E Book Syntesis ZSM 5

ZSM-5 type zeolites:
Synthesis and use in gasphase reactions with ammonia
F.J. van der Gaag

ZSM-5 type zeolites:
ZSM-5"type zeolites:
Proefschrift
ter verkrijging van de graad van doctor aan de

Technische Universiteit Delft, op gezag van de
Rector Magnificus, prof.dr. J.M. Dirken, in
het openbaar te verdedigen ten overstaan van
een commissie door het College van Dekanen
daartoe aangewezen, op 14 december 1987 te
16.00 uur, door
Frederik Jan van der Gaag,
geboren te Delft
scheikundig ingenieur,
TR diss
1595
Dit proefschrift is goedgekeurd door de promotor:
prof.dr.ir. H. van Bekkum.
STELLINGEN
1. Thermische degradatie van polyvinylchloride (PVC) wordt tegengegaan door

toevoegen van metaalzepen (bv. Ca-, Ba-, of Zn-stearaat). Gezien het
werkingsmechanisme lijkt de benaming stabilisator voor verbetering
vatbaar.
2. Het refereren naar artikelen door het overnemen van referenties zonder de
literatuur zelf te lezen kan de nodige gevaren opleveren en ook tot
kettingeffecten aanleiding geven. Zo leidt een klein verschil in
paginanummers ertoe dat de MeAPO-molekulaire zeven niet als een recente
vinding, doch als n van de oudst beschreven zeolieten gezien zouden
moeten worden.
D.W. Breek, "Zeolite Molecular Sieves, structure, chemistry and use", J.

Wiley & Sons, New York 1974, p. 27.
A. Damour, Ann. Mines, 17, (1840), 191.
A. Damour, Ann. Mines, 17, (1840), 202.
3. Het door Ohrui en medewerkers gegeven mechanisme voor de werking van

galactose-oxidase is aan bedenking onderhevig.
H. Ohrui, Y. Nishida, H. Hori, H. Meguro, Abstr. 4th Eur. Carbohydr.

Symp, Eds. F.W. Lichtenthaler, K.H. Neff, (1987), p. B 11.
4. De door Fukui en Tanaka voorgestelde racemisatie van (+)-menthol is

chemisch niet eenvoudig uitvoerbaar.
S. Fukui, A. Tanaka, Enzyme Eng., 6, (1982), 191.
5. Het gebruik van elektronische apparatuur in een chemisch laboratorium

vraagt om bijzondere maatregelen in verband met corrosieproblemen.
6. Gezien de ervaringen met de fonnosereactie dient bij het onderzoek naar

een eerste stap bij de methanolconversie over ZSM-5 type zeolieten (de
Methanol-to-Gasoline reactie) ook rekening gehouden te worden met
autokatalyse via sporen Cz-verbindingen.
A. Butlerow, Justus Liebigs Ann. Chem., 120, (1861), 295.

R. Breslow, Tetrahedron Lett. 1959, 22.
R.F. Socha, A.H. Weiss, M.M. Sakharov, J. Catal., 67, (1981), 207.
A.P.G. Kieboom, H. van Bekkum, Reel. Trav. Chim. Pays-Bas, 103. (1984), 1
7. Het gebruik van apparatuur voor de versnelde (foto-)degradatie van bv.

kunststoffen (bv. "Weather-O-Meters") als model voor de natuurlijke
veroudering heeft nog enkele duistere kanten.
8. Het Europarlement zou, naar voorbeeld van internationale

wetenschappelijke congressen, het Engels als voertaal dienen aan te
wijzen.
9. Het valt op dat de elementkleuren (waterstof, zuurstof en stikstof) van

molekuuIraode11en en van gasflessen niet in harmonie met elkaar zijn.
10. De benaming "zelfklevende lijm" is enigermate misleidend; de Amerikaanse
term "pressure sensitive adhesive" ("drukgevoelige lijm") is een betere
omschrijving.
11. In octrooiliteratuur inzake zeolietsynthese wordt veelal ten onrechte

niet expliciet vermeld of er al dan niet geroerd wordt tijdens de
kristallisatie.
S.T. Wilson, B.M.T. Lok, E.M. Flanigen, Eur. Pat. EP 0.043.562 (1981).
H.W. Grose, E.M. Flanigen, US Pat. 4.061.724 (1977).
F.J. van der Gaag

14 december 1987
To Sylvia.
CONTENTS
1. Introduction 1
History 1
Structure 5
Synthesis 8
Analysis 10
ZSM-5 special properties 13
Literature 16
2. Identification of ZSM-type and other 5-ring containing

zeolites by i.r. spectroscopy 18
Introduction 18
Experimental 19
Results and discussion 19
References 24
3. Template variation in the synthesis of zeolite ZSM-5 26

Introduction 26
Experimental 27
References 35
4. Isomorphous substitution in zeolite ZSM-5 37

Introduction 37
Experimental 38
Conclusions 43 '
References 43
5. A note on the effect of the template on the acid features
and the particle size of ZSM-5 zeolites 45
Introduction 45
Experimental 45
Literature 49
6. Ammoxidation of toluene over modified ZSM-5 type

catalysts 50
Introduction 50
Experimental 51
Literature 60
7. Reaction of Ethanol and Ammonia to Pyridines

over Zeolite ZSM-5 61
Introduction 61
Experimental 62
Results 63
Discussion 68
Conclusions 70
References 70
8. Reaction of Ethanol and Ammonia to Pyridines

over ZSM-5-Type Zeolites 72
Introduction 72
Experimental 73
Results 73
Discussion 76
Conclusions 78
References 78
9. The formation of 2,6-lutidine from acetone, methanol
and ammonia over zeolite ZSM-5 79
Introduction 79
Experimental 80
Mechanistic experiments and considerations 87
Literature 93
10. Exploratory work on silicon aluminum phosphate

molecular sieves and related materials 94
Introduction 94
Experimental 98
Conclusions 104
Literature 105
Summary 106
Samenvatting 108
Dankwoord 111
Curriculum vitae 112

I
Introduction 1 HISTORY
I N T R O D U C T I O N
HISTORY
The first zeolitic species, stilbite, was described in 1756 by Cronstedt

[1]. This type of new materials, crystalline aluminosilicates, was named
zeolites, due to its behaviour upon heating (see Figure 1). The crystals
produced water vapor when heated in a blowpipe.
Figure 1: Zeolite powder appears to be boiling upon heating.
The next important event in zeolite science was the discovery of the
reversible hydratation-dehydratation character of zeolites by Damour
[2], almost a century later (1840). This property provided one of the more
important uses of zeolites both in industry and in the laboratory, namely
as a drying agent for liquids and gases.
= 302 . - i ri-
Ccttc experience ritre sur Ie mmc chan-
ESSAIS tillon , et sur un autre morceau d'opale de Hon-
grie pesiint o 5r ,3135 , m'a toujours prsent des
Sur quelques mmrnux connus sous Ie nom resul ia Is ideittiques et qui ne me laissent aucun
de .quartz rsirte; d o u l c s u r l a propiit que posscle 1'opale de pci-
ihe et1 d'absorber f'acilement une notablequanlit
r-ar M. A. DAMOUR. d'eau.
Figure 2: Extract form the original literature.
Some decades later another important property of zeolites, the cation

exchange capacity, was discovered (Eichhorn, 1858). This property opened a
new world of applications, ranging from the removal of cations from
aqueous solutions (e.g. as Ca binder in washing powder or capture of
radioactive ions by exchange) to the modification of the adsorptive and
catalytic properties of the zeolite.
In 1896 the idea was advanced that the structures of zeolites consist of
open spongy frameworks. Friedel [3] observed that various liquids such as
alcohol, benzene, chloroform and carbon disulfide were occluded by
zeolites. Grandjean [4], who studied the adsorption of gases, observed
that the zeolite chabazite adsorbs ammonia, air, hydrogen, carbon
disulfide, hydrogen sulfide, iodine and bromine. However, vapors of
acetone, diethyl ether and benzene were essentially not adsorbed. McBain
suggested the expression molecular sieve to describe this phenomenon of
selective adsorption. Barrer et al. performed much of the pioneering
work on this property of zeolites [5]. The often encountered high
selectivity of zeolite adsorbents is based on two principles:
a) separations based upon size of the adsorbates in relation to the

zeolite's pore size.
b) separations based on the different strength of adsorption due to
different polarizability of the adsorbates and/or different
strength of cation coordination in relation to the zeolite's polarity
and cations.
The number and available amounts of natural zeolites of consistent
quality were limited. This has led to a search for synthetic zeolites, in
which Barrer also played an important role. The search resulted in the
large scale preparation of the zeolite types A and Y by the Union Carbide
Corporation in the 1950's [6,7].
The almost unlimited availability of synthetic zeolites induced an
enormously increased effort in zeolite research. Soon zeolites were
discovered as catalysts. Especially in acid-catalyzed reactions zeolites
are powerful after exchange of the cations for ammonium, hydronium or rare
earth (HE) ions. In 1959 the first industrial application of a zeolite
catalyst was introduced by the Union Carbide Corporation with a zeolite Y
isomerization catalyst [8]. Three years later the industrial use of
zeolite catalysists really started off with the introduction of a rare
earth-exchanged X zeolite as a cracking catalyst [9]. Newer
developments are the dealuminated Y type zeolites, which share a high

stability and high acid strength. Nowadays most cracking units use zeolite
catalysts.
Another field of fast growing interest is hydroisomerization. Here

straight-chain hydrocarbons are converted into their branched isomers.
Zeolite catalysts containing Pt or Pd (e.g. Pt(0)-containing H-Mordenite
in the Shell Hysomer process [10]) are ideal for the reaction. A further
development of this process is the Shell-Union Carbide Total Isomerization
Process (TIP, see Figure 3)[11], in which linear hydrocarbons are
isomerized in a first stage and then separated in a branched and a linear
fraction over another zeolite (A-type) column. The linear hydrocarbons are
recycled to the isomerization step. Here two applications of zeolites are
used: as a catalyst and as a selective adsorbent.
The increase in branched hydrocarbons is very important in view of the

use as gasoline, where a higher octane number is required. Branched
hydrocarbons have a higher octane number than the linear isomers. A TIP
plant can increase the octane number of the Cs, C6 fraction of gasoline by
as much as 20 points, so the addition of lead can be reduced. This is
important in those cases where an exhaust catalyst is used, since even
small traces of lead deactivate the catalyst completely. In 1985 over 20
TIP plants were in operation.
H2 PURGE PLUS NORMALS
Figure 3: Flowsheet TIP process [11].

A relatively recent important discovery in the zeolite field is the

invention of the so-called "pentasil"-type zeolites, of which ZSM-5
[12](1972) is the bestknown member. The reaction for which ZSM-5 is most
frequently cited is the MTG (Methanol-To-Gasoline) reaction which converts
a methanol feed to a hydrocarbon fraction containing aliphatic as
well as aromatics compounds (<= Cio) in the gasoline boiling range and
with good gasoline properties. An installation using this process has
recently been started up in New Zealand. Other important applications
include catalytic dewaxing and p-xylene technology (see later).
Present consumption volumina of the various uses of zeolites are shown
schematically in Figure 4.
subdivision catalysts subdivision catalysts
a: detergent builders; b: catalysts; c: adsorbants; d: desiccants; e: new applications.

Catalysts subdivided in: f: miscellaneous; g: aromatics processing; h: isomerization; i: hydrocracking;
j : catalytic cracking.
Figure 4: Use of synthetic zeolites in 1986 and 1990 (*1000 tons).
The latest inventions in the zeolite field include the A1PO-, SAPO-,
MeAPO- and MeAPSO- molecular sieves [13,14]. These materials have a
lattice consisting of Al and P tetrahedra (A1P0) with incorporation of
secondary or tertiary ions like Si (SAPO), Co, Mg and/or Mn (MeAPO and
MeAPSO sieves). This family of molecular sieves includes novel structures
as well as pore structures which have an analogon in the families of
zeolite molecular sieves.
This thesis deals mainly with pentasil-type zeolites, so in the

following part of this introduction particularly properties of ZSM-5 will
be discussed.
STRUCTURE
Zeolites are crystalline aluminosilicates, which contain in their

natural forms ions of Group IA and Group H A elements such as Na, K, Mg
3+
and Ca. The structure is composed of tetrahedra of an Al or Si 4+ ion
surrounded by four 0 2 - ions. The Al and Si atoms are referred to by the
2
term "T-atoms" because of their tetrahedral coordination. Each 0 " ion is
shared between two neighbouring tetrahedra, so an average formula of TO2
results. In the case of a. Si tetrahedron this will give an electrically
neutral unit, whereas an Al tetrahedron bears a negative charge. This
charge has to be compensated to yield electrically neutral crystals. The
zeolite contains cations to neutralise the charge on the Al tetrahedra.
Thus, zeolites are represented by the general formula:
Mx/n [(Al02)x(Si02)y] .WH20
n is the valence of the charge balancing cation M, w is the number of

water molecules per unit cell, and the sum of x and y are the total number
of tetrahedra per unit cell. The Si/Al ratio (y/x) ranges from 1 to 5 for
the classical zeolites. Pentasil type zeolites have a higher Si/Al ratio,
e.g. 11 or higher for ZSM-5. The Si/Al ratio cannot be lower than 1. In
that case the Loewenstein rule (no adjacent Al tetrahedra) will be
violated.
It may be noted that lattice defects, e.g. hydroxyl nests in ZSM-5, may
occur in as synthesized zeolites, as shown in recent investigations [15].
Other ions can also be incorporated as T-atom in a zeolite lattice;
phosphorus(V), germanium(IV), gallium(III) and boron(III) are well-
known examples. A prerequisite is that the T-atoms (ions) can to. adopt a
tetrahedral configuration in an oxidic lattice. In these cases the strict
definition of a zeolite no longer applies: a zeolite should be an
aluminosilicate. Samples containing other T-atoms than Si and Al will have
to be described as, for instance, borosilicate molecular sieves.
Introduction 6 STRUCTURE
The alternative lattice ions can be incorporated during synthesis,

but in recent years it has become clear that in principle all ions in a
zeolite can be exchanged. Well-known are for instance dealumination
procedures in which the Al ions are replaced by Si by treatment with SiCl4
vapour [16]. Von Ballmoos showed that the oxygen ions are also subject to
exchange reactions using H2 1 8 0 at 95C [17]. Especially hydroxyl-oxygens
show fast exchange; bridging (T-O-T) oxygens exchange 40 times slower.
The TO2 tetrahedra are the primary building units. In these units the
differences between Al and Si are neglected. These primary building units
are linked through the oxygen ions to form larger building blocks, the
secondary building units (see Figure 5). Linking the secondary building
a O O
SIR D4R
T,0 4-1 T.O 5-1 T0 4--
Figure 5: Building units in zeolite structures.
units together yields the smallest unit of the lattice bearing all
properties of this lattice: the unit cell. The zeolite structure can be
generated by translating the unit cell in the crystallographic directions.
A unit cell of zeolite ZSM-5 is shown in Figure 6. The secondary building
(b)
Figure 6: The ZSM-5 structure, view in the straight channel
(left, SBU and 5-ring chain).
unit for ZSM-5 is the T12O20 block also shown in Figure 6. The ZSM-5 unit
cell contains 96 T-atoms (with an observed maximum of 8 Al atoms
(Si/Al>ll), cf. Chapter 3) and 192 O-atoms.
The complete zeolite structure does not fill the complete space. It
contains cavities in the form of cages and channels. These pores will
contain the adsorbed species when the zeolite is filled with an adsorbate.
The intracrystalline space is substantial: a zeolite can have a void
volume of up to 0.48 ml/ml (0.31 ml/g for H2O adsorption in CaA zeolite,
[1], p.428). Zeolite ZSM-5 has a pore system as shown in Figure 7: it
Figure 7: Channel structure of ZSM-5.
consists of a system of intersecting straight and sinusoidal channels. For

clarity, the channels in the schematic drawing in Figure 7 are drawn with
a smaller diameter than actually is the case. In the photograph the
channels are shown in the right scale. The void volume of this zeolite is
0.17 ml/g, so this zeolite has a higher structural density than for
instance zeolite A. The channels in ZSM-5 have a diameter of 0.50 to 0.56
nm, leaving enough space to allow passage of aromatic nuclei like benzene,
(p-)xylene and pyridine(s). Figure 8 shows a drawing of the top view of
the intersections in the ZSM-5 structure. Note that many figures given in
literature do not give the proper geometry. The diameter at the
intersections is much larger, reaching in some directions 1 nm, thus
allowing reactions to occur with intermediates or transition states with
diameters larger than 0.6 nm.
Figure 8: Top view of ZSM-5 channels showing large space at the

intersections
SYNTHESIS
Several zeolites (analcime, mordenite and stilbite) occur naturally.

Some natural zeolites have also been synthesized, important
representatives being mordenite and X and Y (isostructural with the
natural faujasite). Several zeolites which are industrially interesting
(e.g. types A and ZSM-5) are synthetic without a natural counterpart.
The synthesis of zeolites is usually performed under hydrothermal
conditions: a silica source, an alumina source and an exchangeable cation
are dissolved in water and the crystallization of the zeolite is effected
by heating the resulting gel (80-200C) for a period of time. To obtain
good dissolution of all chemicals a high pH is applied by adding a base
(e.g. NaOH). The so-called "low-silica"-zeolites (A, X, Y) can be
synthesized as described above. The synthesis of the
"high-silica"-zeolites like ZSM-5 is more difficult: an organic
structure-directing agent generally has to be added to obtain the desired
product. For the synthesis of ZSM-5-type zeolites a range of "templates"
has been reported (table 1, [18]). The effectivity of some of these
templates is discussed in Chapter 3 of this thesis.
Introduction 9 SYNTHESIS
TABLE 1: Templates reported for the synthesis of zeolite ZSM-5.

Tetrapropylammonium halide Methylquinuclidine
Tetraethylaramonium halide Morpholine
Tripropylamine Ethylenediamine
Diprbpylamine Diethylenetriamine
Propylamine Triethylenetetraamine
1,6-diarainohexane Dipropylenetriamine
1,6-hexanediol Dihexamethylenetriamine
1,5-diaminopentane Di-n-butylamine
Ethanolamine Ethanol
Propanolamine Ethanol + ammonia
Pentaerythritol Glycerol
The template is believed to play two roles in directing zeolite

synthesis: firstly by promoting the formation of the desired building
blocks in the gel [19], and secondly by acting as a hydrophobic pore
filler to prevent dissolution and recrystallization of already formed
crystals [20]. Several analysis methods show that in the as-synthesized
sample the pores are almost completely filled with the template molecules
(see Figure 9).
S p a c * filling drawing of T P A ' i n flrt

i i i a n t a l l o n * ho win o tha packing tn tha
linuaoldai channal (van d*r W a a l * radii uaad).
Figure 9: TPA in ZSM-5 (light atoms: zeolite lattice, dark atoms:

TPA), from [22].
Some of the templates shown in Table 1 will be locked in the zeolite

pores after synthesis. In these cases the as-synthesized zeolites have to
be activated before application. Activation requires a high temperature
treatment (e.g. 550C) to decompose the organic species and to remove
Introduction 10 SYNTHESIS
water from the pores. In some cases the high temperature may damage the
zeolite structure. Recently an alternative technique was developed in
this laboratory by Maesen et al. [21] using a rf-plasma. Here the
temperature is low (less than 100C) and activation is effected by the
combined action of low pressure and reactive plasma.
ANALYSIS
In zeolite science two types of analysis have to be distinguished:

regarding the resulting crystal structure and as to the chemical
composition. In most cases another separation can be made: between the
as-synthesized and the activated (calcined) samples, as sometimes small
lattice changes can be observed during calcination.
Structural analysis.
Structural analysis is performed by X-ray diffraction. This technique

gives direct information about the crystal structure of the sample. For
zeolite samples it is usual to apply a powder technique, because synthetic
zeolites generally are powders of 1-10 urn particle diameter. Special
synthesis methods allow the preparation of large (>200 urn) crystals which
can be analysed in more detail using a single crystal technique.
Thus a recent X-ray structural analysis of as-synthesized ZSM-5 gives
details on the lattice and on the location and conformation of the TPA
template [22]. X-ray diffraction data give a way of determining the
crystalline species present in a sample, but amorphous impurities cannot
be detected. It should be stressed that X-ray diffraction techniques need
a minimum crystal size to detect the structure. This size is in the order
of 4 times the unit cell dimension (e.g. for ZSM-5 in the order of 8 nm)
[23]. A compilation of computer-simulated X-ray diffraction powder
patterns is given by Von Ballmoos [24]. The XBD pattern of ZSM-5 is shown
in Figure 10.
Introduction 11 ANALYSIS
A second method, infrared spectroscopy, allows a quick identification of

some zeolites. This analysis method is treated in detail later in this
thesis. Infrared spectroscopy gives information about the occurrence of
specific structures in the lattice. These structures are absent in
amorphous phases, thus giving a way of estimating the amount of
amorphous impurities. For infrared spectroscopy the minimum particle size
needed for the detection of the zeolite structures is smaller than
required in X-ray analysis. This technique has been used to show the
presence of ZSM-5 type particles in an X-ray amorphous material [23]. A
crystal size of a few unit cells (2-4 nm) has been mentioned. The IR
spectrum of ZSM-5 is shown in Figure 10.
Another method, MAS-NMR[25], allows to focus in principle on all nuclei

having a magnetic moment in the zeolite. Frequently reported are the use
of 13C-NMR to study the template or occluded organic species, the use of
23 27
e.g. Na-NMR to study the exchangeable ions and the use of A1 and
29
Si-NMR to study the T-atoms in the lattice. The last two techniques
(27A1 and 29Si-NMR) allow an estimation of the chemical composition (Si/Al
ratio) of the sample by integration of the peaks obtained for Si
surrounded by 0 Al and 4 Si, by 1 Al and 3 Si and so on. A more accurate
way of determining the Al content of the zeolite lattice is by . use of
27
Al-nutation-MAS-NMR [26]. In this method tetrahedrally coordinated
(lattice-) Al and octahedrally coordinated (extra-lattice-) Al can be
distinguished. Combined with the results from the chemical analysis this
yields an accurate Si/Al ratio. Detailed studies are reported by Fyfe et
29
al. [27,28]. At high Si/Al ratios the Si NMR spectrum of ZSM-5 shows
substantial fine structure for the Si(OAl) peak (see Figure 10). The
observed multiplicity arises from crystallographically non-equivalent
tetrahedral units of Si(OAl) silicons. This may be explained by assuming
no less than 24 non-equivalent Si sites in the unit cell. X-ray
diffraction shows either 12 (orthorombic structure) or 24 unique locations
(monoclinic structure). Phase transition can be achieved by thermal
Introduction 12 ANALYSIS
treatment [29] or by adsorbing or desorbing e.g. ammonia.
XHD
UwlluUiu I
30 40 60
28
NMR
SUOAI) ( SI, A | ) =
Si (IAD/
~i 1 1 1 r -i 1 1 1 r
i 1 i i 1 -i
,J\
1 1 1 1 i 1 1 1 1 ~i 1 1 1T-
- 8 0 - 9 0 -100 -110 -120 150 100 50 O - 5 0 - 8 0 - 9 0 - 1 0 0 -110 -120 150 100 50 0 - 5 0
ppm from TMS ppm from A I ( H 2 0 ) | * ppm I r o m TMS ppm from AI(H 2 0)J*
IR
Figure 10: XRD [24], IR and NMR [27] spectra of ZSM-5

To
obtain
=~~~. inflation about"
exact
materials b u t .ie zeolite sample cheml
ln r
our work two basic / o d s w e r e used: AAS

(atonlic
md
XRF (X-ray uorracence spectrometry).
Predecomposition' jf tte-^sample- For AAS the sample is deco
hydrofluoric acid yie>'ins a solution u
P o n which analysis is
The XRF method y^ss discs prepared by decomposing the zeolite a
ni ithium
h temperature'' l borate mixtures. The results obtained by both
methods are co ârable. It will be clear that not all elements can be
analysed by e a c h method: it will, for instance, be impossible to analyse
for boron using the XRF method.
C
ZSM-5 SPECIAL PROPERTIES
. .
Zeolite ZSM-5 is a special type of zeolite. It is a "high-silica"-
zeolite, which gives it most of its special properties. Zeolite ZSM-5 is
moderately hydrophilic to highly hydrophobic (depending on the Si/Al
ratio), whereas zeolites like the types A, X and Y are very hydrophilic.
The number and type of cations compensating the lattice charge are an
important factor as to this property. Zeolite ZSM-5 has a very high
temperature (>1000C) and acid stability (down to pH=3). The last property
makes it possible to obtain the hydrogen form directly by exchanging the
zeolite in a dilute hydrochloric acid solution without large Al-losses. To
convert the "low-silica"-zeolites to the hydrogen form they have to be
exchanged with an ammonium salt solution and then calcined to decompose
the ammonium ions.
The ZSM-5 structure allows the introduction of alternative T-atoms (B,

Ga, Fe etc.) during synthesis. The structural properties of the zeolite
remain unchanged, just the unit cell dimensions change slightly (see
Figure 11 for the relation between cell dimensions and B content of a
borosilicate sample [30]). The catalytic (especially the acidic)
H-ZSM-5 have a very
aat the acid strength in
Al content of the sample. The
Les where the Next Nearest Neighbour
Ps not an Al tetrahedron. For ZSM-5 this
for all permissible Si/Al ratios (Si/Al > 11).
tie special pore structure (the channel diameter is
the same as the diameter of an aromatic ring) this yields an
'combination of activity, selectivity and stability in numerous
atalytic reactions. Some examples are: the conversion of methanol [32]
(and/or ethanol [33] or higher alcohols [34]) to a hydrocarbon fraction in
the gasoline range or to ethene, the alkylation of toluene with methanol
to form (p-)xylene[35], the disproportionation of toluene to benzene and
(p-)xylene[35,36] and selective cracking paraffins [37].
Among these applications of zeolite ZSM-5 two are especially noteworthy:

the (p-)xylene formation and the catalytic "dewaxing" of gas-, fuel- or
lubricating oil. Both applications show the shape-selective properties of
the catalyst.
It has been mentioned that the channels of ZSM-5 allow the passage of
aromatic nuclei. Para-substituted benzenes like p-xylene will also pass
L
Introduction 14 ZSMT5 SPECIAL PROPERTIES
properties will be significantly modified. ThusA so-called T-atom
substitution during synthesis renders a powerful tool to tailor the
catalytic activity of a ZSM-5-type zeolite.,

i
= 20.12 b
5380 20.08 13.34 c< /
13.32 (f
=< 5360 20.04 ! ^ ^ - 13.30
|5340 \ < 20.00 \^

OÔ
15320 \ 19.96:
|S300 - \ S 19.92
.= 5280 \ " 19.88
D 5260 \ 19.84
5240 \ 19.80
\ ^_&b
t 1 \ 1 1
0 1 2 3 4 5 0 1 2 3 4 5
B/unii cell B/unit cell
Figure 11: Variation of (a) unit cell volume and (b) individual cell
\
parameters as function of boron content [30].
Due to the low aluminium content the acid sites in H-ZSM-5 have a very
high acid strength. Barthomeuf [31] shows that the acid strength in
zeolite-type materials is related to the Al content of the sample. The
acid strength is maximal for samples where the Next Nearest Neighbour
(NNN) of an Al tetrahedron is not an Al tetrahedron. For ZSM-5 this
condition is fulfilled for all permissible Si/Al ratios (Si/Al > 11).
Together with the special pore structure (the channel diameter is
approximately the same as the diameter of an aromatic ring) this yields an
unique combination of activity, selectivity and stability in numerous
catalytic reactions. Some examples are: the conversion of methanol [32]
(and/or ethanol [33] or higher alcohols [34]) to a hydrocarbon fraction in
the gasoline range or to ethene, the alkylation of toluene with methanol
to form (p-)xylene[35], the disproportionation of toluene to benzene and
(p-)xylene[35,36] and selective cracking paraffins [37].
Among these applications of zeolite ZSM-5 two are especially noteworthy:
the (p-)xylene formation and the catalytic "dewaxing" of gas-, fuel- or
lubricating oil. Both applications show the shape-selective properties of
the catalyst.
It has been mentioned that the channels of ZSM-5 allow the passage of
aromatic nuclei. Para-substituted benzenes like p-xylene will also pass

w
~Y

Introduction
/
13 STRUCTURE
Chemical composition. 1 ,
To obtain exact information about the fractions of the starting

materials built in in the zeolite sample chemical analysis is required. In
our work two basic methods were used: AAS (atomic absorption spectrometry)
and XRF (X-ray fluorescence spectrometry). Both methods require a
predecomposition of the sample. For AAS the sample is decomposed using
/
hydrofluoric acid, yielding a solution upon which analysis is performed.
The XRF method uses'glass discs prepared by decomposing the zeolite at
high temperature/in lithium borate mixtures. The results obtained by both
methods are comparable. It will be clear that not all elements can be
analysed by, each method: it will, for instance, be impossible to analyse
for boron using the XRF method.
ZSM-5 SPECIAL PROPERTIES
Zeolite ZSM-5 is a special type of zeolite. It is a "high-silica"-

zeolite, which gives it most of its special properties. Zeolite ZSM-5 is
moderately hydrophilic to highly hydrophobic (depending on the Si/Al
ratio), whereas zeolites like the types A, X and Y are very hydrophilic.
The number and type of cations compensating the lattice charge are an
important factor as to this property. Zeolite ZSM-5 has a very high
temperature (>1000C) and acid stability (down to pH=3). The last property
makes it possible to obtain the hydrogen form directly by exchanging the
zeolite in a dilute hydrochloric acid solution without large Al-losses. To
convert the "low-silica"-zeolites to the hydrogen form they have to be
exchanged with an ammonium salt solution and then calcined to decompose
the ammonium ions.
The ZSM-5 structure allows the introduction of alternative T-atoms (B,

Ga, Fe etc.) during synthesis. The structural properties of the zeolite
remain unchanged, just the unit cell dimensions change slightly (see
Figure 11 for the. relation between cell dimensions and B content of a
borosilicate sample [30]). The catalytic (especially the acidic)
Introduction 15 ZSM-5 SPECIAL PROPERTIES
easily, whereas the transport of e.g. o- and m-xylene will be slower.

