Evolution of the microstructure and microhardness of a new wrought Ni–Fe based superalloy during high temperature aging

167

CHAPTER IV

POTENTIAL MEMBERS OF THE PENTASIL FAMILY OF HIGH-SILICA ZEOLITES

INTRODUCTION The advent of zeol ites ZSM-5 and ZSM-ll, propri eta ry zeol ites from Mobil Oil Company, has triggered extremely large research efforts by other companies and also by academics and research institutes. Apparently numerous ZSM-5- and ZSM-ll-like materials seem to exist that differ only in minor detail from the originally described materials. In this respect the ZSM-5silicalite dispute has already been mentioned in Chapter 1. Materials have been described, mainly in the patent literature, that differ from ZSM-5 mainly in their chemical composition, their X-ray diffraction pattern, their sorption capacity or their detailed catalytic behaviour. Although the differences may be sufficient in some instances for a patent to be granted in certain countries, it does not necessarily mean that they belong to different structure types. In this present chapter, data on some of these ZSM-5- and ZSM-ll-l ike materials will be examined and their differences from or similarities to the originally described materials will be stressed. In order to be able to do so, it is necessary to elaborate on the crystallographic structure of ZSM-5 and ZSM-11.

CRYSTALLOGRAPHIC STRUCTURE OF ZSM-5 and ZSM-11 The framework structures of ZSM-5 and ZSM-11 have been solved by Kokotailo and co-workers (refs. 1,2) and Flanigen et al. (ref. 3) derived the framework topology of silicalite. A stereo plot of a ZSM-5 ( denoted as an MFI structure type) and ZSM-11 (MEL structure type) was given by Meier and Olson (ref.4). Experimental and calculated powder diffraction data on ZSM-5 have been published by von Ballmoos (ref. 5) and the structure refinement of TPA-ZSM-5 was published by Baerlocher (ref.6). The secondary building units in both MEL and MFI are 5-1 units, containing a five-membered ring of T-atoms (Al or Si) (refs. 1-4,6,7).

168

The structures can also be viewed as being based on pentasil units (Photograph v.r.a) , which are joined to form chains or columns (Photograph Volob)o When adjacent columns are related by reflection, the basic layer, the so-called pentasil layer, is formed, which is common to both ZSM-5 and ZS~1-11

(refs. 7,8). A model of such a pentasil layer is shown in Photograph

V.2.

PHOTOGRAPH V.l. A model representing (a), the pentasil unit and (b), the pentasil chain, common to ISM-5 and ISM-II zeolites. The tetrahedra represent Si(Al) T-atoms and the sticks indicate the diameter of the T-atom connecting oxygen atoms.

169

PHOTOGRAPH V.2.

A model representing a pentasil layer, common to ZSM-5 and

ZSM-ll zeolites.

All structures containing these specific configurations (pentasil unit, chain or layer) have been described by the generic name PENTASIL (ref.l). This designation refers to "a remarkable and apparently continuous series (ref. 3) of porotecto silicates, exhibiting common X-ray diffraction patterns with

respect

characteristics"

to

significant

(ref.

10).

lines

indicating

common

Only the two end-members

structural

(ZSM-5 and ZSM-lI)

correspond to discrete structure types (MFI and MEL, respectively) and will therefore be found in an atlas of zeolite structure types (ref.4). The most symmetrical (ref.2).

pentasil

The unit

zeolite is ZSM-lI, which cell

dimensions

are

2.01

has

a tetragonal

and 1.34 nm for

symmetry a and c ,

respectively (refs. 2,4). The structure type consists of pentasil joined in related

such a way that neighbouring by a

reflection

layers,

layers are enantiomeric and are

(a) (ref.7). A model of ZSM-ll in the three

crystallographic directions of the crystal is shown in Photograph V.3. The framework atoms circumscribe a two-dimensional

network of straight pores,

which intersect perpendicularly. These pores are identical in the 11001 and

170

jOlOl

crystallographic directions and consists of ten-membered rings of

(T-O) atoms. If neighbouring pentasil layers are related by an inversion and thus are also enantiomeric, the framework of ZSM-5 is generated (ref.7). The unit cell of such a crystal is orthorhombic (reL1) with the dimensions a = 2.01, b = 1.99 and c = 1.34 nm (refs. 2,4). In this way the 10-MR pores along the [010[ direction remain unaltered whereas along the 11001 direction the straight set of pores of ZSM-11 disappear and are replaced with a sinusoidal set of pores, intersecting the straight set perpendicularly. A framework model of ZSM-5 is shown in Photograph V.4 along these two crystallographic directions. In Photograph V.5 framework models show how the two sets of pores intersect in the two pentasil end-members and also illustrate the nature and shape of the pore intersections. In ZSM-ll, two types are present with different sizes: type (large) and type II intersections (small). In the 11001 crystallographic direction type I and type II intersections alternate. Along a pore in the 10101 direction, either type I or type II intersections are present. In ZSM-5 intersections type III of a size intermediate between type I and II are present. The framework topology of silicalite, or of fluoridesilicalite (ref.11), "a silica polymorph with properties similar to those of silicalite", is identical with that of zeolite ZSM-5 (reL12). Further discussions on this issue, relevant for crystallographers but less so in the present context, can be found in the discussions of the 5th International Zeo1ite Conference (reL13). The unit cell of both pentas il end-members consists of 96 tetrahedra (refs. 1-4). The straight channels along 10101 or b show an elliptical shape and have a free cross-section of 0.57-0.58 x 0.51-0.52 nm (ref.3). The zig-zag or sinusoidal channels along 11001 or a are nearby circular and have a free cross-section of 0.54 ± 0.02 nm (ref.3). With the crystallographic data a theoretical channel length per unit cell (ref.14) can be calculated. For ZSM-5 and ZSM-ll, its value is 8.8 and 8.0 nm, respectively (refs. 14,15) if the diameters of the pore intersections are counted twice. Another important structural difference between MFI and MEL is the presence of four 4-MRs per unit cell in the former structure and eight 4-MRs per unit cell in the latter.

171

PHOTOGRAPH V.3. Framework models of zeolite ZSM-ll !0101,110ol and [0011 crystallographic directions.

viewed along

the

172

173

PHOTOGRAPH V.4.

Framework model of zeolite lSM-5 viewed along the

11001 crystallographic directions.

10101 and

174

175

PHOTOGRAPH V.5. Illustration of the two types of pore intersections present in

ZS~l-lI

(A) and of sinusoidal

(B) and straight pores (C) in the

direction in ZSM-5 and ZSM-ll, respectively.

11001

176

177

INTERGROWTHS IN THE PENTASIL FAMILY OF ZEOLITES As pentasil layers can be assembled via at least two symmetry operations (a reflection or an inversion), it seems a priori possible that in the same crystal this may occur to different extents. In these instances neither pure nor

ZS~'-5

pentasil

pure

ZSM-ll

is

obtained

but

intergrowths

(ref.?)

of

the

two

end-members. The generation of such an intergrowth starting from

individual pentasil layers is shown in Fig. V.l.A.

It is evident that this

phenomenon influences the pore shape (Fig. V.2) in the ilOOI direction and also the concentration of type I, II and III pore intersections. In fact, the sequence of the different types of intersections of the pores in the 11001 direction with those in the [0101 direction can be varied without limit (Fig. V.3). Crystallographically, the presence of intergrowths will mainly influence the dimension

of the

unit cell

in

situation for the pure end-members (a

the a direction.

=

In

contrast to the

2.0 nm), the minimum value

of a is

4.0 nm and can be expressed in the following more general way (refs. 22,23) :

= 4.0

a(nm)

where n is an Fig. V.l (0

2.0n

+

integral i 0)

(IV.l) number.

