This invention is directed to novel benzyl quaternary ammonium compounds and their synthesis. The compounds have valuable utility as organic directing agents in the crystallization of a silicate structure which, in turn, is useful as a catalyst component, sorbent, and/or ion-exchanger. More particularly, this invention is concerned with benzyl quaternary ammonium compounds synthesized by selective alkylation of the bridgehead nitrogen of tropane or quinuclidine with a benzyl salt.

FIELD OF THE INVENTION 
This invention is directed to novel benzyl quaternary ammonium compounds 
and their synthesis. The compounds of this invention are novel compounds 
having valuable utility as organic directing agents in the crystallization 
of a silicate structure, which, in turn, is useful as a catalyst 
component, sorbent, and/or ion-exchanger. More particularly, this 
invention is concerned with benzyl quaternary ammonium compounds 
conveniently and reproducibly synthesized by reaction of a readily 
available benzyl salt with either quinuclidine or tropane. 
DESCRIPTION OF THE PRIOR ART 
Tropane, or 8-methyl-8-azabicyclo[3.2.1]octane, having the formula 
##STR1## 
is a known compound detailed in The Merck Index, 10th ed., No. 9580. A 
number of substituted derivatives of tropane are also detailed in The 
Merck Index, 10th ed., as follows. 
tropine, No. 9586, 
tropentane, No. 9582, 
tropeine, No. 9581, 
tropine benzylate, No. 9587, 
tropacine, No. 9576, 
tropacocaine, No. 9577, and 
atropine, No. 878. 
Tropine, or endo-8-methyl-8-azabicyclo[3.2.1]octan-3-ol, having the formula 
##STR2## 
can be prepared as in U.S. Pat. Nos. 2,366,760 and 2,746,976, incorporated 
herein by reference. 
Tropentane, or 1-phenylcyclopentanecarboxylic acid 
8-methyl-8-azabicyclo[3.2.1]oct-3-yl ester, having the formula 
##STR3## 
is prepared from tropine and 1-phenylcyclopentanecarboxyl chloride. 
Tropeine is a name given to esters of tropine in general, while tropine 
benzylate, or endo-.alpha.-hydroxy-.alpha.-phenylbenzene-acetic acid 
8-methyl-8-azabicyclo[3.2.1]oct-3-yl ester, has the formula 
##STR4## 
Tropacine, or endo-.alpha.-phenylbenzeneacetic acid 
8-methyl-8-azabicyclo[3.2.1]oct-3-yl ester, having the formula 
##STR5## 
is prepared from tropine and diphenylacetyl chloride as in Swiss Patent 
202,181, incorporated herein by reference. 
Tropacocaine, or exo-8-methyl-8-azabicyclo[3.2.1]octan-3-ol benzoate having 
the formula 
##STR6## 
is prepared by heating pseudotropine with water and benzoic anhydride. 
Atropine, or endo-(.+-.)-.alpha.-(hydroxymethyl)benzeneacetic acid 
8-methyl-8-azabicyclo[3.2.1 ]oct-3 -yl ester, has the formula 
##STR7## 
Quinuclidine, or 1-azabicyclo[2.2.1]octane, has the formula 
##STR8## 
SUMMARY OF THE INVENTION 
This invention provides novel benzyl quaternary ammonium compounds having 
the formula 
##STR9## 
wherein R is 
##STR10## 
and X is an anion selected from the group consisting of halide (e.g., 
iodide, chloride, or bromide); hydroxide; nitrate; sulfate; perchlorate; 
and bisulfate. Synthesis of said compound by reaction of a benzyl salt 
with either quinuclidine or tropane is also provided.

EMBODIMENTS 
As will be noted from the above formula for the benzyl quaternary ammonium 
compounds of this invention, the present compounds are synthesized by 
alkylation selectively at the bridgehead nitrogen of the starting material 
compound, selected from the group consisting of tropane and quinuclidine, 
with a benzyl salt, such as, for example, benzyl halide. This reaction is 
conducted in a suitable solvent, such as, for example an alcohol of from 1 
to about 8 carbon atoms, e.g., ethanol. The starting material compounds 
must be soluble in the solvent chosen. 
The compounds of this invention are benzylquinuclidinium and 
benzyltropanium compounds, such as, for example, the halide, hydroxide, 
nitrate, sulfate, perchlorate, or bisulfate. 