Passage of higher substituted aromatics (when formed at an intersection)
is even more limited, so these will probably be converted before leaving
the zeollte[38]. Therefore, alkylatipn. of toluene with methanol . and
disproportionation of toluene will yield a xylenes mixture with a higher
p-xylene content than the thermodynamic equilibrium.
The catalytic dewaxing of heavy oil fractions is a (hydro-)cracking

process in which only the linear ("waxy") hydrocarbons are involved.
Branched hydrocarbons are too large to enter the zeolite's pores. The
products of a dewaxing unit are a fraction with a boiling range comparable
to that of the feed fraction 'and a gasoline fraction. The pour point of
the gas-, fuel- or lubricating oil will be lowered (e.g. for a lubricating
oil from 7C to -12C and for a middle distillate ' from 32C to -18C
[39]), which drastically improves the properties of these oils at low
temperatures. Dewaxing of gas oil (diesel fuel) lowers the temperature at
which "fogging" occurs. This phenomenon is encountered during the winter
when the linear paraffins form clouds and plug the fuel lines of the car.
In this thesis the unique catalytic properties of ZSM-5 type zeolites

will be demonstrated in two . new gas phase reactions, namely the
conversion of ethanol and ammonia to pyridines (Chapters 7 and 8) and the
ammoxidation of toluene to benzonitrile (Chapter 6). Further chapters
describe the detection and analysis of ZSM-5 zeolites using infrared
spectroscopy (Chapter 2) and experiments on the synthesis of zeolite ZSM-5
using a range of templates (Chapter 3) and a range of substituting T-atoms
introduced during synthesis (Chapter 4). In Chapter 10 some data will be
given on experiments with molecular ..' sieves from the SAPO- and MeAPO
group, as these systems might offer the possibility of synthesizing
materials with anion exchange properties (here the lattice has to carry a
surplus of positive charge). It will be shown that the SAPC type materials
can be effectively used in the catalytic ammoxidation of toluene (cf.
Chapter 6).
Introduction 16 LITERATURE
LITERATURE
1. D.W. Breck, "Zeolite Molecular Sieves, structure, chemistry and use",

J. Wiley & Sons, New York 1974.
2. A. Damour, Ann. Mines, 17, (1840), 202.
3. G. Friedel, Bull. Soc. Fr. Mineral. Cristallogr., 19, (1896), 14, 96.
4. F. Grandjean, Compt. Rendu, 149, (1909), 866.
5. R.W. Barrer, "Zeolites and Clay Minerals as Sorbent and Molecular
Sieves", Academic Press, London 1978.
6. R.M. Milton, U.S. Patent 2.882.243 (1959).
7. R.M. Milton, U.S. Patent 2.882.244 (1959).
8. R.M. Milton, in "Molecular Sieves", Soc. Chem. Ind., London, (1968),
p.199.
9. C.J. Plank, E.J. Rosinski, W.P. Hawthorne, Ind. Eng. Chem., Prod. Res.
Dev., 3, (1964), 165.
10. H.W. Kouwenhoven, Mol. Sieves Int. Conf. 3rd, Adv. Chem. Ser., 1973,
(121), 529.
11. I.E. Maxwell, Proc. Shell Zeol. Catal. Conf., (1986), 2.
12. R.J. Argauer and G.R. Landolt, US Patent 3.702,886 (1972).
13. S.T. Wilson, B.M. Lok, C A . Messina, T.R. Cannan, E.M. Flanigen, ACS
Symp. Ser., 218, (1983), "Intrazeolite Chemistry", G.D. Stucky, F.G.
Dwyer. Eds., p.79.
14. E.M. Flanigen, B.M. Lok, R.L. Patton, S.T. Wilson, Pure & Appl. Chem.,
58, (10), (1986), 1351.
15. G. Boxhoorn, A.G.T.G. Kortbeek, G.R. Hays, N.C.M. Alma, Zeolites
1984, (4), 15.
16. J. Klinowski, J.M. Thomas, M.W. Anderson, C A . Fyfe, G.C. Gobbi,
Zeolites 1983. (3), 5.
17. R. von Ballmoos, W.M. Meier, J. Phys. Chem., 1982, (86), 2698.
18. B.M. Lok, T.R. Cannan andC.A. Messina, Zeolites, 1983, (3), 282.
19. G. Boxhoorn, O. Sudmeijer, P.H.G. van Rasteren, J.C.S., Chem. Coramun.,
1983, 1416.
20. J. Keijsper, M. Mackay, J. v.d. Berg, A.G.T.G. Kortbeek, M.F.M. Post,
Prep. KNCV Katal. Symp., 1986, 39.
21. Th. L. Maesen, J.C.S., Chem. Commun., in press.
22. H. van Koningsveld, H. van Bekkum, J.C. Jansen, Acta Cryst., B43,
(1987), 127.
23. P.A. Jacobs, E.G. Derouane, J. Weitkamp, J.C.S., Chem. Commun.,
1981. 591.
24. R. von Ballmoos, "Collection of Simulated XRD Powder, Patterns for
Zeolites", Butterworth, Guildford, (1985).
25. J.M. Thomas, J. Klinowski, Adv. Catal., 33, (1985), 199-374.
26. A. Samoson, E. Lippmaa, G. Engelhardt, U. Lohse, H.G. Jerschkewitz,
Chem. Phys. Lett., 134. (1987), (6), 589.
27. C.A. Fyfe, G.C. Gobbi, G.J. Kennedy, J. Phys. Chem., 1984. (88),
3248.
Introduction 17 LITERATURE
28. C.A. Fyfe, G.C. Gobbi, J. Klinowski, J.M. Thomas, S. Ramdas, Nature,
296. (1982), 530.
29. H. van Koningsveld, J.C. Jansen, H. van Bekkum, Zeolites, in press.
30. B.L. Meyers, S.H. Ely, N.A. Kutz, J.A. Kaduk, E. van den Bossche, J.
Catal., 91, (1985), 352.
31. D. Barthomeuf, Mat. Chem'. Phys., 1987, (17), 49.
32. e.g. T. Mole, J.A. Whiteside, D. Seddon, J. Catal., 82, (1983), 261.
33. e.g. J.C. Oudejans, P.F. van den Oosterkamp, H. van Bekkum, Appl.
Catal., 3, (1982), 109.
34. e.g. O.A. Anunziata, O.A. Orio, E.R. Herrero, A.F. Lopez, C.F. Perez,
A.R. Suarez, Appl. Catal., 15, (1985), 235.
35. e.g. L.B. Young, S.A. Butter, W.W. Kaeding, J. Catal. , 76, (1982),
418.
36. e.g. N.R. Meshram, S.G. Hegde, S.B. Kulkarni, Zeolites 1986. (6),
37. e.g. R.B. Borade, S.G. Hegde, S.B. Kulkarni, P. Ratnasamy, Appl.
Catal., 13, (1984), 27.
38. I.E. Maxwell, J. Inclusion Phenom., 1986. 4, (1), 1-29.
39. S.P. Donnelly, J.R. Green, Oil Gas J., 1980. 78, (43), 77-81,84.
18
IDENTIFICATION OF ZSM-TYPE AND OTHER 5-RING CONTAINING ZEOLITES BY I.R.

SPECTROSCOPY
J.C. Jansen, F.J. van der Gaag, and H. van Bekkum

Laboratory of Organic Chemistry. Delft University of Technology,
Julianalaan 136, 2628 BL Delft. The Netherlands
ABSTRACT
The mid i.r. spectra have been recorded of the pentasil family, of the
mordenite group, of ZSM-39 and Melanophlogite, and of the structurally
unknown ZSM-34 and ZSM-35. It is concluded that i.r. spectroscopy enables
fast differentiation of ZSM-type zeolites.
INTRODUCTION
During a current investigation program on the synthesis of ZSM-type

zeolites a fast method to achieve a first differentiation of products
including both the identification and the estimated purity was required.
For this purpose i.r. spectroscopy and X-ray powder diffraction (XRD) were
selected. Occasionally also scanning electron microscopy (SEM) and X-ray
fluorescence (XRF) were applied.
For a more precise characterization of the known i.r. spectra of some
2-4 -1
ZSM-zeolites the mid infrared spectra (1500-400 cm ) of a series of
five-membered ring containing zeolites were recorded including both
synthetic and natural materials. In this paper we present i.r. data on the
members of the pentasil family, i.e. Silicalite, ZSM-5, ZSM-11, and
9
Boralite; of the mordenite group , i.e. Mordenite, Ferrierite, Epistilbite,
Dachiardite, and Bikitaite, of the clathrate group, i.e. ZSM-39 and the
natural polymorph Melanophlogite, and of the structurally unknown zeolites
ZSM-34 and ZSM-35. Especially the absorption bands near 1200 and 550 cm
assigned by Jacobs et al. and Vedrine et al. to the presence of
five-membered ring systems, were studied.
fiR
Based on the known crystal structures of most of the above mentioned
zeolites it was attempted to acquire an empirically consistent assignment of
the near 1200 and the 550 cm absorption bands.
19
For the determination of the estimated purity.of especially ZSM-5 the i.r.
optical density ratio of the 550 and 450 cm bands of the pentasil products
4
was examined since different values have'been published .
EXPERIMENTAL
Materials
For the synthesis of ZSM-type zeolites Aerosil (type 200 Degussa) as the
silica source was added to aqueous solutions of organic template.
Subsequently an aqueous solution of sodium aluminate was added under
vigorous stirring. The gel being formed almost instantaneously was heated at
453 K and stirred in 30 ml autoclaves for 48 h. The solid product was washed
three times with distilled water and dried at 373 K for four hours.
Subsequently the zeolites were heated at a rate of 1 K/min to 773 K and
calcined at this temperature overnight. The natural zeolites, which were
obtained from several mineral collections, were air dried.
Methods and apparatus

The mid infrared spectra were recorded on a Perkin Elmer 521 spectrometer
using the KBr pellet technique. To identify all zeolite samples used the
X-ray powder diffraction data were obtained with a Type II Guinier de Wolff
camera. Only zeolitic materials which were pure according to X-ray analysis
were used in the present i.r. work. The silica alumina ratio of ZSM-5 was
determined by XRF using a PW 1400 PHILIPS Rntgen spectrometer. The
crystallinity and the particle size of the ZSM-species SEM was studied with
a Jeol Jxa-50A electron microanalyser.
RESULTS AND DISCUSSION
o
The members of the pentasil family together with the complete mordenite
g
group , their origin and silica.alumina ratio are listed in Table 1. The
common secondary building unit (SBU) in these zeolite types is the 5-1
unit giving five-membered rings of T-sites in the framework
5 ~
structures . The five-membered rings of the synthetic ZSM-39 and the natural
polymorph Melanophlogite of the clathro group are part of the polyhedra
building units as depicted in Figure 1. The crystal structures of ZSM-34 and
ZSM-35 are unknown. In column four and five of Table 1 the space group of
the structures is given and the number of 2-fold screw axes per unit cell
able to generate chains of five-membered rings from a typical motif of
20
T-sites indicated by dots in Figure 2. The last column of Table 1 contains

the type of typical five-membered ring blocks as presented in Figure 3 and
the number of blocks per unit cell.
Tabl* 1 Chemical and structural data of zeolites containing Springs
Zeolite type and origin Si/AI Space g r o u p 2, axes" Number of c 5-ring

chainsV2i blocks/UC
Silicalite l' X 5 1 Pnma 4 4 8 A. 8 B

ZSM-5' 17.4 5 1 Pnma 4 4 8 A, 8 B
Boraltte' 13.9* 5 1 r^nrna 4 4 8 A, 8 B
ZSM-11' 13.8 5 1 Mm2 4 4 8 A. 8 B
Mordenite (Fasatal, It.)' 5.0 5 1 Cmcm 4 1 8 8
Ferrierite (Vincenza, It.) 5.0 5 1 Immm 4 1 88
Epistilbite IGanagawa, Jpn.t
Dachiardite (Niigata, Jpn.)
3.0
4.0
5
5
1
1
C2/m
C2Jm

2

I
4 3
4 B
Bikitaite (Bikitaite, Hhod.) 2.0 5 1 P2, 2 1 4 C
ZSM-39' X n a. Fd3m n.a
Melanophlogile (Girgenti, It.) x n a. P67mm n.a
ZSM-34' 13.4 u u. u.
ZSM-35' 9.0' u u. u.
'Secondary b u i l d i n g unit
"Only the 2-fold screw axes w h i c h arrange five-membered rings i n t o chains
' N u m b e r of five-membered rings per 2! axis [Figure 2)
" N u m b e r and types of five-ring blocks per unit cell as depicted in Figure 3
"Si/B ratio
'Synthesized in this laboratory
" A t o m i c reactant ratio
Figure 1 Polyhedra building units of Z S M - 3 9 la.c) and Melanophlogite

(a.b)
The most important i.r. data in the framework absorption region of the
zeolite types are given in Table 2. As examples the spectra of ZSM-5,
Epistilbite, Dachiardite, Bikitaite and ZSM-39 are shown in Figure 4.
Especially the structure sensitive absorptions around 1200 and 550 cm are
of interest to differentiate the zeolite types. The external asymmetric
stretching vibration around 1225 cm is clearly present in the i.r. spectra
of either the structures with four chains of five-membered rings arranged
around a 2-fold screw axis as in the pentasil family or with one chain of
five-merabered rings on the 2-fold screw axis as in the mordenite group,
shown in Figure 2a and b ^ respectively. Although the space group of the
Epistilbite structure indicates the presence of 2-fold screw axes, in this
structure no five-membered ring chains are generated. However, the presence
21
of pseudo-five-membered ring chains might be the cause of the shift of the

near 1200 cm absorption band to 1175 cm
In the Dachiardite structure the absorption band at 1210 cm could be
caused by the presence of five-membered ring chains, containing 2-fold screw
axes. A large shift compared to the other members of the mordenite group is
seen in the spectrum of Bikitaite: though 2-fold screw axes are present the
absorption band of the chains is found at 1105 cm . Perhaps this shift is
due to the low silica alumina ratio
No absorption was found near 1200 cm in the i.r. spectrum of ZSM-39 and
Melanophlogite. According to the structure data no five-membered ring chains
are present in these structures.
In the unknown structure of ZSM-35 chains of five-membered rings are
possible since the absorption at 1232 cm was demonstrated in the i.r.
spectrum of the structure whereas the reverse is true for the also unknown
ZSM-34.
Z.
Figure 2 (a) Four five-membered ring chains arranged around 2-fold

screw axis; m o t i f of 12 f-sites is indicated by dots, (b) One
five-membered ring chain on 2-fold screw axis; motif of 3 T-sites is
indicated by dots
22
Table 2 l.r. data between 1500-400 c m " ' of zeolites containing five rings
Asym. s t r e t c h ' Sym. stretch'
Zeolite types External" Internal External Internal Double* " r i n g TO' bend
Lit. data* 1150-1050 1250-950 820-750 720-650 650-500 500-420

Silicalite 1 1225(shl
1225lshl
10931s)
10931s!
790(wl
790|wl
5501m) 4501s!
ZSM-5
1228(sh) 10961s)
S50(m) 450lsl
8oralite
1225lshl
800lwl
790lwl
550tml 4S0IS)
ZSM-ll
Mordenite 1223(shl
10931s)
1045UI 800|w)

720(wl
5501ml
580. 5 6 0 M
450lsl
4501s)
Ferrierite 1218lsh| 10601s) 780M 695M 563M 4551s)
Epistilbile 1175lshl 10501s) 795M 690lw) 563(wl 455(s)
Dachiardite I210lsh) 1050(s) 775(w) 670lw) 558lwl 4401s)
782lwl 6801m)
Bikitaite 110S(sh) 968{s)
790|w|
4601s)
ZSM-39
10901s)
4601s)
Melanophlogite
ZSM-34
11181s)
1060(s)
795(w>
7851ml

635. 580. 5 5 0 ( w l
465(S|
1070(sl 790M
4651s)
ZSM-35 1232(sh)
810(w)
5901ml 4601s)
Aerosil
llOOIs)
4681s!
'l.r. assignments according to Flanigen era/."

b
Five-membered ring block vibrations according to Jacobs et a/, and Vedrine ef at.3'
According to Jacobs et al. and Vedrine et al. the second structure sensitive
absorption band in the pentasil structures at 550 cm is caused by double
five-membered ring blocks of Type A as depicted in Figure 3. Type A is a 5-5
block containing two parallel faces of nearly planar five-membered rings.
However, in the pentasil structures also five-membered ring blocks are
present of Type B (Figure 3) which is a 5-3 block with four faces of
puckered five-membered rings in the envelope mode. The absorption band at
550 cm in the pentasil structures is therefore tentatively assigned to the
Figure 3 Types of five-membered ring blocks; A, 5-5 block; B. 5-3 block;

C, 5-3-1 block
presence of a combination of Type A and Type B blocks. For the mordenite

group an absorption is observed near 560 cm which is in the range
3 4
reported ' for structures with Type B blocks. An exception is Bikitaite,
which zeolite shows no absorption near 550 cm . Bikitaite does not contain
five-membered ring blocks of Type A and B. A five-membered ring containing
block present in the Bikitaite structure is depicted in Figure 3 and called
a 5-3-1 block. The 5-3-1 block is a 5-3 block with one additional T-site
resulting into two five-membered ring faces in the envelope mode and two six
rings. Another difference between Bikataite and the other members of the
mordenite group is the relatively strong absorption band at 680 cm in the
23
i.r. spectrum of Bikitaite.

Absorptions near 550 cm were also absent in the i.r. spectra of ZSM-39 and
Melanophlogite. This is in agreement with the absence of Type A and Type B
like blocks in these structures.
The weak absorptions at 635 cm , 580 cm and 550 cm in the spectrum of
ZSM-34 are considered to be related to the presence of Type B blocks in the
structure. The spectrum of the ZSM-35 structure is almost a pentasil-like
spectrum except for the large shift of the 550 cm absorption band to 590
cm which could probably be related to the presence of Type A blocks in the
structure.
It can be concluded that the presence of the near 1200 and 550 cm i.r.
bands is indeed related to five-membered ring chains and blocks,
respectively. The frequency shift of the i.r. bands is depending upon the
particular zeolite type. Thus fast differentiation of zeolites containing
five-membered rings via i.r. spectra is of great importance.
.o
a
1500 1000 500 v/crrr
Figure 4 I.r. spectra IKBr pellets) of Z S M - 3 9 ( I I , Z S M - 5 (2). Dachiardiie

(3). Epistilbue (4) and Bikitaite 15)
24
The influence of very small crystals, d < 2 pm, must be sorted out because
of a bad solution of the structure sensitive bands near 1200 and 550
cm and the poor X-ray diffraction pattern.
Furthermore, a remark can be made regarding the use of i.r. spec.troscopy in
determining the purity of zeolite ZMS-5 samples. The most important impurity
in the pentasils, amorphous silica, has an absorption band at 450 cm and
-1 4
does not show a band at 550 cm . Therefore, as earlier reported , the
optical density ratio of the 550 and 450 cm bands could indicate if pure
and well crystallized samples are present. Upon measuring physical mixtures
of pure ZSM-5 and Aerosil we found this ratio to decrease linear with
increasing amounts of amorphous silica present. According to earlier
2 3
investigators ' and our present findings the optical density ratio of the
550 and 450 cm bands is 0.8 for all pure pentasil samples (calcined at 823
4
K ) . This value contradicts the proposal of other workers that each pentasil
member has a different ratio value. A constant ratio is consistent with the
fact that all pentasil members (cf. Table 1) contain the same type and
number of five-membered ring blocks per unit cell. It may be noted that the
presence of organic template or adsorbed molecules influences the optical
density ratio. Thus proper activation is required.
In conclusion the i.r. technique allows an estimate of the purity of the
pentasil samples and gives valuable information regarding the structure of
five-membered ring containing zeolites.
ACKNOWLEEMENT
We wish to thank Mr. N.M. van de Pers and Mr. J.F. van Lent of the
Laboratory of Metallurgy for making the Guinier de Wolff photographs and Mr.
D.P. Nelemans of the same laboratory for the SEM photographs. Mr. G.F.
Herlaar is thanked for discussions. We are grateful to Prof. K. Koopmans and
Mr. Th.W. Verkroost of the Department of Mining Engineering for the X-ray
analysis of ZSM-5 and to Mr. C. Blotwijk of the same department for
supplying the specimen of Bikitaite and Melanophlogite. We thank Dr. L.P.
van Reeuwijk of the ISRIC (the former International Soil Museum) for
supplying the specimen of Epistilbite.
REFERENCES
1. Gaag, F.J. van der, Jansen, J.C., and Bekkum, H. van, A p p l . Catal.,
il. (1985), 261.
25
2. Ballmoos, R. von, PhD Thesis, E.T.H. Zurich, 1981.

3. Jacobs, P.A., Beyer, H.K. , and Valyon, J. , Zeolites, 1981, .1, 161.
4. Coudurier, G. , Naccache, C., and Vedrine, J.C., J. Chem. Soc. Chem.

Comm.. 1982, 1413.
5. Meier, W.M. and Olson, D.H., 'Atlas of Zeolite Structure Types', Juris
Druck and Verlag AG, Zurich, 1978.
6. Schlenker, J.L., Dwyer, F.G., Jenkins, E.E., Rohrbaugh, W.J., Kokotailo,
G.T., and Meier, W.M., Nature, 1981, 224, 340.
7. Smith, J.V., Fifth Int. Conf. on Zeolites - Recent Prog. Rep. and Disc,
(Eds., Seriale, R. , Colella, C., and Aiello, R.), Heyden, London, 1981,
228.
8. Kokotailo, G.T. and Meier, W.M., Chem. Soc. Spec. Publ., 1980, 33, 133.
9. Breek, D.W., 'Zeolite Molecular Sieves: Structure, Chemistry and Use',
John Wiley and Sons, New York, 1974, 122.
10. Gramlich-Meier, R. and Meier, W.M., J. of Solid State Chemistry. 1982,
44, 41.
11. Flanigen, E.M., 'Zeolite Chemistry and Catalysis', (Ed. Rabo, J.A.),
Adv. Chem. Ser.. 1976, 171, Ch. 2.
26
TEMPLATE VARIATION IN THE SYNTHESIS OF ZEOLITE ZSM-5
F . J . VAN DER GAAG, J . C . JANSEN, and H. VAN BEKKUM

Laboratory of Organic Chemistry, D e l f t University of Technology, .
Julianalaan 136, 2628 BL Oei f t , The Netherlands.
(received 25 February 1985, accepted 22 March 1985)
ABSTRACT
The a b i l i t y of several organic template molecules in the synthesis of ZSM-5
type zeolites was studied under standard conditions of temperature and time
using s t a r t i n g Si/Al r a t i o s ranging from 4 to (19.2 to 0 A l / u c ) . 1,6-Hexane-
d i o l , 1,6-hexanediamine, 1-propanol, 1-propanamine, p e n t a e r y t h r i t o l and t e t r a -
propylammonium bromide (TPA-Br) were used as templates. The z e o l i t e s obtained
were analyzed by X-ray. d i f f r a c t i o n a n d . i n f r a r e d spectroscopy for c r y s t a l l i n i t y
and by X-ray fluorescence for chemical composition. Scanning e l e c t r o n micro
graphs were made of selected samples.
The range of the s t a r t i n g Si/Al r a t i o s giving pure ZSM-5 product increases
ih' : the f o l l o w i n g template order: alcohols < amines < t e t r a p r o p y l ammonium b r o
mide. Both 1,6-hexanediamine and TPA-Br give good r e s u l t s for low s t a r t i n g
Si/Al r a t i o s .
The observed maximum content of 8 Al/uc of ZSM-5 i s discussed i n terms of
special Al s i t e s connecting s i l i c a l a y e r s .
INTRODUCTION
In general z e o l i t e ZSM-5 i s synthesized in a hydrothermal system c o n t a i n i n g
an alumina source, a s i l i c a source and an organic template molecule. The t e t r a
propyl ammonium ion (TPA) was the f i r s t organic molecule which was reported [1]
to be capable of inducing ZSM-5 f o r m a t i o n . Later i n v e s t i g a t i o n s showed t h a t the
use of TPA allows the synthesis of ZSM-5 z e o l i t e s with a Si/Al ratio ranging
from 11 to (which corresponds to 8 to 0 Al/uc) [ 2 ] .
Other organic molecules reported to induce ZSM-5 formation a r e , for example,
1,6-hexanediol [3] and 1-propanol [ 4 ] . A review on the use of d i f f e r e n t tem
plates in z e o l i t e synthesis has recently been given by Lok et a l . [ 5 ] . Derouane
and Gabelica and coworkers [ 6 , 7 , 8 ] investigated the process of forming the ZSM-
5 phase and the role of the a l k a l i metal c a t i o n s , using the templates TPA-Br
and tetrabutylammonium bromide.
ZSM-5 z e o l i t e s have a number of properties which are not dependent on the
chemical composition, i . e . the Si/Al r a t i o of the sample, l i k e c r y s t a l struc
t u r e , pore size and pore volume, X-ray d i f f r a c t i o n pattern and r e f r a c t i v e index
[9]. Many other properties of ZSM-5 do vary w i t h the composition. In different
applications of ZSM-5 c e r t a i n ranges of composition a r e , t h e r e f o r e , favoured or
required. Ion exchange capacity, catalytic activity and hydrophobicity are
examples of composition-dependent p r o p e r t i e s .
27
In our laboratory the e f f e c t of varying Si/Al r a t i o on the e f f i c i e n c y of