The sequence of pentasil

layers shown in

corresponds to a repeat distance of 4.0 nm. A regular

repetition of pentasil layers connected via a sequence of symmetry operations such as

(0 0

0

i

0

0

0

i ) would create a unit cell dimension of 8.0 nm in

the a direction (ref.23). The existence of local

..

intergrowths in ZSM-ll and ZSM-5 crystals

has

been demonstrated experimentally by Thomas and co-workers using mainly highresolution electron microscopy and optical diffractometry (refs. 16-20). As this kind of "defect" is generally encountered in so-called "pure" ZSM-5 or ZSM-ll,

it does not mean that

phase

pure ZSM-5 or ZSM-ll crystals are

impossible to synthesize. Indeed, a report exists in which these intermediate structural

variants

could not be

detected

(ref.

21).

Unfortunately,

authors did not elaborate on the origin of the pentasil intergrowhts are easily detectable (refs. (ref. 21).

the

samples in which

16-20) or are completely absent

ZSM-11

cr

o

o

[100J

ZSM-5

o

o

ZSM-5

o

o

'-

ZSM-11

6'

[oo~

FIGURE V.I. Generation of an intergrowth of the pentasil family of zeolites. (A) stacking of a (0 pentasil layers; (B) a pentasil layer.

A

0) sequence of

~

00

-.]

179

FIGURE V.2. Section of a pore in the 11001 crystallographic direction of the structure shown in Fig.V.1. Intersections of this pore with the channels in the 10101 crystallographic direction are of type I, II or III.

6 I

6 I

FIGURE V.3. Section through two parallel pores in the 11001 direction illustrating the relationship between the stacking sequence of the pentasil layers and the sequence of type I,ll and III cavities.

180

EXPERH1ENTAL DISCRIMINATION BETWEEN PURE ZSM-5, ZSM-II ZEOLITES AND THEIR INTERGROWTHS X-ray diffraction (XRD) patterns constitute a generally used way of discriminating between discrete zeol ite phases. As a result of its highest symmetry in the pentasil class of materials, ZSM-II shows the lowest number of diffraction peaks. As indicated earlier, the absence of a diffraction line at 9.06 °28 using Cu Ka radiation (third line in ZSM-5) (Chapter III) is a first rough indication of a pure MEL phase. This is not, of course, a sufficient criterion to identify unambiguously a pure ZSM-II phase, as small crystal

samples

of

ZSM-5

or

its

intergrowths

with

ZSM-ll will

cause

considerable peak broadening and an eventual disappearance of this peak in the more intense peak close to 8.80 °28. The only satisfactory way to identify pure ZSM-II is to index ~ peaks, even those with weak intensities, using the tetragonal symmetry class. Only when this is possible does strong evidence exist that a given pentasil sample is pure ZSM-II. The discrimination between a pure ZSM-5 phase and an intergrowth by XRD alone is therefore hardly possible. A semi-quantitative measure for doing so was given earl ier, based on the relative intensity of the XRD peaks around 8.80 and 9.06 °28. The highest intensity ratio of the 9.06 to 8.80 °28 peaks, in the authors' experience, never exceeded 0.60 for hydrated and uncalcined samples. A literature survey of these peak intensities is given in Table V.1 for the sake of comparison. Several remarks can be made in this respect: i.

Only in one case is this ratio higher than 0.60, but the data refer to a dehydrated sample (refs. 5,6) ; futher, no deta il s of the ori gi n of the sample were given, but considering the identity of the author (ref. 6) it might well be that it is similar to the sample which has a ratio of 0.61 (ref.32). The latter sample was synthesized under highly dilute cond it ions.

ii.

Unfortunately, we have been unable to

determine this ratio using a

sample considered to be pure ZSM-5 by Mobil researchers; only for ZSM-5 that is not phase pure can peak intensities for the XPD spectrum be found in the literature; the ratio in this instance is 0.48.

181

TABLE V.l. Literature values of XRD intensity ratios of the 9.06 (III) to 8.80 (II) 028 peaks a

Sample

ZSM-5 type ZSM-5 ZSM-5 + unidentified phase High-silica ZSM-5 P-containing ZSM-5 type

ZSM-5 type ZSM-5 ZSM-5

a,

peak height of

Ref.

IrrI/I rr

hydrated

0.32 0.40 0.48 b 0.35 0.58 0.55 0.44 0.41 0.21 0.68 c 0.61

uncalcined

24 25 26 27 28 29(Table 1) 29(Table 2) 29(Table 3) 30 31 32

samples;

b,

measured from the

diffraction pattern shown; c, 19.08/18.87'

As al ready mentioned, local intergrowths can be directly viewed using high-resolution electron microscopy (HREM). Unfortunatly, it is not possible to quantify the degree to which intergrowths are present in a particular crystal, or in a whole sample. Ul tra-high-resolution microscopy allows crystal regions of approximately 30 by 35 nm to examined for the existence of regular, trrequt ar and random isolated intergrowths (ref.46). In such images the eye readily discerns intergrowths of less than a unit cell.

182

Extended strips of semi-regular intergrowths of ISM-ll seem to occur very often in samples considered to be ISM-S (ref.46). As the theoretical channel lengths of the pores in a ISM-S or a ISM-II unit cell are different (refs.I4,IS), careful adsorption work might allow one to estimate to a certain extent the phase purity of a pentasil sample. Gabelica et al. (ref.I4) determined the amount of organic material retained after a particular synthesis and calculated the degree of pore volume filling. It was concluded that in agreement with a maximum pore filling model, the synthesis of pentasils in the presence of tripropylamine gives a phase rich in ISM-II, whereas with tributylamine an intergrowth rich in ISM-S could be obtained. With triethylamine and tripentylamine only amorphous phases are obtained. The authors (ref.7S) speculated that the maximum space filled by four such entities does not correspond to a unit cell space length of 8.0 or 8.8 nm. Sorption of hydrocarbons on pure ISM-S and ISM-II (ref.IS) showed that the degree of pore filling was also dependent on the size of the sorbate : for small n-alkanes (C I - CS)' complete pore fill ing occurs on ISM-S via an end-to-end type of adsorption of the sorbate molecules and at the pore intersections two molecules are accommodated; with the same sorbate molecules the pores of ISM-II are filled via the same type of sorption but only in one crystallographic direction. Intermediate behaviour is therefore expected to reflect the presence of an intergrowth. The so-called Mobil Contraint Index (CI) characterizes medium-pore zeolites in catalytic conditions. The sample has to be in the acid form (the residual organics have to be burned off and the residual Na+ ions exchanged by H+) and the cracking of hexane and 3-methylpentane has to be investigated under specific conditions (ref.33). It is defined as follows (ref.33) : CI

109IO Ifraction of hexane unconverted I 10910 Ifraction of 3-methylpentane unconverted I

For H-ISM-S and H-ISM-ll, CI values of 8.3 and 8.7, respectively, were reported (ref. 38). As the pore sizes of ZSM-S and ZSM-ll are similar, differences in the CI values are the result of differences in transition states for hydride transfer of both feed molecules in the pores (ref.74). Apparently, this catalytic test reaction is insensitive to the differences in size and shape between type I and II pore intersections (in ZSM-II) and type III pore intersections (in ZSM-S). Moreover, it seems that at least for ISM-S, the exact values of CI are also dependent on several non-structural parameters, including the silica-alumina ratio of the zeolite, the reaction temperature and the presence of impurities (ref.34).

