualitatively the transport of molecules
with dierent shape and/or size in the microporous
framework of zeolites with two discrete sets of pores
[4,20].
Restricted transition state-type selectivity occurs when
the spatial conguration around a transition state or a
263
264
Fig. 10. Schematic representation of the three types of shape-selectivity. Concerning the restricted transition state-type selectivity: the lower
transition state molecule is easier to accommodate in the cavities than the upper one [1]. Reproduced by permission of Wiley-VCH, Weinheim.
Fig. 11. Inverse shape selectivity observed for the skeletal multiple branching of n-hexane in large pore zeolites. AFI microporous solids represent the
optimum pore diameter [4]. Reproduced by permission of Elsevier, Amsterdam.
A schematic presentation of the latter type shapeselective eects in zeolites and related microporous solids is given in Fig. 12.
265
Fig. 12. Shape-selective environments in dierent zeolite structure types: (a) large molecules have access to interrupted cavities and channel
intersections for pore mouth catalysis; (b) molecules are plugged into the pore aperture; (c) molecules are converted in multiple pore mouths
according to key-lock catalysis; (d) molecules are converted in the intra-crystalline shape-selective environment [4]. Reproduced by permission of
Elsevier, Amsterdam.
266
Table 1
Overview of zeolites and related microporous materials used as catalysts in dierent modied forms on an industrial or pre-industrial scale in
connection with the corresponding processes [30,33]
Zeolite/microporous material
MWW (MCM-22)
MFI (ZSM-5)
ERI (Erionite)
LTL (KL-type zeolites)
CHA (SAPO-34)
FER (Ferrierite)
TON (Theta-1, ZSM-22)
AEL (SAPO-11)
Table 2
Most advanced gasoline specications proposed in the World-Wide
Fuel Charter (WWFC) [35]
Parameter
Low octane gasoline [(MON + RON)/2]
High octane gasoline [(MON + RON)/2]
Oxygen (wt.% max.)
Benzene (vol.%)
Aromatics (vol.%)
Olens (vol.%)
Sulfur (ppm)
86.8
93.0
2.7
1.0
35.0
10.0
510
C1C4 cut
C5 to about 180 C
130300 C
150370 C
higher than 370 C
267
268
Fig. 14. Mechanism of the n-paran isomerisation [36]. Reproduced by permission of Elsevier, Amsterdam.
269
270
Fig. 16. Paran Total Isomerisation Process (TIP) [36]. Reproduced by permission of Elsevier, Amsterdam.
271
Fig. 17. Reaction mechanism for the acid catalysed skeletal isomerisation of n-butenes [11]. Reproduced by permission of Imperial College Press,
London.
272
halides and supported phosphoric acid. Later, environmentally more friendly zeolite catalysts have been introduced successfully, with medium-pore size zeolites as the
most promising systems since the competing (bi-molecular) oligomerisations can be lowered within the limited
space available in the smaller channels of these microporous solids. Among the medium pore sized zeolites those
having a one-dimensional channel structure (like ZSM22 and Theta-1, both having the TON structure, as well
as ZSM-23) turned out to be the best catalysts. They gave
the highest yield of isobutene by working at relatively
low temperatures (below 400 C) and with a low olen
partial pressure. The selectivity to isobutene has been
shown to improve be decreasing the density of the
Brnsted acid sites (increasing Si/Al ratio) and by
decreasing their acid strength by replacing lattice aluminium by other trivalent cations, like gallium and iron. This
behaviour is explained by suppression of bi-molecular
reactions leading to side-products as the acid sites become more and more isolated, and can be regarded as
indirect evidence that isobutene is mainly formed via a
mono-molecular mechanism, as shown in Fig. 17 [11,39].
Finally, a ferrierite based catalyst has been introduced by Shell, giving high yields of isobutene at
350 C and long catalyst lifetimes [60]. This behaviour
has been attributed to the particular structure of ferrierite possessing intersecting 10- and 8-membered ring
channels, which induce the selective formation of trimethyl pentene dimers and their cracking into C4 fragments, including isobutene [61].
In conclusion, quite active and selective alkene isomerisation catalysts can be prepared from microporous
solids by combining the proper pore architecture with
the presence of isolated and/or mild Brnsted acid sites
[39].