ZSM-type c a t a l y s t s in e . g . ammoxidation [ 10J and aromatization [11] is under
investigation.
In order to obtain knowledge of the templating potency of d i f f e r e n t organic
molecules a series of ZSM-5 samples has been synthesized, starting out w i t h
different Si/Al r a t i o s and d i f f e r e n t organic template molecules. Standard con
d i t i o n s [ 5 ] of temperature and reaction time were chosen. The organic molecules
used were: TPA-Br, 1,6-hexanediol, 1,6-hexanediamine, 1-propanol, 1-propan-
amine, and p e n t a e r y t h r i t o l , a t e t r a o l which resembles TPA as to s t r u c t u r e . Two
s i l i c a sources, a e r o s i l and waterglass, were applied i n t h i s study.
EXPERIMENTAL
The ZSM-5 samples were prepared according to the general d i r e c t i o n s given by
Casci et al . [ 3 ] .
The c r y s t a l l i z a t i o n was performed in stainless steel (type 316) autoclaves
(35 ml volume) a i r t i g h t e n e d by a t e f l o n r i n g and containing teflon-coated mag
netic s t i r r e r b a r s . Nine autoclaves were placed in an e l e c t r o n i c a l l y controlled
heated aluminum carrousel equipped with magnetic s t i r r e r d r i v e s , as shown i n
Figure 1 .
Figure 1 . Stainless steel autoclave and alu.ninum carrousel used for ZSM-5 syn
thesis experiments.
28
Chemicals.
Reagents were: a e r o s i l s i l i c a (S1O2, Aerosil 200, Degussa), sodium hydroxide
(NaOH.H20, Merck Suprapur), sodium aluminate (NaA102, 41 wt% Na 2 0, 54 wt%
Al23 Riedel-de Haehn), 1,6-hexanediol (Aldrich), 1,6-hexanediamine (Aldrich
and Merck), 1-propanol (Merck), 1-propanamine (Merck), tetrapropylammonium b r o
mide (Aldrich), pentaerythritol (BOH), waterglass (sodium s i l i c a t e solution,
26.7 w U S1O2, 8.1 w t t Na20, Lamers & Indemans), s u l f u r i c acid (96 wt% H 2 S0 4 ,
Lamers & Indemans) and aluminum s u l f a t e (Al2(S04)3.18H2O, .Merck).
Aerosil as s i l i c a source
Each autoclave was charged with 1.55 g (25.8 mmole) aerosil suspended i n 20
ml demineralized water. To t h i s suspension a s o l u t i o n containing sodium hydrox
i d e , sodium aluminate and organic template was added under s t i r r i n g . The t o t a l
amount of NaOH in the s o l u t i o n was kept a t 8.11 mmole. The amount of NaA102 was
adjusted to obtain a range of S i / A l ratios i n the g e l , which u s u a l l y formed
w i t h i n a few seconds. The amount of template was 8.57 mmole ( 1 , 6 - h e x a n e d i o l ,
1.013 g; 1,6-hexanediamine, 0.993 g; pentaerythritol, 1.167 g; 1-propanol,
0.515 g; 1-propanamine, 0.506 g; TPA-Br, 2.29 g ) . The molar composition of the
gel (as oxides) was: 1.00 Si0 2 :0-0.14 Al 2 0 3 :0.333 template:0.157'Na 2 0:48.8 H 2 0.
Waterglass as s i l i c a source
Each autoclave was charged with a mixture of 7.44 g (30.38 mmole S i 0 2 . 2.18
mmole Na20) waterglass and 6.67 g demineralized water, to which a s o l u t i o n of
0.261 g (2.55 mmole) 96% s u l f u r i c acid, 11.76 mmole template (1,6-hexanediol,
'.";', i . 3 9 ' g ; 1,6-hexanediamine, 1.37 g; p e n t a e r y t h r i t o l , 1.60 g; 1-propanol, 0.707
g; 1-propanamine,; 0.695 g ; TPA-Br, 3.13 g) and aluminum s u l f a t e in 10.67 ml
water was added under..-stirring. The amount of aluminum s u l f a t e was adjusted to
obtain, a range of S/Al r a t i o s i n the g e l , which usually formed w i t h i n a few
,. seconds. The molar composition of the gel (as oxides) was: 1.00 Si02:0-0.11
Al 2 0 3 :0.382 tempi ate :0 .208 Na 2 0:31.7 H20 . ":
In both procedures the autoclaves were closed and s t i r r e d at 448 K for 44
hours. After c o o l i n g , the solids were c o l l e c t e d by f i l t r a t i o n and washed three
times with demineralized water. The samples were dried overnight at 373 K and
analyzed by i n f r a r e d spectroscopy ( I R ) a n d X-ray d i f f r a c t i o n (XRD). A number of
' samples was analyzed as well by X-ray fluorescence (XRF) for chemical composi-
:
, t i o n ,and by scanning electron micrography (SEM) for morphology. IR spectra were
recorded on. a Perkin-Elmer 521 spectrometer, using KBr p e l l e t s . XRD analyses
were performed using an Enraf-Nonius Type I I Guinier-de Wolff camera and CuKa
r a d i a t i o n . XRF analyses were made on a P h i l i p s PW 1400 rbntgen spectrometer
using l i t h i u m borate glass p e l l e t s containing the disclosed sample. SEM micro
graphs were made using a Jeol JXa-50A electron microanalyser.
29

A number of samples which were pure ZSM-5 according to XRD and IR were
submitted to XRF analyses. The analysis data are p l o t t e d in Figure 2.
10
Al/uc (prod)
0
0 2 4 6 8 10
Al/uc (gel)
Figure 2 . XRF analysis data, p l o t t e d as Al/uc in synthesis gel v s . Al/uc in

ZSM-5 product, silica source waterglass: x: 1,6-hexanediamine; +: 1,6-hexane-
v
diol; silica source A e r o s i l : : TPA-Br; o: 1,6-hexanediamine; : 1,6-hexane-
diol.
Figure'2 shows t h a t the r a t i o (Al/uc p r o d u c t ) / ( A l / u c gel) i s somewhat larger

than u n i t y for a l l compositions except one. Thus i t can be concluded that a l u
minum i s preferably incorporated in the s o l i d m a t e r i a l . This is i n agreement
with the r e s u l t s of Romannikov et a l . [12] and Gabelica et al . [ 8 ] .
In the s o l i d s t a t e Al-NMR spectrum [13] recorded from a sample containing
7.46 Al/uc ( i n the product, synthesis from Aerosil and TPA) no signal of o c t a -
29
hedral Al was observed. Furthermore from Si-NMR spectra of the same sample a
l a t t i c e Si/Al r a t i o of 13 (6.9 Al/uc) was e s t i m a t e d . I t can be concluded t h a t
a l l Al i n the sample is incorporated i n the z e o l i t e lattice.
SEM micrographs indicated the growth of larger crystals when using a synthe
s i s mixture w i t h a lower aluminum content, as shown in Figure 3. This has also
been observed by Gabelica et al . [8] and Romannikov et al . [;12]. The l a t t e r
authors suggest an increase in c r y s t a l l i z a t i o n rate with an increase of Si/Al
r a t i o . When Aerosil was used as s i l i c a source, the c r y s t a l s were usually b e t t e r
shaped compared to the c r y s t a l s formed w i t h waterglass as s i l i c a source. This
is assumed to be caused by a lower rate of c r y s t a l growth i n the case of Aero
sil .
30
t e m p l a t e : TPA
aerosl
S i / A l * 35
S i / A l 174
S i / A l = oo
Figure 3. SFM micrographs showing the effect of variation in Si/Al r a t i o on

crystal size.
31
The p u r i t y of the samples was judged from the recorded IR s p e c t r a , e s p e c i a l

ly from the bands a t 1220, 550 and 450 c m " 1 . The bands at 1220 and 550 cm" 1 a r e
structure-sensitive peaks [14] a r i s i n g from 5-ring chain and 5 - r i n g block vi
b r a t i o n s , r e s p e c t i v e l y . The p u r i t y of the sample can be estimated from the op
t i c a l density r a t i o of the 550 and 450 cm bands, which should be 0.8 for pure
ZSM-5 [ 1 4 ] . X-ray diffractograms were also used for ZSM-crystall i n i t y estima
t i o n and i d e n t i f i c a t i o n of i m p u r i t i e s . Main impurities were alpha quartz (sili
con-rich formulations), mordenite and natroalumite (NaA^tSO^tOH^) (alumi
num-rich formulations, waterglass method) and near-kenyaite ( c f . [ 3 ] ) . In Fi
gure 4 the estimated ZSM-5 p u r i t i e s of the various products obtained are p l o t
ted versus the c a l c u l a t e d number of aluminum atoms per u n i t c e l l [15].
Figure 4 c l e a r l y shows t h a t amines allow a wider range of Al/uc-values to be
used to prepare ZSM-5 i n a pure state than the corresponding a l c o h o l s . TPA p r o
vides the widest range o f pure ZMS-5 products, ranging from 0 t o 8 A l / u c . The
small templates (propanol, propanamine) give better r e s u l t s when a double molar
amount of these templates i s used. TPA allows the use of smaller amounts of
t h i s template, e . g . h a l f the molar amount (of the standard formulations given
in the experimental s e c t i o n ) . The use of waterglass as s i l i c a source gives a
higher crystallinity compared to Aerosil . Similar results were obtained by
Derouane, Gabelica and coworkers [ 6 ] , who determined the time f o r 100% ZSM-5
c r y s t a l l i n i t y for active s i l i c a to be approximately six times the time for wa
t e r g l a s s . I t is obvious t h a t waterglass gives a higher c r y s t a l l i z a t i o n rate.
The precise r o l e of the organic template molecules in z e o l i t e synthesis is
s t i l l a matter of much dispute ( c f . [ 5 ] ) . The good performance of TPA as a tem
p l a t e has been r e l a t e d by Boxhoorn et a l . to the i n t e r a c t i o n and reordering of
i n i t i a l l y formed complex s i l i c a t e anions by the TPA cation [ 1 6 ] . Other elements
in the TPA templating potency may be i t s charge and the e f f i c i e n t filling of
the z e o l i t e l a t t i c e . When the pores of ZSM-5 are completely f i l l e d with TPA,
the z e o l i t e contains 4 TPA/uc. Additional counter charge can be i n the form o f
sodium (higher number of Al/uc) or hydroxide ions (lower number of A l / u c ) . It
is obvious that a positively charged species is the best complexant for an
anion. Perhaps template a c t i o n of non-charged organic molecules may also be r e
lated in first instance to i n t e r a c t i o n with the complex s i l i c a t e anions. In
t h i s view amines are better templates because they easier form H-bond complexes
w i t h the Si-OH terminal groups of the s i l i c a t e anion, compared t o a l c o h o l s . In
the synthesized z e o l i t e s the neutral templates are expected to act as l i g a n d s
for sodium ions s i t u a t e d at c r o s s - s e c t i o n s . The resemblance of Na(template) 4 t o
TPA i s clear t h e n .
Figures 2 and 4 show a maximum aluminum content o f approximately 8 A l / u c .
This maximum number is also mentioned in the l i t e r a t u r e [ 2 ] . The exact c r y s t a l -
lographic p o s i t i o n s of the aluminum Ions i n the ZSM-5 l a t t i c e are s t i l l under
discussion. F r i p l a t et al . [17] conclude from non-empirical mechanical c a l c u l a
tions that the Al atoms w i l l be p r e f e r e n t l y located at p o s i t i o n s T2 and T12
32
&
e synthesis of
ate [ 5 ] , the
^nge of app
.ia amines
4.
v' < u :.<**
^ W1 *><c
fcV
A^
^
* ^--catal.,
/ ' a n d H. va
^ ' 9 8 3 (D. 01 s
49' 536.
..iÔosterkamp, and H. >
.el. M a s t i k h i n , S. Hocevar,
^.-ormed by Dr. N.C.M. Alma (Shell Rese

ûer Gaag, J . C . Jansen, and H. van Bekkun
titutipn in ZSM-5
he direct (two-step-)conversion of synthesis

e-containing ZSM-5-type zeolites show a
raction [5].
s the . synthesis and analysis of ZSM-5 type
ther than Al and Si present in the synthesis
ized in sealed glass containers in an oven at

ing for 2 weeks. Two methods were used: the,
uPont) as the silica source, and the second
. In all experiments tetrapropylammoniuni bromide
the template. The molar gel composition was:
20 TPA-Br; 1500 H2O when using Ludox, and 100
5 TPA-Br; 1950 H2O when using waterglass. The
added in the form and the amount given in Table
as performed,using X-ray diffraction and infrared
olume was measured thermogravimetrically by the
t ca. 40C) in a calcined sample (550C) of the
ies of the samples were determined by NH3-TPD on
subsequently calcined sample.
ntroduction, an as-synthesized T-atom substituted

the non-Na and non-TPA cations incorporated in
e the following characteristics:
tructure according to spectroscopie techniques,
kept in mind.that the T-atoms should fit in a

rdination, whereas their size should not introduce
lattice [10,11].
i
34
(a) '(b)
Figure 5. Possible Al positions in ZSM-5 w i t h a maximum of 8 A l / u c . (a) along

[010] a x i s , f o u r - r i n g positions (T9, T10) shown, (b) along [100] a x i s , single
T - s i t e positions (T3, T4) shown.
(positions as denominated by Olson et a l . [ 1 8 ] ) . Two other sets of locations

can be suggested based on c r y s t a l l o g r a p h i c c o n s i d e r a t i o n s . F i r s t l y , the a l u m i
num atoms could be located i n the four-membered rings in the ZSM-5 s t r u c t u r e
(see Figure 5a) (positions T9 and T10). Secondly, the aluminum atoms could be
located in single positions on both sides of the i n t e r s e c t i o n s of the ZSM-5
channels (T3 and T4), as shown i n Figure 5b. Both p o s i t i o n s can explain the ob
served maximum number of e i g h t aluminum atoms per u n i t cell.
When z e o l i t e ZSM-5 and the members of the mordenite group are compared, one
can see that more or less corrugated s i x - r i n g sheets c o n s t i t u t e major building
elements in both groups of z e o l i t e s [19, c f . 2 0 ] . For mordenite and f e r r i e r i t e
the aluminum positions have been reported by Meier [21,22]: in the mordenite
structure the silica sheets are interconnected by four-membered rings of J-L
s i t e s and in the f e r r i e r i t e s t r u c t u r e by six-membered rings with Si and Al a l /
t e r n a t e l y positioned in both s u b - u n i t s . The interconnection between the sheets
i n the ZSM-5 s t r u c t u r e i s made by four four-membered rings of T-sites perûnit
c e l l and eight s i n g l e T-sites ( c f . Figure 5 ) .
The s t r u c t u r e - s e n s i t i v e analysis methods also reveal an increase i n crystal -
u n i t y with decreasing number of Al/uc (especially noticeable with samp.les pre-
pared with TPA). Using XRD a decrease i n XRD l i n e w i d t h was n o t i c e d . This may be
explained by mentioning the p o s s i b i l i t y of a change i n u n i t c e l l parameters due
to aluminum enrichment i n the rim of the c r y s t a l s , which was detected by von/
Ball moos [ 2 3 ] . // I
33
Figure 4. Estimated ZSM-5 content of solids plotted vs. Al content of synthesis

mixture, expressed as Al/uc of ZSM-5. (a) 1-propanol as template, (b) 1,6-hexa-
nediol, (c) pentaerythritol, (d) 1-propanamine, (e) 1,6-hexanediamine, (f) TPA-
Br. Silica sources: Aerosil (v ), waterglass (0). Aerosil, amount of template
doubled (X) (in a and d ) . Waterglass, half amount of template (X) (in f).
35
CONCLUSIONS
It is demonstrated t h a t for the synthesis of ZSM-5, under conditions recom
mended for 1,6-hexanediol as template [ 5 ] , the p u r i t y of the z e o l i t e product
depends on the template used. The range of applicable s t a r t i n g silica/alumina
r a t i o s increases going from alcohols via amines to TPA as a template. More spe
c i f i c a l l y the order i s :
p e n t a e r y t h r i t o l < propanol < hexanediol < propanamine < hexanediamine < TPA.
Casci et al . [ 3 j claim a range of Si/Al r a t i o s for 1,6-hexanediol from 10 t o
100, preferably 20 to 60. Our investigations show a narrower range, S i / A l =
15-25, of a p p l i c a t i o n .
In general, i t can be said t h a t in the synthesis of ZSM-5 with a high Si/Al
ratio (low number of A l / u c ) , templates l i k e 1,6-hexanediamine or TPA should b e '
used t o obtain a 100% c r y s t a l l i n e ZSM-5 product. Samples prepared using water-
glass as s i l i c a source have a higher crystallinity than those prepared from
Aerosil . This i s in accordance with the r e s u l t s of Derouane, Gabelica and co-
workers { 6 ] .
An unique location of A l , e . g . i n the f o u r - r i n g s of ZSM-5, can account for
the observed maximum of 8 Al per u n i t c e l l and i s in harmony w i t h aluminum po
s i t i o n s in zeolites of the mordenite group.
ACKNOWLEDGEMENTS
The authors would l i k e to thank Mr. J . F . van Lent and Mr. N.M. van der Pers
for the XRD analyses and Mr. D.P. Nelemans ( a l l of the Laboratory of M e t a l l u r
gy) for the SEM micrographs. P r o f . K. Koopmans and Mr. Th.W. Verkroost (Depart
ment o f Mining Engineering) are thanked for the XRF analyses. Dr. N.C.M. Alma
(Shell Research B.V., Amsterdam) is g r a t e f u l l y thanked for the s o l i d state
27
Al-NMR a n a l y s i s . Mr. G.F. Herlaar is thanked for discussions.
REFERENCES
1 R.J. Argauer and G.R. Landolt, US Patent 3.702.886.

2 See, for example, R. von Ballmoos, Ph.D. Thesis, ETH Zurich, 1981.
3 J . L . Casci, B.M. Lowe, and T.V. Whittam, Eur . Pat. A p p l . 0.042.225.
4 T. Mole and J.A. Whiteside, J . C a t a l . , 75 (1982) 284.
5 B.M. Lok, T.R. Cannan, and C .A. Messina, Z e o l i t e s , 3 (1983) 282.
6 E.G. Derouane, S. Detremmerie, Z. Gabelica, and N. Blom, A p p l . C a t a l . , 1
(1981) 201.
7 Z. Gabelica, E.G. Derouane, and N. Blom, Appl. Catal., 5 (1983) 109.
8 Z. Gabelica, N. Blom, and E.G. Derouane, Appl. Catal., 5 (1983) 227.
9 D.H. Olson, W.0. Haag, and R.M. Lago, J. Catal., 61 (1980) 390.
10 J.C. Oudejans, F.J. van der Gaag, and H. van Bekkum, in "Proc. Sixth
Intern. Conf. Zeolites", Reno 1983 (D. Olson and A. Bisio, Eds.),
Butterworth, Guildford, 1984, p. 536.
11 J.C. Oudejans, P.F. van den Oosterkamp, and H. van Bekkum, Appl. Catal., 3
(1982) 109.
12 V . N . Romannikov, V.M. Mastikhin, S. Hocevar, and B. Drzaj, Zeolites, 3
(1983) 311.
13 Analysis performed by Dr. N.C.M. Alma (Shell Research B.V., Amsterdam).
14 F . J . van der Gaag, J . C . Jansen, and H. van Bekkum, Z e o l i t e s , 4 (1984) 369.
36
15 Calculated from Si/Al in the synthesis gel, assuming 96 T-atoms per unit
cell .
16 G. Boxhoorn, 0. Sudmeijer, and P.H.G. van Kasteren, J. Chem. S o c , Chem.
Commun., (1983) 1416.
17 J.G. Fripiat, F. Berger-Andr, J.M. Andr, and-E.G. Derouane, Zeolites, 3
(1983), 306.
18 D.H. Olson, G.T. Kokotailo, and S.L. Lawton, J. Phys. Chem., 85 (1981)
2238.
19 F.J. van der Gaag, J.C. Jansen, and H. van Bekkum, to be published.
20 E.M. Flanigen, J.M. Bennett, R.W. Grose, J.P. Cohen, R.L. Patton, R .M.
Kirchner, and J.V. Smith', Nature, 271 (1978) 512.
21 W.M. Meier, R. Meier, and V. Gramlich, Z. Kristallogr., 147 (1978) 329.
22 W.M. Meier, "Constituent sheets in the zeolite frameworks of the mordenite
group", p. 99, in "Natural Zeolites", (L.B. Sand and F.A. Mumpton, Eds.),
Pergamon Press, 1978.
23 R. von Ballmoos and W.M. Meier, Nature, 289 (1981) 782.
Substitution in ZSM-5 37
IS0MORPHOS SUBSTITUTION IN ZBOLITB ZSM-5.
SUMMARY
ZSM-5 type zeolites were synthesized using synthesis

mixtures containing various ions other than Na, Si and Al.
Structural analysis of the products invariably confirmed
the ZSM-5 structure, however it appears that incorporation
into the lattice is limited to Al, Fe and Ti.
INTRODUCTION
T-atom substitution is a versatile tool to tailor a zeolite's
properties. Especially catalytic activity can be altered by substitution.
An example is the decrease of the acid strength of H-ZSM-5 upon
incorporating B instead of Al. It is well known that zeolites can be
synthesized using Si or Ge and Al, B or Ga as T-atoms. Numerous patents
claim the use of T-atoms other than Si and Al in zeolite ZSM-5 synthesis
[e.g. 1-5]. Recently more detailed studies on the substitution of
T-atoms, concerning both catalytic activity and the location of the
substituting ion, were published [6-12]. Some authors claim that almost
any metal forming a badly soluble hydroxide can be incorporated into a
zeolite lattice. However, lone et al. [10,11] have stressed that it is
also necessary that these ions should prefer a tetrahedral coordination.
This limits the range of suitable elements considerably with as best-known
members B, Be, Al, Ga and Fe. Kustov et al. [12] have recently
published a spectroscopie investigation of the Fe ions in ferrisilicate
ZSM-5 samples. Only a part of the Fe is found to be incorporated in the
lattice; the other part is present in extralattice locations.
Another characteristic property of a well-crystallized zeolite sample

might be its colour. In the case of Fe built in the materials have
been reported to be white [18], provided coloured counter-cations are
absent. Some of these materials (especially the Fe-containing samples) may
38 Substitution in ZSM-5
be interesting in view of the direct (two-step-)conversiqn of synthesis

gas into hydrocarbons, e.g. Fe-containing ZSM-5-type zeolites show a
high selectivity to the C3+-fraction [5].
The present paper describes the . synthesis and analysis of ZSM-5 type
zeolites with various ions other than Al and Si present in the synthesis
formulation.
EXPERIMENTAL
All zeolites were synthesized in sealed glass containers in an oven at
100C with occasional shaking for 2 weeks. Two methods were used: the
first using Ludox HS-40 (DuPont) as the silica source, and the second
using waterglass (Merck). In all experiments tetrapropylammonium bromide
(TPA-Br) was applied as the template. The molar gel composition was:
100 Site; x Ta; 20 NaOH; 20 TPA-Br; 1500 H2O when using Ludox, and 100
Si02; x T2; 11.9 0H-; 19.5 TPA-Br; 1950 H2O when using waterglass. The
secondary T-atom (T2) was added in the form and the amount given in Table
1. Structural analysis was performed using X-ray diffraction and infrared
spectroscopy. The pore volume was measured thermogravimetrically by the
adsorption of n-hexane (at ca. 40C) in a calcined sample (550C) of the
zeolite. The acid properties of the.samples were determined by NH3-TPD on
an ammonium-exchanged and subsequently calcined sample.

As mentioned in the introduction, an as-synthesized T-atom substituted
ZSM-5 type zeolite with the non-Na and non-TPA cations incorporated in
the lattice, should have the following characteristics:
1) exhibit the ZSM-5 structure according to spectroscopie techniques,
2) colourless (white),
Moreover it should be kept in mind.that the T-atoms should fit in a
tetrahedral oxygen coordination, whereas their size should not introduce
too much strain in the lattice [10,11].
Table 1: Substituted ZSM-5 type z e o l i t e s , synthesis conditions and analytical data.

k
Ion added fors coordi Si/X Si- CO. our ) XRD result IR p u r i t y n-hexane hexane/IR
nation') (gel) source before/after calc (structure) (I) ads (il/g) (1/9)
Hg I I MgCh 6 45 Ludox white white ZSM-5 102.6 0.140 0.136
Ca I I Ca(0Hh 6 19 Ludox white white ZSM-5 83.3 0.124 0.148
Sr I I SrfNthh 6 45 Ludox white white ZSM-5 82.3 0.131 0.159
Hn I I Hn(0Ach 6,(4t,4s) 45 Ludox brownish brownish ZSM-5 94.6 0.134 0.142
Fe I I FeS0 4t,(6) 24 Ludox white white ZSH-5 92.0 0.151 0.164
Fe I I I Fe2(S0<b 4t,6 45 Ludox white white ZSH-5 85.4 0.138 0.162
Co I I CoSOt 6,(4t) 45 Ludox pink purple ZSH-5 93.8 0.114 0.122
Hi I I NiS0 6,(4s,4t) 18 Ludox green grey ZSM-5 93.3 0.153 0.164
Cu I I CuCh d6,4t,(4s) 45 Ludox blueish brwn/bluc ZSM-5 91.9 0.128 0.139
Zn I I ZnSOi 4t 37 Ludox white white ZSM-5 80.0 0.142 0.178
Cr I I I Cr(N0i) 6,(d4t)<) 45 Ludox green yellow ZSM-5 91.6 0.142 0.155
V V NH1VO3 d6,(4t) 45 Ludox white white ZSM-5 93.1 0.147 0.158
Te VI HzTeO* 6,(4t) 45 Ludox white white ZSH-5 83.4 0.136 0.163
Hn I I Hn(0Ach 6,(4t,4s) 45 HG brownish brownish ZSH-5 82.0 0.138 0.168

Fe I I FeS0 4t,(6) 45 HG white white ZSM-5 77.9 0.132 0.170
Fe I I I Fez(S0)j 4t,6 45 HG white white ZSH-5 76.4 0.136 0.178
Co I I C0SO4 6,(4t) 45 HG pink purple ZSH-5 80.5 0.140 0.174
Ni I I NiS0 6,(4s,4t) 45 HG green beige ZSH-5 69.8 0.128 0.134
Cu I I CuCh d6,4t,(4s) 45 HG blueish blue ZSH-5 83.4 0.155 0.186
Zn I I ZnS0 4t 45 HG white white ZSH-5 73.5 0.108 0.138
Hg I I Hgh 11 ) 4t 45 HG white white ZSH-5 95.0 0.151 0.159
Ti IV') Ti0S0*H:0! 4t 45 HG white white ZSH-5 74.0 0.149 0.201
Zr IV Zr0ChtHz02 4t,6,)7 45 HG white white ZSM-5 86.9 0.127 0.146
V V NHV0J d6,(4t) 45 HG white white ZSH-5 92.0 0.144 0.157
"} preferred coordination nuuber: 4s=square planar, 4t=tetrahedral, 6-octahedral,

a d prefix eans distorted; between brackets: alternative non-preferred configurations. [15]
b
) after calcination at 550C.
c
) data for Cr ( l i t ) ; Cr(VI) w i l l accowodate 4t.
d
) Hgh hardly dissolved.
) zeolite crystallization 2 days at 180C.
The results of the syntheses, including data on the above-mentioned

properties, are l i s t e d in Table 1. The pore volume was measured to verify
whether or not pores are obstructed by e x t r a - l a t t i c e clusters of the
T-atom oxide or hydroxide. For a well-crystallized ZSM-5 sample a value of
0.18 ml/g has been accepted for the adsorption of n-hexane [13] at 40C.
The purity of the sample' can be estimated from the IR spectrum [14] as a
convenient means of analysis. Table 1 also shows the hexane adsorption of
the various materials normalized via IR purity to pure ZSM-5 (=hexane/IR).
The data in Table 1 show that all syntheses yield a product with a ZSM-5
type structure. Infrared data show a substantial variation in zeolite
crystallinity from 70-100*. Nevertheless, the ZSM-5 structure is also
clearly evident in the samples of relatively low crystallinity. It should
be noted that amorphous materials cannot be detected using routine X-ray
diffraction, whereas the difference is clear in infrared spectra.
The amount of n-hexane adsorbed, normalized to a pure ZSM-5 together

with the colour of the sample, can be used to judge whether the ion is
properly incorporated into the lattice or not. A white sample with a
normalized adsorption of more than 0.16 ml hexane/g (allowing 10% for
experimental errors) is supposed to have the substituting ions
incorporated in the lattice. This leaves the samples prepared from gels
containing Fe(III), Fe(II) and Ti(IV), and -for Ludox as the silica
source- Zn(II) and Te(VI). It may be noted that these ions will all fit
in a tetrahedral coordination, except for Te(VI) which prefers an
octahedral coordination. Coloured impurities however cannot be observed
in this case, because Te salts (as well as Ti and Zn salts) are white.
Ball et al.[9] use MAS-NMR to show that Zn is only partially
incorporated in a Silicalite lattice.
The incorporation of the substituting ions in a zeolite lattice may have

an analogon in the phosphates: it is well-known that the phosphates of
B(III), Al(III), Ga(III), Fe(III), As(III) and Sb(III) show a structure
resembling that of quartz.
In addition to the present analyses chemical analytical data of the
ZSM-5 samples will be required in order to establish the presence of the
T2 atoms quantitatively.
Table 1: S u b s t i t u t e d ZSM-5 type z e o l i t e s , synthesis c o n d i t i o n s and a n a l y t i c a l data.
Ion added fore coordi Si/X Si- colour 6 ) XRD result IR purity n-hexane hexane/IR
nation') (gel) source before/after calc (structure) (I) ads ( i l / g ) (1/9)
Hg I I MgCh 6 45 Ludox white white ZSH-5 102.6 0.140 0.136
Ca I I Ca(0Hh 6 19 Ludox white white ZSM-5 83.3 0.124 0.148
Sr I I SrlNOsh 6 45 Ludox white white ZSH-5 82.3 0.131 0.159
Hn I I Mn(0Ac)2 6,(4t,4s) 45 Ludox brownish brownish ZSH-5 94.6 0.134 0.142
Fe I I FeS0 U,(6) 24 Ludox white white ZSH-5 92.0 0.151 0.164
Fe I I I FezfSOOs 4t,6 45 Ludox white white ZSH-5 85.4 0.138 0.162
Co I I CoSO 6,(4t) 45 Ludox pink purple ZSH-5 93.8 0.114 0.122
Hi I I NiS0 6,(4s,4t) 18 Ludox green grey ZSH-5 93.3 0.153 0.164
Cu I I CuCh d6,4t,(4s) 45 Ludox blueish brwn/blue ZSH-5 91.9 0.128 0.139
Zn I I ZnS0< 4t 37 Ludox white white ZSH-5 80.0 0.142 0.178
Cr I I I Cr(N<h)j 6,(d4t)<) 45 Ludox green yellow ZSH-5 91.6 0.142 0.155
VV NH4VO3 d6,(4t) 45 Ludox white white ZSH-5 93.1 0.147 0.158
Te VI HzTeOi 6,(4t) 45 Ludox white white ZSH-5 83.4 0.136 0.163
Hn I I HnlOAch 6,(4t,4s) 45 HG brownish brownish ZSH-5 82.0 0.138 0.168