18:3

To distinguish between MFI and MEL structure types and hence characterize their intergrowths, a catalytic reaction can only be useful if it allows one to estimate the rel ative amounts of

type I,

II or I I I intersections in a

given amount of pentasil material. Therefore, a reaction is needed for which contraints on the formation of the transition state influence the reaction selectivity. In principle many reactions behave in this way (refs.35,36) but only the hydroisomerization of n-decane has been studied in sufficient detail (ref.37). isomers,

For

the

branching

reaction

of

n-decane

it was found that certain product

into

its

methylnonane

ratios were mainly structure

dependent and did not vary substantially with reaction conditions and sample acidity or crystal morphology. Therefore, a refined constraint index (CIO) was defined at 5% conversion of n-decane (see also Chapter III) : amount 2-methylnonane formed amount 5-methylnonane formed It turned out that in sterically restricted environments, branching occurred preferentially near the end of the hydrocarbon chain. Clo values of 6.8 and 2.7 have been reported (ref.37) for ZSM-5 and ZSM-ll, respectively, samples with comparable chemical therefore

be

useful

composition and morphology. This criterion should

in

determining

pentasil

intergrowths

in

a

more

quantitative way. In search of a confident criterion for estimating the overall nature of a pentasil

sample,

the catalytic Cl " criterion was plotted against the XRD

criterion, IIII/III

in Fig. V.4. There is a surprisingly good correlation

between these criteria. As, for reasons explained already, Clo is sensitive to the concentration of type 1,11 and

III

intersections in a sample and

therefore measures directly the phase purity of a pentasil sample, the XRD criterion, although less accurate, seems also to be sensitive to the phase purity of a pentasil sample. More recently, the 29Si MAS NMR (magic angle spinning nuclear magnetic resonance) spectra of highly siliceous ZSM-5 and ZSM-11 zeolites were shown to

be

different

with

respect

to

chemical

intensities of these signals (ref.8).

shift

values

and

relative

They should therefore constitute a

fingerprint of the zeolite structure (ref.8).

In early low-resolution work

(ref. 76,77) the intensity ratio of the - 115 ppm peak in ZSM-11 to ZSM-5 was found to be 2,

irrespective of the Al content of the samples.

This was

correlated with the different numbers of 4-MRs present in the two structures, viz., 8 and 4 spectra,

in ZSM-11 and ZSM-5, respectively. Later high-resolution 29Si

however,

showed

a

peak-height

ratio equal

to one

for the same

184

spectral line (ref.B). For dealuminated ZSM-5 and ZSM-11, the spectral intensities of the different lines agree with the number of non-equivalent Si atoms that can be derived from the proposed structures for the two materials. In ZSM-5, the intensities of the outermost resolved peaks at - 109 or -116 ppm to the total resonance envelope is 1: 24 (refs.7,76,77) as required by the space group proposed for this zeolite (ref.47). For similar reasons, the ratio of the most intense resonance line of zeol ite ZSM-ll to the total resonance envelope should be 16 : 96 (a maximum of 16 crystallographically

8

pure MEL

pure

MFI~

6

o

o

2l.-

o

....L-

0.2

----L

0.4

..L...-J

0.6

FIGURE V.4. Plot of the refined contraint index (CIO) against the peak height ratio of specific X-ray peaks (1111/111) for pentasil samples synthesized in the presence of: 1, diaminooctane; 2, diaminoheptane; 3, benzyltriphenylphosphonium chloride; 4, diaminohexane; 5, an equimolar mixture of octylamine and tetraethylammonium hydroxide; 6, tetrapropylammonium bromide; 7, dodecyltrimethylammonium chloride and 8,diaminopentane. The syntheses followed are those described earlier for the diaminoalkanes(Part. r., p. 20) and, for the quanternary ions, that described with TBP (Chapter III, p. 157).

unique Si atoms exist per unit cell), which corresponds to the experimental ratio of 1: 6.4 (ref.l). The 29Si spectra of the pentasil end-members seem to be sufficiently different to be able to distinguish qualitatively between intergrowths. To put this on a more quantitative basis, however, will require a substantial amount of further work.

SYMMETRY CHANGES OF ZSM-5 ZEOLITES Wu et al.

(ref.39) were

the first

to

observe a "reversible, displacive

transformation" of the orthorhombic symmetry of ZSM-5 into a monocl inic form on certain treatments. Subsequently this observation has been confirmed by several other workers (refs. 39-45) using both XRD and 29Si MAS NMR. The most striking observations are summarized in Table V.2. Changes

in

the

XRD

lines

and

in

systematically on certain treatments.

the

29Si

MAS

NMR

spectrum

occur

In the former instance they can be

attributed to a symmetry change from orthorhombic to monoclinic and vice versa; in the latter instance, changes occur in a parallel way but are not understood in detail.

NMR shows that a similar effect also occurs in ZSM-II

(ref.7), which, however, has not yet been attributed to particular symmetry changes. In the XRD lines of ZSM-5, the following reversible changes occur, "resul ting from crystal

symmetry changes between

topologically equivalent

forms", which do not imply a difference in framework structure (ref.39) : i.

the intensities of the lines at about 7.9 and 8.8 °2e increase when extra-framework inorganic or

organic material

fill ing the pores

is

removed. It should be stressed that the IIII/III ratio changes only from ..0.42 to 0.38, implying that this criterion for estimating the degree

of

intergrowths

can

probably

be

used

irrespective

of

the

sequence of treatments to which a particular ZSM-5 sample has been subjected; ii. lines at about 11.9 and 12.5

°2e decrease in intensity;

iii. singlets are replaced by doublets (at 23.2, 24.4, 29.2 and 48.6 °2e) and vice versa (at 14.7 and 23.9 Crystallographic

computations

on the

°2e). line

positions

confirm

that

these

changes are consistent with the symmetry changes mentioned (ref.39). Typical changes in the XRD lines from orthorhombic to monoclinic symmetry are shown schematically

in Fig V.5.

70-3,000 70-3,000 70-3,000 450 450 130 130 40 <160 >160 >3,000 high high

TPA/Na-ZSM-5 H/Na-ZSM-5 H-ZSM-5 Sil i ca1i te Sil i ca1ite Sil ical ite Sil ical ite

ZSM-5 ZSM-5 Silicalite TPA-ZSM-5 H-ZSf'iI-5

ZS~1-5

Si0 2/A1 203

Starting sample

Calcination + NH 4 exchange Moisture adsorption NH 3 adsorption Calcination Calcination Calcination Calcination Calcination Calcination Calcination Calcination p-xylene adsorption p-xylene adsorption

Treatment

-

<383 873 748 873 773 873 823 823 <798

-

811

Temp./K

0 0

-

-

-

0 0 m

m m 0 m 0 m 0 0 0 0 0 0 m

Symmetry from to

XRD XRD XRD XRD XRD XRD XRD XRD XRD XRD XRD XRD + NMR XRD + NMR

Technique

39 39 39 45 45 45 45 45 41 41 42 44 44

Ref.

TABLE V.2. Treatments for which the orthorhombic (0) - monoclinic (m) symmetry transition and vice versa is observed in the MFI structure type.

gs

.....

....

5

L

....

r-

l-

l-

l-

l-

l-

l-

...L

I

I

I

I

I I I I

I

I I

9

III

I

I

I

I

I

I I I

i

I

l 13

...1.

I

I I

17

I

I

21

I

1111 29

.V II

degrees 28

25

!r "

II

i

33

FIGURE V.5. Changes in the XRD lines of Z5M-5 samples with orthorhombic symmetry on changing to a monoclinic symmetry after calcination and exchange with ammonium (after ref.3g).

Q,)

....c:

c

U)

~

I"'"

i

1

37

I

I

41

...1.

45

I

11.

49

1

I I I I

>-'

00

-J

188 It is now unequivocally established that the orthorhombic-monoclinic symmetry change in the MFI structure type: i. is a reversible transformation (Table V.2); ii. is dependent on its aluminium content (the higher the Si0 2/A1 203 ratio, the easier the transformation occurs on certain treatments (ref.39), including calcination and sorption). iii. is temperature dependent (refs. 42,43). Calcined ZSM-5 at room temperature is orthorhombic for Si0 2/A1 203 < 160 (ref.41). The transformation temperature (Tt) changes as follows with the chemical composition (ref.42) :

> 460

317 - 325 295 <272 < 110 iv. occurs on adsorption over a small concentration range, suggesting that a phase transition mechanism occurs (ref.44). 198

OVERVIEW OF SOME PENTASIL-TYPE ZEOLITES CLAIMED IN THE LITERATURE In previous paragraphs in this chapter, several possible reasons have been discussed as to why XRD 1ines can change in position and intensity in pentasil zeolites. In addition to the already mentioned changes in symmetry c1ass dependi ng on the sample his tory, the presence of i ntergrowth s , the crystallite size and the chemical composition will also influence the dimensions of the unit cell and therefore the 1ine positions. Moreover, in addition to intergrowths the formation of mechanical ZSM-5/ZSM-11 mixtures is another possibility, e.g. using C2 - C5 n-alkylamines (ref.75). With ZSM-5, the unit cell increases when the number of heteroatoms (in casu, Al) increases (refs.48,49). Patent attorneys may consider such variations sufficient for granting a patent but scientifically this does not necessarily mean that a new zeol ite structure type has been synthesized. The material s that are described below have often been the subjects of granted patents or patent applications and, according to their XRD lines, belong to the pentasil family of zeolites. For all these particular pentasil materials, several examples are given in the respective patents and consequently they can be synthesized in a reproducible manner, at least by the authors of the patents. Their peculiarities will also be summarized below.

