Process for preparing medium pore size zeolites using neutral amines

The present invention relates to a process for preparing medium pore size zeolites using small, neutral amines capable of forming the zeolite, the amine containing (a) only carbon, nitrogen and hydrogen atoms, (b) one primary, secondary or tertiary, but not quaternary, amino group, and (c) a tertiary nitrogen atom, at least one tertiary carbon atom, or a nitrogen atom bonded directly to at least one secondary carbon atom, wherein the process is conducted in the absence of a quaternary ammonium compound.

BACKGROUND OF THE INVENTION 
1. Field of the Invention 
The present invention relates to a process for preparing medium pore size 
zeolites using neutral amines. 
2. State of the Art 
Medium pore size zeolites, such as those designated SSZ-32 and ZSM-23, and 
methods for making them are known. For example, U.S. Pat. No. 5,053,373, 
issued Oct. 1, 1991 to Zones, discloses the preparation of zeolite SSZ-32 
using an N-lower alkyl-N'-isopropylimidazolium cation as an organic 
templating agent. Likewise, U.S. Pat. No. 4,076,842, issued Feb. 28, 1978 
to Plank et al., discloses the preparation of zeolite ZSM-23 using a 
cation derived from pyrrolidine as the template. 
U.S. Pat. No. 4,205,053, issued May 27, 1980 to Rollmann et al., discloses 
a process for manufacturing zeolites such as medium pore size, 
multidimensional ZSM-5 in which the shape or some other feature of the 
microscopic crystals is controlled by including in the forming solution an 
organic basic nitrogen compound in addition to an organic nitrogenous 
template. Examples of the basic nitrogen compound include amines such as 
tributylamine, trimethylamine, diisobutylamine, cyclohexylamine, 
isobutylamine, diisopropylamine, cycloheptylamine, n-octylamine, 
triethylamine, tert-octytamine, piperidine and piperazine. 
Copending U.S. patent application Ser. No. 08/407,432, filed Mar. 17, 1995 
of S. I. Zones and Y. Nakagawa entitled "Preparation of Zeolites Using 
Organic Template and Amine" discloses that zeolites, including medium pore 
size, unidimensional zeolites, can be prepared using a mixture of an amine 
component comprising (1) at least one amine containing one to eight carbon 
atoms, ammonium hydroxide, and mixtures thereof, and (2) an organic 
templating compound capable of forming the zeolite in the presence of the 
amine component, wherein the amine is smaller than the organic templating 
compound. Examples of the amines include isopropylamine, isobutylamine, 
n-butylamine, piperidine, 4-methylpiperidine, cyclohexylamine, 
1,1,3,3-tetramethylbutylamine and cyclopentylamine and mixtures of such 
amines. 
It has now been found that medium pore size zeolites can be prepared using 
small, neutral amines such as isobutylamine, diisobutylamine, 
trimethylamine, cyclopentylamine, diisopropylamine, sec-butylamine, 
2,5-dimethylpyrrolidine and 2,6-dimethylpiperidine instead of the 
previously used organic templating agents. 
SUMMARY OF THE INVENTION 
In accordance with the present invention, there is provided a process for 
preparing a medium pore size zeolite which comprises: 
(a) preparing an aqueous solution from (1) sources of an alkali metal 
oxide, alkaline earth metal oxide or mixtures thereof; (2) sources of an 
oxide selected from the oxides of aluminum, iron, gallium, indium, 
titanium, or mixtures thereof; (3) sources of an oxide selected from 
oxides of silicon, germanium or mixtures thereof; and (4) at least one 
small, neutral amine capable of forming the zeolite, said amine containing 
(a) only carbon, nitrogen and hydrogen atoms, (b) one primary, secondary 
or tertiary, but not quaternary, amino group, and (c) a tertiary nitrogen 
atom, at least one tertiary carbon atom, or a nitrogen atom bonded 
directly to at least one secondary carbon atom; 
(b) maintaining the aqueous solution under conditions sufficient to form 
crystals of the zeolite; and 
(c) recovering the crystals of the zeolite, 
wherein said process is conducted in the absence of a quaternary ammonium 
compound. 