Fe I I FeS04 4t,(6) 45 HG white white ZSH-5 77.9 0.132 0.170
Fe I I I Fe2(S0b 4t,6 45 UG white white ZSH-5 76.4 0.136 0.178
Co I I CoS0 6,(4t) 45 HG pink purple ZSH-5 80.5 0.140 0 : 174
Mi I I HiS0 6,(4s,4t) 45 HG green beige ZSH-5 69.8 0.128 0.184
Cu I I CuCh d 6 , 4 t , ( 4 s ) 45 UG blueish blue ZSH-5 83.4 0.155 0.186
Zn I I ZnS0 4t 45 HG white white ZSH-5 73.5 0.108 0.138
Hg I I Hgl2 d ) 4t 45 UG white white ZSH-5 95.0 0.151 0.159
U IV') Ti0S04+Hi02 4t 45 UG white white ZSH-5 74.0 0.149 0.201
Zr IV ZrOCli+HzOz 4 t , 6 , ) 7 45 HG white white ZSH-5 86.9 0.127 0.146
VV NHWO3 d6,(4t) 45 HG white white ZSH-5 92.0 0.144 0.157
') preferred coordination nueber-. 4s=square planar, 4t=tetrahedral, 6;octahedral,

a d prefix aeans distorted; between brackets: alternative non-preferred configurations. [15]
b
) after calcination at 550C.
c
) data for Cr(III); Cr(Vl) will accowodate 4t.
') Hgl2 hardly dissolved.
') zeolite crystallization 2 days at 180C.
The r e s u l t s of the s y n t h e s e s , including data on the above-mentioned
properties, are l i s t e d in Table 1. The pore volume was measured t o verify
whether or not pores are obstructed by extra-lattice clusters of the
T-atom oxide or hydroxide. For a w e l l - c r y s t a l l i z e d ZSM-5 sample a value of

0.18 ml/g has been accepted for the adsorption of n-hexane [13] at 40C.
The purity of the sample' can be estimated from the IR spectrum [14] as a
convenient means of analysis. Table 1 also shows the hexane adsorption of
the various materials normalized via IR purity to pure ZSM-5 (=hexane/IR).
The data in Table 1 show that all syntheses yield a product with a ZSM-5
type structure. Infrared data show a substantial variation in zeolite
crystallinity from 70-100*. Nevertheless, the ZSM-5 structure is also
clearly evident in the samples of relatively low crystallinity. It should
be noted that amorphous materials cannot be detected using routine X-ray
diffraction, whereas the difference is clear in infrared spectra.
The amount of n-hexane adsorbed, normalized to a pure ZSM-5 together

with the colour of the sample, can be used to judge whether the ion is
properly incorporated into the lattice or not. A white sample with a
normalized adsorption of more than 0.16 ml hexane/g (allowing 10% for
experimental errors) is supposed to have the substituting ions
incorporated in the lattice. This leaves the samples prepared from gels
containing Fe(III), Fe(II) and Ti(IV), and -for Ludox as the silica
source- Zn(II) and Te(VI). It may be noted that these ions will all fit
in a tetrahedral coordination, except for Te(VI) which prefers an
octahedral coordination. Coloured impurities however cannot be observed
in this case, because Te salts (as well as Ti and Zn salts) are white.
Ball et al.[91 use MAS-NMR to show that Zn is only partially
incorporated in a Silicalite lattice.
The incorporation of the substituting ions in a zeolite lattice may have

an analogon in the phosphates: it is well-known that the phosphates of
B(III), Al(III), Ga(III), Fe(III), As(III) and Sb(III) show a structure
resembling that of quartz.
In addition to the present analyses chemical analytical data of the
ZSM-5 samples will be required in order to establish the presence of the
T2 atoms quantitatively.
Information about the acid properties can be obtained with temperature

programmed desorption of ammonia from ammonium-exchanged and calcined
ZSM-5 samples. During ion exchange of Cr-containing samples (using
either NH4C1 or HC1 solutions as exchange reagents), the exchange solution
turned yellow, indicating extraction of Cr from the sample. Repeated (3
times) ion exchange using a 0.5 M HC1 solution yields a green (Cr(III))
sample and an almost colourless exchange solution after the
last exchange. Chemical analysis shows that only the first exchange
results in a significant decrease in Cr content of the sample, indicating
two types of Cr present in the as-synthesized material. Note that only
the substituting elements with a 2+ or 3+ valency will yield cation
exchange capacity and the possibility of generating acid properties.
Boro-, chromo- and ferrisilicate (all ions having valency 3+) are reported
to show acid properties [7,8], all with a lower acid strength than a
corresponding [Al]-ZSM-5 sample. [Cr]-ZSM-5 samples used in the
ammoxidation of toluene (see Chapter 6) show a good activity and
selectivity. In these samples the zeolite pore system will still be
accessible to the reactants.
TPD experiments on most of the samples of Table 1 show hardly any

ammonia-desorption at temperatures above 350C. The only samples with a
measurable high-temperature desorption are the zeolites containing
Fe(III) (Ludox, WG) and Mn(II) (Ludox), and, with a smaller desorption,
Fe(II) (Ludox, WG). Figure 1 shows the NH3-TPD curves of a ferrisilicate
and of an aluminosilicate ZSM-5 sample with a comparable hetero-atom
content. The acid strength of the former zeolite is somewhat lower, as
was also shown by other Workers by means of several analytical methods
[12,16,17]. The sample containing Mn has a much lower acid strength, as
evidenced by a lower desorption temperature (390C compared to 440-480C
for Fe(III)). It should however be noted that the manganosilicate zeolite
contains some non-zeolitic impurities, as judged from the brownish colour
of the sample.
Substitution in ZSM-5
Figure 1: TPD curve of a ferrisilicate and an aluminosilicate ZSM-5

zeolite sample, a) [Fe(III)]-ZSM-5 (Ludox, Si/Fe=45); b)
[Al]-ZSM-5 (Ludox, Si/Al=50).
The amount of substitution seems to be limited to a low T2 content (e.g.

less than 2-4 T2/UC). Attempts to synthesize a ferrisilicate sample with a
higher content (8 Fe/uc, Si/Fe=ll) yielded a brown sample. Mossbauer
analysis [19] of this sample showed the presence of two types of Fe, which
are assumed to be an extra-lattice-type and an incorporated type.
Mossbauer measurements on samples with a lower Fe content proved
S7
impossible so far due to the low sensitivity without Fe enrichment.
CONCLUSIONS
Crystalline ZSM-5-type zeolites can be synthesized from gels containing
various ions other than Al and Si. Only ions which may be tetrahedrally
coordinated appear to be incorporated in the lattice.
Temperature programmed desorption of ammonia shows that only the ferri-
silicate ZSM-5 sample exhibits acidic properties comparable to those of
aluminosilicate ZSM-5 samples. The Ti(IV)silicate sample does not exhibit
acidity, according to expectations.
Other ions are expected to be present as impurities in the zeolite

channels or on the outer surface. These ions can usually be extracted
using a HCl or a NH4CI solution, as described for the partial exchange of
a Cr containing sample. However, addition of these ions to the synthesis
gel can be used to influence the catalytic properties of the zeolite as
extra-lattice entities, (cf. Chapters 6, 9 and 10)
LITERATURE
1. F.G. Dwyer, E.E. Jenkins, US Patent 3.941.871 (1976).

2. L.Marosi, J. Stabenow, M. Schwarzmann, Ger. Offen. 2.831.631 (1980).
3. M. Taramasso, G. Manara, V, Fattore, B. Notari, Ger. Offen. 2.924.915
(1980).
4. J.A. Hinnekamp, V.V. Walatka, Ger. Offen. 3.215.069 (1981).
5. J.K. Minderhoud, T. Huizinga, S.T. Sie, Eur. Patent 173.381 (1984),
CA 104, P209940s (1986).
6. R. Szostak, T.L. Thomas, J. Catal., 100, (1986), 555.
7. T. Inui, A. Miyamoto, H. Matsuda, H. Nagata, Y. Makino, K. Fukuda,
F. Okazumi, "Proc. VII Int. Zeol. Conf.", (Eds. Y. Murakami,
A. Iijima, J.W. Ward), Tokyo 1986, p.859-866.
8. R.B. Borade, A.B. Halgeri, T.S.R. Prasada Rao, "Proc. VII Int. Zeol.
Conf.", (Eds. Y. Murakami, A. Iijima, J.W. Ward), Tokyo 1986,
p.851-858.
9. W.J. Ball, S.A.I. Barri, S. Cartlidge, B.M. Maunders, D.W. Walker,
"Proc. VII Int. Zeol. Conf.", (Eds. Y. Murakami, A. Iijima, J.W.
Ward), Tokyo 1986, p.951-956.
10. K.G. lone, L.A. Vostrikova, A.V. Petrova, V.M. Mastikhin, in: "Proc.
VIII Int. Congr. Catal.", Berlin 1984, vol. IV, p.519.
11. K.G. lone, L.A. Vostrikova, V.M. Mastikhin, J. Mol. Catal., 31,
(1985), 355.
12. L.M. Kustov, V.B. Kazansky, P. Ratnasamy, Zeolites 7, (1987), 79.
44
Substitution in ZSM-5
13. D.H. Olson, W.O. Haag, R.M. Lago, J. Catal., 61, (1980), 390.
14. J.C. Jansen, F.J. van der Gaag, H: van Bekkum, Zeolites, 4, (1984),
369.
15. F.A. Cotton, G. Wilkinson, "Advanced Inorganic Chemistry", J. Wiley &
Sons, New York, 1980.
16. W.J. Ball, J. Dwyer, A.A. Garforth, W.J. Smith, "Proc. VII Int. Zeol.
Conf.", (Eds. Y. Murakami, A. Iijima, J.W. Ward), Tokyo 1986,
p.137-144.
17. C.T.-W. Chu, C D . Chang, J. Phys. Chem., 89, (1985), 1569.
18. R. Szostak, V. Nair, T.L. Thomas, J. Chem. Soc, Faraday Trans. I,
83, (1987), 487.
19. Measurements of Dr. A.M. v.d. Kraan, IRI, Delft, which are gratefully
acknowledged.
Morphology and acid site distribution of ZSM-5 zeolites. 45
A note on the effect of the template on the acid features and the particle
size of ZSM-5 zeolites.
Abstract: A series of ZSM-5 zeolites was synthesized using different templates under fast crystallization
conditions using Aerosil and waterglass as the silica source. It seems that the more effective the template,
the smaller the crystals formed. It is concluded that a pronounced p state NH3-desorption is related to the
presence of imperfections in the zeolite crystals.
Introduction: Temperature Progammed Desorption (TPD) of volatile bases like ammonia is used to
characterize the acid sites of zeolites. Three desorption peaks are distinguished in the TPD of ammonia
from zeolite H-ZSM-5: the a, p and ypeak, with maxima at 400,500 and 775 K[1], respectively. The a state
peak is ascribed to the desorption of physisorbed NH 3 . The p and y state peaks are ascribed to Lewis and
Bransted acid sites, respectively.
Previous experiments[2] showed that the 'template strength' in forming (and stabilizing) ZSM-5 zeolite is
in the order: TPA > 1,6-hexanediamine > 1 -propanamine > 1,6-hexanediol > 1 -propanol > pentaerythritol.
SEM micrographs (Figure 1) indicate that the morphology changes in the same order from particles without
crystalline appearance to well-crystallized samples. Although only shown here for Aerosil as silica source,
similar micrographs are obtained for samples prepared using waterglass. This note will show that the results
obtained using NHg-TPD experiment bear a relation to the particle size of and the template used in the
preparation of the ZSM-5 crystals.
Experimental: ZSM-5 zeolites were synthesized using tetrapropylammonium bromide (TPA-Br),

1,6-hexanediamine, 1,6-hexanediol, pentaerythritol (PET), 1-propanamine and 1-propanol as template.
The zeolites will be referred to as ZSM-5 (TPA), ZSM-5 (hexanediamine) etc. Aerosil and waterglass were
used as silica source, and the corresponding Al sources were sodium aluminate and aluminum sulphate.
Synthesis was performed in stainless steel autoclaves for 48 hours at 180C as described in earlier [2]. The
products were identified as pure ZSM-5 zeolites using X-ray diffraction and infrared spectroscopy. An
exception is the sample prepared from waterglass using PET as the template. Infrared spectroscopy,
showed this sample to contain some amorphous material. The. zeolites were calcined at 823 K and
ammonium exchanged using 2M NH 4 CI (10 ml/g) at 353 K for 1 hour. The zeolites were dried at 373 K
prior to further use. All zeolites had a charged Si/AI ratio of 35 (silica source Aerosil) or 45 (silica source
waterglass). AAS analysis of part of the samples (after dissolution in HF) showed that the chemical
composition of the product is close to as the composition of the synthesis mixture[2].
A sample of F-Silicalite [3] was included for comparison.
NH3-TPD spectra were measured on 100 mg samples of the NH4-ZSM-5 zeolites. Before recording the
spectrum the zeolite was heated to 873 K in the TPD apparatus under flowing nitrogen. The sample was
then cooled to ca 300 K and a flow of NH 3 was adsorbed for half an hour. After displacement of the NH 3
vapour with nitrogen the sample was heated at a rate of 10 K/min in flowing nitrogen. The rate of N H 3
Morphology and acid site distribution of.ZSM-5 zeolites.
46
Figure 1: SEM micrographs showing the particle size of the zeolite samples (Aerosii used as silica
source).
desorption was measured using a thermal conductivity detector. Peak areas (corresponding to amounts of
desorbed ammonia) were determined by cutting out and weighing the peaks. The homogeneity of the
paper was checked.
BET surfaces were determined on an Areameter using a single point method.
Results and discussion: Typical NH 3 -TPD spectra of the zeolites are shown in Figure 2. Ratios
between the areas under the TPD peaks (and therefore relative amounts of desorbed NH3) are presented
as bar graphs in Figure 3, together with BET surface areas. In the TPD spectra of ZSM-5 (TPA) and ZSM-5
(hexanediamine) the a state desorption looks more pronounced than in the other spectra indicating a
relatively better crystallized pore system.
Figure 2: NH3-TPD spectra of ZSM-5-type zeolites. Templates used: a: TPA; b: 1,6-hexanediamine;

c: 1-propanamine; d: 1,6-hexanediol; e: 1-propanol; f: PET.
The. a/y ratio in Figure 3 is about the same for all templates in the Aerosil as well as the waterglass
experiments suggesting that pore volume variations and number of Bronsted sites go parallel (bearing in
mind a constant Al content). The ct/p ratio in the spectrum of ZSM-5(TPA) and to a lesser extend in the
spectrum of ZSM-5 (hexanediamine) are high compared to the spectra of the other templates. Apparently
there is less material causing (3 state desorption (e.g. extra-lattice Al, lattice imperfections, side products)
formed using the first two templates than when using the other templates.
Obviously, the same trend appears to be present considering the yp ratio in Figure 3. Consistent with the
48 Morphology and acid site distribution ot 2SM-5 zeolites.
above explanation is the higher BET area of ZSM-5 (TPA) compared to the BET areas of the other
templates. Low pore blocking and highly crystalline material creating the proper surface area is expected to
result from the high templating strenght of TPA in ZSM-5 crystallization.
Aerosil
Y/fi 0-/Y <*/$> BET area
Waterglass
Vr'fb a/Y C*/|S BET area
Figure 3: Bar graphs showing NH3-TPD and BET data for samples of ZSM-zeolites prepared using
different templates.
As shown in Figure 1 the crystal size and agglomeration of crystallites seems to depend upon the typical
template used in the synthesis mixture. As discussed the differences in the above mentioned particle size
influence the TPD spectra, as reflected in the variations in Figure 3. A strong template yields a faster
nucleation (and therefore smaller crystallites) and a better formed crystal structure (i.e. a better defined
TPD spectrum). In spite of the spheroid appearance of the crystals, the pore structure is better formed and
accessible to adsorbates.
It is concluded that:
-Using the template TPA, aluminum is more regularly incorporated as T-atom in the lattice system than with
the other templates studied.
-1,6-hexanediamine is the second to TPA in this respect.
-The other templates show more pronounced Lewis acid features according to the TPD spectra.
-A well-formed pore system (according to TPD) corresponds to badly formed crystals (shown in SEM
micrographs) and vice versa, in the series studied.
-The present findings underline the necessity to establish of the quality of a zeolite sample using
a combination of techniques.
Literature:
1. N.Y. Topsee, K. Pedersen, E.G. Derouane, J. Catal., 70, (1981), 41.
2. F.J. van der Gaag, J.C. Jansen and H. van Bekkum, Appl. Catal., 17, (1985), 261.
3. E.M. Flanigen, R.L. Patton, US Patent 4.073.865, (1976).
50 Ammoxidation of toluene
AMMOXIDATION O F TOLUENE OVER

M O D I F I E D Z S M - 5 TYPE C A T A L Y S T S .
F . J . van der Gaag, G.F. Herlaar and H. van Bekkum,

Laboratory of Organic Chemistry, Delft U n i v e r s i t y of Technology,
J u l i a n a l a a n 136, 2628 BL DELFT, The Netherlands.
ABSTRACT.
Toluene was ammoxidized over modified ZSM-5 type
zeolites as catalysts. Modification was performed by
(partial) T-atom substitution of Fe and Cr for Al in the
synthesis gel and by ion exchange. Especially zeolites
CuCrH-ZSM-5 and CuH-[Fe]-ZSM-5 proved to combine high
activity in the ammoxidation at 350 C with high
selectivity to benzonitrile.
INTRODUCTION.
Ammoxidation is a process converting hydrocarbons containing activated
methyl groups such as toluene, the xylenes and propene to the
corresponding nitriles. As for the synthesis of benzonitrile, several
studies have been published, envisaging the use of mixed oxides consisting
of vanadium, molybdenum and chromium [1,2]. Also catalysts with low
oxidation power such as solid acids like Si02-Al203, Zr02-Si02 and
Ti2-Si02 were found to possess ammoxidation activity [3]. For the
oxidation of toluene and related aromatics Jonson et al. [4] recently
have suggested a relation between an infrared vibration of oxidic
catalysts and the activity of the catalyst; high activity is reported for
CuO, Cr23 and Fe23 catalysts, which have an infrared vibration near 520
1
cm" . Ohorodnik et al. [5] demonstrated that impregnation of a bismuth-
phosphomolybdate propene ammoxidation catalyst with an Fe solution
increases the activity. Deactivated catalysts can be restored to their

Ammoxidation of toluene 51
original activity by impregnation.

In a previous paper [6] we reported on the ammoxidation activity of a
Cu-H exchanged ZSM-5 type zeolite catalyst in converting toluene into
benzonitrile. When water was added to the feed, a significant increase in
activity and selectivity was observed. Water is supposed to play a role
either as a ligand to the Cu ion, in proton transport and/or as a decoking
agent. Optimum selectivity to benzonitrile was observed at 350C.
In this paper we present data on the ammoxidation activity of a

series of exchanged and T-atom substituted ZSM-5-type catalysts. In
particular the effect of Fe- and Cr-incorporation was studied, as these
metals have been shown to enhance the ammoxidation activity of amorphous
catalysts.
EXPERIMENTAL.
Catalysts.
Zeolite ZSM-5-type catalysts were synthesized according to the patent
literature [7-10]. Two procedures were used, one using Aerosil as the
silica source and the other using waterglass.
The first procedure comprised mixing an Aerosil (Degussa) suspension
with a solution containing sodium hydroxide, the secondary T-atom(s)
source and the template TPA-Br, 1,6-hexanediol or 1,6-hexanediamine [11]
(Janssen Chimica), followed by crystallization for 48 hours in a
Teflon-coated autoclave at 180C with stirring.
The second method comprised mixing a waterglass solution with a solution
containing sulfuric acid, the secondary T-atom(s) source and TPA-Br,
followed by a crystallization under the same conditions as for method 1.
The secondary T-atom was supplied as sodium aluminate (Aerosil method,
Riedel-de Haehn), aluminum sulfate (waterglass method, Merck),
chromium(III)sulfate (Merck) or ferrous sulfate (UCB). When the secondary
T-atom is not Al, the zeolite is denoted [X]-ZSM-5, with X being the guest
T-atom. [Fe]- and [Al,Fe]-ZSM-5 were prepared using TPA-Br as the
template, 1,6-hexanediamine was used for [Cr]- and [Al,Cr]-ZSM-5.
In both procedures the synthesis product was filtered, washed and dried.
The ZSM-5-type structure was inspected by X-ray diffraction. The
as-synthesized samples were white and remained white during calcination at
550C. An exception is [Cr]-ZSM-5, which was light-green after drying and
yellow after calcination, showing that part of the Cr is not incorporated
in the lattice. H-exchange was performed by exchanging the calcined
zeolite twice with a 0.5 M HC1 solution (100 ml/g of zeolite, 80C, 0.5
hr). Under these conditions part of the Cr was leached out of the
[Cr]-zeolites, as evidenced by a yellow colour of the exchange solution
after filtration. The effect of Cr-extraction during H-exchange was .
monitored in a separate experiment. AAS analysis of [Cr,Al]-ZSM-5 samples
(see Table 2) show that the Cr content decreases from 0.88 Cr/uc
(Si/Cr=100) to 0.45 Cr/uc (Si/Cr=195) during the first exchange.
Subsequent exchanges do not cause a significant further decrease in Cr
content. The Al content of this sample was constant at 6.5 Al/uc
(Si/Al=13.6).
M"+-exchanged MH-ZSM-5 zeolites were prepared by exchanging H-ZSM-5
twice using a 0.05/n M solution, of the desired metal ion (100 ml/g of
zeolite, 80C, 0.5 hr). AAS analyses of [Fe]-ZSM-5 and Cu-[Fe]-ZSM-5
samples showed Si/Fe=19 and a Cu content of the latter sample of 0.91 wtfc
Cu (17 % exchange),
The catalysts were dry pressed, crushed and sieved to obtain particles
of 1.4-2.0 mm diameter.
Apparatus and procedure.
The catalyst (usually 3 g) was placed in a fixed-bed continuous flow
glass microreactor. The reactor was placed in an electronically
controlled fluid-bed oven and heated to the reaction temperature. The

reaction mixture was then passed over the catalyst using air as the
carrier gas. Standard reaction conditions are as follows : molar
composition: toluene: ammonia: water: oxygen=l:2:6:4.7, WHSV(toluene)=
0.17 hr" 1 , reaction temperature 350C. The product mixture was analyzed by
on-line gas chromatography, and, if necessary, components were identified
by GC/MS. The selectivity to benzonitrile and the toluene conversion are
almost constant after the first few hours of reaction. A typical
conversion versus time plot is given in Figure 1. The analytical data
reported in the following were obtained after a reaction time of
approximately 4 hours.
16 20 24
t(hr)
FIGURE 1: Typical plots for toluene conversion ( ) and selectivity to

benzonitrile ( ) vs. time-on-stream, Standard conditions,
catalyst: CrH-ZSM-5(25).
RESULTS AND DISCUSSION.
The product mixture of the toluene ammoxidations usually contains
toluene, benzene, benzonitrile and carbon dioxide. Sometimes traces of
benzyl alcohol and benzaldehyde were observed. Hydrogen cyanide appears to
be absent (tested using a 'Draeger' detection tube).
The results for the ammoxidation of toluene over several M"*-exchanged

ZSM-5-type catalysts are summarized in Table 1. Highest activity is

exhibited by CuH-ZSM-5, FeH-ZSM-5 and CrH-ZSM-5, whereas the highest
selectivity to benzonitrile is shown by CuH-ZSM-5(25.7) and
NiH-ZSM-5. The activity sequence agrees with the observations made by
Jonson et al. [4] for the oxidation of toluene to benzaldehyde over
oxidic catalysts. Here a very high activity is reported for CuO, Cr203 and
Fe203 and a lower activity for NiO and ZnO. The oxidation activity is
related by these authors to an 1R vibration near 520 cm"1 and with semi
conducting properties of the oxide. Both conditions are fulfilled in a
ZSM-5-type zeolite.
TABLE 1: Ammoxidation results*> for M-exchanged ZSM-5-type catalysts.
Catalyst Si/Al Conversion Selectivity (wt%) to

type (gel) (wtX) benzonitrile benzene CO2
Na-ZSM-5 25.7 7.1 52.6 39.9 7.5
H-ZSM-5 25.7 14.2 60.5 38.1 1.4
CuH-ZSM-5 25.7 100 78.0 18.7 3.3
CrH-ZSM-5 24.9 98.5 45.7 52.4 1.9
FeH-ZSM-5 25.7 100 1.9 93.0 5.1
NiH-ZSM-5 25.7 24.0 80.5 17.8 1.7
ZnH-ZSM-5 25.7 10.3 28.9 67.4 3.7
CuCrH-ZSM-5 25.7 100 92.3 3.2 4.5
CrCuH-ZSM-5 25.7 100 84.4 14.0 1.6
CuH-ZSM-5 44.5 100 29.5 65.1 5.4
CrH-ZSM-5 44.5 96.8 92.3 6.3 1.4
CuCrH-ZSM-5 44.5 100 57.2 38.3 4.5
CrCuH-ZSM-5 44.5 100 73.6 22.9 3.5
*' Results after 4 hours on stream, conditions: 350C, WHSV(toluene)=

0.17 hr"1, standard feed composition.
In our previous work [6] we showed CuH-ZSM-5 zeolite to be much more

selective in the toluene ammoxidation than CuY catalysts. Fraenkel et
al. [12] also show that Cu-ZSM-5 zeolites are much more active in
ammoxidation (of methylnaphthalenes) than other Cu-exchanged zeolites.
These authors conclude that the ZSM-5 outer surface structure is involved
in the catalytic process, as for methylnaphthalenes the reaction would
seem to be restricted to the outer surface of the zeolite because of the
molecular dimensions. It might be noted that ZSM-5 has a much stronger