73

0.05 - 0.23 0.02 0.025 - 0.05 0.022 - 0.050 0.003 - 0.125 0.003 - 0.125 0.014 - 0.033 0.05 0.05 0.1 - 0.02

Si0 2/H20

64 - 150 59 - 88 60 - 300 89 40 - 20,000 30 - 3,000 200 - 2,000 30 30 20 - 300

Si0 2/ A12°3

-

0.3 0.51 0.9 0.22 - 1. 0 - 1. 0 - 0.8 0.08 0.08 0.5 - 3.0 0.05 0.39 0.05 0.12 0.1 0.1 0.2

R/Si0 2

0.1 0.17 0.02 0.09 0.01 0.01

0.3 0.43 0.3 0.18 0.2 0.2

?

0.09 0.9

?

-

OH/Si0 2

c, CAS

TEA alcohols polyamines pentaerythritol TPA TBA TPA carboxylic acids tartaric acid 1,8 diamino-4ami nomethyloctane

R

a, actual spread of experimental data shown in the examples; b, preferred conditions claimed in the patent; crystalline aluminosilicates; d, F- is necessary so that F-/Si0 2 = 0.2 - 0.8.

TZ-01 AZ-01 b

ZSM-ll b CASb,c,d

72

50 54,ex.1 56 58 59 59 65 71

ZS~1-8a

ZETA-3 a NU-4 a NU-5 a rSM-5 b

Ref.

Zeol ite

TABLE V.3. Conditions for the synthesis of various zeolites belonging to the pentasil group of materials with sodium as inorganic alkali ion

w

( 1)

-

190

TABLE V.4. Templates used for the synthesis of some proprietary pentasil zeolites

Zeol ite

Templates

Ref.

ZSM-8 ZETA-l ZETA-3 NU-4 NU-5

TEA TPA; cetyltrimethylammonium isopropanol; glycerol; alcohol mixture TEPA a; TETA b; N,N-diethylethylenediamine Pentaerythritol or its oligomers

51 53 54 56 58

a, TEPA

tetraethylenepentamine; b, TETA = triethylenetetramine.

TABLE V.5. Characterization of some proprietary pentasil materials based on some XRD lines in terms of the intergrowth percentage of ZSM-ll in ZSM-5

Zeol ite

ZSM-8 a ZETA-l a ZETA-3 a H-NU-5 a NU-5 a H-NU-5 b

Ref.

50 53 54 56 58 58

Proprietary holder

IIII/Ill

% intergrowth

Mobil

0.24 0.13 0.09 0.28 0.49 0.44

60 78 85 53 18 27

leI leI leI leI leI

(ZSM-ll in ZSM-5)

a, as synthesized forms; b, hydrogen form, after removal of organic material and acid treatment.

191

1.

ZSM-8 (refs. 50-52)

This member of the pentasil family of zeolites is a Mobil proprietary material, with an X-ray diffractogram very similar to that of ZSM-5 (Fig.V.9.1), synthesized under the conditions used for ZSM-5 (Table V.3) but with TEA (tetraethy"lammonium) as a specific template (Table V.4). According to the XRD criterion handled for intergrowth characterization, the Mobil material seems to be a 40:60 ZSM-5-ZSM-11 intergrowth. Moretti et al. (ref.60) classified the material as ZSM-5, whereas Gabel ica et al. (ref.52), using a laboratory made sample (8-14 ~m aggregates of 1-2 ~m tubular crystals) consider it to be a ZSM-5-rich intergrowth, based on its 90% pore filling (compared with TPA-ZSM-5) with TEA after synthesis. Using the n-decane hydroisomerization reaction, a CI o value of 5.6 was also obtained for a laboratory made sample. This value is slightly below that of ZSM-5 (CI O 6.5), categorizing this sample as a ZSM-5-rich intergrowth. The efficiencies of the synthesis of ZSM-8 and other pentasils are compared with that of ZSM-5 in Fig.V.6. It is our experience that in the presence of TPA zeolite ZSM-5 can be easily synthesized with 100% efficiency based on the sil ica involved. In Fig. V.6, literature data either confirm this (with the experimental points on the diagonal 1ine of a graph of chemical composition of the gel plotted against that of the zeol ite) or indicate an equal preference of the ZSM-5 matrix for Si and Al. The latter has now been sufficiently proved not to be true (see Chapter I), which allows us to conclude that Fig.V.6 is a measure of the synthesis efficiency. The data for ZSM-8 in Fig.V.6 indicate a significantly decreased efficiency of synthesis, which can possibly be related to the different nature of the template used for ZSM-5 (TPA) and for ZSM-8 (TEA). According to Moretti et al., "ZSM-8" can be obtained using tributylheptylammonium, trioctylmethylammonium, diethylmorpholinium, ethylpentylpiperidinium or ethylquinolinium cations or with tributyl- and tripropylamine (ref.60). The assignment as ZSM-8 is, however, not disputed (ref. 60). The sorption capacities of several pentasil zeolites are compared in Fig. V.7. ZSM-5 and ZSM-8 show comparable sorption data for m-xylene but are distinctly different for cyclohexane. In view of the proposed structural assignment of this zeolite such a difference should not exist, so that more detailed work is needed to clarify this issue.

192

150

ZSM-5

e

I I

I

oQ)

NU-4 i;;./ T.

N

..C")

oC\I

100

C

-ZETA-3


-,

C\I

o

--

a

(f)

50

~-8

0-

o

a

O~~

o

L-

50

L-

100

~

150

FIGURE V.6. Preference of pentasil zeolites for aluminium incorporation from the synthes i s gel to the zeol ite with s i 1i ca as reference, obta i ned by comparing the SiO Z : A1 203 ratio in the synthesis gel with the composition of the crystallites. a, ZSM-8 (ref.48); b, ZETA-3 (ref.50); c, NU-4 (ref.52); d, NU-5 (ref.54); e, ZSM-5 (Part I, recipe IO.a); f, ZSM-5 (ref.52).

19:1

2. ZETA-l (ref.53) According to the inventor of this material ZSM-5, and

can

only

be

synthesized with

(ref.53), it is related to

solid silicic

acid

as

a silica

source. Surprisingly, in a recent review of the synthesis and properties of certain l CI proprietary zeolites (ref.5?), this material According

to

its

X-ray

diffractogram

(Fig.

is not mentioned.

V.9.2)(ref.60),

it definitely

belongs to the pentasil family, is very rich in ZSM-ll (Table V.5), but is synthesized

with

similar

templates

to

ZSM-5 (Table

capacities for n-hexane, cyclohexane and

V.4).

The

sorption

p-xylene are comparable to those

of ZSM-5 (Fig.V.7), but it is not accessible to m-xylene, indicating that the pores are only accessible to molecules with a kinetic diameter of 0.6 nm or less

(ref.53)

Ethylbenzene,

which

has

the

same

kinetic

diameter

as

cyclohexane, also hardly enters the ZETA-l pores. The discrepancy between the sorption data of ZETA-l and ZSM-5 for these sorbates is only apparent as their kinetic flexibility.

diameters

do not account for

the differences

Indeed, cyclohexane can undergo configurational

in

molecular

changes (from

boat to chair form), which can explain the lower sorption capacity of ZETA-l for ethyl benzene compared with ZSM-5. The XRD 1 ines can be indexed in the tetragonal system, such as ZSM-ll, but with a unit cell size of a c

=

=

2.23 and

4.24 nm (ref.53), as required for a pentasil intergrowth. All these data

indicate that ZETA-l is a ZSM-ll-rich pentasil intergrowth, containing pore occlusions. The presence of pore occlusions can also be derived from the low intensity of the XRD lines in the 7-9 °20 region, compared with those between 22 and 25 °20 (Fig.V.9.2.) and compared with those of ZSM-8 (Fig.V.9.l) and ZSM-5 (Fig.I.3.3).