The synthesis method utilized for preparation of the compounds of this 
invention involves contacting the appropriate starting material compounds 
in a suitable solvent medium at alkylation reaction conditions including a 
temperature of from about ambient to reflux, and a pressure of from 
atmospheric to about 500 psig, preferably about atmospheric. The time 
required for the reaction will, of course, depend upon such factors as 
temperature and pressure, as well as relative concentrations of reactants 
and desired degree of reaction, but usually will be from about 10 hours to 
about 4 days. 
The reflux temperature of reaction limitation will depend upon the amount 
and nature of solvent used. Generally, the reaction mixture will comprise 
tropane or quinuclidine and alkylating agent benzyl salt in the mole ratio 
of from about 0.75 to about 1.25 moles alkylating agent/mole tropane or 
quinuclidine, and from about 5 to about 10 moles solvent. 
A suitable solvent, preferably polar, may be used in the reaction. Such 
solvents include an alcohol of from 1 to about 8 carbon atoms, ether of 
from 2 to about 10 carbon atoms, or combinations thereof, especially 
methanol, ethanol, acetone, and/or diethyl ether. The tropane or 
quinuclidine must be soluble in the solvent chosen to at least about 90 
percent. The preferred solvent will be essentially water-free, as will the 
reaction mixture in which the present compounds are produced. Choice of 
solvent will determine to a substantial degree the reflux temperature 
limitation at which the reaction will proceed to a product benzyl 
quaternary ammonium compound. For example, a solvent of ethanol will 
determine reflux temperature of about 70.degree. C. Methanol solvent will 
establish the reflux temperature at about 65.degree. C. 
Compounds of the present invention are useful as directing agents in the 
synthesis of crystalline silicate. Such silicate is useful as a catalyst 
component, sorbent, and/or ion-exchanger. Such silicate is prepared from a 
reaction mixture containing sources of an alkali or alkaline earth metal 
oxide, an oxide of aluminum, an oxide of silicon, water, and the directing 
agent compound, as is exemplified hereinafter. Such reaction mixture will 
have a composition, in terms of mole ratios of oxides, within the 
following ranges: 
______________________________________ 
SiO.sub.2 /Al.sub.2 O.sub.3 
15 to 1000 
H.sub.2 O/SiO.sub.2 
5 to 200 
OH.sup.- /SiO.sub.2 
0 to 3 
M/SiO.sub.2 0 to 3 
R*/SiO.sub.2 0.02 to 1.0 
______________________________________ 
wherein R* is the cation of the directing agent compound of this invention 
and M is the alkali or alkaline earth metal cation. 
Crystallization of the silicate can be carried out at either static or 
stirred condition in a suitable reactor vessel, such as, for example, 
polypropylene jars of teflon-lined or stainless steel autoclaves. The 
total useful range of temperatures of the silicate crystallization is from 
about 80.degree. C. to about 250.degree. C. for a time sufficient for 
crystallization to occur at the temperature used, e.g., from about 12 
hours to about 100 days. Thereafter, the crystals are separated from the 
liquid and recovered. The reaction mixture can be prepared utilizing 
materials which supply the appropriate oxides. Such materials may include 
sodium silicate, silica hydrosol, silica gel, silicic acid, sodium 
hydroxide, a source of aluminum, and the directing agent compound. 
It should be realized that the reaction mixture oxides can be supplied by 
more than one source. The reaction mixture can be prepared either 
batchwise or continuously. Crystal size and crystallization time of the 
crystalline silicate material will vary with the nature of the reaction 
mixture employed and the crystallization conditions. 
The following examples illustrate the present invention. 
EXAMPLE 1 
Benzylquinuclidinium halide, i.e., bromide, was synthesized by reacting 
benzylbromide and quinuclidine in absolute ethanol solvent in a flask 
equipped with a reflux condenser, a thermometer and a stirrer. The flask 
was charged with 60.0 grams of benzylbromide with 200 ml of absolute 
ethanol. Then 33.4 grams of quinuclidine dissolved in 300 ml of absolute 
ethanol was transferred to the flask. Heating and stirring of the flask 
reaction mixture commenced immediately. 
The reaction mixture was refluxed (.about.70.degree. C.) overnight with 15 
stirring before quenching the reaction vessel in a dry ice-acetone bath to 
-40.degree. C. The cold crystalline product was separated from the 
solvent, filtered, and washed with anhydrous diethylether on a Buchner 
funnel. The crystals were dried in an air stream, then chemically 
analyzed. The benzylquinuclidium bromide product of this example was found 
to be composed of 56.13 wt. % C, 7.46 wt. % H, 4.66 wt. % N and 28.13 wt. 