-1
infrared vibration near 520 cm than most other zeolites. FeH-ZSM-5 has
a low selectivity for benzonitrile and produces mostly benzene. This can
be caused by problems during Fe-exchange of the zeolite. In this
procedure some ferric hydroxide precipitated, even though the exchange was
performed in an acidic solution under nitrogen. Incorporating Fe in the
zeolite under conditions where no ferric hydroxide precipitation can
occur might be an effective way of increasing the catalytic activity
without affecting selectivity. Chromium is especially selective when
present in a zeolite with a relatively high Si/Al ratio (selectivity
increases from 45.7* to 92.3% when the Si/Al ratio is increased from 24.9
to 44.5). It may be noted that treatment of a zeolite with a
chromium(III) solution is reported to cause, besides exchange, also
dealumination of the zeolite [13].
The doubly exchanged catalysts, and especially CrCuH-ZSM-5 (first
exchanged with Cu(II) and then with Cr(III)) are very active.
Selectivity (not only for the Cr exchanged samples) depends on the Si/Al
ratio, here with the higher ratios being less selective.
In another approach, Fe and Cr ions were introduced during synthesis
of the zeolites generally in the absence of Al. The results of
ammoxidation experiments with [Fe]-ZSM-5 and [Cr]-ZSM-5 catalysts are
shown in Table 2. These materials can contain some non-zeolitic material.
H-[Cr]-ZSM-5 and H-[Al,Cr]-ZSM-5 catalysts are indeed more active than
H-ZSM-5. However, these catalysts are less active than the best catalysts
in Table 1. H-exchange has a positive effect on the selectivity of the
chromium-containing ZSM-5 type catalysts, as can be seen from the
comparison between the ZSM-5 catalyst and the corresponding H-ZSM-5

material. In this case, the unexchanged material probably contains some

occluded extra-lattice chromium, which causes a low ammoxidation activity
and a high selectivity for benzene. During acid exchange the surplus
TABLE 2: Ammoxidation results*' for [X]-ZSM-5-type catalysts.
Catalyst Si/Al Si/X Temperature Conversion SelectiveLty (wt*) to

type (gel) (gel) <C) (wt*) benzonitrile benzene CO2
H-ZSM-5 25.7 - 350 14.2 60.5 38.1 1.4
H-[Al,Cr]-ZSM-E 25 80 350 86.6 77.6 20.4 2.0
H-[Cr]-ZSM-5 - 88 335 35.0 85.8 9.8 4.4
H-[Cr]-ZSM-5 - 88 350 75.1 86.4 12.3 1.3
[Al,Cr]-ZSM-5 25 80 350 94.0 41.9 53.2 4.9
[Cr]-ZSM-5 - 88 350 100 24.1 71.3 4.6
H-[Fe]-ZSM-5 - 45 360 99.8 76.9 12.3 10.8
CuH-[Fe]-ZSM-5 - 45 295 40.0 92.9 1.9 5.2
CuH-[Fe]-ZSM-5 - 45 310 67.3 94.3 1.8 3.9
CuH-[Fe]-ZSM-5 - 45 325 97.7 95.1 2.8 2.1
CuH-[Fe]-ZSM-5 - 45 340 99.4 94.4 1.5 4.1
* > Results after 4 hours on stream, WHSV(toluene)= 0.17 hr-1 , standard feed
composition.
chromium is leached out of the zeolite, causing a somewhat lower total

activity and a higher selectivity to benzonitrile.- During the
ammoxidation reaction the colour of the [Cr]-ZSM-5 catalyst changed from
yellow to light green, indicating a change from Cr(VI) to Cr(III). This is
a sign that the remaining chromium is still not totally incorporated in
the zeolite lattice. It is questionable whether Cr ions can be introduced'
in the zeolite lattice. lone [10] states that only ions with a tetrahedral
coordination (Al, B, Be, Ga and Fe) can be built in.
The H-[Fe]^-ZSM-5 catalysts combine a very high activity and a high

selectivity to benzonitrile, especially when they are used in the
CuH-exchanged modification. The latter catalyst possesses the highest
selectivity to benzonitrile of all catalysts tested. This also indicates
that FeH-ZSM-5 contains non-zeolitic Fe (oxide) particles instead of
exchanged Fe ions. Note that the results are obtained at even lower
temperatures compared to an experiment with a Cr-containing catalyst.
In Figure 2 conversion and selectivity are plotted versus reaction
temperature. The conversion increases with increasing temperature reaching
100* at 325C, while selectivities stay almost constant.
295 310 325 3<0 360
FIGURE 2: Effect of reaction temperature on conversion & selectivities in

the aimnoxidation of toluene over CuH-[Fe]-ZSM-5(45),
WHSV(toluene)=0.17 h" 1 , standard feed composition; conversion,
x benzonitrile, + benzene, o CO2.
FIGURE 3:Selectivities. and conversion in toluene ammoxidation for

[Fe,Al]-ZSM-5. zeolites vs. Fe content. Standard reaction
conditions; conversion, o benzonitrile, x benzene, + CO2.
The effect of the Fe content of the zeolites was examined using a series
of [Al,Fe]-ZSM-5 catalysts, synthesized according to both the Aerosil and
the waterglass method. The results for the waterglass-based catalysts are
shown in Figure 3. For the Aerosil-based catalysts a similar picture is
obtained.
The plots show that the toluene conversion increases with increasing Fe
content, whereas the changes in selectivities are not pronounced. This
shows that the Fe ions are catalytically active. In Chapter 4 evidence
is produced that Fe ions are built in in the zeolite lattice.
OO" OOH
NH, / H,C /
Cu(ll) Cu(l) Cu(ll)
-@ Cu(l> - -
/\
Snhfmwa 1a
U NH, 'WO
o?- cw
r
'/MM/M'jd///
^ Zeoliet : m
4WAWMM
^ Z e o l i e t wy/w.
H,0 NH,
o- o-^ NH
777T?7Tr777777777777/
% Zeoliet:^^
Scheme lb /y///////////////////
SCHEME 1: Possible reaction mechanisms.
Thus, the catalytic activity is found to increase with increasing Fe
content of the [Al,Fe]-ZSM-5 catalysts as well as upon Cu (or Cr)
exchange of the zeolite while in both cases the selectivity remains almost
constant. This suggests a mechanism in which both the exchanged ion (Cu,
Cr) and the secondary T-atom can play a role. The present experiments do
not allow the formulation of a detailed mechanism. However, the following
considerations can be made.
First, ammonia may be assumed to be present as NH4+ and NH3 in
equilibrium with (residual) Bronsted acid sites of the zeolite as well as
liganded (as NHa and also - in view of the reaction temperature - as NH2-)
to the Cu (or Cr) ions. Oudejans et al. [6] showed using EPR that copper
is mainly present in Cu-ZSM-5 as single Cu(II) ions. For Cu it could not
be shown that Cu(II) is reduced to Cu(I) under reaction conditions, but
catalysts containing Cr show that reduction is indeed taking place by
changing from yellow (Cr(VI)) to green (Cr(III)). Moreover, it is known
that Cu(II) can be reduced to Cu(I) by NH3 [14]. This led Oudejans et
al. to suggest a mechanism in which toluene enters into a (Rideal-like)
reaction with 02" and NH2 ligands of a Cu(II) site in which hydrogen is
transferred from toluene to oxygen with simultaneous C-N bond formation
and electron uptake by the Cu (see Scheme la). . Here nitrogenated
intermediates are formed.
Secondly, a mechanism can be formulated on the analogy of literature

[16,17] on the ammoxidation over e.g. bismuth molybdate catalysts. In such
a mechanism a hydrogen is abstracted from the methyl group of toluene,
forming a benzylic species. This species may be transformed into
benzonitrile as indicated schematically in Scheme lb. It can be imagined
that the Fe and Cr ions incorporated in the zeolite lattice play a role in
this mechanism. It may be noted that oxygenated species (benzyl alcohol,
benzaldehyde) were detected in small amounts in the experiments.
The present data do not allow the formulation of a more definite
mechanism of the ammoxidation of toluene over ZSM-5-type zeolitic
catalysts.
LITERATURE.
1. J.J.J. den Ridder, Thesis, Delft University of Technology, 1981.

2. Y. Murakami, M. Niwa, T. Hattori, S. Osawa, I. Iguahi and H. Ando,
J. Catal., 49, (1977), 83.
3. M. Niwa, M. Sago, H. Ando and Y. Murakami, J. Catal., 69, (1981), 69.
4. B. Jonson, R. Larsson and B. Rebensdorf, J. Catal., 102, (1986), 29.
5. A. Ohorodnik, K. Sennewald, H. Erpenbach and H. Vierling, Ger. Offen.
2.104.223 (1972), Ger. Offen. 2.127.996 (1972), Ger. Offen. 2.127.997
(1972), Ger. Offen. 2.155.776 (1973), Ger. Offen. 2.155.777 (1973).
6. J. C. Oudejans, F.J. van der Gaag and H. van Bekkum, in "Proc. VI Int.
Zeol. Conf.", Reno 1983, Publ. 1985, p.536.
7. L. Marosi, Ger. Offen. 2.831.630 (1982).
8. M.R. Klotz, US Patent 4.405.502, US Patent 4.405.504 (1983).
9. T. Inui, 0. Yamase, K. Fukuda, A. Itoh, J. Tarumoto, M. Morinaga, T.
Hagiwara and T. Takegami, in "Proc. VIII Int. Congr. Catal.",
Berlin 1984, vol. Ill, p.569.
10. K.G. lone, L.A. Vostrikova, A.V. Petrova and V.M. Mastikhin, in "Proc.
VIII Int. Congr. Catal.", Berlin 1984, vol. IV, p.519.
11. F.J. van der Gaag, J.C. Jansen and H. van Bekkum, Appl. Catal., 17,
(1985), 261.
12. D. Fraenkel, B. Ittah and M. Levy, in "Poster Preprints VII Int. Zeol.
Conf.", Tokyo 1986, p.271.
13. W.E. Garwood, N.Y. Chen and J.C. Bailar Jr., Inorg. Chera., 15, (5),
(1985), 1044.
14. I.E. Maxwell and E. Drent, J. Catal., 41, (1976), 412.
15. S.L.T. Andersson, J. Catal., 98, (1986), 138.
16. J.D. Burrington, C.T. Kartisek, R.K. Grasselli, J. Org. Chem., 46,
61
REACTION'OF ETHANOL AND AMMONIA TO PYRIDINES OVER ZEOLITE ZSM-5
F.J. VAN DER GAAG, F. LOUTER, J.C. OUDEJANS1 and H. VAN BEKKUM
Laboratory of Organic Chemistry, Delft University of Technology, Julianalaan 136,
2628 BL Delft, The Netherlands.
Present address: Unilever Research Laboratory, Olivier van Noortlaan 120,
3133 AT Vlaardingen, The Netherlands.
(Received 2 December 1985, accepted 10 March 1986)
ABSTRACT
Pyridine bases are formed by reacting ethanol and ammonia in the presence of
air in a.continuous flow microreactor over zeolite ZSM-5. Optimum selectivity to
pyridine and optimal conversion are obtained using a HZSM-5 catalyst with Si/Al =
65 at temperatures between 600 and 650 K. Other catalysts i.e., Co-, Fe- or Cd-
HZSM-5, HY, HMordenite or amorphous silica-alumina show lower selectivity and/or
activity. When air as a vector gas is replaced by nitrogen, no pyridines are
formed. For the ethanol-ammonia reaction to pyridines a mechanism is suggested.
INTRODUCTION
Since the discovery of zeolite ZSM-5 numerous ZSM-catalyzed reactions have
been studied. The conversion of methanol and ethanol to hydrocarbons [1-3], the
alkylation of benzene [4], the isomerization of xylenes [5], the alkylation [6]
and disproportionation of toluene [7] are the most frequently reported.
A relatively small number of recent papers deal with reactions catalyzed by
zeolite ZSM-5 in which ammonia is one of the reactants [8-17]. The synthesis of
amines from alcohols, ethers or olefins was reported in the patent literature
[8,11,12,16]. Zeolites like ZSM-5, erionite and cl inoptilolite were found to
increase the selectivity of the reaction of alcohols to primary amines.
Cu-H-exchanged ZSM-5 type zeolites were reported to be good catalysts in the
ammoxidation of toluene [17]. The addition of water to the feed had a beneficial
effect on the activity and selectivity.
The production of (methyl-)pyridines from acetaldehyde and ammonia over
zeolite HZSM-5 was reported in the patent literature [9]. Depending on the cation
of the zeolite the formation of acetonitrile was observed. Recently 2-methyl-
pyridine was found to be the principal side product of phenol amination to aniline
over zeolite ZSM-5 at high temperature (783 K) [13]. Aniline can also be converted
to 2-methylpyridine under similar conditions [14,15]. The conversion is low and
many byproducts are found.
From the data available it is clear that in the absence of oxygen in the
reactant mixture zeolite ZSM-5 is able to catalyze the conversion of ethanol and
ammonia to amines.
62
Here we present data on the reaction of ethanol and ammonia over zeolite ZSM-5
in the presence of oxygen. H+-exchanged as well as metal ion exchanged zeolites
have been studied. For comparison also HY, HMordenite, and an amorphous silica-
alumina have been included. The influence of some variables on the formation of
N-containing compounds (particularly heteroaromatics) is shown and a mechanism
is suggested.
EXPERIMENTAL
Materials
Zeolite ZSM-5 was prepared as described in the literature [20] using tetra-
propylammonium bromide as the organic template. Silicalite was prepared according
to the patent literature [21] with NH.F added to the synthesis mixture. The
zeolites'were calcined overnight at 823 K before further use. H -exchanged zeolites
were prepared by ion exchange in 0.5 M HC1 at ca. 353 K for 0.5 h. (10 g zeolite
per 1 solution), followed by thorough washing with water and repeating the pro
cedure. M( )-exchanged zeolites were prepared by ion exchange of HZSM-5 in a
0.05/n M solution of the desired ion under the conditions for H-exchange.
Zeolite HY was prepared by ion exchange of NaY (SK-40, Union Carbide) in an
0.1 M NH.C1 solution (10 g zeolite per 1 solution) for 1 day at room temperature,
followed by calcination at 673 K.
Zeolite HMordenite (Zeolon 100H, Norton) and amorphous silica-alumina catalysts,
HA-HPV and LA-LPV cracking catalysts (Ketjen), were used without exchange.
All catalysts were dry pressed, crushed and sieved to obtain a sieve fraction
of particles of 1.4-2.0 mm.
Procedure
The apparatus used in the catalytic experiments is essentially the same as
described by Oudejans [19].
The catalyst (3 g) was placed in a fixed-bed continuous flow glass reactor of
8 mm internal diameter. The reactor was placed in an electronically controlled
fluid.bed oven. The carrier gas (usually air) was passed through two thermostatted
saturators containing ethanol and an aqueous 0.5 M ammonia solution, respectively.
The desired flows of the reactants were obtained by adjusting and controlling the
temperature of the saturators and the two flows of the carrier gas. Standard
conditions were chosen such that the molar ratio of the reactants was: NH-^C-Hj-OH:
HgOiOg = 1:3:6:9.
' The.saturated gas streams were mixed and fed to the reactor at WHSV (ethanol) =
0.17ih.. . The gas mixture leaving the reactor was analyzed by online gas chromato-
graphy using a 3 m 10% PEG on Chromosorb column with FID for organic components
(temperature programmed operation) and a 1 m PORAPAK Q column with TCD for
inorganic components (e.g., CO and C0, isothermal operation). Peak integration
was performed by a computer connected to the gas chromatographs. If necessary
products were identified by GC-MS using a Varian 44 S mass spectrometer.
63
> Al/uc
FIGURE 1 Conversion and selectivity (wt%) plotted vs. Al atoms per unit cell in
the ethanol-ammonia reaction over H Z S M - 5 . ^ , 0 conversion; | ,Q selectivity
to pyridine; V ,A selectivity to ethene; reaction temperature: 613 K ( 0 , | ,
V . ) and 633 K ( O . D . A )
RESULTS
Several catalysts have been tested in the conversion of ethanol and ammonia
to pyridine bases. The results of these experiments will be presented and discussed
in terms of the influence of single catalyst and reaction parameters on conversion
and selectivity.
Effect of Si/Al ratio of ZSM-5 zeolites

Data of experiments with HZSM-5 zeolites are presented in Table 1 and Figure 1.
Major products in the ethanol-ammonia reaction - in the presence of water and
using air as the vector gas - are ethene, diethyl ether and pyridine. Other
components in the product mixture include acetaldehyde, ethylamine, acetonitrile
and toluene. Ethyl acetate and 3- and 4-picoline are generally present in amounts
< 0.5%. Oxidation to carbon dioxide is substantial but in general lower than 20%
(wt%) respectively 8.5% on carbon.
The data show that there is an optimum in pyridine selectivity at relatively
high Si/Al ratios.
64
TABLE 1
Effect of Si/Al ratio in the ethanol-ammonia reaction3 over HZSM-5
Si/Al Al/uc Temp. Conv. Selectivity / wt% to:b

/K 1% ethene diethyl acetal- ethyl-
ether dehyde amine
12.3 7.2 613 59.9 51.4 8.0 3.0 < 0.1

12.3 7.2 628 93.4 72.6 0.8 0.5 < 0.1
12.5 7.1 613 21.6 29.7 12.0 4.7 0.8

15.4 5.8 613 19.3 40.9 4.4 1.9 0.3
15.4 5.8 633 40.8 71.3 4.9 2.8 0.3
20.3 4.5 653 83.9 90.5 0.6 < 0.1 < 0.1
26.3 3.5 613 46.8 26.3 5.4 1.7 0.4

26.3 3.5 633 88.0 63.1 0.3 0.4 < 0.1
26.3 3.5 653 98.1 76.3 1.6 < 0.1 < 0.1
27.3 3.4 623 53.0 56.9 3.4 1.7 0.4

27.3 3.4 643 97.7 72.5 < 0.1 < 0.1 < 0.1
55.5 1.7 613 34.0 23.4 7.1 3.0 2.2

55.5 1.7 633 22.9 24.0 13.1 5.0 3.5
55.5 1.7 653 35.8 36.0 9.0 2.9 1.7
55.5C 1.7 613 18.0 32.9 15.4 9.5 < 0.1
131.1 0.7 593 11.3 10.0 7.8 5.7 6.8

131.1 0.7 633 29.3 27.3 6.9 3.6 3.5
131.1 0.7 653 50.8 51.0 2.7 2.8 1.2
0 608 8.1 2.2 1.2 19.3 6.4
0 638 14.4 6.1 0.6 22.6 3.0
00
0 663 32.8 9.6 0.4 31.7 2.7
a
Molar ratio NH 3 :C 2 H 5 0H:H 2 0:0 2 = 1:3:6:9, WHSV (ethanol) = 0.17 h"1.
Composition of product mixture after 4 h on stream.
cExperiment with 1% 0 in N- vector gas instead of air.
It is also observed that with increasing number of Al atoms per uc the con
version increases, as the number of acid sites increases. Zeolites with a high Al
content show an increased selectivity to ethene.
In general, deactivation of the HZSM-5 catalysts is hardly observed under
the conditions used; after an initial period of a few hours a steady state is
reached, in which conversion and selectivity stay almost constant over a period
of at least 48 hours.
65
acetonitrile toluene pyridine 2-picoline CO
3.7 < 0.1 13.4 4.6 14.3

2.7 < 0.1 6.1 < 0.1 17.3
5.2 < 0.1 11.7 6.8 11.6
4.1 3.4 10.2 5.1 20.8

0.1 3.7 5.5 1.6 7.3
0.1 2.1 1.4 0.3 4.9
8.1 < 0.1 36.2 8.0 11.7

3.5 2.1 12.4 0.5 17.3
1.6 0.4 7.5 < 0.1 14.0
4.6 < 0.1 18.8 3.9 10.2

2.8 < 0.1 14.5 < 0.1 10.2
3.0 < 0.1 47.6 2.5 8.9

2.1 < 0.1 33.6 2.4 13.3
2.5 < 0.1 31.5 1.8 12.0
6.4 4.4 23.4 4.9 0.1
3.3 < 0.1 43.8 2.5 20.0

3.1 < 0.1 33.5 0.8 21.2
2.4 < 0.1 27.9 0.4 11.7
0.1 12.6 16.0 < 0.1 38.1

2.6 11.9 7.0 < 0.1 39.7
5.6 0.5 2.6 < 0.1 44.3
E f f e c t o f metal exchange i n z e o l i t e ZSM-5

Table 2 shows the analysis data of c a t a l y t i c experiments performed with some
metal ion exchanged HZSM-5 z e o l i t e s . In g e n e r a l , HZSM-5 c a t a l y s t s show b e t t e r
conversion and/or s e l e c t i v i t y to p y r i d i n e than the MHZSM-5 z e o l i t e s . FeHZSM-5
shows a r e l a t i v e l y high a c t i v i t y f o r deep o x i d a t i o n and therefore a low s e l e c t i v i t y
to p y r i d i n e . NaZSM-5 shows hardly any a c t i v i t y .
Influence of the type o f Si-Al-catalyst

The r e s u l t s of experiments w i t h d i f f e r e n t types of z e o l i t e and w i t h amorphous
c a t a l y s t s are given in Table 3.
A l l c a t a l y s t s i n Table 3 a r e , more or l e s s , capable of forming pyridines from
TABLE 2
Ethanol-ammonia reaction using MHZSM-5 catalysts.
Catalyst Si/Al M/uc Temp. Conv. Selectivities/wt% to:

/K /% ethene diethyl acetal- ethyl - aceto- pyridine 2-picol ine 3/4- co2
ether dehyde amine nitrile picoline
CdHZSM-5 28.5 0.11 623 39.7 48.0 7.5 1.9 0.6 2.1 16.5 4.1 2.4 16.8
FeHZSM-5 17.9 0.38 598 75.2 10.6 5.3 5.1 0.8 13.8 10.6 < 0.1 < 0.1 53.7
CoHZSM-5 16.5 0.25 613 19.9 33.4 17.1 8.7 2.2 2.2 7.4 3.7 3.5 18.4
CoHZSM-5 16.5 0.25 633 46.7 56.9 7.8 4.0 1.0 3.0 5.0 1.9 2.2 18.2
05
05
TABLE 3
Other Si-Al catalyst types
Catalyst Si/Al Temp. Conv. Selectivities/wt% to:

/K /% ethene diethyl acetal- ethyl- aceto- pyri- CO.
ether dehyde amine nitrile dine
HMordenite 5 598 56.6 88.8 1.6 < 0.1 < 0.1 1.5 < 0.1
HMordenite 5 623 97.2 87.4 0.4 0.6 < 0.1 1.6 < 0.1
HY 2.5 598 34.1 49.2 4.8 4.0 0.7 6.4 2.0
HY 2.5 623 86.2 61.7 2.7 0.6 < 0.1 8.3 1.6
HA-HPV a 613 43.7 16.3 2.1 1.5 41.7 4.4 1.7
LA-LPV b 613 44.1 36.6 6.5 2.2 7.5 8.5 6.2
a
25 wf A1 2 0 3
b
13 wtS Al,0 o
68
ethanol and ammonia in the presence of oxygen. Comparison of the catalysts shows
that HZSM-5 is a superior catalyst in this reaction. In addition, HZSM-5 catalysts,
especially Si-rich preparations (Si/Al > 23, Al/uc < 4 ) , show a low rate of coking,
in contrast to other Si-Al catalysts, e.g., HY. With Al-rich HZSM-5 catalysts
some coking is observed but the activity is hardly affected after 48 h on stream
whereas other Si-Al catalysts deactivate.
Influence of reaction temperature

From Table 1 the following effects of increasing reaction temperature can be
observed:
(i) The conversion of ethanol increases.
(ii) The selectivity of the reaction to pyridine bases decreases and the selecti
vity to ethene (and C0 ? ) increases.
(iii) The selectivity within the group of pyridine bases shifts towards the un-
substituted product.
Effect of feed composition

Oxygen content of the vector gas. On decreasing the oxygen content of the
carrier gas from 20 vol% (air) to ca. 1 vol% the yield of pyridine decreases.
The yields of diethyl ether and substituted pyridines increase. When using nitrogen
as a carrier gas a product mixture comprised mainly of ethene, diethyl ether and
ethylamine is obtained. A decrease in oxygen content thus leads to a decrease in
oxidized products (substituted pyridines are less dehydrogenated than pyridine
itself).
Ammonia and water content. Obviously, when no ammonia is fed to the reactor
no nitrogen-containing compounds can be formed. Moreover, in the absence of ammonia,
ethanol is almost completely oxidized to C0 ? and H ? 0. Ammonia therefore inhibits
deep oxidation reactions on HZSM-5 catalysts.
When no water is present in the feed the HZSM-5 catalyst deactivates and coke
formation is observed. It may be concluded that water assists in preventing coke
formation and keeping the zeolite surface clean.
DISCUSSION
A comparison of the optimum reaction conditions reported here with the results
obtained in the conversion of ethanol without ammonia [3] shows that here a
considerably higher temperature is required to obtain a good degree of conversion.
Obviously this is caused by partial poisoning of the catalytically active (acid)
sites by ammonia and the product bases. Nayak and Choudhary [22] found pyridine
to be the most effective poison for HZSM-5 in the conversion of alcohols and
olefins to aromatics. They also reported an increased rate of coking on pyridine
poisoned HZSM-5 catalysts (Si/Al = 17), probably caused by the lack of strong
acid sites. These sites remove coke by cracking reactions. We also find coke
69
formation on Alrrich zeolites, but not on Si-rich zeolites. Here cracking activity
seems to be high enough to keep the catalyst surface clean.
Water has a positive effect on the selectivity and the stability of the catalyst.
Water vapor can assist in desorbing the product bases from the catalyst. Also
the rate of coke formation is decreased by addition of water vapor to the feed.
For the conversion of ethanol and ammonia to pyridines two mechanisms can be
envisaged: one involving carbenium ions, oligomerization, amination, ring closure
and aromatization and the other via dehydrogenation of ethanol to acetaldehyde,
aldolization/retroaldolization, reaction with ammonia, cyclization and aromati
zation. Because the use Of ethene or propene as a feedstock instead of ethanol
was found not to result in pyridine formation, the second mechanism is preferred.
Some pathways are depicted in a simplified way in Scheme 1.
O, NH,
CH 3 CH 2 OH CH,CHO
3 . .... Pyridines
non-acid acid sites
sites
NH, NH,
-p CH 3 CH 2 NH 2 U- CH 3 CN
H*
o2 CH,CH 2 OH ||
C H f = C H 2 CHjCOOH CH3C-0-CH2CH3
C H 3 C H r O - C H 2 C H 3
H
SCHEME 1 Possible mechanism for reaction of C?H,-0H and NH, to pyridines.
The first step for the formation of pyridines from ethanol and ammonia is
supposed to be the dehydrogenation of ethanol to acetaldehyde. Acetaldehyde and
ammonia are then converted to pyridines. Both steps have been separately reported
in the 1iterature.
Matsumura et al. [24] showed that acetaldehyde can be produced from ethanol
over ZSM-5 zeolites containing little or no acid sites. Protonated ZSM-5 zeolites
catalyze the dehydration of ethanol. In our experiments the acid sites are for
the most part poisoned by NH 3 and the product bases. The dehydrogenation reaction
could be catalyzed by the resulting non-acidic sites though a detailed molecular
picture is lacking. Matsumura et al. use an oxygen-free feed and a somewhat higher
reaction temperature. Adding oxygen as a hydrogen acceptor to the feed might lower
the reaction temperature needed. Shabtai et al. [25] found that type X zeolites
70
are able to catalyze the dehydrogenation of alcohols in the presence of aldehydes

as hydrogen acceptor at temperatures between 373 and 453 K. Table 1 and Figure 1
show that zeolites with increasing Al content show a shift in selectivity from
acetaldehyde to ethene. This can be explained in terms of an increasing number
of proton sites being in equilibrium with pyridinium and ammonium sites.
Chang and Lang [9] described the conversion of acetaldehyde and ammonia to
pyridines over HZSM-5. A higher reaction temperature (ca. 725 K) and feed rate
(LHSV = 1) are used here under oxygen-free conditions.
Optimum selectivity to pyridines is found at an Al content where catalysis of
acetaldehyde production and conversion to pyridines is balanced. At this point
.the number of acidic sites has to be high enough to assure enough activity for
pyridine formation and low enough to assure ethanol dehydrogenation over non-acidic
sites. At increasing temperature the rate of the former reaction increases more
than the rate of the dehydrogenation (possibly caused by a lower fraction of
acidic sites poisoned by N-compounds). As a result, optimum selectivity to
pyridines is found at a higher Si/Al ratio at higher temperatures.
Further reactions on the zeolite catalysts comprise:
(i) conversion to ethene and diethyl ether over the acid sites.
(ii) ammoxidation of ethanol or acetaldehyde to acetonitrile.
(iii) oxidation to acetic acid, followed by esterification to ethyl acetate.
(iv) total oxidation of reactants or products to carbon dioxide and water.
CONCLUSIONS
Pyridine bases can be produced from ethanol and ammonia in the presence of
oxygen, using HZSM-5 catalysts. The presence of water in the feed mixture has a
positive effect on selectivity, activity and stability of the catalyst, therefore
direct processing of aqueous ethanol, as obtained by fermentation processes, is
possible. For optimum conversion and selectivity to pyridines under standard flow
and concentration conditions temperatures between 600 and 650 K and a HZSM-5
catalyst with Si/Al = 65 should be selected.
A mechanism starting with the partial oxidation of ethanol to acetaldehyde,
followed by stepwise conversion to pyridine bases, is suggested.
REFERENCES
1 S.L. Meisel, J.P. McCullough, C.H. Lechthaler and P.B. Weisz, Chem. Techn.,
' 6 (1976) 86.
2 C D . Chang and A.J. Silvestri, J. Catal., 47 (1976) 249.
3 J.C. Oudejans, P.F. van den Oosterkamp and H. van Bekkum, Appl. Catal., 3
(1982) 109.
4 e.g. K.H.' Chandawar, S.B. Kulkarni and P. Ratnasamy, Appl. Catal., 4 (1982) 287.
5 US Patents 3,751,504 (1975); 3,751,506 (1975); 3,755,483 (1975); 4,159,282
(1979); 4,159,283 (1979).
6 P.J. Lewis and F.G. Dwyer, Oil Gas Journal, 75 (1977) 55.
7 P.B. Weisz in "Stud. Surf. Sci. Catal., 7, New Horizons in Catalysis", eds.
T. Seyama and K. Tanabe (Elsevier, Amsterdam and Kodanska Ltd., Tokyo, 1981) p.3.
!
71
8 W.W. Kaeding, US Patent 4,082,805 (1982).