194

0000000

10

~Q:=.9:-

••••••••

>-0-0

"C

-----_.

(1)

.c

o (/)

-

x x x x

X

x

0000000 1-0-0-

~o

--- ZSM-5

0000000

-0-ZSM-11

•••••••

oooZETA-1

X )(

x x x

xxZETA-3

>-

... NU-5

x x x x

....

ZSM-8

------ ------ ------ ------

~

5

-

~

o

x x x x x x \~~

water

0.28

n-

cyclohexane 0.42 0.60

p-

~i~~~

ggggggg 0000000

methylxylene benzene 0.60 0.62 0.60

sorbate and kinetic diameter/nm

FIGURE V.l. Room temperature adsorption of various sorbates on different pentasil zeolites: Z5M-8 (ref.51), Z5M-5 (ref.51), Z5M-ll (ref.53), ZETA-1 (ref.53), ZETA-3 (ref.55) and NU-5 (ref.58).

195

3. ZETA-3(refs.54,55) ZETA-3

is

another pentasil

zeolite that can

be synthesized in

the

absence of N-containing organics, but with alcohols (Table V.4). For ZSM-5 similar synthesis procedures have been discussed (Chapter II). It should be stressed that at that time of the discussion no distinction was made between individual materials of the pentasil group; they were all considered as pure ZSM-5. Moreover, no data are available in the literature cited at that time, that

would

allow

one

to

categorize

these

ZSM-5

materials

as

potential

intergrowths. ZETA-3 is a ZSM-5-type material (refs.54,55,60) (Fig.V.9.3) synthesized under similar conditions of basicity and chemical composition (Table V.3), can

be categorized as

ZSM-ll-rich (Table V.5), and has

capacity than ZETA-l for cyclohexane and p-xylene

a lower sorption

(Fig.V.?). Its synthesis

efficiency is only slightly lower than that of ZSM-5 (Fig.V.6). Continuing the interpretation of the data in this figure as "template efficiency", it follows that alcohols are very efficient agents for ZETA-3 synthesis, either as "true" templ ates or as pore fill i ng agents. 4. NU-4 (refs.56,57) NU-4 zeolite is an ICI proprietary material that permanently exhibits monoclinic symmetry (ref.56,57) (Fig.V.9.4), in contrast to ZSM-5, for which the

monoclinic-orthorhombic

conversion

is

reversible

and

for

which

the

as-synthesized form is orthorhombic. It seems to be a random intergrowth (50% ZSM-ll) (Table V.5), synthesized in the presence of polyamines (Table V.4) under conditions of basicity, content of organics and chemical composition comparable to those for other pentasil zeolites (Table V.3). It is therefore a pentasil zeolite with the lowest possible symmetry (refs. 56,57). The synthesi s efficiency of NU-4 (and in

the context of the present

interpretation of the polyamine template molecules) is only slightly lower than that for ZSM-5 (and TPA). The crystals of NU-4 are large (3 - 100 ~m), prismatic and twinned (ref.56). It has a sorption capacity comparable to that of

ZSM-5

for

sorbates with

kinetic

diameters

smaller

than

0.6

nm

but

permanent pore occlusions impede the fast adsorption of m-xylene (Fig.V.S). The permanent presence of pore occlusions of H-NU-4 compared with H-ZSM-5 is also evident when the intensity of the XRD lines at small °28 are compared. For NU-4

they are very low in intensity (Fig.V.9.4). In order to synthesize

this zeolite as a pure phase free of any NU-lO (another high-silica zeolite, described in Chapter VI), very low H and high OH/Si0 ratios, or both 2 20/Si02

196

are needed. In other words, the synthesis gel has to be very concentrated and basic, as both parameters are interdependent. Typical effects of changes in these parameters on the crystallization time and on the nature of the phases synthesized are given in Table V.6. The data clearly show that a higher basicity (compare I with II and III) substantially decreases the crystallization time for NU-4 or that a lower concentration at equal basicity (compare IVa with IVb) gives ultimately a different zeolite.

10.--------------="1 p-xylene

5

o

o ~-......I---L.-----'---l.-..-.....J o

1

4

5

FIGURE V.8. Diffusion plot of p- and m-xylene sorption on the H-forms of ZSM-5 and NU-4 zeolites (after data in ref.56).

197

TABLE V.6 Synthesis of NU-4 zeolites (calculated from the data in ref.56)

I (ex.3 a)

SiOZ/HZO SiO Z/A1 Z0 3 R/SiO Z Na/SiO Z OH/SiO Z Crystal 1ization Time/days Temp./K Zeolite phase

II (ex.9)

I II (ex.10)

IVa (ex.7)

IVb (ex.7)

0.OZ5 60 0.33 0.60 0.06

0.OZ5 61.8 0.33 0.56 O.OZ

0.OZ5 61.8 0.33 0.56 0.15

0.OZ5 96.3 0.Z8 0.6Z 0.05

(0.05)b 96.3 0.Z8 0.6Z 0.05

Z 453 NU-4

5 453 NU-4

1 453 NU-4

40 378 NU-10

4 378 NU-4

a, ex. = example (described in ref.56). b, more concentrated gel obtained by refluxing before autoclaving. With N,N'-diethylethylenediamine as template it seems difficult to obtain pure NU-4 (ref.56). When K replaces Na in an otherwise identical gel (ref.56), NU-10 is obtained instead of NU-4. Supplementary addition of salts to the gel (e.g., NaCl) accelerates the crystallization but is difficult to remove after crystallization. and therefore influences the sorption characteristics of NU-4 (ref.56). At the same time either a quartz or a cristobalite co-crystallizes (ref.56). 5. NU-5 (refs. 57,58) This ICI proprietary material also has an XRD pattern similar to that of ZSM-5 (Fig. V.9.5), but with additional lines and intensity changes. It also seems to be very close to a ZSM-5-rich intergrowth (Table V.5) synthesized under conditions comparable to those for ZSM-5 (Table V.3) but with pentaerythritol as the basic template molecule. The hexane sorption capacity is comparable to that of ZSM-5 (Fig.V.5), but in contrast to this material it does not allow cyclohexane or m-xylene into its intracrystall ine void

198

volume. The p-xylene sorption capacity for both materials remains unaltered, however. This pentasil material therefore seems to be very suitable for the isolation of p-xylene from a mixture of its configurational isomers (ref.58). 6. OTHER PENTASILS Zeolite ZBM-IO (ref.6I) is possibly another ZSM-ll-rich member of the pentasil family, synthesized in the presence of polyamines. Depending on the nature of the amine, the lowest Si0 material

is

obtained

varies

ratio for which a crystalline 2/A1203 from 38 (dihexamethylenetriamine) to 19

(triethylenetetramine). Assuming that all aluminium is in the framework, the latter value corresponds to nine Al atoms in a pentasil unit cell containing 96 T-atoms. This is close to the theoretical maximum of eight Al atoms per unit cell of ZSM-5, or to half of the theoretical Al-capacity of ZSM-II. Another pentasil-like zeolite with catalytic properties differing from those of ZSM-5 was prepared in absence of organics using regular ZSM-5 seeds (ref.62). Its X-ray diffractogram in shown in Fig.V.9.6. TRS has

an XRD pattern (Fig.V.9.?)

that is unique (ref.63). Careful

examination shows the presence of pentasil lines (p) and of cristobalite (c), but also of lines at specific positions or with unusual intensities (x). The available data (ref.63) do not allow one to decide whether this is a new zeolite or a mixture of several phases. Zeolite MB-28

is

synthesized

in

the presence of diethylpiperidinium

(ref.64) and is classified by one of the inventors in another publication (ref.60) as ZSM-5-like. Some of the pentasil lines (indicated by (x) in Fig. V.9.8), however, show very unusual intensities.