% Br. 
EXAMPLE 2 
Benzyltropanium halide, i.e., bromide, was synthesized by reacting 
benzylbromide and tropane in absolute ethanol solvent in a flask equipped 
with a reflux condenser, a thermometer and a stirrer. The flask was 
charged with 60.0 grams of benzylbromide with 300 ml of absolute ethanol. 
Then 37.6 grams of tropane dissolved in 300 ml of absolute ethanol 30 was 
transferred to the flask. Heating and stirring of the flask reaction 
mixture commenced immediately. 
The reaction mixture was refluxed (.about.70.degree. C) overnight with 
stirring before quenching the reaction vessel in a dry ice-acetone bath to 
-40.degree. C. The cold crystalline product was separated from the 
solvent, filtered, and washed with anhydrous diethylether on a Buchner 
funnel. The benzyltropanium bromide product crystals were then dried in an 
air stream. 
The following examples show utility of the benzyl quaternary ammonium 
compounds of this invention as crystallization directing agents in 
manufacture of synthetic crystalline silicate. In the examples, whenever 
adsorption data are set forth form comparison of sorptive capacities for 
2,2-dimethylbutane (2,2-DMB) and n-hexane, they were Equilibrium 
Adsorption values as follows. 
A weighed sample of the calcined adsorbant was contacted with the desired 
pure adsorbate vapor in an adsorption chamber, evacuated to less than 1 mm 
and contacted with 40 Torr of n-hexane or 2,2-DMB vapor, pressures less 
than the vapor-liquid equilibrium pressure of the respective adsorbate at 
30.degree. C. for n-hexane and 90.degree. C. for 2,2-DMB. The pressure was 
kept constant (within about .+-.0.5 mm) by addition of adsorbate vapor 
controlled by a manostat during the adsorption period, which did not 
exceed about 8 hours. As adsorbate was adsorbed by the new crystal, the 
decrease in pressure caused the manostat to open a valve which admitted 
more adsorbate vapor to the chamber to restore the above control 
pressures. Sorption was complete when the pressure change was not 
sufficient to activate the manostat. The increase in weight was calculated 
as the adsorption capacity of the sample in mg/g of calcined adsorbant. 
When Alpha Value is examined, it is noted that the Alpha Value is an 
approximate indication of the catalytic cracking activity of a catalyst 
compared to a standard catalyst and it gives the relative rate constant 
(rate of normal hexane conversion per volume of catalyst per unit time). 
It is based on the activity of silica-alumina cracking catalyst taken as 
an Alpha of 1 (Rate Constant =0.016 sec.sup.-1 ). The Alpha Test is 
described in U.S. Pat. No. 3,354,078; in the Journal of Catalysis, 4, 527 
(1965); 6, 278 (1966); and 61, 395 (1980), each incorporated herein by 
reference as to that description. The experimental conditions of the test 
used herein include a constant temperature of 538.degree. C. and a 
variable flow rate as described in detail in the Journal of Catalysis, 61, 
395. 
When X-ray diffraction data are provided, they were collected with a 
Scintag diffraction system, equipped with a germanium solid state 
detector, using copper K-alpha radiation. The diffraction data were 
recorded by step-scanning at 0.02 degrees of two-theta, where theta is the 
Bragg angle, and a counting time of 10 seconds for each step. The 
interplanar spacings, d's, were calculated in Angstrom units (A), and the 
relative intensities of the lines, I/I.sub.o is one-hundredth of the 
intensity of the strongest line, above background, were derived with the 
use of a profile fitting routine (or second derivative algorithm). The 
intensities are uncorrected for Lorentz and polarization effects. 
EXAMPLES 3-13 
Experiments were conducted for synthesis of crystalline product material. 
In these experiments, Al.sub.2 (SO.sub.4).sub.3. 18H.sub.2 O and KOH 
pellets were dissolved in deionized water. Benzylquinuclidinium bromide 
prepared in Example 1 above was then dissolved in the solution. Colloidal 
silica sol (30 wt. % SiO.sub.2) was then mixed into the solution. The 
mixture was stirred for 2 minutes to produce a uniform, fluid hydrogel, 
having, respectively, the compositions shown in Table I where R* is the 
cation of benzylquinuclidinium bromide. 