9 C D . Chang and W.H. Lang, US Patent 4,220,783 (1980).
10 R. Bicker and R. Erckel, Eur. Patent 0,046,897 (1981).
11 Neth. Patent 82.01523 (1981).
12 H.S. Fales and J.O.H. Peterson, Eur. Patent 0,039,918 (1981).
13 C D . Chang and P.D. Perkins, Zeolites, 3 (1983) 298.
14 C D . Chang and P.D. Perkins, US Patent 4,388,461 (1983).
15 C D . Chang and P.D. Perkins, Eur. Patent 0,082,613 (1983).
16 M. Deeba and W.J. Ambs, Eur. Patent 0,077,016 (1983).
17 J.C. Oudejans, F.J. van der Gaag and H. van Bekkum, in "Proc. Sixth Intern.
Conf. Zeolites", Reno 1983, eds. D. Olson and A. Bisio (Butterworth, Guildford,
1984), p.536.
18 J.C. Oudejans and H. van Bekkum, Neth. Patent Application 82.02884 (1983).
19 J.C. Oudejans, Thesis, Delft University of. Technology (1984).
20 F.J. van der Gaag, J.C.Jansen and H. van Bekkum, Appl. Catal., 17 (1985) 261.
21 E.M. Flanigen and R.L. Patton, US Patent 4,073,865 (1978).
22 V.S. Nayak and V.R. Choudhary, Appl. Catal., 9 (1984) 251.
23 R.M. Dessau and R.B. LaPierre, J. Catal., 78 (1982) 136.
24 Y. Matsumura, K. Hashimoto, S. Watanabe and S. Yoshida, Chem. Lett., 1 (1981)
121.
25 J. Shabtai, R. Lazar and E. Biron, J. Mol. Catal., 27 (1984) 35.
72
Reaction of Ethanol and Ammonia to Pyridine over ZSM-5-Type

Zeolites
F.J. van der Gaag, F. Louter, and H. van Bekkum
Laboratory of Organic Chemistry, Delft University of Technology, Julianalaan 136,
2628 BL Delft, The Netherlands
Reaction of ethanol and ammonia in the presence of air and

water over ZSM-5-type catalysts affords pyridine as one of
the major products. Other products include ethene, diethyl
ether, ethylamine, acetonitrile and carbon dioxide. Data are
presented for zeolite H-ZSM-5, for H-Boralite and for iron-
containing H-ZSM-5 zeolites. For H-Boralite and H-ZSM-5 the
pyridine selectivity is found to depend on the Si/B and Si/Al
ratio, respectively. Increasing the iron content of H-ZSM-5
(Fe) systems leads to higher activity whereas the effect on
the selectivity is relatively small.
Other variables studied include reaction temperature and
space velocity. A mechanism for the ethanol-ammonia reaction
to pyridines is suggested.
INTRODUCTION
Numerous ZSM-catalyzed reactions have been reported since the discovery of
zeolite ZSM-5. The conversion of ethanol and methanol to hydrocarbons [1-3], the
alkylation of benzene [4], the isomerization of xylenes [5], and the alkylation
(6) and disproportionation of toluene [7] are the most frequently studied.
ZSM-catalyzed reactions in which ammonia is one of the reactants have received
less attention [8-18] so far. The synthesis of amines from alcohols, ethers or
olefins was reported in the patent literature [8,11,12,16]. The selectivity of the
reaction of alcohols to primary amines was found to be increased by using zeolites
like ZSM-5, erionite and clinoptilolite as' the catalysts.
Cu-H-ZSM-5 proved to be a good catalyst for the ammoxidation.of toluene [17].
The addition of water to the feed had a beneficial effect on the activity and
stability. .
The production of (methyl-)pyridines from acetaldehyde and ammonia over zeolite
ZSM-5 was reported in the patent literature [9]. Depending on the cation of the
zeolite acetonitrile formation was observed. Recently high temperature (783 K)
phenol amination to aniline over zeolite ZSM-5 was reported [13] and was found to
yield 2-methylpyridine as the principal side product. Conversion of aniline under
similar conditions also yielded 2-methylpyridine [14,15]. The conversion is low
and many by-products are found.
From the data available it is clear that in the absence of oxygen in the
reactant mixture zeolite ZSM-5 is able to catalyze the conversion of ethanol and
ammonia to amines.
We have shown recently [18] that in the presence of oxygen zeolite ZSM-5
catalyses the reaction of ethanol and ammonia to pyridines. Here we present data
on the reaction of ethanol and ammonia over some T-atom substituted ZSM-5-type
zeolite catalysts, together with additional data for the reaction over H-ZSM-5.
Water was used as a component of the reaction mixture in view of earlier observed
beneficial action and in view of the option of direct processing of aqueous
ethanol as obtained by fermentation. The influence of the degree of T-atom sub
stitution, the space velocity and the reaction temperature has been studied. A
mechanism is discussed.
73
EXPERIMENTAL
1. Materials
All zeolites have been prepared as described for ZSM-5 in the literature [19].
Tetrapropylaminoniura bromide was used as the organic template. For Boralite,
Aerosil was used as the silica source and sodium aluminate was substituted by a
mixture of boric acid and sodium hydroxide. For Fe-containing ZSM-5 zeolite
{II-ZSM-5 (Fe)) either Aerosil or waterglass was used as the silica source and
iron(II)sulfate was added to the synthesis mixture. The Fe-containing zeolites are
completely white, so it can be concluded that iron is built in on T-atom sites.
Silicalite was prepared according to the patent literature [20], with NH H F added
to the synthesis mixture. H-ZSM-5 and H-ZSM-5 (Fe)' were analyzed by AAS.
The 2eolites were calcined overnight at 823 K before further use. H -exchange
was performed by ion exchange in 0.5 M HCl at ca. 353 K for 30 minutes (10 g
zeolite per 1 solution), followed by thorough washing with water and repeating the
procedure. All catalysts were dry pressed, crushed and sieved to obtain a sieve
fraction of particles of 1.4-2.0 mm.
2. Procedure
The apparatus used in the catalytic experiments is essentially the same as
described by Oudejans [21].
The catalyst (1-3 g) was placed in a fixed-bed continuous flow microreactor.
The reactor was placed in an electronically controlled fluid bed oven. Ammonia and
ethanol were fed to the reactor by bubbling air through thermostatted saturators.
Standard molar reactant composition was: NH 3 :C 2 H 5 OH:H 0:02 = 1:3:6:9.
The gas mixture leaving the reactor was analyzed by online gas chromatography
using a 3 m 10% PEG on Chromosorb column with FID for organic components
(temperature programmed operation) and a i m PORAPAK Q column with TCD for
inorganic components (e.g. CO and C0 2 l isothermal operation). Peak integration was
performed by a computer connected to he gas chromatographs. If necessary products
were identified by GC-MS using a Varian 44S mass spectrometer.
RESULTS
The results of the experiments on the conversion of ethanol and ammonia to
pyridines will be presented in terms of single catalyst or reaction parameters on
conversion and selectivity.
1. Effect of Si/B ratio of Boralite zeolites

Data of experiments with H-Boralite zeolites are presented in Table 1 and
Figures 1 and 2. After 3 hours an essentially constant selectivity together with a
Table 1. Effect of Si/B ratio in the ethanol-ammonia reaction over H-Boralite.

Si/B B/uc temp. conv. S e 1 e c t 1 V i t i e s t o (wt
K X ethene diethyl acetal- ethyl- aceto- toluene pyri- 2-pico- C0C
ether dehyde amine nitrile dine line
10.5 e 613 20.1 8.5 2.1 12.2 11.6 11.2 0.4 21.7 1.0 29.7
10.5 e 633 50.0 12.6 0.8 8.3 14.5 11.9 1.1 31.3 < 0.1 16.8
10.5 a 653 98.2 22.6 < 0.1 1.2 < 0.1 3.9 12.6 17.1 < 0.1 16.9
21 4.4 613 13.5 1.7 0.9 6.8 11.1 16.7 < 0.1 31.5 < 0.1 27.9
21 4.4 633 30.2 2.5 0.4 1.9 10.4 22.8 < 0.1 34.9 < 0.1 26.9
42 2.2 613 11.8 13.6 7.7 8.8 7.6 3.1 < 0.1 46.2 1.7 11.3
42 2.2 633 24.1 16.7 4.5 5.9 5.8 3.4 < 0.1 48.0 0.9 12.9
12 2.2 653 43.1 27.3 2.6 2.9 3.6 4.a < 0.1 42.7 0.3 14.9
42 2.2 673 80.8 36.0 0.3 2.2- 0.5 7.2 < 0.1 39.8 < 0.1 13.2
04 1.1 617 9.9 2.5 1.0 15.8 16.1 0.2 5.7 16.0 < 0.1 26.6
01 1.1 613 30.4 4.4 0.5 6.3 23.8 15.5 < 0.1 20.6 < 0.1 21.5
01 1.1 663 46.9 10.9 0.4 18 19.0 15.2 3.5 21.1 < 0.1 23.0
" 0 608 0.1 2.2 1.2 19.3 6.4 < 0.1 12.6 16.0 < 0.1 38.1
0 638 14.1 6.1 0.6 22.6 3.0 2.6 11.9 7.0 < 0.1 39.7
0 663 32.0 9.6 0.4 31.7 2.7 5.6 0.5 2.6 < 0.1 44.4
Molar ratio NH,:C,ll,0H: H ( 0:0, = 1:3:6:9, W1ISV (ethanol) s 0.17 h-

Rcoctant composition of synthesis mixture.
Composition if product mixture after 4 hrs on stream.
74
600 625 650 675

temp, K
Fig. 1. Conversion and selectivity (wt X) Fig. 2. Temperature effect on

plotted vs. B atoms per unit cell ethanol-aramonia reaction over
(conversion: x, +; selectivity H-Boralite (2.2 B/uc,
to pyridine: , o; to C0: k, A; conversion: +; selectivities:
x, , A: 613 K, +, o, A: 633 K ) . x, ethene; , acetonitrile;
o, pyridine; A, C 0 ) .
slowly decreasing activity was observed. Major products in the ethanol-amraonia

reaction - in the presence of water and oxygen (air) - are ethene, ethylamine,
acetonitrile and pyridine. Other components in the product mixture include
acetaldehyde, diethyl ether and toluene. Ethyl acetate and methylpyridines are
generally present in amounts < 0.5%.
Oxidation to carbon dioxide is substantial but in general less than 30 wt % resp.
15* on carbon and distinctly lower -than observed for Silicalite. For Boralite
zeolites, the picture is very much like ZSM-5 zeolites: with increasing number of
B atoms per unit cell the conversion increases, as the number of acid sites
increases. The data show that there is an optimum in pyridine selectivity at
relatively high Si/B ratios (ca. 42). We have reported similar results for H-ZSM-5
catalysts [18] with an optimum at Si/Al = 65.
Caution has to be taken with respect to B-rich zeolites: here B-containing
compounds were detected in the product mixture. This causes the catalyst
composition to change.
2. Effect of Fe content of Fe-containing ZSM-5-type catalysts

Table 2 shows the effect of the Fe content of the ferro-alumino-silicate ZSM-5
catalysts. The conversion increases with increasing Fe content. It is noteworthy
that the deep oxidation does not increase with higher Fe content of the zeolite
system. For the other selectivities the picture is more complex. There are dif
ferences between catalysts prepared with waterglass and with Aerosil as the silica
source. NH3-TPD experiments also show differences between the two types of
catalyst: The maximum of the "c"-peak (desorption near 750 K) of the ammonia-
desorption is 20-30 K higher for samples prepared from waterglass compared to
samples prepared from Aerosil. Waterglass as a silica source therefore appears to
yield zeolites which, after H -exchange, have acid sites with a somewhat higher
acid strength than Aerosil-prepared samples. From Table 2 it then seems that the
H-ZSM-5 (Fe) zeolites with the more moderate acid properties give a higher
selectivity for pyridine.
Figure 3 gives plots of the conversion and selectivities of the reaction of
75
Table 2. Effect of Si/Fe ratio in the ethanol-animonia reaction over H-ZSM-5 (Fe),
temperature 615 K.
Silica
scurce
si/r* Sl/Al Te/uc conv.
ethcne diethyl
S 1 e c
ecetel-
1 v 1
ethyl-
1 e
ethyl
t o <"t
aceto-
>b
pyi- 2-picB- CO
* ether dchj-de enlne acetate nit rile dine. Une
WC 170 43 0.55 30.8 12.0 8.6 0.2 15.4 3.2 10 3 25.5 3.2 21 6
HC 571 40 0.16 14.7 8.4 5.1 2.3 1.4 2.8 5 9 38.2 10.1 22 2
WC 1200 40 O.OU 11.4 8.9 9.3 2.0 1.0 6.2 4 2 20.8 B.9 24 3
AE 109 71 0.50 28.5 8.B 5.6 < 0.1 0.6 2.5 12 2 48.1 1.4 20 7
AE 1010 UO 0.00 13.3 17.0 8.0 0.6 3.4 4.0 4 2 26.3 10.4 23 C
AE 71 0.00 7.7 11.6 17.2 3.3 2.6 4.0 3 37.8 7.5 13 0
-
h f*01"1- r a t i o KK :C,H.OII 1 1 , 0 : 0 , 1 : 3 : 6 : 0 , MISV ( e l h a n o l ) > 0 . 1 7 h-'.
i t i u n o f product n i K t u r e a f t e r 4 h re on a r e n * .
c
WC w e t e r a l u , AE = A e r o e i l .
O 5 10 15 ' 20
t(hr)
Fig. 3. Plot of the conversion and selectivities vs. runtime for the ethanol-
animonia reaction (catalyst: H-ZSM-5 (Fe), Si/Fe = 189; Si/Al = 71, Aerosil
(+, conversion; selectivities: , ethene; *, ether; x, CH 3 CN; o, pyridine;
a, coz).
ethanol and ammonia over a H-ZSM-5 catalyst (Si/Al = 71, Si/Fe = 189, Aerosil)
versus the time-on-stream. After approximately 4 hours a steady state is reached.
Most catalysts used in this study give a similar picture.
76
3. Effect of space velocity with H-ZSM-5 zeolite

This effect has been studied with an aluminosilicate H-ZSM-5 catalyst, with
Si/Al = 55.5. This catalyst showed the best pyridine selectivity and a fair
conversion in the comparison between aluminosilicate catalysts [18]. Results are
shown in Table 3.
Table 3. Effect of space velocity in the ethanol-ammonia reaction .

HIlSVb conv. S e l e c t i v i t l o s to (wt *)
h-' X ethene diethyl ecetal- ethyl- ethyl eceto- pyri- 2-pico- 4-pico- C0 t
ether dehyde eroine acetate nitrile dine line line
0.17 12.8 6.4 7.4 3.2 1.7 5.7 4.0 44.5 9.2 2.8 15.2
0.35 6.4 5.5 12.8 6.3 3.1 6.8 3.8 36.4 7.7 < 0.1 17.7
0.67 3.7 7.3 IS.2 6.3 4.2 7.6 < 0.1 33.5 5.9 < 0.1 16.9
1.00 2.9 6.0 20.8 9.8 4.4 6.1 < 0.1 33.2 6.6 < 0.1 13.2
neaotor temperature 615 K..H-2SM-5 catalyst (Si/Al = 55.5).
WHSV aa I ethanol/(e.catalyst.hr).
As could be expected, the conversion decreases with increasing space velocity. The
changes in selectivities are an indication for possible mechanistic pathways. The
selectivity for acetaldehyde and ethylamine increase with increasing space
velocity, whereas the selectivity for acetonitrile decreases, indicating that
acetaldehyde and ethylamine are first formed during reaction, whereas this is not
the case for acetronitrile. Diethyl ether is another initial product, whereas
pyridine obviously is formed later.
Applying the high WHSV a series of experiments was performed at different
reaction temperatures. The results are given in Table 4. The space velocity was
kept constant at a value of 1.0 h l . At the high temperature the product mixture
simplifies and consists almost entirely of ethene and pyridine. Deep oxidation is
relatively low.
Table 1. Effect of reaction temperature on the ethanol-ammonia reaction

to pyridines
Temp. Conv. S e 1 e c t i v i t i e s t o (wt X)
K ethene diethyl acetal ethyl ethyl aceto pyri 2-pico- CO t
* ether dehyde amine acetate nitrile dine line
615 2.9 6.0 20.8 9.8 4.4 6.1 < 0.1 33.2 6.6 13.2
615 7.7 12.9 16.5 8.9 1.7 4.5 3.0 32.3 4.1 16.3
670 19.1 28.8 9.7 5.7 0.4 1.2 2.0 35.8 3.4 13.2
693 61.2 55.5 0.9 0.4 0.3 0.3 2.5 30.2 0.9 8.9
H-ZSM-5 catalyst, Si/Al = 55.5.
DISCUSSION
As shown earlier [18], a comparison of the reaction conditions for the etha
nol-ammonia reaction to pyridines and the conversion of ethanol without ammonia
[3] shows that for the former reaction a considerably higher temperature is needed
to obtain a fair degree of conversion. This is obviously caused by (partial)
poisoning of catalytically active (acid) sites by ammonia or the product bases.
Nayak and Choudhary [22] reported pyridine to be the most effective poison for
H-ZSM-5 in the reaction of olefins and alcohols to aromatics. They also found an
increased rate of coking on pyridine-poisoned catalysts (Si/Al = 17), probably
caused by the lack of strong acid sites. These sites are said to remove coke by
cracking reactions. On low Si/B zeolites we also detect coke formation, together
with loss of boron from the catalyst whereas on Si-rich zeolites hardly any coke
is formed. Relatively high acid sites density appears to promote coking in the
present reaction.
For the ethanol-ammonia reaction to pyridines two mechanisms can be envisaged:
one involving carbenium ions, oligomerization, amination, ring closure and
aromatization [23] and the other via dehydrogenation of ethanol to acetaldehyde,
aldolization/retroaldolization, reaction with ammonia, cyclization and aromatiza
tion. Because experiments substituting ethene or propene for ethanol as a feed
stock under the present conditions show no pyridine formation, the second
mechanism is preferred. High temperature reaction (693 K) at WHSV = 1 . 0 h- 1 yields
77
more ethene and more or l e s s the same percentage of p y r i d i n e than lower tempera
t u r e r e a c t i o n s . This i s a l s o in favonr of mechanism 2.,Some pathways a r e d e p i c t e d
in a s i m p l i f i e d way in Scheme 1.
O N H , or CH.CHjNH,
CH CH OH * CHjCHO > Pyndlne
non- acid sites .
> CH.COOH
H*
CHJC-O-CHJCH,
^ C H . C H - N H2
H' 3 non-acid sites
Scheme 1. Possible mechanism for reaction of C 2 H 5 0H and NH 3 to pyridines.
The first step for the formation of pyridines is supposed to be the dehydrogena-
tion of ethanol to acetaldehyde or the amination of ethanol to ethylamine. Acetal-
dehyde and ethylamine and/or ammonia are then converted to pyridines. Both reac
tion steps have been separately reported in the literature.
Matsumara et al. [24] showed that ZSM-5 zeolites containing little or no acid
sites are able to catalyze the reaction of ethanol to acetaldehyde. They suspect
Fe impurities in the zeolite to catalyze this reaction. The dehydration of ethanol
is catalyzed by protonated ZSM-5 zeolites. In the ethanol-ammonia reaction the
acid sites are at least partiallly poisoned by NH 3 and the product bases. The
dehydrogensition reaction can be catalyzed by the resulting non-acidic sites though
a detailed molecular picture is lacking. Matsumura et al. use an oxygen-free feed
and a somewhat higher reaction temperature. The reaction temperature needed might
be lowered by the presence of oxygen as a hydrogen acceptor. Isomorphous
substitution of Fe for Si in the zeolite lattice seems to have the same effect:
ferro-alumino-silicate zeolites are more active than iron-free catalysts.
Table 1 shows that zeolites with increasing B content (except for the 8 B/uc
sample) show a shift in selectivity from acetaldehyde to ethene. This can be
explained by assuming that an increasing number of acid sites is in equilibrium
with ammonia- and pyridine-poisoned sites.
Chang and Lang [9j showed that acetaldehyde and ammonia can be converted to
pyridines over H-ZSM-5 catalysts. The reaction is performed under oxygen-free
conditions at 723 K- and LHSV = 1. Our experiments showed that from an oxygen-
containing feed pyridines can be formed at 693 K (WHSV = 1 h - 1 ) .
Optimum selectivity to pyridines will be found at an acid sites content where
catalysis of acetaldehyde production and -consumption to pyridines is balanced.
This explains why iron-containing catalysts are more active: the rate of
acetaldehyde production is higher (catalyzed by Fe) so the rate of pyridine forma
tion can be increased. Comparing two catalysts from Table 2 (H-ZSM-5 containing
0.55 Fe/uc, prepared from waterglass and H-ZSM-5 containing 0.50 Fe/uc, prepared
from Aerosil) illustrates again that a catalyst with a higher number of strong
acid sites (the former catalyst) has a lower selectivity for pyridine (25.53) than
a zeolite with less and milder acidic sites (selectivity = 48.151).
Further reactions on the zeolites comprise:
(i) conversion of ethanol to ethene and diethyl ether over acid sites
(ii) anunoxidation of ethanol or acetaldehyde to acetonitrile
(iii) oxidation to acetic acid, followed by esterification to ethyl acetate
(iv) amination of ethanol to ethylamine over acid sites
(v) oxidation of ethylamine to acetonitrile
(vi) total oxidation of reactants or products to carbon dioxide and water.
78
CONCLUSION
Pyridine bases can be produced from ethanol and ammonia in the presence of
oxygen using H-ZSM-5 type catalysts. ZSM-5 zeolites with partial or complete
isomorphous substitution of B or Fe for Al in the zeolite lattice also are
catalytically active in the pyridine forming reaction. Using boron the performance
of the catalyst is somewhat less than an aluminosilicate H-ZSM-5 catalyst, whereas
incorporation of small amounts of iron increases the conversion without bringing
about large changes in selectivity. The yield of pyridine can be increased by
increasing both reaction temperature and space velocity. At WHSV = 1.0 h- 1 and
693 K a product mixture consisting chiefly of ethene and pyridine (and carbon
dioxide) is formed.
A mechanism starting with partial oxidation of ethanol to acetaldehyde,
followed by stepwise conversion to pyridine bases, can be suggested.
ACKNOWLEDGEMENTS
The authors would like to thank Mr. J.P. Koot (Laboratory of Analytical
Chemistry) for the AAS analyses and Mr. J.F. van Lent and Mr. N.M. van der Pers
(Laboratory of Metallurgy) for the XRD analyses of the used zeolites. Dr. H.W.
Kouwenhoven is thanked for valuable discussions.
REFERENCES
1. S.L. Meisel, J.P. McCullough, C.H. Lechthaler, andP.D. Weisz, Chem. Techn.,
6, 86 (1976).
2. C D . Chang and A.J. Silvestri, J. Catal. , 47, 249 (1976).
3. J.C. Oudejans, P.F. van den Oosterkamp, and H. van Bekkum, Appl. Catal., 3,
109 (1982).
4. e.g. K.H. Chandawar, S.B. Kulkarni, and P. Ratnasamy, Appl. Catal., 4, 287
(1982).
5. US Patents 3,751,504 (1975); 3,751,506 (1975); 3,755,483 (1975); 4,159,282
(1979); 4,159,283 (1979).
6. P.J. Lewis and F.G. Dwyer, Oil Gas Journal, 75, 55 (1977).
7. P.B. Weisz, in "Stud. Surf. Sci. Catal., 7, New Horizons in Catalysis", eds.
T. Seyama and K. Tanabe (Elsevier, Amsterdam, and Kodanska Ltd., Tokyo, 1981).
R. W.W. Kaeding, US Patent 4,082,805 (1982).
9. C D . Chang and W.H. Lang, US Patent 4,220,783 (1980).
10. I!. Bicker and R. Erckel, Eur. Patent 0,046,897 (1981).
11. Neth. Patent 82.01523 (1981).
12. H.S. Fales and J.O.H. Peterson, Eur. Patent 0,039,918 (1981).
13. C D . Chang and P.D. Perkins, Zeolites, 3, 298 (1983).
14. C D . Chang and P.D. Perkins, US Patent 4,388,461 (1983).
15. C D . Chang ami P.D. Perkins, Eur. Patent 0,082,613 (1983).
16. M. Deeba and W.J. Arabs, Eur. Patent 0,077,016 (1983).
17. J.C. Oudejans, F.J. van der Gaag, and H. van Bekkum, in "Proc. Sixth Intern.
Conf. Zeolites", Reno 1983, eds. D. Olson and A. Bisio (Butterworth,
Guildford, 1984), p. 536.
18. F.J. van der Gaag, F. Louter, J.C. Oudejans, and H. van Bekkum, Appl. Catal.,
in press.
19. F.J. van der Gaag, J.C. Jansen, and H. van Bekkum, Appl. Catal., 17, 261
(1985).
20. E.M. Flanigen and R.L. Patton, US Patent 4,073,865 (1978).
21. J.C. Oudejans, Thesis, Delft University of Technology (1984).
22. V.S. Nayak and V.R. Choudhary, Appl. Catal., 9, 251 (1984).
23. R.M. Dessau and R.B. LaPierre, J. Catal., 78, 136 (1982).
24. Y. Matsumura, K. Hashimoto, S. Watanabe, and S. Yoshida, Chem. Lett., 1981.
(1), 121.
Formation of 2,6-lutidine 79
THE FORMATION OF 2.6-LUTIDINE FROM ACETONE,
METHANOL AND AMMONIA OVER ZEOLITB ZSM-5.
F.J. van der Gaag, R.J.O. Adriaansens and H. van Bekkum,

Delft University of Technology, Laboratory of Organic Chemistry,
Julianalaan 136, 2628 BL DELFT, The Netherlands.
and P.C. van Geem, DSM Research BV.,

P.O.Box 18, 6160 MD Geleen, The Netherlands.
ABSTRACT
2,6-Lutidine is formed from acetone, methanol and ammonia
over ZSM-5 type zeolitic catalysts. Selectivity to
2,6-lutidine is found to be highest at relatively high Si/Al
ratios. At the higher Si/Al ratios a lower steady state
adsorption of lutidine (0.6 lutidine/Al) is present under
reaction conditions. A mechanism is discussed taking into

13
account an experiment with C-labeled methanol.
INTRODUCTION.
2,6-Dimethylpyridine (2,6-lutidine) is the starting chemical for the
manufacture of several industrially interesting products. A number of
syntheses of 2,6-lutidine have been reported. Most promising thusfar is
the direct methylation of 2-methylpyridine (2-picoline) with methanol.
Thus, 2-picoline and excess methanol are fed over a Ni-containing catalyst
at a temperature of 260C [1,2]. Similarly, pyridine can be alkylated over
Raney-Ni, Raney-Co, Raney-Cu or Raney-Fe at 200C [3]. Good initial
conversion and selectivity are obtained, however catalyst deactivation is
severe. Another route is the synthesis from acetone, ammonia and
formaldehyde:
+ 2H2 + H2
2 (CH3)2 CO CH20 NH3 fOl
80 Formation of 2,6-lutidine
Patent literature [4,5,6] claims the use of promoted amorphous
silica-alumina catalysts, together with high temperatures (resp.
350-550C, 420C and 450C) and high space velocities. Yields ranging from
29 to 483> are reported, starting from reaction mixtures containing an
excess of ammonia (molar ratio ammonia/ acetone is 2.7-2.8).
In this paper we report on the synthesis of 2,6-lutidine over a
crystalline aluminosilicate catalyst, zeolite ZSM-5. Reaction of ethanol,
ammonia and air to pyridines over zeolite ZSM-5 showed the dehydrogenation
ability of this catalyst [7]. These properties prompted us to attempt
lutidine synthesis from acetone, ammonia and methanol as a potential
formaldehyde precursor. The effects of a variation in Si/Al ratio of the
ZSM-5-zeolite and some other reaction parameters were studied. For
comparison Mordenite and H-Y were included.
EXPERIMENTAL.
Catalysts,
Zeolite H-ZSM-5 and Silicalite were synthesized according to a procedure
adapted from the patent literature [8,9). The procedure comprised mixing
an Aerosil (Degussa) suspension with a solution of sodium hydroxide, the
template, tetrapropylammonium bromide (TPA-Br) [8] (Chemische Fabriek
Zaltbommel, the Netherlands) and sodium aluminate (Riedel-de Haehn),
followed by crystallization for 48 hours in a teflon-coated autoclave at
180C under stirring [9]. Finally, the product is filtered and washed. The
molar gel composition was SiCte: NaOH: TPABr: H20= 1:0.35:0.165:47.8. The
Si/Al ratio of the gel was varied from 12.7 to infinity (Silicalite). The
zeolites are denoted ZSM-5(X), with X is the Si/Al ratio in the
synthesis mixture. The actual Si/Al ratio of the zeolites is shown in
Table 1. Zeolite compositions were analyzed by AAS. After drying and
calcination (550C, overnight) all ZSM-5 type zeolites were exchanged
twice using a 0.5 M HCl solution (100 ml/g, 80C, 0.5 hr). This procedure
is known to yield an exchange degree of over 95*.