Based on this XRD

pattern

the MB-28 materi a1 coul d also belong to the mordenite family (see Chapter X). Also, a ZSM-ll-like pentasil has been claimed (ref. 65) using fluoride ions in the synthesis gel, under conditions otherwise comparable to those for pentasils (Table V.3). Some peaks (indicated by (x) in Fig.V.9.9) have very unusual

intensities. In this way, a unique crystal morphology is obtained.

The crystals are "pillar-like octahedra whose vertices and edges have been worn" (ref.65), with a length of at least 10 um. "Ultrasil" zeolites are denoted as properties are

similar to

those

"one of those new zeolites whose

of ZSM"

vibration bands around 550, 595 and 625 cm(refs.I5,67,68).

Therefore,

it

is

I

(ref.66).

The specific

lattice

are typical of pentasil zeolites

evident

(ref. 66) ZSM-5 is meant by ZSM and ultrasil

that

in

the

original

article

is yet another member of the

pentasil family. In the same way, a high-silica Ultrazet zeolite is said to be a "Polish counterpart of the ZSM-5" (ref.69) ,while TsVKs are its "Soviet analogues"(ref.70).

65

CAS a

Toray Asai K.K

-

a, CAS: crystalline aluminosilicates.

73

72

66 69 70

Montedison

64

MB-28

Ultrasil Ul trazet TsVK TZ-Ol AZ-l

BASF Teijin Petrochem. Snam Progetti

61 62 63

ZBM-IO CAS a TRS

Mitsubi shi

Patent holder

Ref.

Zeolite

TABLE V.7. Characteristics of some pentasil-like proprietary zeolites

Characteristics

ZSM-ll-like according to XRD ZSM-5 seeds, pentasil-like Pentasil-lines + cristobalite lines + TPA unknown lines diethylpiperidinium Pentasil lines with very unusual intensities ZSM-ll-like, with very unusual peak TPA intensities, synthesized with F Pentas il TPA ? ZSM-5 ? ZSt1- 5 Pentasil intergrowth (55% ZSM-5) Tartaric acid Pentasil-like, with constrained pore 1,8-diamino4-aminoethyloctane access

-

Polyamines

Template

'"-' so «o

200

Pentasil-like materials have also been synthesized in the presence of carboxylic acids such as succinic, o-toluic, citric and salicylic acid (ref.71), under conditions comparable to those for other pentasils (Table V.3). In an attempt to replace the expensive and corrosive quaternary ammonium ions with their "offensive odour" (ref.72) in the synthesis of high-silica zeolites, zeolite TZ-Ol was claimed, using tartaric acid under otherwise comparable conditions to obtain pentasil zeol ites (Table V.3). TZ-Ol, according to the XRD lines, is pentasil-like (Fig. V.9.l0) and, depending on the criterion considered, could be a random intergrowth. A zeolite denoted as TZ-02, synthesized under similar conditions but with salycilic acid, belongs to the mordenite family according to its XRD lines. Zeolite AZ-l (ref.73) is a high-silica zeolite synthesized in the presence of 1,8-diamino-4-aminomethyloctane, which shows a pentasil-like XRD spectrum with unusual line intensities (Fig. V.9.11). According to its sorption data it has a significantly lower pore accessibility than ZSM-5. Indeed, pyridine is sorbed in comparable amounts on both materials, whereas the adsorption ratios of pyridine to 4-methylquinoline are 250 and 20 on AZ-l and ZSM-5, respectively (ref.73). Some useful characteristics of the zeolites discussed here are summarized in Table V.7. This overview is meant to be as complete as possible, but only U.S. and European patents have been systematically consulted. Even then, new pentasil materials might have escaped us. The aim of this section has been two-fold: i. to give the reader who does not follow the patent literature in detail an impression of the complexity of the situation with regard to new zeolites and the family to which they belong; and ii. to give to the same reader a collection of useful data that will be of much help in his own synthetic efforts in this area.

5.0

- ,

-

f-

f-

f-

-

f-

IJ

I

13.0

I 11.1

9.0

17.0

I ,II I

21.0

.I I

III IL

25.0

I h, 29.0

I 33.0

37.0

I

41.0

II

a

45.0

2

sL

FIGURE V.9.1. ZSM-8(Nederl.Octrooiaanvrage 7.014.807. Table A)

, 53.0

46.00 42.00 10.00 10.00 12.00 12.00 9.00 13.00 18.00 20.00 10.00 100.00 57.00 25.00 30.00 26.00 9.00 18.00 8.00 10.00 11.10 10.00 9.70 7.42 6.35 5.97 5.69 5.56 4.25 4.07 4.00 3.85 3.82 3.75 3.71 3.64 3.43 3.34 3.31 3.13

49.0

1/10

d [0. 1nm]

GO

o

5.0

-

9.0

II

I

13.0

17.0

I . III, I ,I .1 21.0

II, I 25.0

•

,

.II. 29.0

33.0

•

,

FIGURE V.9.2. ZETA-1 (G.Offenl. 2,548,695, Table 1)

37.0

•

•

41.0

,

,

e

45.0

,

2

t.

,

49.0

,

11.12 9.97 9.72 7.44 6.35 6.04 :.98 5.56 5.00 4.60 4.34 4.26 4.00 3.84 3.82 3.75 3.72 3.65 3.05 2.98

•

d [0. inm]

•

53.0

I1Io 30.00 23.00 3.00 7.00 8.00 7.00 7.00 8.00 4.00 6.00 7.00 8.00 7.00 100.00 77.00 38.00 44.00 31.00 7.00 10.00

""

"" o

5.0

~

t-

~

(... I

I

9.0

13.0

III

17.0

,I

I

I

21.0

25.0

I

.L

,I

29.0

33.0

,

FIGURE V.9.3. ZETA-3(G.Offenl. 2.548.695. Table 2)

,

I

37.0

I

I

41.0

I

,II ,

e

45.0

2

sL

49.0

I

10.97 9.85 7.36 6.30 5.94 5.S7 5.52 5.33 4.58 4.33 3.98 3.82 3.73 3.70 3.63 3.04 2.97 2.93 2.00 1.99

I

d [0. 1nm]

53.0

I

r/re

35.00 23.00 8.00 10.00 6.00 7.00 9.00 15.00 7.00 9.00 7.00 100.00 14.00 34.00 28.00 10.00 11.00 11.00 8.00 8.00

ec w

o

5.0

f-

f-

f-

f-

f-

f-

f-

f-

f-

f-

f-

f-

f-

f-

f-

f-

f-

f-

f-

9.0

I I

,

, I 1.11

13.0

I

I

17.0

J

I,

I

21.0

25.0

I

III.

29.0

I

I

I

33.0

FIGURE V. 9.4. NU-4 (aa-mede) (E.P. A. 65. 401. ex. 3)

I

I

37.0

I

, 41.0

I

45.0

I

2 9

t.