3.5. Aliphate alkylation
Aliphate alkylation in connection with oil renery refers to a technology dealing with the partial conversion
of the C4 cut (isobutane and n-butenes) into the socalled alkylate. This alkylate represents a very high quality and valuable component for the renery gasoline
pool due to the high octane numbers of the formed isooctanes, preferentially represented by the trimethylpentanes. Current alkylation technology applies either
hydrouoric (UOP and Phillips) or sulfuric acid (Stracto
and Kellogg). These traditional processes suer from
several safety risks and drawbacks, like the high toxicity,
volatility and corrosiveness of hydrouoric acid and the
high catalyst consumption of sulfuric acid, which requires a regeneration plant close to the alkylation facility. Therefore, replacement of the existing alkylation
processes by new technology based on non-toxic, noncorrosive and environmentally friendly solid acid catalysts is one of the most important research challenges
in the eld of heterogeneous catalysis. Signicant research during the last two decades resulted in a variety
of dierent solid acids capable to produce an alkylate
with the same quality features as the conventionally
manufactured product. However, none of the alternative
solid catalysts have been commercially applied so far,
mainly due to the short catalyst lifetime caused by the
decline of their hydride transfer activity [14,39].
The mechanism of aliphate alkylation has been described in Section 2.4 for the case of isobutane/n-butene
alkylation. Due to typical side reactions like oligomerisation and classical cracking the question arises as to
how long the formed product can be considered as an
alkylate. Arbitrarily, Weitkamp et al. placed this limit
at a content of alkanes in the C8 product fraction of
90 mol.% [62]. In the example shown in Fig. 18, the alkylation stage then ends after about half an hour. This illustrates that the time-on-stream (TOS) behaviour of the
solid catalysts is still unsatisfactorydue to the decline
of the hydride transfer activity. In addition, the ratio between the trimethylpentanes (TMP) and the dimethylhexanes (DMH) formed can be taken as a measure of the
alkylation/oligomerisation ratio for a certain solid acid
catalyst [11]. However, future research within this sub-
Fig. 18. Conversion of a liquid isobutane/1-butene mixture on a CeY zeolite. Composition of the C8 fraction (temperature 80 C, isobutane/1-butene
ratio = 11, pressure: 31 bar) [63]. Reproduced by permission of Wiley-VCH, Weinheim.
273
274
renery, where low-octane naphtha components (normal- and cycloalkanes) are converted into high-octane
isoalkanes and aromatics suitable for gasoline production. The catalytic reforming process consists of a number of hydrogenation and dehydrogenation reactions, in
addition to isomerisation, cyclisation and cracking with
respect to the formation of isoalkanes and aromatics.
The process is run at 425525 C with hydrogen pressures in the range of 0.53.0 MPa [39].
Conventional reforming catalysts are based on Pt/Cl
and PtSn supported on alumina, however, the focus
here will be concentrated on zeolite based reforming catalysts. The non-acidic Linde Type L zeolite (LTL, with
potassium as counter ions) as support for Pt and Ba
has been investigated by several groups [8082]. The
presence of highly dispersed Pt clusters inside the zeolite
channels and the shape-selective eects imposed by the
mono-directional framework structure of the KL-zeolite
is responsible for the very good aromatisation performance of this zeolite, which has a pore diameter of
0.71 nm. One of the main drawbacks of this zeolite is
the high sensitivity towards sulfur poisoning, responsible for the fast catalyst deactivation. The preparation
method and especially the Pt incorporation have a
strong inuence of the catalyst performance with respect
to activity and stability [39].
Other zeolite based reforming catalysts have been
investigated as well, like Pt/ZSM-12, Pt/Beta and sulded Pt/Cs-Beta [83,84]. Finally, large-pore boro-silicate
based zeolites (B-Beta, B-SSZ-33, B-SSZ-24 and B-SSZ31) have been patented by Chevron as reforming catalyst [85].
275
Fig. 21. Trends in catalytic cracking catalyst performance [36] Reproduced by permission of Elsevier, Amsterdam.
276
Product
LPG
Gasoline
Catalytic reforming feeds
Jet fuels
Diesel fuels
Heating oils
Olen plant feedstocks
Lube oils
FCC feedstocks
277
Fig. 22. Basic catalytic hydrocracking reactions [39]. Reproduced by permission of Wiley-VCH, Weinheim.
278
However, the incorporation of zeolites into the catalyst formulation during the 1960s represents a real
break-through with respect to an enhanced catalytic performance of hydrocracking catalysts [100]. The zeolite
based hydrocracking catalysts show a higher activity
(due to a higher acid strength), higher thermal and
hydrothermal stability, better resistance to sulfur and
nitrogen containing catalyst poisons as well as lower
coking rate, thus prolonging the catalyst lifetime
[101,102].