The hydrogel of each experiment was then transferred to a 300 ml stainless 
steel autoclave equipped with a stirrer. The autoclave was capped and 
sealed; and 400 psig of inert gas was introduced into the autoclave. 
Stirring and heating were started immediately. Crystallizations were 
carried out at 170.degree. C. with stirring. 
Crystalline products were recovered, filtered, washed with deionized water, 
and dried on a filter funnel in an air 20 stream under an infrared lamp. 
The dried crystalline powder products were then submitted for X-ray 
diffraction and chemical analysis. 
TABLE I 
______________________________________ 
Mixture Composition (mole ratios).sup.1 
SiO.sub.2/ 
K.sup.+ / 
Reaction 
Example Al.sub.2 O.sub.3 
SiO.sub.2 
time, days 
Product 
______________________________________ 
3 10 1.10 7 Zeolite 
4 25 0.62 7 Zeolite 
mixture 
5 30 0.57 7 Zeolite 
6 30 0.57 2 Zeolite 
7 30 0.57 7 Zeolite 
8 30 0.57 7 Zeolite 
9 30 0.57 3 Zeolite 
10 60 0.43 7 Zeolite 
11 60 0.43 7 Zeolite 
12 70 0.41 7 Zeolite 
13 180 0.34 7 Zeolite + 
.alpha.-quartz 
______________________________________ 
.sup.1 H.sub.2 O/SiO.sub.2 = 40, OH.sup.- /SiO.sub.2 = 0.30, R*/SiO.sub.2 
= 0.20 
The X-ray diffraction data for the as-synthesized products of Examples 8 
and 9 are presented in Tables II and III, respectively. 
TABLE II 
______________________________________ 
Interplanar 
d-Spacing (A) 
I/I.sub.o 
______________________________________ 
10.87 95 
9.18 7 
6.55 14 
5.86 6 
5.57 5 
5.43 12 
5.02 1 
4.68 26 
4.59 5 
4.35 100 
4.23 &lt;1 
4.17 31 
4.12 54 
3.94* &lt;1* 
3.77 40 
3.69 1 
3.61 11 
3.54 6 
3.43 39 
3.37 27 
3.32* 5* 
3.28 6 
3.25 7 
3.22 2 
3.18 8 
3.12 2 
3.06 11 
2.99 3 
2.930 2 
2.886 1 
2.844 6 
2.814 &lt;1 
2.788 3 
2.715 3 
2.660 5 
2.605 3 
2.561 5 
2.537 3 
2.511 4 
2.464 6 
2.173 4 
______________________________________ 
*Peak attributed to unidentified impurity phase 
TABLE III 
______________________________________ 
Interplanar 
Spacing (A) 
I/I.sub.o 
______________________________________ 
10.91 73 
9.21 6 
6.57 16 
5.87 5 
5.58 5 
5.43 12 
5.03 2 
4.97* &lt;1* 
4.69 27 
4.59 4 
4.36 100 
4.23 7 
4.17 28 
4.13 58 
3.95* 1* 
3.77 64 
3.70 1 
3.61 17 
3.55 10 
3.44 42 
3.37 26 
3.33 7 
3.30 5 
3.29 8 
3.26 8 
3.22 6 
3.18 9 
3.12 2 
3.07 16 
3.00 7 
2.934 3 
2.889 4 
2.845 10 
2.816 4 
2.790 5 
2.716 5 
2.661 8 
2.607 5 
2.561 7 
2.536 4 
2.513 7 
2.464 11 
2.173 4 
______________________________________ 
*Peak attributed to unidentified impurity phase 
Chemical analysis results for the as-synthesized products of Examples 4, 5, 
7, 8, 10, 11, and 12 are presented in Table IV. 
TABLE IV 
______________________________________ 
Moles Composition.sup.(1) 
Moles C/ per Mole Al.sub.2 O.sub.3 
Al/ K.sup.+ / 
R*.sup.(2) / 
Example 
Mole N N.sub.2 O: 
K.sub.2 O: 
SiO.sub.2 
100 Td 
100 Td 
100 Td 
______________________________________ 
4 17.1 0.45 0.71 20 9.0 6.4 4.1 
5 13.0 0.83 0.18 25 7.4 1.3 6.1 
7 17.5 0.55 0.99 26 7.1 7.1 3.9 
8 17.1 0.58 0.93 24 7.7 7.1 4.5 
10 17.0 0.64 1.36 32 5.9 8.1 3.9 
11 15.7 1.32 0.21 46 4.2 0.88 5.5 
12 17.4 1.58 0.45 66 2.9 1.3 4.6 
______________________________________ 
.sup.(1) Calculated on the basis of 100(SiO.sub.2 + AlO.sub.2) tetrahedra 
.sup.(2) R* = benzylquinuclidinium cation 
There appears to be no clear trend in the alkali metal content per 100 
tetrahedra, but there does appear to be approximately 4-6 template cations 
per 100 tetrahedra in the zeolite framework of the products from examples 
listed in Table IV, indicating templating activity for the 
benzylquinuclidinium cation. 