In a preferred embodiment, the present invention provides said process 
which is performed in the absence of any nitrogen-containing organic 
templating agent other than the small, neutral amine of this invention. 
Preferably, the medium pore size zeolites prepared by the process of this 
invention have unidimensional channels. 
The present invention also provides this process further comprising 
replacing alkali and/or alkaline earth metal cations of the recovered 
medium pore size zeolite, at least in part, by ion exchange with a cation 
or mixture of cations selected from the group consisting of hydrogen and 
hydrogen precursors, rare earth metals, and metals from Groups IIA, IIIA, 
IVA, IB, IIB, IIIB, IVB, VIB, and VIII of the Periodic Table of Elements. 
The present invention also provides a medium pore size zeolite composition, 
as-synthesized and in the anhydrous state, whose general composition, in 
terms of mole ratios, is as follows: 
______________________________________ 
YO.sub.2 /W.sub.2 O.sub.3 
.gtoreq.15 
Q/YO.sub.2 
0.02-0.10 
M.sub.2/n /YO.sub.2 
0.015-0.10 
______________________________________ 
wherein Y is silicon, germanium or a mixture thereof; W is aluminum, 
gallium, indium, iron, titanium, or mixtures thereof; Q is at least one 
small, neutral amine capable of forming said zeolite, said amine 
containing (a) only carbon, nitrogen and hydrogen atoms, (b) one primary, 
secondary or tertiary, but not quaternary, amino group, and (c) a tertiary 
nitrogen atom, at least one tertiary carbon atom, or a nitrogen atom 
bonded directly to at least one secondary carbon atom; M is an alkali 
metal cation, alkaline earth metal cation or mixtures thereof; and n is 
the valence of M (i.e., 1 or 2), wherein said composition does not contain 
a quaternary ammonium compound. 
The present invention also provides a preferred embodiment of this 
composition wherein said composition does not contain any 
nitrogen-containing organic templating agent other than the small, neutral 
amine. 
Preferably, the as-synthesized medium pore size zeolite has unidimensional 
channels. 
Among other factors, the present invention is based on the discovery that 
medium pore size zeolites, particularly medium pore size zeolites having 
unidimensional channels, can be made using small, neutral amines such as 
isobutylamine, diisobutylamine, trimethylamine, cyclopentylamine, 
diisopropylamine, sec-butylamine, 2,5-dimethylpyrrolidine and 
2,6-dimethylpiperidine. It is particularly surprising that no other 
organic template (for example, a small amount of quaternary ammonium 
cation) is needed to induce the crystallization of the medium pore size 
zeolites. It is also surprising that zeolitic materials with silicon oxide 
to aluminum oxide molar ratios on the order of 15 or greater can be 
prepared with these neutral amines. 
Use of the small, neutral amines in the present invention provides several 
advantages. For example, the small, neutral amines are inexpensive 
compared to previously used organic templating agents. These amines are 
also easy to remove from the channel system of the zeolite product, and 
are potentially recyclable. In addition, they can be very selective for 
making some zeolites, and may result in formation of a product having very 
small crystallites which exhibit performance advantages. It has also been 
observed that in some cases the rate of crystallization of the product 
zeolite using this method is very fast. 
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS 
The present invention comprises: 
(a) preparing an aqueous solution from sources of oxides capable of forming 
a medium pore size zeolite and at least one small, neutral amine capable 
of forming said zeolite, said amine containing (a) only carbon, nitrogen 
and hydrogen atoms, (b) one primary, secondary or tertiary, but not 
quaternary, amino group, and (c) a tertiary nitrogen atom, at least one 
tertiary carbon atom, or a nitrogen atom bonded directly to at least one 
secondary carbon atom such as isobutylamine, diisobutylamine, 
trimethylamine, cyclopentylamine, diisopropylamine, sec-butylamine, 
2,5-dimethylpyrrolidine and 2,6-dimethylpiperidine; 
(b) maintaining the aqueous solution under conditions sufficient to form 
crystals of the zeolite; and 
(c) recovering the crystals of the zeolite, 
wherein said process is conducted in the absence of a quaternary ammonium 
compound. 