The rst generation of Y zeolites (either in their
hydrogen form or exchanged with rare-earth cations)
used in catalytic hydrocracking contained a high
amount of lattice aluminium, which resulted in a high
unit cell size. However, the use of ultrastable Y zeolites
(USY) synthesised by steam dealumination made it possible to control not only the number and strength of acid
sites but also the amount of extra-framework aluminium
as well as the degree of mesoporosity or secondary
porosity. As the severity of the steaming increases, the
density of acid sites decreases along with the unit cell
size. Hydrocracking catalysts synthesised from USY
zeolites with low unit cell sizes (a0 < 2.445 nm) produce
less gas but higher liquid yields and are more selective
towards middle distillates. Furthermore, acid-leached
dealuminated Y zeolites are more active and selective towards middle distillates than parent USY. The presence
of secondary porosity in USY zeolites (due to steam
dealumination) as well as the macroporosity of the for-
Fig. 23. Creation of a secondary pore structure in Y zeolite as a result of dealumination [103]. Reproduced by permission of Imperial College Press,
London.
279
Catalytic dewaxing has been connected to the medium pore zeolites and related microporous solids, including ZSM-5, ZSM-11, ZSM-23 and SAPO-11 [109]. BP
introduced the rst generation dewaxing catalysts,
which was based on mordenite in order to remove normal alkanes from lube oils. However, Mobils discovery
of ZSM-5 forced the development of the next generation
of dewaxing catalysts, applicable to both gas oils
(MDDW process) and lube oils (MLDW process). The
new generation of ExxonMobil catalysts (MSDW: Mobil Selective DeWaxing) selectively converts linear longchain parans to their corresponding isoparans
instead of cracking to lower molecules. Studies in this
direction involved zeolite Beta and MCM-22 as catalyst
components. Chevron commercialised their Isodewaxing process, which is based on isomerisation rather than
cracking as well, using SAPO-11 as dewaxing catalyst
[110]. Finally, AKZO-FINA, Criterion/Zeolyst/Lyondell and others oer catalytic dewaxing technology and
catalysts as well [36,95,109].
In conclusion, the most recent developments within
catalytic dewaxing have been concentrated on dewaxing
by means of shape selective isomerisation rather than
cracking. Examples of catalysts which exhibit shape
selective isomerisation properties include SAPO-11
and zeolite Beta. The SAPO-11 catalyst has the advantages of both low cracking activity and good isomerisation activity while suppressing the formation of
Fig. 24. Catalytic dewaxing of gas oil using shape selective ZSM-5 as catalyst [108] (top: gas chromatograph before catalytic dewaxing, bottom: gas
chromatograph after catalytic dewaxing, RT means retention time). Reproduced by permission of Elsevier, Amsterdam.
280
281
282
The mechanism of the light alkane aromatisation involves the initial dehydrogenation of parans to form
lower olens and hydrogen, followed by olen oligomerisation and cyclisation reactions to produce aromatics,
in which hydrogen transfer plays an important role
[36], see also Fig. 25.
Several zeolite based industrial processes have been
introduced with respect to the aromatisation of light
alkanes. The most known process is BP/UOPs CYCLAR process using C3/C4 renery gases as feedstock
and Ga/H-ZSM-5 as catalyst (15 wt.% Ga, Si/Al ratio
between 15 and 30). However, other technologies are
known, including Mobils M2 Forming process (using
H-ZSM-5), Chevrons AROMAX process applying
C6C8 alkanes as feed and Pt/L zeolite as catalyst as well
as Selectoforming over erionite [128]. An advantage for
the CYCLAR process is the fact that signicant
amounts of hydrogen are formed, which is needed in
the renery and which makes this process economically
very attractive [11].
The preferred catalyst for alkane aromatisation is Ga/
H-ZSM-5. The incorporation of Ga can be performed
either by direct synthesis, impregnation or ion exchange.
The success of the modied H-ZSM-5 catalyst is connected to the limited coke formation by using this
zeolite. Ga modication improves this behaviour even
more [128]. Besides gallium, other metals such as Zn,
Pt, Ni and Ag have been used in combination with
ZSM-5 for the light alkane aromatisation, however,
the Ga- and Zn/H-ZSM-5 modied catalysts are the preferred systems. Finally, Pt/KL zeolite has been applied
in the selective formation of benzene from hexane.
There is a strong interest in the aromatisation of ethane since this compound is an important component of
both renery and natural gases. However, from a thermodynamic point of view, it is very dicult to convert
ethane into aromatic hydrocarbons, since a highly
unstable primary carbenium ion will be formed in the
acid catalysed oligomerisation step, whereas for higher
alkanes a more stable secondary carbenium ion is
formed. Anyway, several investigations have been reported using Pt, Pd, Ga or Zn modied H-ZSM-5 zeolites and temperatures of about 575 C [39,128130].