H-Mordenite (large pore: Zeolon 900H, Norton, and small pore: Alite 150.
(Na-form), Soc. Chim. de la Grande Paroisse) and zeolite Y (Na-LZY-5Z,
Union Carbide Corporation, Linde Division) were commercial zeolites.
Small pore Mordenite was converted to the H-form by repeated exchange with
1 M NlfcNOs (80C), followed by calcination under shallow bed conditions at
420C. Benzene adsorption showed that ,the . zeolite still possessed small
pore properties. H-Y was obtained by exchanging Na-Y with an 1M NH4NO3
solution at 80C, followed by calcination. Analysis showed 8435 exchange of
the sodium ions.
The catalysts had a particle size of 0.3-0.5 mm, obtained by dry
pressing, crushing and sieving of the zeolites.

13
C-labeled methanol (99* 1 3 C ) was obtained from Aldrich.
Procedures.
The catalyst (1-2 g) was introduced in a fixed bed continuous flow
stainless steel microreactor (internal diameter 4 mm, length 120, mm) and
heated to the reaction temperature (usually 450C). The reactants were
then pumped into the reactor by means of two HPLC . pumps (Gilson model
302). No carrier gas was used. The condensed products (18C) of the
reaction were analyzed by GC, and, if necessary, by GC-MS.
Adsorption/TPD experiments with 2,6-lutidine were carried out in a
GC-type apparatus according to Choudhary and Akolekar [12].
RESULTS AND DISCUSSION.
The reaction of acetone, ammonia and methanol (or formaldehyde).
generally leads to a product mixture with a rather complex composition.
The reaction products comprise: 2,6-lutidine, 2,4-lutidine, 2-picoline,
collidine (trimethylpyridine), a tetramethylpyridine, methylcyclohexenone,
mesityl oxide, 4-methyl-4-penten-2-one, butanone, acetonitrile, toluidines
and some other benzene derivatives. The ratio of 2,4-lutidine to
2,6-lutidine formed is always less than 0.05. Gases like ethene, propene,
butene and trimethylamine are also produced.
Some initial experiments were performed with the reaction of acetone,
formaldehyde, ammonia and water over H-ZSM-5 (Si/Al=96) and H-Y (molar
feed composition: acetone: formaldehyde: ammonia: water = 1.0: 1.0: 2.0:
5.5, (formaldehyde as 1,3,5-trioxane), WHSV(acetone)= 0.30 h~ l .
Formaldehyde is fed as trioxane - which compound decomposes at reaction
conditions to formaldehyde - to avoid condensation reaction of
formaldehyde and ammonia before entering the reactor. In
these experiments catalyst activity as well as lutidine selectivity were
found to decrease relatively rapidly, especially in the case of H-Y as the
catalyst.
Activity and selectivity were found to increase upon replacing
formaldehyde by methanol in the subsequent experiments. Reaction
conditions were: feed composition (molar ratio): acetone: methanol:
ammonia: water = 1.0:1.0:0.4:2.8, WHSV(acetone)= 0.97 h" 1 , temperature
350C.
The influence of the aluminum content of the zeolite catalyst was
determined by analysis of the condensed products of the first 7 hours of
reaction. The results are shown in Table 1.
Sometimes the condensate of 7-22 hours was also analyzed for comparison,
generally showing some gradual decrease of catalyst performance.
Silicalite does not catalyze the formation of 2,6-lutidine, showing that
lutidine formation requires the presence of acid sites. The conversion of
both methanol and acetone increases with increasing Al content of the
ZSM-5 zeolite, whereas the reverse is true for the selectivity to
2,6-lutidine. The ZSM-5 type pore system also plays a role, as can be seen
from the comparison with H-Mordenite and H-Y.

TABLE 1: Effect of zeolite type and composition on conversion

and on 2,6-lutidine selectivity.
Catalyst Si/Al Conversion b ) (*) Selectivity c> Amount of product

a
> acetone methanol to 2,6-lutidine(%) condensed d> (%)
Silicalite >2000 28.3 42.0 0.0 70.8
H-ZSM-5(96) 89.9 62.8 84.7 12.9 . 84.0
H-ZSM-5(23) 14.6 78.5 86.2 8.9 67.0
H-ZSM-5(12.7) 11.1 92.4 96.4 6.2 46.1
H-Mord (LP) 5.85 31.0 62.2 3.4 75.6
H-Mord (SP) 5.56 46.8 48.7 0.5 67.1 .
H-Y 2.05 96.7 97.6 1.1 37.1
Reaction conditions: 350C, WHSV(acetone)=0.97 h"1 , molar feed

composition: acetone: methanol: ammonia: water=1.0: 1.0: 0.4: 2.8.
a)
The number between brackets denotes the gel Si/Al ratio.
b
> Conversion reactant X=(l-(moles X condensed)/(moles X fed))*100&
O ( 2*moles 2,6-lutidine condensed )*100%
(moles acetone fed*conversion acetone)
d
> (weight of condensate)/(weight of feed)*100&
Table 1 shows that H-Mordenite (small pore) hardly gives rise to the
formation of 2,6-lutidine. This can be understood because the pores in
this zeolite are too small to allow formation and passage of the product
2,6-lutidine. The product of the experiment with zeolite H-Y as a catalyst
contains a large amount of volatile products, resulting in a low product
recovery. Methanol is probably converted into dimethyl ether, which is not
condensed under the conditions used. A plot of the 2,6-lutidine
selectivity versus aluminum content is shown in Figure 1.
In order to get a picture of the zeolite pore filling with 2,6-lutidine
(and other basic products formed) under reaction conditions some
adsorption and desorption experiments were carried out. TPD experiments
show that 2,6-lutidine desorbs from the weak acid sites of the H-ZSM-5
catalysts below 350C. Desorption from Bronsted acid sites was not
observed at temperatures up to 500C. This desorption can be expected at
approximately 700C.
/ s e l e c t i v i t y
2 - 6 lutidine + HZSM5I96)
i
\+HZSM5<23>
+ HZSM5 (12-7)
\
\
\
+ H M o r d LP
' +HY
30 40
Al
CM
FIGURE 1: 2,6-Lutidine selectivity plotted vs Al content.
TABLE 2: 2,6-Lutidine adsorption on H-ZSM-5 catalysts at 325C
catalyst catalyst calculated adsorbed lutidine/Al

weight pore 2,6-lutidine
(mg) volume (wl) volume (1)
H-ZSM-5(12.7) 404.1 68.7 30 0.526
H-ZSM-5(23) 420.9 71.5 20 0.589
H-ZSM-5(218) 459.2 77.7 2.5 0.619
Zeolite pore volume was calculated from the weight (170 ;ul/g).
Adsorption experiments of 2,6-lutidine on H-ZSM-5 at 325C show an

adsorption of ca. 0.6 lutidine molecule per Al atom in the zeolite lattice
(see Table 2). Apparently a part of the acid sites is not strong enough to
keep the lutidine adsorbed at 325C. This is in agreement with the results
of Datka and Tuznik [10], who show, by IR spectroscopie measurements, that
there are two kinds of Bronsted acid sites for pyridine adsorption. The
strong acid sites which account for about 60* of the Al atoms, still
adsorb pyridine at a temperature of 325C [10].
Silicalite has been omitted in Figure 1. The graph shows a
relationship between the aluminum content (the number of acid sites) of
the zeolite and the selectivity to 2,6-lutidine. In the synthesis of
pyridine from ethanol and ammonia over zeolite ZSM-5 a similar effect has
been observed: a relatively high Si/Al ratio is advantageous for the
selectivity and the stability of the catalyst [7,11]. The behaviour of
H-Mordenite (large pore) and HY in the lutidine synthesis might indicate
that other factors such as the zeolite structure have a strong influence
on the reaction sequence.
The influence of the reaction temperature on the selectivity and
conversion was determined using H-ZSM-5(96) as the catalyst, which zeolite
showed the highest selectivity to 2,6-lutidine in the zeolite screening.
The results are shown in Table 3.
TABIE 3: Influence of temperature on conversion and selectivity
Temperature (C) Conversion a > ( & ) Selectivity b>(Ss) Amount of product

acetone methanol to 2,6-lutidine condensed (3S)C)
' 400 33.0 31.5 16.0 85.2
450 66.8 84.7 12.9 84.0
500 93.1 77.7 15.6 76.2
Reaction conditions: WHSV(acetone)=0.97 h~ l , molar feed composition:

acetone: methanol: ammonia: water=1.0: 1.0: 0.4: 2.8, H-ZSM-5(96) catalyst.
a
> Conversion reactant X=(l-(moles X condensed)/(moles X fed))*100%
b> Selectivity=( 2*moles 2,6-lutidine condensed )*100S
c
> *condensed=(weight of condensate)/(weight of feed)*100%
As expected, the conversion increases with increasing reaction tempe
rature. At 400C the numerous byproducts (like methylcyclohexenone and
mesityl oxide) are present in small amounts only. The condensate of the
reaction at 500C consists of two phases, an aqueous phase and an organic
phase. The organic phase contains, besides 23* (w/w) 2,6-lutidine as
the main component, more than 75 other components, generally each in

concentrations of less than IX. The aqueous phase contains over 30

compounds, among which'2.63> (w/w) 2,6-lutidine.
At a higher reaction temperature (i) more low-molecular weight products
and (ii) more non-hydrophilic products are formed. Considering the almost
constant selectivity and the increasing conversion with increasing
temperature, it appears that the 2,6-lutidine yield goes up with
temperature.
The influence of the space velocity was investigated using H-ZSM-5(96)

as a catalyst and a reaction temperature of 450C. Data are given (Table
4) for the condensate of the first 7 hours of reaction, and for the
condensate'of 7-22 hours (between brackets).
TABLE 4: Influence of WHSV on conversion and selectivity
WHSV (h~l) Conversion a >(X) Selectivity b>(X) Amount of product

acetone acetone methanol to 2,6-lutidine condensed (X)c>
0.243 94.3(62.2) 86.7(70.0) 10.9(23.7) 58.2(71.0)
0.969 62.8(50.6) 84.7(69.0) 12.9(11.3) 84.0(88.1)
1.938 48.4 69.4 11.4 82.0
Conditions: molar feed composition: acetone: methanol: ammonia: water=

1.0:1.0:0.4:2.8, H-ZSM~5(96) catalyst, 450C.
a)
Conversion reactant X=(l-(moles X condensed)/(moles X fed))*100%
b) Selectivity=( 2*moles 2,6-lutidine condensed )*100%
c
> *Condensed=(weight of condensate)/(weight of feed)*100%
The conversion increases with decreasing space velocity. The selectivity

to 2,6-lutidine is more or less constant. In general, conversion decreases
with increasing time-on-stream.
The influence of the reactant composition was examined by varying the

acetone/methanol ratio and the ammonia/acetone ratio in some experiments
using H-ZSM-5 (96) as the catalyst at 450C. The results, shown in Table
5, suggest that the selectivity to 2,6-lutidine based on acetone converted
is hardly affected by the acetone/methanol r a t i o .
TABLE 5: Influence of reactant composition on conversion and selectivity. 3 >
molar feed coiposition conversion"(I) selectivity to cl HHSV" Aount of product

acetorie:ethanol:anonia:water acetone aethanol 2,6-lutidine (overall) condensed'1 (I)
1 4 0.41 2.78 60.3 86.8 14.3 5.94 73.2
1 1 0.41 2.78 62.8 84.7 12.9 2.69 84.0
1 0.5 0.67 4.57 35.5 34.7 15.9 5.11 82.3
1 1 1.64 11.11 36.0 53.5 21.6 5.31 56.9
> H-ZSM-5(96) catalyst, 450C, results for the first 7 hours of reaction.
" NHSV h"1, HHSV(acetone) constant at 0.97 /hr.
c
' Conversion reactant X=(l-(oles X condensedj/Uoles X fed))*1002
<i) Selectivity;) 2*moles 2,6-lutidine condensed )*100I
(soles acetone fed*conversion acetone)
ei
ICondensed:(weight of condensate)/(weight of feed)*100I
The stoichiometric ammonia/acetone r a t i o to form 2,6-lutidine is 0.5.

Increasing the ammonia/acetone r a t i o to 1.64 results in an increase in
selectivity to 2,6-lutidine. The positive influence of an excess of
ammonia may be due to improved trapping of reactive carbonyl
intermediates (cf. mechanistic considerations) by ammonia, thus inducing
higher lutidine s e l e c t i v i t y .
Mechanistic experiments and considerations.

To investigate the way methanol is built in in 2,6-lutidine an
13
experiment with C-labeled methanol was carried out. The reaction
conditions were: catalyst H-ZSM-5 (96), WHSV(acetone)= 0.30 h" 1 , molar
13
reactant composition: acetone: C-methanol: ammonia: water= 2.0: 1.0:
4.0: 13.7, reaction temperature: 450C. The condensed products were
fractionated and the fraction containing 2,6-lutidine was analyzed with
GC/MS. Apart from labeled 2,6-lutidine (l*i 3 C), 2,4-lutidine (1*13C) and
trimethylpyridine (2*13C) were also detected. Purification by preparative
13
gas chromatography yielded pure C-labeled 2,6-lutidine, which was
13 13 13
analyzed by C-NMR. The C (from the C-methanol) appeared to be
88
Formation of 2,6-lutidine
present at the 4-position exclusively. Thus the reaction can be formulated
as:
C H 0 H
3 , r<^CN
ô NH3 o^x AN^

The by-product 2-picoline nay be formed by demethylation of 2,6-lutidine
l3
and therefore it is likely that the labeled C-atom is built in here too
at the 4-position. The 2,4-lutidine observed is probably formed by ring
closure of mesityl oxide or 4-methyl-3-penten-2-one, which has been
detected in the product mixture. Then the labeled carbon atom is expected
at the 6-position.
13
The trimethylpyridine, which is labeled twice in the C-methanbl
experiment is either formed by methylation of a dimethylpyridine with
methanol or by reaction of two molecules methyl ethyl ketone (or methyl
vinyl ketone) with ammonia. In either case, there is one labeled atom
present at the 4-position in the ring and one in a methyl group.
As to the mechanism of this condensation/aromatization the labeling
result leaves three possible routes for the formation of 2,6-lutidine from
acetone, methanol and ammonia.
Mechanism I involves the formation of methyl vinyl ketone either by
condensation of acetone and methanol followed by a dehydrogenation or
directly from acetone and formaldehyde, where formaldehyde is formed by
dehydrogenation of methanol. As to the latter reaction recent work has
shown methanol to be readily dehydrogenated over a Silicalite catalyst
under similar conditions [13]. Methyl vinyl ketone reacts in further
steps with another acetone molecule and ammonia followed by H-transfer
processes to form 2,6-lutidine.

MECHANISM I.
H2Q H,
\ = 0 CH3OH
-H20 O
V=0 CH20
> 0
-2H,
O
N A,
-NH,
2H
2o v
o o
In an attempt to get more insight into a role of methyl vinyl ketone
we performed some explorative experiments on the reaction of methanol...and
conversion
100 -i methanol
/. / product
recovered / conversion
acetone
1
80 - ' 80-
conversion
60 - 60-
methanol
40 ^^\conversion 40
acetone
20 - 20 - mesityl oxide
selectivities: - toluene
mesityl oxide xylene
0 :metnyi ethyl keton .methyl ethyl ketone
1
1 1 1 I
3 2 4 6 8 4 6 8
runtime (hr) -- runtime (hr)
FIGURE 2: Conversions and selectivities for the conversion of acetone

and methanol. WHSV(acetone) = 1.14 h"1 , molar ratio
acetone/methanol=l.
A: CaX catalyst, 300C; B: H-ZSM-5(96) catalyst, 450C.
acetone. When performing this reaction over zeolite ZSM-5 at 450C a
complex mixture of relatively high molecular weight products was
obtained including, as expected, aromatic compounds. Some methyl ethyl
ketone (< 5 X) was found to be present in the product mixture. To prevent
the product undergoing consecutive reactions on a highly active (ZSM-5)
catalyst we used in a second experiment zeolite Ca-X while lowering the
reaction temperature to 300C. The other reaction conditions were:

1
WHSV(acetone)=l.15 h" , molar reactant composition: acetone: methanol =
1:1. The results are shown in Figure 2.
Though a Ca-X zeolite catalyst is much less active than H-ZSM-5 numerous
products were formed, mostly in low concentrations. Mesityl oxide,
methylcyclohexenone and methyl ethyl ketone were present in measurable
quantities. Methyl vinyl ketone was mot found, indicating that this
product is either very reactive or no real intermediate. The first
possibility is the most likely considering the dehydrogenating properties
of ZSM-5 catalysts [7,11].
The first step in the mechanism can also be the formation of methyl
vinyl ketone (MVK) directly from reaction between formaldehyde and
acetone. Addition of acetone in a fast Michael-reaction then will lead to
2,6-heptadione. Ring closure with ammonia, dehydration and dehydrogenation
yields 2,6-lutidine. This reaction is reported to yield 2,6-lutidine [14].
To verify this mechanism, methyl vinyl ketone was reacted with acetone
and ammonia under the present conditions (catalyst: H-ZSM-5(96), 450C,
WHSV(total feed)=1.97 h' 1 , MVK: acetone: ammonia: water= 1:2.2:5.5:35.7).
Indeed, 2,6-lutidine is formed though selectivity is rather low, i.e.
6*. Presumably the high concentration of methyl vinyl ketone causes side
reactions, which do not take place when methyl vinyl ketone is formed in
situ from methanol and acetone.
MECHANISM II
H,0 \ MH *yr I l*CH3OH

> NH,
+
CH 2 0
H20
A N'
-2H, <S
O y*^
Another mechanism (II) starts with formation of acetonimine which can
react in a fast reaction with acetone to yield a Schiff's base. Reaction
with methanol or formaldehyde then gives the triene product which might
undergo intramolecular ring closure with subsequent zeolite-catalyzed
dehydrogenation to 2,6-lutidine.
A third mechanism (III) starts again with reaction of acetone and
methanol or acetone and formaldehyde to yield methyl ethyl ketone or
methyl vinyl ketone, respectively. Again, formaldehyde is probably
formed by dehydrogenation of methanol over the catalyst [13]. Condensation
of this product with ammonia and then with acetone gives a diene system,
which upon ring closure and dehydrogenation will yield 2,6-lutidine.

92
Formation of 2,6-lutidine
MECHANISM I I I '
\ "H2 ( *NH3 C ' ^ ( \
J^~Xx !
Except for methyl ethyl ketone none of the above-mentioned reaction
intermediates were found in the product mixture, which means that the
intermediates are either very reactive under reaction conditions or do not
exist.
The present data do not allow us to draw any conclusions about the
validity of the mechanisms, so additional work is required to
discriminate between them.
ACKNOWLEDGEMENT.
We thank DSM Research BV. for financial and technical support, and Mr.
L.H.W. Jansen for his technical assistance in performing the experiments.
We are also grateful to Dr. H. W. Kouwenhoven for valuable discussions.

LITERATURE.
1. US Patent 3.354.165 (1967); US Patent 3.334.101 (1967).

2. H. Kashiwagi, S. Enomoto, J. Chem. Soc. Japan, 1980, (4), 551.
3. Japan Patent 79.24.878 (1979).
4. Japan Patent 72.22.579 (1972).
5. Japan Patent 72.31.935 (1972).
6. Japan Patent 72.46.070 (1972).
7. F.J. van der Gaag, F. Louter, J.C. Oudejans and H. van Bekkum, Appl.
Catal., 26, (1982), 191.
8. US Patent 3.702.886 (1972).
9. Eur. Patent 0.042.225 (1981).
10. J. Datka and E. Tuznik, J. Catal. 102, (1986), 43.
11. F.J. van der Gaag, F. Louter and H. van Bekkum, in: "Proc. VII Int.
Zeol. Conf.", Tokyo 1986, Eds. Y. Murakami, A. Iijima, J.W. Ward, p.763.
12. V.R. Choudhary and D.B. Akolekar, J. Catal., 103, (1987), 115.
13. Y. Matsumura, K. Hashimoto and S. Yoshida, J.Catal., 100, (1986), 392.
14. L.I. Verachchagin and I.L. Kotlyarevskii,Isvest. Akad. Nauk. SSSR, Otdel
Khira. Nauk, 1960, 1632, CA 55, 8404 i.
94 SAPO- molecular sieves
Exploratory work on Bilicon aluminum phosphate
molecular sieves and related materials.
INTRODUCTION
Aluminum phosphate molecular sieves (AlPO's) are a new class of
inorganic microporous materials [1,2]. These materials, which were
discovered by Flanigen et al.f 1], have structures much like those of
the alumino-silicate zeolites. The crystal structure is composed of AIO4
and PO4 tetrahedra, with a molar ratio of approximately 1. The lattice of
an aluminum phosphate molecular sieve is therefore almost electrically
neutral, yielding hardly any ion exchange capacity and having a low
polarity. In fact, the polarity of the so-called AlPO-family lies between
the polarity of the low-silica zeolites (e.g. types A, X and Y) and that
of Silicalite, as judged by H2O adsorption.
As mentioned above, the structure of the AlPO's consists of AIO4- and
PO4-tetrahedra linked together via the oxygen ions. Each oxygen is thus
shared between two tetrahedra, yielding a net formula of TO2 (T
representing an Al or P atom). Because each type of tetrahedron bears a
charge (+1 for a PO4- and -1 for an AIO4 tetrahedron), Loewensteins rule
is expected to apply to both types of tetrahedra. Odd-membered rings of
T-atoms should consequently not occur in the structure of the
AlPO-zeolites. The family of AIPO4-molecular sieves comprises both novel
structures and structures with have an analogon in the families of
"classical" (aluminosilicate) zeolites. However, structures containing
odd-membered rings of T-atoms have indeed not been found. Figure 1 shows
some structures of AlPO-type molecular sieves.

SAPO- molecular sieves 95
Figure 1: Structures of zeolitic aluminophosphates: a: A1P0-5;

b: AlPO-11; c: A1PO-17; and of two often encountered impurities:
d: metavariscite and e: AIPO4.I.5H2O
The lattice of the aluminum phosphate molecular sieves is in theory
electrically neutral. When slight deviations from the ideal Al/P molar
ratio (0.8-1.2 instead of exactly 1.0) are used a charge could be
introduced in the lattice. In the case of an excess of Al tetrahedra the
lattice would bear a net negative charge, giving rise to cation exchange
96
SAPO- molecular sieves
properties. These properties are also found in the classical zeolites
where the lattice also bears a negative charge. Specially interesting
would be those materials where an excess of P tetrahedra is present.
Here the charge on the lattice would be positive, yielding anion
exchange properties. If it would be possible to synthesize these
materials, zeolite science would be allowed to enter the field of
base-catalysed reactions by using OH"-exchanged AlPOa-molecular sieves.
Presently the zeolite technology is limited to acid-catalysed reactions or
one has to rely on suppression of the acidic properties, e.g. by
Cs-exchange of a zeolite.
A further expansion of the family of AlPO-zeolites is the isomorphous
substitution in these materials. Substitution of Si in the lattice yields
the SAPO (Silicon, Aluminum, Phosphorus Oxide) molecular sieves [3].
Theoretically three types of substition are possible:
a: introduction of a Si tetrahedron on the position of Al,
b: introduction of a Si tetrahedron on the position of P, and
c: introduction of two Si tetrahedra on the position of one Al
and one P tetrahedron.
It will be clear that only types a and b will yield charge on the lattice,
a positive charge for type a and a negative charge for type b
substitution. In the case of type c the electrically neutral unit AIPO4
will be substituted by the neutral unit Si24. In this chapter it will be
shown that only substitution types b and c are found to occur.
Also other substitutions can be envisaged: there is no reason at all to
limit the . substitution to Si. Numerous other metal ions can be
incorporated. Reported examples include: Co, Mg, Mn etc.[4-6]. It is also
possible to perform double substitution, i.e. to incorporate for instance
both Si and Co [4,5], Samples synthesized in this manner are generally
described as MeAPC or MeAPSO- molecular sieves. Patent literature claims

the possibility of introduction of up to 14 substituting metal ions [7],
alone or in combination with Si or other ions. It will be clear that this
gives even more ways of substitution. Experiments described in this
chapter will show that only those substitutions yielding an electrically
neutral or negatively charged lattice will occur.
It is noteworthy that the substituted AlPO-molecular sieves can be
envisaged to be derived from the parent material: all SAPO-, MeAPO- and
MeAPSO-structures are closely related to the corresponding AlPO-structure.
Using X-ray powder diffraction it is virtually impossible to distinguish
between a substituted and a non-substituted A1P0 structure.
Synthesis of A1P0 molecular sieves is effected by mixing a phosphorus
source (usually ortho-phosphoric acid), an aluminum source (usually an
active form of alumina, like pseudo-boehmite or gamma-alumina) and a
structure-directing agent (a template as described for the synthesis of
ZSM-5 type zeolites). The resulting gel is then heated in an autoclave for
a period of time (100-250C for 1 to 30 days, depending on the desired
structure). A profound difference between the classical (Al/Si-) zeolites
and the AlPO-derived families is the synthesis. Whereas the classical
zeolites are usually synthesized in an alkaline medium, the synthesis
mixture of the AlPO-families has a low pH.
This chapter describes the synthesis of several samples of SAPO-, MeAPO-
and MeAPSO- molecular sieves, their analysis and their properties. One of
the most important properties is the basicity of the sample. This has been
tested using the alkylation of toluene with methanol as a probe reaction.
An acidic catalyst will cause alkylation to occur at the ring, yielding
xylenes and higher substituted benzenes. A basic catalyst will induce
side-chain alkylation, with ethylbenzene and styrene as the products. The
effect of the incorporation of T-atoms other than Si, Al and P is studied
using the ammoxidation of toluene as a test reaction. The activity and
selectivity of catalysts from the AlPO-families is compared to the

properties of ZSM-5 type catalysts'.
EXPERIMENTAL
A number of SAPO and MeAPSO molecular sieve samples were prepared,
following the examples described in patent literature [7-11]. A general
procedure consists of the mixing of the alumina source (pseudo
boehmitej Dispural, Condea) and the phosphate source (85* H3PO4, Merck),
followed by the addition of the sources of the substituting T-atoms'. After
thorough mixing the template is added and the mixture was autoclaved for
the desired time at 150 C. Five closely related synthesis methods were
used, according to Hef 7-11.
The solid samples obtained were analysed using X-ray diffraction, atomic
absorption spectrometry and clorimetry. The XRD powder data enabled to
detect the presence of A1PO-5 phases, as well as a non-microporous
aluminum phosphate hydrate and some boehmite and other members of the
AlPO-molecular sieve family.
The adsorption properties were determined using NH3-TPD and
thermogravimetric adsorption of water and cyclohexane. Toluene adsorption
was determined in a slightly different way, i.e. by the weight difference
between a dried (400C) sample and a sample containing toluene adsorbed
in an desiccator filled with toluene vapour.
Some of the samples were tested in a reaction to determine their
catalytic activity. Two reactions were used: the alkylation of toluene
with methanol to investigate whether basic properties are present, and the
ammoxidation of toluene. In the first reaction the following conditions
were applied: WHSV(toluene)=0.17 hr _1 , molar reactant ratio: methanol:
toluen= 1:1, reaction temperature 250C. The second reaction provides the
possibility to compare the AlPO-family molecular sieves to the ZSM-5
family (see Chapter 5 ) . Reaction conditions were: WHSV(toluene)-0.17 hr" 1 ,
molar reactant ratio: toluene: ammonia: water= 1:2:6, reaction

SAPO- molecular s i e v e s 99
temperature: 350C.
As mentioned above, molecular s i e v e s of the A1PO- (and r e l a t e d ) families
can be synthesized by mixing an alumina source, a phosphate source and a
template. The members of the r e l a t e d f a m i l i e s are obtained by adding the
extra component t o the g e l . Here the samples were s y n t h e s i z e d by preparing
Table 1: Synthesis conditions for the z e o l i t e c a t a l y s t samples.
Saeple No. Synth Tiae Sources1' for Tea- Sel olar ratio (P205=1.00) XRD
type" (hr) Ai P Si Metal plate AI2O3 S1O2 Metal Tenplate result0'
SAPO-5 1 8 120 8oeh PA Aeros - EtsN 1.05 0.04 - 1.5 5,H