EXAMPLES 14-16 
Zeolite products of Examples 6, 7, and 8 were weighed into quartz boats, 
then placed into a Heviduty.RTM. tube furnace and sealed with nitrogen gas 
flowing through the furnace tube. The heating of the furnace was begun at 
2.degree. C./minute from room temperature to 538.degree. C. When the 
furnace reached the maximum temperature, the flowing gas was switched to 
air, and the calcination of the zeolite was continued for 15 hours before 
termination. 
The air calcined samples were ammonium exchanged with 1M NH.sub.4 NO.sub.3 
at 80.degree. C. for 6 hours. After ammonium exchange, the zeolites were 
filtered, washed with deionized water, and dried in an air stream on the 
filter funnel under an infrared heat lamp. 
The calcination procedure was repeated on the ammonium-exchanged materials 
in the tube furnace in the same manner as described above, except this 
time the samples were held at 538.degree. C. for 8 hours to convert them 
to the hydrogen form of the zeolite. Examples 14, 15, and 16 products were 
zeolite materials from the products of Examples 6, 7, and 8, respectively. 
EXAMPLE 17 
Samples of the hydrogen form product zeolites of Examples 14, 15, and 16 
were tested for acid catalytic activity in the Alpha Test and found to 
have Alpha Values of 521, 164, and 510, respectively. 
Constraint Index 
A convenient measure of the extent to which a crystalline material provides 
control to molecules of varying sizes to its internal structure is the 
Constraint Index (CI) of the material. Zeolites which provide a highly 
restricted access to and egress from their internal structures have a high 
value for the Constraint Index, and zeolites of this kind usually have 
pores of small size, e.g., less than 5 Angstroms. On the other hand, 
zeolites which provide relatively free access to their internal structures 
have a low value for the Constraint Index and usually have pores of large 
size, e.g., greater than 8 Angstroms. The method by which Constraint Index 
is determined is described fully in U.S. Pat. No. 4,016,218, incorporated 
herein by reference for details of the method. 
Constraint Index values for some typical zeolites are as follows: 
______________________________________ 
CI (at test temperature) 
______________________________________ 
ZSM-4 0.5 (316.degree. C.) 
ZSM-5 6-8.3 (371.degree. C.-316.degree. C.) 
ZSM-11 5-8.7 (371.degree. C.-316.degree. C. 
ZSM-12 2.3 (316.degree. C.) 
ZSM-20 0.5 (371.degree. C.) 
ZSM-22 7.3 (427.degree. C.) 
ZSM-23 9.1 (427.degree. C.) 
ZSM-34 50 (371.degree. C.) 
ZSM-35 4.5 (454.degree. C.) 
ZSM-48 3.5 (538.degree. C.) 
ZSM-50 2.1 (427.degree. C.) 
MCM-22 0.6-1.5 (399.degree. C.-454.degree. C.) 
TMA Offretite 3.7 (316.degree. C.) 
TEA Mordenite 0.4 (316.degree. C.) 
Clinoptilolite 3.4 (510.degree. C.) 
Mordenite 0.5 (316.degree. C.) 
REY 0.4 (316.degree. C.) 
Amorphous Silica-alumina 
0.6 (538.degree. C.) 
Dealuminized Y 0.5 (510.degree. C.) 
Erionite 38 (316.degree. C.) 
Zeolite Beta 0.6-2.0 (316.degree. C.-399.degree. C.) 
______________________________________ 
EXAMPLE 18 
The Constraint Index of the hydrogen form product zeolite of Example 15 was 
determined to be 0.3 at 316.degree. C. This value falls within the 
classification of the more open structures having 12-membered rings. 
Hence, it is concluded from the catalytic Constraint Index Test result 
that the zeolite product of Example 7 contains at least a 12-membered ring 
structure. 