I

49.0

I

I

53.0

16.00 20.00 15.00 B.OO 6.00 B.OO 6.00 9.00 13.00 10.00 13.00 6.00 100.00 69.00 51.00 50.00 27.00 22.00 12.00 9.00

11.30 11.10 10.0B 9.90 9.77 5.75 5.65 4.63 4.39 4.29 4.12 4.04 3.BB 3.B5 3.74 3.73 3.6B 3.65 3.47 3.33

I

IlIa

d [0 . 1nm]

""

"" o

5.0

f-

l-

f-

~

f-

~

f-

f-

f-

f-

f-

f-

f-

f-

f-

f-

f-

f-

•

9.0

I

•

13.0

1,,1

17.0

.111

.I 21.0

II

25.0

II

29.0

I

33.0

FIGURE V. 9.5. NU-5 (as- made) (E. P. A. 54. 386. ex. 1)

I

37.0

I

41.0

I

II

e

45.0

2

sL

I

•

I

53.0

11.11 10.02 9.96 9.74 6.36 5.99 5.70 5.59 4.37 4.27 4.10 3.86 3.82 3.75 3.72 3.64 3.32 3.05 2.99 2.98

49.0

IlIa

70.00 41.00 37.00 18.00 14.00 15.00 12.00 13.00 15.00 15.00 14.00 100.00 70.00 39.00 54.00 31.00 12.00 12.00 13.00 13.00

d [0 . 1nm]

o '" en

5.0

f-

f-

~

f-

~

f-

~

f-

~

f-

-

~

'-

f-

I

9.0

II

I

I

13.0

III

I

17.0

I

21.0

I II II

25.0

II 1.1

29.0

I

33.0

37.0

2

e

41.0

45.0

I

i.

FIGURE V.9.6. crystalline aluminosilicate(E.P.A. 94,693, Table A)

I

53.0

37.00 24.00 9.00 7.00 8.00 8.00 14.00 7.00 100.00 75.00 45.00 53.00 33.00 10.00 19.00 10.00 16.00 18.00 18.00 8.00 11.26 10.11 6.05 5.74 5.61 4.39 4.28 4.04 3.86 3.83 3.75 3.74 3.66 3.46 3.36 3.33 3.06 3.00 2.98 2.96

49.0

I1Io

d [0. 1nm]

"" o en

5.0

f-

l-

f-

l-

I

9.0

I

13.0

I

21.0

I .I Il

17.0

I

25.0

29.0

FIGURE V.9.7. TRZeG.Offen.2.924.870.Fig.1)

33.0

.I

37.0

I

I

41.0

I

45.0

I

2 9

t.

I

49.0

I

53.0

I

35.30 25.50 17.70 35.00 70.95 25.50 27.30 100.00 78.40 47.00 54.60 35.30 25.50 100.00 50.90 15.70 19.60 50.90 35.00 15.70 11.47 10.04 9.11 7.25 5.60 5.06 4.07 3.90 3.86 3.78 3.74 3.70 3.46 3.42 3.18 3.07 2.99 2.90 2.70 2.49

I

IlIa

d [0 . 1nm]

-1

o

co

5.0

I

I

9.0

I.

I

I

13.0

I II

JI

I

17.0

I I. I

I

21.0

25.0

III. I

I 29.0

33.0

FIGURE V.9.8. MB-28 (calcined) (E.P.A.2i. 445. ex.i)

I

37.0

41.0

I

e

.I 45.0

2

t.

53.0

13.00 7.00 4.00 4.00 22.00 5.00 30.00 5.00 4.00 8.00 6.00 6.00 100.00 4.00 7.00 5.00 11.00 7.00 5.00 6.00

11.16 10.01 9.05 5.57 4.26 3.97 3.84 3.83 3.75 3.72 3.65 3.46 3.35 2.98 2.46 2.13 1.82 1.54 1.38 1.38

49.0

I1Io

d [0 . 1nml

~

tV

t.

5.0

I

9.0

13.0

I

17.0

21.0

25.0

I

29.0

I

I

33.0

37.0

I

41.0

e

45.0

2

FIGURE V.9.9. crystalline aluminosilicate (as-made) (E.P.A.31. 255. ex.i)

49.0

11.30 10.00 5.01 3.84 3.75 3.72 3.65

I

d[0.1nm]

53.0

IlIa 13.00 94.00 22.00 100.00 24.00 25.00 15.00

t:2 Cl5

5.0

...

...

I

I

9.0

I

13.0

I JII

17.0

dI

21.0

J .1 II" I 1.1

25.0

II..

J

29.0

•

I. '.1 33.0

FIGURE V.9.10. TZ-01(as-made) (E.P.A. 57.016.ex.1)

37.0

I •.

•

I

41.0

I

49.0

• I

53.0

49.00 33.00 11.00 8.00 9.00 12.00 10.00 13.00 10.00 100.00 82.00 50.00 55.00 27.00 15.00 9.00 10.00 16.00 9.00 11.00

11.30 10.09 9.82 6.75 6.40 6.04 5.75 5.61 4.39 3.86 3.83 3.76 3.74 3.66 3.47 3.38 3.06 2.99 2.02 2.00

III.

e

45.0

.1.

2

sL I1Io

d [0. 1nm]

,.... "" o

5.0

f-

r-

f-

f-

r-

f-

r-

f-

r-

f-

r-

f-

r-

f-

r-

f-

r-

r-

r-

I

9.0

I

I

13.0

I

17.0

I

I

21.0

I

I

25.0

I

29.0

I

I

33.0

I

FIGURE V. 9 .11. AZ-1 (as-made) (E. P. A.113, 116, ex .1)

I

I

37.0

I

41.0

e

45.0

2

t.

49.0

11.32 10.16 9.93 5.06 5.01 3.85 3.77

d [0. 1nm]

53.0

18.42 100.00 100.00 18.42 15.79 57.89 36.84

I1Io

"" >-' >-'

212

REFERENCES 1. G.T. Kokotailo, S.L. Lawton, D.H. Olson and W.M. Meier, Nature ~ (1978) 437 and D.H. Olson, G.T. Kokotailo, S.L. Lawton and W.M. Meier, J. Phys. Chern. ~ (1981) 2238. 2. G.T. Kokotailo, P. Chu, S.L. Lawton and W. H. Meier, Nature 275 (1978)119. 3. E.M. Flanigen, J.M. Bennett, R.W. Grose, J.P. Cohen, R.L. Patton, R.M. Kirchner and J.V. Smith, Nature ~ (1978) 512. 4. W.M. Meier and D.H. Olson, Atlas of Zeolite structure types, Structure Commission IZA, 1978, Polycrystal book service, Pittsburgh. 5. R. von Ballmoos, Collection of simulated XRD powder patterns for zeolites, Butterworth, Guildford, 1984, p.74. 6. C. Baerlocher, Proceed. 6th Int. Zeolite Conference, D. Olson and A. Bisio, eds., Butterworths, Guildford, 1984, p.823. 7. G.T. Kokotailo and W.M. Meier, Chern. Soc. Spec. Publ. ~ (1980) 133. 8. C.A. Fyfe, G.T. Kokotailo, G.J. Kennedy and C. De Schutter, J.C.S. Chern. Commun. (1985) 306. 9. W.M. Meier, ref. 7, p.274. 10. G.T. Kokotailo, ref. 7, p.214. 11. E.M. Flanigen and R.L. Patton, U.S.P. 4,073,865 (1978), assigned to Union Carbide Corp .. 12. G.D. Price, J.J. Pluth, J.V. Smith, T. Araki and J.M. Bennett, Nature ~ (1981) 818. 13. Recent Progress Reports and Discussion, 5th Int. Conf. Zeolites, R.Sersale, C. Colella and R. Aiello, eds., Giannini, Naples, 1980, p.210-225. 14. Z. Gabelica, E.G. Derouane and N. Blom, A.C.S. symp. Ser. 248 (1984) 219. 15. P.A. Jacobs, H.K. Beyer and J. Valyon, Zeolites 1 (1981) 161. 16. J. Thomas, G.R. Millward and S. Ramdas, A.C.S. Symp. Ser. ~ (1983) 181. 17. J.M. Thomas, S. Ramdas, G.R. Millward, J. Klinowski, M. Audier, J. Gonzalez-Calbet and C.A. Fyfe, J. Sol. St. Chern. ~ (1982) 368. 18. J.M. Thomas, A.C.S. Symp. Ser. III (1983) 445. 19. S. Ramdas, J.M. Thomas, P.W. Betteridge, A.K. Cheetham and E.K. Davies, Angew. Chern. ~ (1984) 629. 20. J.M. Thomas and C. Williams, Chemical Reactions in Organic and Inorganic Constrained Systems, R. Setton, ed., Nato ASI Ser., Reidel, Dordrecht, C165 (1985)49. 21. J.M. Thomas, G.R. Millward, S. Ramdas, L.A. Bursill and M. Audier, J.C.S. Faraday Disc. ~(1981)345.