3.12. Natural gas upgrading/gas conversion technologies
The evolution of the known crude oil and natural gas
reserves world-wide indicates a dramatic increase in the
latter compared to a levelling o concerning the crude
oil. This trend is expected to continue, which willin
addition to the price development with respect to the
crude oil based upgradingmost likely generate a gradual shift towards the application of natural gas as a feedstock for the production of fuels and petrochemicals.
This situation has forced an enhanced global interest
in processes, which can convert natural gas into liquids
and higher added value productswithout going via
methanol as intermediate. This route is known as the
gas to liquids (GTL)-technology, based on the
FischerTropsch route. The interest to manufacture
fuels and petrochemicals from natural gas is driven by
the desire to apply this technology directly, for example
at remote natural gas eld sites, in order to minimize
transportation costs and gas burning at the recovery
sites [36].
The following sub-chapters will deal with the
GTL-technology, based on the FischerTropsch
route as well as the methanol to hydrocarbon conver-
Fig. 25. Simplied reaction mechanism for the aromatisation of propane over modied H-ZSM-5 catalysts [11]. Reproduced by permission of
Imperial College Press, London.
283
284
Fig. 26. Methanol to hydrocarbons reaction path [132]. Reproduced by permission of Elsevier, Amsterdam.
Fig. 27. Gasoline and distillate production via methanol and Mobils ZSM-5 technology [132]. Reproduced by permission of Elsevier, Amsterdam.
285
286
12 < CI
1 < CI < 12
CI < 1
287
Fig. 29. Spaciousness index (SI) for dierent zeolites and related
microporous materials [141] (data taken from Ref. [155]). Reproduced
by permission of Wiley-VCH, Weinheim.
Fig. 28. Modied or rened constraint index (CI*) for dierent zeolites
[141] (data taken from Refs. [149151]). Reproduced by permission of
Wiley-VCH, Weinheim.
nonane is the kinetically preferred isomer in 10-membered ring zeolites, the amount of 2-methylnonane
formed from n-decane at low conversions increases relative to the other methylnonanes with decreasing pore
width of the zeolite.
Fig. 28 summarises CI* values taken from the literature [149151]. The CI* values for 10-membered ring
zeolites cover a broad range from about 3 to 15, which
represents a range where the CI* is quite suitable.
The only feature which the CI and CI* values have in
common is that their numerical values increase with
decreasing pore size of the zeolites under investigation.
On the other hand, the modied or rened constraint
index CI* is of little use concerning the pore width characterisation of 12-membered ring zeolites or related
microporous materials. However, there is another index
based on a dierent test reaction which is complementary to the CI* value, the so-called spaciousness index
(SI) for the characterisation of 12-membered zeolites
[141].
4.4. Spaciousness index
The mechanisms of hydrocracking and isomerisation
of cycloalkanes and n-alkanes are essentially identical.
However, dierent carbon number distributions have
been observed for the hydrocracking of n-alkanes and
cycloalkanes, respectively, both of them consisting of
10 carbon atoms. Weitkamp et al. registered during
hydrocracking of C10 cycloalkanes the formation of isobutane and methylcyclopentane almost exclusively in
the absence of spatial constraints. The carbocation
intermediates which govern the selectivity of hydrocracking of C10 cycloalkanes seem to be perfectly suited
for investigating the space availablecovering the entire
range of 12-membered ring zeolites and related microporous materials [141,152,153].
The spaciousness index (SI) is dened as the yield
ratio of isobutane and n-butane in the hydrocracked
288
Fig. 30. Isomerisation and disproportionation of m-xylene using acidic catalysts: Main reaction pathways [141]. Reproduced by permission of WileyVCH, Weinheim.
Finally, the isomer distribution of the trimethylbenzenes reects the restricted transition state selectivity as
well, when discussing the hindered formation of 1,3,5trimethylbenzene in mordenite as compared to a larger
amount of this isomer using zeolite Y as catalyst.
The m-xylene test reaction has found certain interest
with respect to probing the pore architecture of zeolites
and related microporous materials, however, the application has been limited concerning the determination
of the pore width of those porous solids [141].
Acknowledgments
The author is indebted to the organisers of the 14th
International Zeolite Conference Pre-Conference School
for the invitation to present this contribution. Thanks
are due to Andreas C. Moller for his assistance in connection with the technical preparation of the gures.
Finally, the author gratefully acknowledges nancial
support from SINTEF and funding from the European
Commission in connection with the TROCAT project
(contract no. G5RD-CT-2001-00520) and BIOCAT
project (contract no. ENK6-CT-2001-00510).
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