As used herein, the term "medium pore size zeolite" refers to zeolites 
which have 10-ring openings in their framework structure. Examples of such 
medium pore size zeolites include those designated SSZ-32, ZSM-23, ZSM-5 
and theta-1 (ZSM-22). 
Preferably, the medium pore size zeolites prepared in accordance with this 
invention have unidimensional channels. As used herein, the term 
"unidimensional" or "unidimensional channels" refers to the fact that the 
pores in the zeolite form channels which are essentially parallel and do 
not intersect. The term "multidimensional" or "multidimensional channels", 
on the other hand, refers to the fact that the pores in the zeolite form 
channels which do intersect each other. 
While not wishing to be bound or limited by any theory, it is believed that 
the small, neutral amines of this invention act as a templating agent in 
the reaction which forms the medium pore size zeolite. This is 
particularly surprising in view of the fact that the organic templating 
agents previously used to prepare medium pore size zeolites typically 
contain at least one quaternary ammonium atom in their structure, whereas 
the small, neutral amines used in the process of this invention do not. 
The process of the present invention comprises forming a reaction mixture 
from sources of alkali and/or alkaline earth metal (M) cations with 
valences n (i.e., 1 or 2); sources of an oxide of aluminum, iron, gallium, 
indium, titanium, or mixtures thereof (W); sources of an oxide of silicon, 
germanium or mixtures thereof (Y); at least one small, neutral amine of 
this invention (Q); and water, said reaction mixture having a composition 
in terms of mole ratios within the following ranges: 
______________________________________ 
Reactants General Preferred 
______________________________________ 
YO.sub.2 /W.sub.2 O.sub.3 
15-100 25-50 
OH.sup.- /YO.sub.2 
0.10-0.40 
0.15-0.30 
Q/YO.sub.2 0.05-0.50 
0.10-0.30 
M.sub.2/n /YO.sub.2 
0.05-0.40 
0.075-0.30 
H.sub.2 O/YO.sub.2 
10-70 25-50 
______________________________________ 
Typical sources of aluminum oxide for the reaction mixture include 
aluminates, alumina, hydrated aluminum hydroxides, and aluminum compounds 
such as AlCl.sub.3 and Al.sub.2 (SO.sub.4).sub.3. Typical sources of 
silicon oxide include silica hydrogel, silicic acid, colloidal silica, 
tetraalkyl orthosilicates, silica hydroxides, and fumed silicas. Gallium, 
iron, and germanium can be added in forms corresponding to their aluminum 
and silicon counterparts. Trivalent elements stabilized on silica colloids 
are also useful reagents. 
The small, neutral amines useful in the practice of this invention are 
those which are capable of forming the desired zeolite (i.e., one having 
medium pore size and preferably unidimensional channels) and which contain 
(a) only carbon, nitrogen and hydrogen atoms, (b) one primary, secondary 
or tertiary, but not quaternary, amino group, and (c) a tertiary nitrogen 
atom, at least one tertiary carbon atom, or a nitrogen atom bonded 
directly to at least one secondary carbon atom. The small, neutral amines 
of this invention may be represented by the following formula: 
EQU (R.sup.1, R.sup.2, R.sup.3)N 
wherein the amine contains only carbon, hydrogen and nitrogen atoms; 
R.sup.1, R.sup.2, and R.sup.3 are H, C.sub.1 -C.sub.4 alkyl groups, or 
R.sup.1 and R.sup.2 together are an alkylene group which forms a 5 or 6 
membered ring with the nitrogen atom, provided, however, that not all of 
R.sup.1, R.sup.2, and R.sup.3 are H; the amine contains a total of about 
three to about eight carbon atoms; and the amine contains a tertiary 
nitrogen atom, at least one tertiary carbon atom, or a nitrogen atom 
bonded directly to at least one secondary carbon atom. Preferably, when 
R.sup.1, R.sup.2, or R.sup.3 is an alkyl group having more than two carbon 
atoms, it is a branched chain alkyl group, such as isopropyl, isobutyl or 
sec-butyl. 