213

22. G.T. Kokotailo, U.S.P. 4,289,607 (1981), assigned to Mobil Oil Corp.. 23. G.T. Kokotailo, E.P.A. 18,090 (1980), assigned to Mobil Oil Corp.. 24. M.A.M. Boersma and M.F.M. Post, E.P.A. 40,444 (1981), assigned to Shell Int. Res .. 25. M. Bourgogne, J.L. Guth and R. Wey, E.P.A. 74,900 (1982), assigned to CFR. 26. C.A. Audeh and W.J. Reagan, U.S.P. 4,430,314 (1984), assigned to Mobil Oi I Corp.. 27. W. Roscher, K.H. Bergk, W. Schwieger, F. Wolf, V. Haedicke, W. Krueger, K.H. Chojnacki, DDR P. 207,186 (1984) assigned to VEB chemiecombinat Bitterfel d. 28. id., DDR P. 207,185(1984). 29. H.P. Rieck, G. offenl. 3,242,352 (1184), assigned to Hoechst AG. 30. W.J. Ball, K.W. Palmer and D.G. Stewart, USP 4,346,021(1982), assigned to BP. 31. C. Barlocher, Proceed. 6th Int. Conf. Zeolites, D. Olson and A. Bisio, eds., Butterworths, Guildford 1984, p. 823. 32. R. von Ballmoos, Diss. ETH 6765, Verlag Sauerlander, Aarau, 1981, p.91. 33. W.J. Frilette, W.O. Haag and R.M. Lago, J. Catal. §2 (1981) 218. 34. for a review: F.R. Ribeiro, F. Lemos, G. Perot and M. Guisnet, in Chemical Reactions in Organic an Inorganic Constrained Systems, R. Setton, ed., NATO ASI Series, Reidel, Dordrecht, C165 (1985) 141. 35. P.A. Jacobs and J.A. Martens, Pure Appl. Chem. Vol. 58 No. 10 (1986) 1329. 36. A. Auroux, H. Dexpert, C. Leclercq and J. Vedrine, Appl. Catal. ~ (1983)95. 37. J.A. Martens, M. Tielen, P.A. Jacobs and J. Weitkamp, Zeolites i (1984) 98. 38. Y.Y. Huang, E.P.A. 95,851(1983), assigned to Mobil Oil Corp. 39. E.L. Wu, S.L. Lawton, D.H. Olson, A.C. Rohrman and G.T. Kokotailo, J. Phys. Chem. 83 (1979) 2777. 40. C.A. Fyfe, S.J. Kennedy, C.T. De Schutter and G.T. Kokotailo, J.C.S. Chem. Commun. (1984) 541. 41. H. Nakamoto and H. Takahashi, Chem. Lett. (1981)1013. 42. D.G. Hay and H. Jaeger, J.C.S. Chem. Commun. (1984) 1433. 43. D.G. Hay, H. Jaeger and G.W. West, J. Phys. Chem. 89 (1985) 1070. 44. C.A. Fyfe, G.J. Kennedy, G.T. Kokotailo, J.R. Lyerla and W.W. Fleming, J.C.S. Chem. Commun.(1985) 740.

214

45. G.E.M. De Clippeleir, R. Cohen, G.L. Debras and H. Van Thillo, E.P.A. 146,525 (1984) assigned to Co,den Technol .. 46. J.M. Thomas and G.R. Millward, J.C.S. Chem. Commun. (1982) 1382. 47. C.A. Fyfe, G.C. Gobbi, J. Klinowski, J.M. Thomas and S. Ramdas, Nature ~ (1982) 530. 48. B.L. Meyers, S.R. Ely, N.A. Kutz, J.A. Kaduk and E. Van den Bossche, J. Catal. 21. (1985) 352. 49. P.A. Jacobs, M. Geelen and M. Tielen, Proceed. Siofok Meeting on Zeolite Catalysis, Acta Phys. Chem. Szegedensis (1985) p.1. 50. Nederl. Octrooiaanvrage 7,014,807(1971), assigned to Mobil Oil Corp .. 51. C.J. Plank, E.J. Rosinski and M.K. Rubin, G. Offenl. 2,049,755 (1971), assigned to Mobil Oil Corp. 52. Z. Gabelica, E.G. Derouane and N. Blom, Appl. Catal. 2 (1983)109. 53. T.V. Whittam, G. Offenl. 2,548,697 (1976), assigned to lCI. 54. T.V. Whittam, G. Offenl. 2,643,929 (1977), assigned to ICI. 55. T.V. Whittam, G. Offenl. 2,548,695 (1976), assigned to lCI. 56. T.V. Whittam, E.P.A. 65,401 (1982) assigned to lCI. 57. J. Dewing, M.S. Spencer and T.V. Whittam, Catal. Rev. Sci. Eng. ~ (1985) 461. 58. T.V. Whittam, E.P.A. 54,386 (1981), assigned to ICl. 59. P. Chu, J.C. Vartuli and J.A. Herbst, E.P.A. 127,399 (1984). 60. E. Moretti, S. Contessa and M. Padovan, Chim. Ind. §l(1985) 21. 61. L. Marosi, J. Stabenow and M. Scharzmann, E.P.A. 34,727 (1981) assigned to BASF. 62. T. Onodera, T. Sakai, Y. Yamasaki, K. Sumitani, E.P.A. 94,693 (1983) assigned to Teijin Petrochem. Ind: 63. M. Taramasso, O. Foriani, G. Manara and B. Notari, G. Offenl. 2,924,870 (1978), assigned to Snam Progetti. 64. R. Le van Mao, O. pilato, D. Moretti, R. Covini and F. Genoni, E.P.A. 21,445 (1980), assigned to Montedison. 65. T. Suzuki, S. Hashimoto and R. Nakano, E.P.A. 31,255(1980) and E.P.A. 53,499 (1982) assigned to Mitsubishi Gas. Chem. Compo 66. A.A. Kubasov, L.B. Gorelik, N.F. Meged', Ya. B. MirskU and T.V. Limova, Russ. J. Phys. Chem. ~ (1981) 1175. 67. G. Coudurier, C. Naccache and J.C. Vedrine, J.C.S. Chem. Commun. (1982) 1413. 68. J.C. Jansen, F. Van der Gaag and H. van Bekkum, Zeolites i (1984) 369. 69. J.M. Berak, B. Kanik, J. Mejsner and B. Kontnik-Matecka, React. Kin. Catal. Lett. 20 (1982) 431.

215

70. S.S. Shepelev and K.G. lone, React. Kin. Catal. Lett.

12.

(1981) 233.

71. K. Iwayama, T. Inoue, K. Sato, N. Hayakawa and M. Fujii, E.P.A. 119,709 (1984), assigned to Toray Ind .. 72. K. Iwayama, T. Kamano, K. Tada and T. Inoue, E.P.A. 57,016 (1982) assigned

to Toray Ind ..

73. M. Chono and H. Ishida, EPA 113,116 (1983) assigned to Asahi Kasei K.K. 74. W.O. Haag and R.M. Dessau, Proceed. 8th Int. Congress Catalysis, Vol.II, Verlag Chemie, Weinheim, 1984, p.302. 75. Z. Gabelica, M. Cavez-Bierman, P. Bodart, A. Gourgue and J.B. Nagy, Stud. Surf. Sci. Catalysis

~

(1985) 55.

76. J.B. Nagy, Z. Gabelica, E.G. Derouane and P.A. Jacobs, Chem. Lett. (1982) 2003. 77. Z. Gabelica, J.B. Nagy, P. Bodart, J. Debras, E.G. Derouane and P.A. Jacobs, Zeolites Science and

Technology, F.R. Ribeiro, A.E. Rodrigues,

L.D. Rollmann and C. Naccache, eds., Nato ASI Ser., M. Nijhoff Publ., E80 (1984) 193.