SAPO-5 2 8 120 Boeh PA Aeros - EtsN 0.94 0.06 - 1.5 H
SAPO-5 3 8 120 Boeh PA Aeros - Et3N 0.96 0.04 - 1.5 5,H
SAPO-5 4 9 64 Bpeh PA Aeros - EtsN 1.00 0.04 - 1.5 34,H
SAPO-5 5 8 16 Boeh PA Aeros - EtsN 0.94 0.06 - 1.5 5,tr B
SAPO-5 6 8 25 Boeh PA Aeros - EtsN 0.94 0.06 - 1.5 5
SAPO-5 7 8 40 Boeh PA Aeros - EtiN 0.94 0.06 - 1.5 5
SAPO-5 10 8 135 Boeh PA Aeros - EtsN 0.94 0.06 - 1.5 5,B
SAPO-5 11 8 159 Boeh PA Aeros - EtsN 0.94 0.06 - 1.5 5,B
Hg-APSO-5 12 10 48 Boeh PA ludox Hg0Ac2 PnN 1.00 0.22 0,22 1.0 36,5
Hg-APSO-5 13 10 72 Boeh PA Ludox HgOAcz PnN 1.00 0.22 0.22 1.0 36,5
Hg-APSO-5 14 10 48 Boeh PA ludox Hg0AC2 TPA0H 1.00 0.67 0.22 1.0 5,36
Hg-APSO-5 15 10 72 Boeh PA Ludox Hg0AC2 TPA0H 1.00 0.67 0.22 1.0 5,36
Hg-APSO-5 16 10 48 Boeh PA Ludox Hg0AC2 PnN 2.00 1.33 0.44 3.0 tr 36,tr 5
Hg-APSO-5 17 10 72 Boeh PA Ludox Hg0Ac2 PnN 1.00 0.67 0.22 1.5 tr 36,tr 5
Hn-APSO-5 18 11 115 Boeh PA Ludox HnOAc2 PnN 1.00 0.22 0.22 1.0 tr 5,tr 36
Hn-APSO-5 19 11 140 Boeh PA Ludox Hn0AC2 PnN 1.00 0.22 0.22 1.0 -
Ti-APSO-5 20 7 68 Boeh PA Ludox TiOS04 PnN 1.00 0.22 0.22 1.0 -
li-APSO-5 21 7 93 Boeh PA Ludox Ti0SO PnN 1.00 0.22 0.22 1.0 5,tr H
Ho-APSO-5 22 11 90 Boeh PA Ludox Na?Ho0. PnN 1.00 0.22 0.22 1.0 -
Ho-APSO-5 23 11 164 Boeh PA Ludox NaiHo0< PnN 1.00 0.22 0.22 1.0 -
" Literature reference miibers.

k
' Sources: Boeh: Pseudo-boehiite; PA: ortho-phosphoric acid; Aeros: Aerosil; Ludox: Ludox HS40.
c
' Structures: 5: AlP0-5-type; 34: AlPO-34-type; 36: AlPO-36-type; B: Boehiite; H: A1P04.X H2O; tr-trace.
a gel with the molar compositions shown in Table 1 and transferring this
gel to Teflon-lined autoclaves. Crystallization was performed at 150C
during the time shown in Table 1.
All samples were filtered or centrifuged, washed and dried after
synthesis.
It should be noted that the particle size of the AlPO-type samples is
usually very small. This can be judged from the fact that filtration of
the samples is slow and that a part of the solids pass the filter paper.
A crystal size of 1-10 jum (as is often encountered in the classical
alumino-silicate molecular sieves synthesis) will allow much faster
filtration. A better separation method for the AlPO-zeolites is
centrifugation. A cake is formed which allows easy decantation of the
supernatant liquid. Washing is performed by adding water, stirring the
sample and repeating the centrifugation procedure.
The catalysts were then subjected to an activation (550C) and an
exchange-procedure (0.05 M NH4CI solution for samples 1-3, 0.05 M HC1
solution for samples 4-23; 10 ml/g of molecular sieve (80C, 0.5 h). For
ammoxidation experiments Cr- and Cu- exchanged samples were obtained by
exchange with 0.017 M Cr(N03) 3 or 0.025 M Cu(N03)z solutions (80C, 0.5 h)
after H-exchange) to enhance catalytic activity. The crystal structure of
the samples was analysed using X-ray diffraction. The results are
summarised in Table 1. The resulting chemical composition of the samples
was determined using colorimetry (P content) and AAS or ICP (Al, Si and Me
content).
The acid sites distribution of the samples was determined by means of
NHa-TPD, whereas the adsorption characteristics were investigated using
the adsorption of water and cyclohexane in a thermogravimetric experiment.
The pore diameter of SAPO-5 samples is large enough to allow the
adsorption of cyclohexane[3]. All analytical results are shown in Table 2.

SAPO- molecular s i e v e s 101
Table 2: Results of the analyses on the c a t a l y s t samples.
Saaple No. Product olar r a t i o " NHs-TPD results*' Adsorbed atounts (wtZ)
AI2O3 SiOz Hetal a b c peaks water cyclohexane toluene
H-SAP0-5 1 1.44 0.00 - 520 112 -

CrH-SAPO-5 la 380 75 - 14.8 3.3 12.7
H-SAPO-5 2 1.33 0.00 -
CuH-SAPO-5 2a 374 140 - 16.4 3.2 6.6
H-SAPO-5 3 1.69 0.08 -

CuH-SAPO-5 3a 527 104 12.1 - 12.0
H-SAPO-5 4 1.06 0.06 - 506 168 123 4.9
H-SAPO-5 5 15.3 14.7 16.1
CuH-SAPO-5 5a 319 112 -
SAPO-5 7 1.69 0.17 -
SAPO-5 8 1.69 0.17 -
H-Hg-APSO-5 12 1.10 1.10 0.22 575 82 - 11.4 - 14.2
Hg-APSO-5 13 1.08 1.08 0.22
H-Hg-APSO-5 14 1.46 0.51 0.29 234 37 - 13.0 6.7 11.1
Hg-APSO-5 15 1.46 0.51 0.29
Hg-APSO-5 16 2.25 1.42 0.42
Hg-APSO-5 17 1.15 0.56 0.26
Hn-APSO-5 18 1.17 0.19 0.05
Hn-APSO-5 19 1.50 0.26 0.05
Ti-APSO-5 20 1.57 0.22 0.05
H-Ti-APSO-5 21 1.18 0.18 0.05 390 48 - 7.6 6.6 10.1
H-Ho-APSO-5 22 1.24 0.14 0.14 33 - - 5.6
a
> PzOs-1.00
b)
TPD results as peak area (arbitrary units) for 100 ag sasple.
The adsorption experiments show that in a most cases where XRD indicates
a microporous structure the pore volume (as determined by the adsorbed
amounts) corresponds to the pore volumes mentioned in the patent
literature. These data lead to the conclusion that the prepared molecular
sieve samples do not contain much amorphous impurities, as in that case a
much smaller adsorption was to be expected.
As shown in Table 2 the SAPO molecular sieves show only weak acid sites
in the NH3-TPD-experiments. Desorption of ammonia at temperatures above
300C was only detected for the SAPO-5 sample number 4. Elemental
102 SAPC molecular sieves
analysis suggest however that all samples should posses cation exchange
properties, because all SAPO samples have a Al/P ratio which is higher
than unity. Sample number 4 also contains a significant amount of Si, so
this may cause the acidity evidenced by the high-temperature ammonia
desorption. Comparison of samples 1 and la (respectively H-SAPO-5 and
CrH-SAPO-5) shows that Cr-exchange reduces the total amount of adsorbed
ammonia to approximately 70%. It can therefore be assumed that about 30%
of the hydronium ions was replaced by Cr.
The SAPO molecular sieves were tested as a catalyst in the alkylation of
toluene with methanol (conditions are given in the experimental
section). A H-ZSM-5 type catalyst tested for comparison yielded almost
complete conversion to xylene and higher methylated benzenes (up to
hexamethylbenzene). The SAPO catalysts should, if synthesis of a sample
with a surplus of P was achieved, yield a product mixture containing
ethylbenzene and/or styrene. The only products that were detected were
xylene and some gaseous products. The conversion is always low (less than
5%). Both the TPD data and the catalytic experiments suggest that the
SAPO zeolites contain no strong acid sites, responsible for either a
high-temperature ammonia desorption or toluene (ring) alkylation activity.
Chemical analysis shows that no anion exchange properties can be expected,
as the samples contain an excess of Al tetrahedra giving the lattice a
negative charge.
The ammoxidation activity was determined in a reaction setup as
described in Chapter 6. The exchange of the catalysts was described above;
note that a M-H-exchanged catalyst underwent a H-exchange procedure
followed by a M-exchange. The results of the ammoxidation experiments are
shown in Table 3. A Cu-H-ZSM-5 catalyst (Si/Al=25.7) is added for
comparison [see Chapter 6 ] . Using SAPO-type catalysts gives rise to a

product mixture consisting mostly of benzene, benzonitrile and some

gaseous products. No products with a higher boiling point were detected.
Table 3: Results of ammoxidation experiments3> with SAPO-type catalysts.
Sample Catalyst Conversion Selectivity (wt*)

no. type (wtX) benzonitrile benzene CO2
- Cu-H-ZSM-5 100 78.0 18.7 3

1 H-SAPO-5 5 75 5 20
la Cr-H-SAPO-5 65 90 5 5
lb Cu-H-SAPO-5 5 95 - -
2a Cu-H-SAPO-5 70 0 10 20
3a Cu-H-SAPO-5 45 60 5 35
4 H-SAPO-34 5 45 5 20
5a Cu-H-SAPO-5 60 90 5 5
12 H-MgAPSO-36 0 0 -
14 H-MgAPSO-5 5 55 15 0
21 H-TiAPSO-5 -5 85 5 0
22 H-MoAPSO-5 0 0 - -
a
> Molar ratio toluene:NHa:H20=1:2:6, WHSV(toluene)=0.17 h"1, 350C.
Table 3 shows that the performance of the AlPO-family of molecular

sieves in the ammoxidation of toluene is comparable to ZSM-5 type
zeolites, especially when a Cu- or Cr-exchanged SAPO-5 catalyst is used.
Catalysts number la and 5a (respectively a CrH-SAPO-5 and CuH-SAPO-5
sample) combine a good conversion and a high selectivity to benzonitrile
and are certainly comparable to corresponding ZSM-5-type catalysts.
However, the samples from the AlPO-family are somewhat more vulnerable to
deactivation due to pore blockage, because they have a unidimensional pore
system.
Note that the H-MoAPSO-5 catalyst (sample no. 22) is inactive. XRD
analysis (see Table 1) showed that this sample was amorphous. It was
tested anyway, because amorphous molybdate catalysts are known to show
ammoxidation activity. The present commercial catalysts consist of
bismuth-molybdenum-phoshate systems, sometimes promoted by treatment with

Fe solutions [12]. Sample 22 therefore appears to contain Mo in an
inactive form.
CONCLUSIONS
Molecular sieves belonging to the AlPO-family (A1PO, SAPO, MeAPO and
MeAPSO sieves) can be synthesised according to the procedures.given in
patent literature. In this work the results of elemental analyses and
catalytic performance (in the alkylation of toluene) suggest that the
structure des not allow the synthesis of samples with a positive charge
on the lattice, i.e. with anion exchange properties. Syntheses
starting with a gel containing a surplus of phosphorus will yield either
a non-microporous product or a microporous product with a neutral or
negative lattice (as judged by chemical analysis of the sample).
Adsorption properties of the samples show that the pores allow

entrance and passage of e.g. water, cyclohexane and toluene.
NH3-TPD shows that SAPO-type molecular sieves do not contain strong acid
sites, as judged from the absence of ammonia desorption at a temperature
above 300 C.
The ammoxidation experiments show that, in addition to the
application in some reactions mentioned in patent literature [4,5,7], the
SAPOs studied can be used in the ammoxidation of toluene. Results are
indeed comparable to the activity and selectivity of ZSM-5 type
catalysts. Since the reaction was cursory explored even better results
may be obtained after adjustment of the reaction conditions for the
special properties of the A1PO type catalysts.
ACKNOWLEDGEMENT
Mr. M.L. van Wijk is thanked for the performance of - the synthetic,
catalytic and adsorption experiments. Mr. J.P. Koot (Laboratory of
Analytical Chemistry) and Mr. J.F. van Lent (Laboratory of Materials

Science) are thanked for performing AAS analyses and the X-ray powder
diffraction on the zeolite samples, respectively.
LITERATURE
1. S.T. Wilson, B.M. Lok, C.A. Messina, T.R. Cannan, E.M. Flanigen, ACS
Symp. Ser., 218, (1983), "Intrazeolite Chemistry", G.D. Stucky, F.G.
Dwyer, Eds., p.79.
2. S.T. Wilson, B.M. Lok, E.M. Flanigen, Eur. Pat. EP. 0.043.562, (1982).
3. B.M. Lok, C.A. Messina, R.L. Patton, R.T. Gajek, T.R. Cannan, E.M.
Flanigen, J. Am. Chem. Soc., 1984, (106), 6092.
4. E.M. Flanigen, B.M.T. Lok, B.K. Marcus, C.A. Messina, S.T. Wilson,
Eur. Pat. EP. 0.158.977 (1985).
5. B.M.T. Lok, B.K. Marcus, C.A. Messina, R.L. Patton, S.T. Wilson, E.M.
Flanigen, Eur. Pat. EP. 0.158.349 (1985).
6. E.M. Flanigen, B.M. Lok, R.L. Patton, S.T. Wilson, Pure Appl. Chem.,
58, (10), (1986), 1351.
7. B.M.T. Lok, B.K. Marcus, L.D. Vail, E.M. Flanigen, R.L. Patton, S.T.
Wilson, Eur. Pat. EP. 0.159.624 (1985).
8. S.T. Wilson, B.M. Lok, E.M. Flanigen, US Pat. 4.310.440 (1980).
9. E.G. Derouane, Eur. Pat. EP. 0.174.122 (1986).
10. B.M.T. Lok, L.D. Vail, E.M. Flanigen, Eur. Pat. EP. 0.158.348 (1985).
11. B.M.T. Lok, B.K. Marcus, E.M. Flanigen, Eur. Pat. EP. 0.161.490 (1985).
12. A. Ohorodnik, K. Sennewald, H. Erpenbach, H. Vierling, e.g. Ger.
Offen. 2.155.777 (1973).
106
S U M M A R Y .
In this thesis the synthesis of ZSM-5 type zeolites, the analysis of

these zeolites and their use in gasphase reactions with ammonia are
described. A last chapter describes experiments involving SAPO-type
materials.
Chapter 1 describes the history of zeolite science and some general

properties of zeolites. Moreover, a more detailed description is given for
ZSM-5 type zeolites, which is used mainly in this thesis.
Chapter 2 describes the use of infrared spectroscopy as a versatile
method for the identification of zeolites. Spectra are given for a number
of 5-ring containing zeolites. It is shown that impurities in a sample
give clear differences in the infrared spectrum. Thus, infrared
spectroscopy can be used for the estimation of the purity of a ZSM-5 type
zeolite sample.
In Chapter 3 the effectivity of a number of templates in the synthesis

is described. The determination of the purity of the obtained samples is
performed using both infrared spectroscopy and X-ray diffraction. It is
shown that TPA gives the best results as a template, followed by
1,6-hexanediamine.
Chapter 4 describes the synthesis of ZSM-5 type zeolites where T-atoms
other than Si and Al are substituted in the framework. It is shown that
only a few ions (e.g. Fe, Ti) are built in in the framework; other ions
seem to be present in other locations. The zeolites synthesized according
to procedures described in Chapters 3 and 4 are used as catalysts in other
parts of this thesis (Chapters 6-9).
In chapter 5 the acid properties of ZSM-5 samples are compared using
temperature programmed desorption of ammonia. It is shown that the samples
(all pure according to other analyses) have different acid properties,
Summary 107
depending on the template used during synthesis. This shows that
characterization of zeolite samples should be performed using as much
analysis techniques as possible.
Chapter 6 describes the use of modified ZSM-5 type zeolites in the
ammoxidation of toluene. The use of unmodified (i.e. only exchanged
samples) was described earlier. Here the use of zeolites modified by
isomorphous substitution (cf. Chapter 4) is reported. The incorporation of
Cr or Fe during synthesis of the catalyst improves the performance in the
reaction. Double exchange (with both Cu and Cr ions) also yields very
active catalysts.
In chapters 7 and 8 the conversion of ethanol and ammonia to pyridines
is described. Chapter 7 describes the use of unmodified ZSM-5 type
catalysts, whereas chapter 8 shows the effect of several modifications.
Good catalytic performance is obtained at temperatures of 300-400C and a
feed composition which may be obtained by evaporation of a fermentation
mixtures. At high temperature and high space velocity product mixtures can
be obtained consisting almost exclusively of pyridine and ethene, thus
allowing easy separation of the product pyridine.
Chapter 9 describes the conversion of acetone, methanol and ammonia to

13
2,6-lutidine. It is shown (by C incorporation) that methanol is built
in at the 4-position of 2,6-lutidine. The reaction conditions were not
extensively optimized, so conversion and selectivity obtained were not as
high as obtained for the pyridine formation as described in the previous
chapters.
Last but not least chapter 10 describes exploratory experiments on
another type of zeolites, i.e. SAPO-type materials. Several samples were
prepared and analyzed. The SAPO-type zeolites were used in toluene
ammoxidation to allow comparison with ZSM-5 zeolites. It is shown that
SAPO molecular sieves can be effectively synthesized and used as a
catalyst.
108
S a m e n v a t t i n g .
In dit proefschrift wordt beschreven hoe zeolieten van het ZSM-5 type
kunnen worden gesynthetiseerd en hoe de producten kunnen worden
geanalyseerd. Tevens wordt het gebruik van deze zeolieten in gasfase
reacties met ammonia beschreven. In een laatste hoofdstuk worden
enige synthese- en katalyse-experimenten met SAPO-molekulaire zeven
beschreven.
Hoofdstuk 1 beschrijft de geschiedenis van de zeoliet-wetenschap en
enige algemene eigenschappen van zeolieten. De zeolieten van het ZSM-5
type, die in dit proefschrift meestal gebruikt zijn, worden wat
uitgebreider beschreven.
Hoofdstuk 2 beschrijft het gebruik van infrarood spectroscopie als een
handige methode voor de identificatie van zeolieten. Van een aantal
zeolieten (waarvan de struktuur vijfringen bevat) wordt het infra-
roodspectrum gegeven. De aanwezigheid van onzuiverheden in een zeoliet
monster veroorzaakt een duidelijke afwijking in het infraroodspectrum,
zodat deze techniek gebruikt kan worden om de zuiverheid van een ZSM-5
monster te schatten.
In hoofdstuk 3 wordt de effectiviteit van een aantal templates in de
synthese van zeoliet ZSM-5 beschreven. Voor de bepaling van de zuiverheid
wordt gebruik gemaakt van infraroodspectroscopie en Rontgendiffractie. Het
blijkt dat TPA de beste resultaten geeft in de synthese van zeoliet ZSM-5,
met 1,6-hexaandiamine als tweede.
In hoofdstuk 4 wordt een onderzoek naar de isomorfe substitutie in het
ZSM-5 rooster beschreven. Hierbij worden de Si of Al ionen uit het rooster
vervangen door andere ionen. Slechts enkele ionen (bv. Fe en Ti) blijken
ingebouwd te worden; andere ionen zijn op andere plaatsen in het zeoliet
aanwezig. In volgende hoofdstukken wordt het gebruik van zeoliet-

Samenvatting 109
monsters, die bereid zijn volgens de methoden die beschreven zijn in de
hoofdstukken 3 en 4, beschreven.
In hoofdstuk 5 worden de zure eigenschappen van ZSM-5 monsters, die
bereid zijn met verschillende templates, vergeleken. Het blijkt dat de
monsters (allen volgens andere analysemethoden zuiver) duidelijk
-verschillende zure eigenschappen hebben. Hieruit blijkt dat voor een
volledige karakterisering van een zeoliet zo veel mogelijk verschillende
technieken gebruikt moeten worden.
Hoofdstuk 6 beschrijft het gebruik van gemodificeerde ZSM-5 zeolieten
als katalysator in de ammoxidatie van tolueen. Het inbouwen van Cr en Fe
tijdens de synthese blijkt de katalytische eigenschappen te verbeteren.
Dubbele wisseling (met zowel Cu- als Cr-oplossingen) geeft ook actievere
katalysatoren.
In hoofdstuk 7 en 8 wordt de omzetting van ethanol en ammonia naar
pyridines beschreven. Hoofdstuk 7 beschrijft het gebruik van omge-
modificeerde ZSM-5 zeolieten. Dit wordt in hoofdstuk 8 uitgebreid met de
invloed van diverse modificaties. Bij temperaturen van 300-400C wordt een
goede omzetting en selektiviteit bereikt, uitgaande van een reactorvoeding
zoals die verkregen zou kunnen worden door ethanol te verdampen uit een
fennentatiemengsel. Bij hoge temperatuur en reactanten-doorzet kan een
produktmengsel verkregen worden dat vrijwel alleen bestaat uit etheen en
pyridine, zodat gemakkelijk een zuivere pyridinefase verkregen kan worden.
Hoofdstuk 9 beschrijft de omzetting van aceton, methanol en ammonia naar

13
2,6-lutidine. Aan de hand van een experiment met C-methanol in de
voeding is aangetoond dat methanol op de 4-positie in 2,6-lutidine wordt
ingebouwd. Bij deze omzetting is minder aandacht besteed aan de
optimalisatie van de reactieomstandigheden, zodat conversie en
selektiviteit niet zo hoog zijn als in de vorige hoofdstukken voor de daar
beschreven reacties.
Als laatste wordt in hoofdstuk 10 enig onderzoek naar de eigenschappen

110
Samenvatting
van een ander type zeoliet, namelijk de SAPO-familie, beschreven. Een
aantal monsters werd bereid en gebruikt in de ammoxidatie van tolueen (dit
om deze molekuaire zeven te kunnen vergelijken met de ZSM-5 zeolieten).
Het blijkt dat de SAPO-familie molekuaire ' zeven goed gesynthetiseerd en
als katalysator gebruikt kan worden.

111
Dankwoord.
Hier wil ik iedereen bedanken die heeft bijgedragen aan de totstand- koming van dit
proefschrift. Tijdens het onderzoek ben ik steeds met plezier bezig geweest. Dit is
grotendeels te danken aan de goede samenwerking met het personeel van de
Vakgroep Organische Chemie en aan de gezellige sfeer in de vakgroep, en met name
de Zeolietgroep.
Ik dank mijn promotor, prof. dr. ir. H. van Bekkum voor de enthousiaste wijze waarop
hij mijn onderzoek heeft begeleid, in de juiste mengeling van sturen en vrijlaten.
De afstudeerders Frans Louter, Bert Herlaar, Roel Adriaansens en Maurice Smits en
Michel van Wijk (stagiar) ben ik erkentelijk voor hun bijdragen aan dit proefschrift. Ook
alle studenten die in de zeolietgroep een practicum of project hebben gelopen wil ik
bedanken voor de samenwerking. Ik dank ook de R'ntgendiffractie-service van de
afdeling Materiaalkunde (J.F. van Lent en N.M. van der Pers) voorde snelle service.
Mijn collega's Rob Ie Fbre, Koos Jansen en later ook Theo Maesen en Patrick
Voogd dank ik voor de prettige sfeer en de vele discussies (ook over niet-chemische
onderwerpen).
Mieke van der Kooy dank ik voor het vele en snelle (type-)werk en Wim Jongeleen
voor alle fraaie tekeningen en posters die hij gemaakt heeft.
Ernst Wurtz dank ik voor de snelle en uitstekende wijze waarop hij voor de meest
onzinnige vragen en problemen mijnerzijds een oplossing vond. Ik dank ook de
instrumentmakerijen voor de glansrijke wijze waarop opdrachten werden uitgevoerd.
Loek van Leeuwen dank ik voor de hulp bij GC-problemen.
112
Curriculum Vitae.
Fred van der Gaag werd geboren op 14 maart 1959 in Delft. In 1977 behaalde hij het
diploma VWO-B op het Christelijk Lyceum Delft. Vervolgens studeerde hij in 1982 af
als ingenieur bij de Afdeling der Scheikundige Technologie van de TH Delft.
In april 1983 trad hij als wetenschappelijk assistent in dienst van de TH en begon, in
aansluiting op zijn afstudeerwerk, aan een promotieonderzoek onder leiding van prof.
dr. ir. H. van Bekkum bij de vakgroep Organische Chemie.
Sinds juli 1987 is hij als researchmedewerker werkzaam bij Fasson (Nederland) B.V.
te Leiden.

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ZSM-5 type zeolites:

Synthesis and use in gasphase reactions with ammonia

F.J. van der Gaag

ter verkrijging van de graad van doctor aan de

Frederik Jan van der Gaag,

1. Thermische degradatie van polyvinylchloride (PVC) wordt tegengegaan door

D.W. Breek, "Zeolite Molecular Sieves, structure, chemistry and use", J.

3. Het door Ohrui en medewerkers gegeven mechanisme voor de werking van

H. Ohrui, Y. Nishida, H. Hori, H. Meguro, Abstr. 4th Eur. Carbohydr.

4. De door Fukui en Tanaka voorgestelde racemisatie van (+)-menthol is

S. Fukui, A. Tanaka, Enzyme Eng., 6, (1982), 191.

5. Het gebruik van elektronische apparatuur in een chemisch laboratorium

6. Gezien de ervaringen met de fonnosereactie dient bij het onderzoek naar

A. Butlerow, Justus Liebigs Ann. Chem., 120, (1861), 295.

7. Het gebruik van apparatuur voor de versnelde (foto-)degradatie van bv.

8. Het Europarlement zou, naar voorbeeld van internationale

9. Het valt op dat de elementkleuren (waterstof, zuurstof en stikstof) van

11. In octrooiliteratuur inzake zeolietsynthese wordt veelal ten onrechte

F.J. van der Gaag

2. Identification of ZSM-type and other 5-ring containing

3. Template variation in the synthesis of zeolite ZSM-5 26

4. Isomorphous substitution in zeolite ZSM-5 37

6. Ammoxidation of toluene over modified ZSM-5 type

7. Reaction of Ethanol and Ammonia to Pyridines

8. Reaction of Ethanol and Ammonia to Pyridines

10. Exploratory work on silicon aluminum phosphate

Curriculum vitae 112

The first zeolitic species, stilbite, was described in 1756 by Cronstedt

Figure 1: Zeolite powder appears to be boiling upon heating.

Some decades later another important property of zeolites, the cation

a) separations based upon size of the adsorbates in relation to the

developments are the dealuminated Y type zeolites, which share a high

Another field of fast growing interest is hydroisomerization. Here

The increase in branched hydrocarbons is very important in view of the

H2 PURGE PLUS NORMALS

Figure 3: Flowsheet TIP process [11].

A relatively recent important discovery in the zeolite field is the

Present consumption volumina of the various uses of zeolites are shown

subdivision catalysts subdivision catalysts

a: detergent builders; b: catalysts; c: adsorbants; d: desiccants; e: new applications.

Figure 4: Use of synthetic zeolites in 1986 and 1990 (*1000 tons).

This thesis deals mainly with pentasil-type zeolites, so in the

Zeolites are crystalline aluminosilicates, which contain in their

Mx/n [(Al02)x(Si02)y] .WH20

n is the valence of the charge balancing cation M, w is the number of

The alternative lattice ions can be incorporated during synthesis,

T,0 4-1 T.O 5-1 T0 4--

Figure 5: Building units in zeolite structures.

Figure 7: Channel structure of ZSM-5.

consists of a system of intersecting straight and sinusoidal channels. For

Figure 8: Top view of ZSM-5 channels showing large space at the

Several zeolites (analcime, mordenite and stilbite) occur naturally.

TABLE 1: Templates reported for the synthesis of zeolite ZSM-5.

The template is believed to play two roles in directing zeolite

S p a c * filling drawing of T P A ' i n flrt

Figure 9: TPA in ZSM-5 (light atoms: zeolite lattice, dark atoms:

Some of the templates shown in Table 1 will be locked in the zeolite

In zeolite science two types of analysis have to be distinguished:

Structural analysis is performed by X-ray diffraction. This technique

A second method, infrared spectroscopy, allows a quick identification of

Another method, MAS-NMR[25], allows to focus in principle on all nuclei

treatment [29] or by adsorbing or desorbing e.g. ammonia.

Figure 10: XRD [24], IR and NMR [27] spectra of ZSM-5

our work two basic / o d s w e r e used: AAS