EXAMPLE 19 
A sample of the hydrogen form product zeolite of Example 16 was subjected 
to sorption evaluation. FIG. 1 shows the 2,2-dimethylbutane (2,2-DMB) 
sorption measurements at 90.degree. C. for this sample. The rapid uptake 
of 2,2-dimethylbutane indicates a very open pore structure. 
EXAMPLE 20 
A sample of the hydrogen form product zeolite of Example 16 was also 
subjected to n-hexane sorption evaluation. FIG. 2 shows the n-hexane 
sorption measurement at 30.degree. C. for this sample. The rapid uptake of 
n-hexane indicates a very open structure. 
EXAMPLES 21-26 
In these experiments, Al.sub.2 (SO.sub.4).sub.3 . 18H.sub.2 O and KOH 
pellets for potassium or NaOH pellets for sodium were dissolved in 
deionized water. Benzyltropanium bromide prepared in Example 2 above was 
then dissolved in the solution. Colloidal silica sol (30 wt. % SiO.sub.2) 
was then mixed into the solution. The mixture was stirred for 2 minutes to 
produce a uniform, fluid hydrogel, having, respectively, the compositions 
shown in Table V where R* is the cation of benzyltropanium bromide. 
The hydrogel of each experiment was then transferred to a 300 ml stainless 
steel autoclave equipped with a stirrer. The autoclave was capped and 
sealed; and 400 psig of inert gas was introduced into the autoclave. 
Stirring and heating were started immediately. Crystallizations were 
carried out at 170.degree. C with stirring. 
Crystalline products were recovered, filtered, washed with deionized water, 
and dried on a filter funnel in an air stream under an infrared lamp. The 
dried crystalline powder products were then submitted for X-ray 
diffraction and chemical analysis. 
TABLE V 
______________________________________ 
Mixture composition (mole ratios).sup.1 
SiO.sub.2 / 
K.sup.+ / 
Na.sup.+ / 
Reaction 
Example Al.sub.2 O.sub.3 
SiO.sub.2 
SiO.sub.2 
time, days 
Product 
______________________________________ 
21 15 -- 0.44 7 Zeolite 
22 25 0.62 -- 7 Zeolite 
23 30 -- 0.37 7 Zeolite 
24 30 0.57 -- 7 Zeolite 
25 30 0.57 -- 7 Zeolite 
26 30 0.57 -- 7 Zeolite 
______________________________________ 
.sup.1 H.sub.2 O/SiO.sub.2 = 40, OH.sup.- /SiO.sub.2 = 0.30, R*/SiO.sub.2 
= 0.20 
Chemical analysis results for the as-synthesized product of Example 24 is 
presented in Table VI. 
TABLE VI 
______________________________________ 
Moles Composition.sup.(1) 
Moles C/ per Mole Al.sub.2 O.sub.3 
Al/ K.sup.+ / 
R*.sup.(2) / 
Example 
Mole N N.sub.2 O 
K.sub.2 O 
SiO.sub.2 
100 Td 
100 Td 
100 Td 
______________________________________ 
24 15.6 0.93 1.5 26.3 7.1 10 6.5 
______________________________________ 
.sup.(1) Calculated on the basis of 100(SiO.sub.2 + AlO.sub.2) tetrahedra 
.sup.(2) R* = benzyltropanium cation 
Since there are approximately 6 template cations per 100 tetrahedra in the 
zeolite framework of the product of Example 24, templating activity for 
the benzyltropanium cation is indicated. 
EXAMPLES 27-29 
Zeolite products of Examples 24, 25, and 26 were weighed into quartz boats, 
then placed into a Heviduty.RTM. tube furnace and sealed with nitrogen gas 
flowing through the furnace tube. The heating of the furnace was begun at 
2.degree. C./minute from room temperature to 538.degree. C. When the 
furnace reached the maximum temperature, the flowing gas was switched to 
air, and the calcination of the zeolite was continued for 15 hours before 
termination. Docket 7585 
The air calcined samples were ammonium exchanged with 1M NH.sub.4 NO.sub.3 
at 80.degree. C. for 6 hours. After ammonium exchange, the zeolites were 
filtered, washed with deionized water, and dried in an air stream on the 
filter funnel under an infrared heat lamp. 
The calcination procedure was repeated on the ammonium-exchanged materials 
in the tube furnace in the same manner as described above, except this 
time the samples were held at 538.degree. C. for 8 hours to convert them 
to the hydrogen form of the zeolite. Examples 27, 28, and 29 products were 
zeolite materials from the products of Examples 24, 25, and 26, 
respectively.