As used herein the term "small" refers to the fact that the amine has a 
total of three to about eight carbon atoms, and the term "neutral" refers 
to the fact that the nitrogen atom does not have a positive charge. While 
some protonation of the amine may occur in solution, it should be 
emphasized that (1) the nitrogen atom of the amine does not have a 
positive charge when in neat form, and (2) the amine does not contain a 
quaternary ammonium atom, i.e., does not contain a nitrogen atom bonded to 
four organic (non-hydrogen) groups. Also, the amines useful in this 
invention are not considered to be linear amines, i.e., they contain some 
branching in their structure (as opposed to a linear amine such as 
butylamine). 
In preparing the medium pore size zeolites in accordance with the present 
invention, the reactants and the small, neutral amine are dissolved in 
water and the resulting reaction mixture is maintained at an elevated 
temperature until crystals are formed. The temperatures during the 
hydrothermal crystallization step are typically maintained from about 
100.degree. C. to about 250.degree. C., preferably from about 140.degree. 
C. to about 200.degree. C. The crystallization period is generally from 
about 2 days to about 15 days, typically about 4 days. Preferably the 
crystallization period is from about 2 days to about 7 days. 
The hydrothermal crystallization is usually conducted under pressure and 
usually in an autoclave so that the reaction mixture is subject to 
autogenous pressure. The reaction mixture should be stirred during 
crystallization. 
Once the crystals have formed, the solid product is separated from the 
reaction mixture by standard mechanical separation techniques, such as 
filtration. The crystals are water-washed and then dried, e.g., at 
90.degree. C. to 150.degree. C. for from 8 to 24 hours, to obtain the 
as-synthesized zeolite crystals. The drying step can be performed at 
atmospheric or subatmospheric pressures. 
During the hydrothermal crystallization step, the crystals can be allowed 
to nucleate spontaneously from the reaction mixture. The reaction mixture 
can also be seeded with crystals of the desired zeolite both to direct, 
and accelerate the crystallization, as well as to minimize the formation 
of any undesired crystalline phases. When seed crystals are used, 
typically about 0.5% to about 5.0% by weight (based on the weight of 
silica used in the reaction mixture) of the seed crystals are added. 
Due to the unpredictability of the factors which control nucleation and 
crystallization in the art of crystalline oxide synthesis, not every 
combination of reagents, reactant ratios, and reaction conditions will 
result in crystalline products. Selecting crystallization conditions which 
are effective for producing crystals may require routine modifications to 
the reaction mixture or to the reaction conditions, such as temperature, 
and/or crystallization time. Making these modifications are well within 
the capabilities of one skilled in the art. 
The medium pore size zeolite product made by the process of this invention 
has an as-synthesized composition comprising, in terms of mole ratios in 
the anhydrous state, the following: 
______________________________________ 
YO.sub.2 /W.sub.2 O.sub.3 
.gtoreq.15 
Q/YO.sub.2 
0.02-0.10 
M.sub.2/n /YO.sub.2 
0.015-0.10 
______________________________________ 
wherein Y is silicon, germanium or a mixture thereof; W is aluminum, 
gallium, indium, iron, titanium, or mixtures thereof; Q is at least one 
small, neutral amine of this invention; M is an alkali metal cation, 
alkaline earth metal cation or mixtures thereof; and n is the valence of 
M, wherein said composition does not contain a quaternary ammonium 
compound. Preferably, Y is silicon, W is aluminum, and M is potassium. 
Typically, the zeolite is thermally treated (calcined) prior to use as a 
catalyst. Usually, it is desirable to remove the alkali metal cation by 
ion exchange and replace it with hydrogen, ammonium, or any desired metal 
ion. The zeolite can be leached with chelating agents, e.g., EDTA or 
dilute acid solutions, to increase the silica/alumina mole ratio. The 
zeolite can also be steamed; steaming helps stabilize the crystalline 
lattice to attack from acids. The zeolite can be used in intimate 
combination with hydrogenating components, such as tungsten, vanadium, 
molybdenum, rhenium, nickel, cobalt, chromium, manganese, or a noble 
metal, such as palladium or platinum, for those applications in which a 
hydrogenation-dehydrogenation function is desired. Typical replacing 
cations can include hydrogen and hydrogen precursors, rare earth metals, 
and metals from Groups IIA, IIIA, IVA, IB, IIB, IIIB, IVB, VIB, and VIII 
of the Periodic Table of Elements. Of the replacing cations, hydrogen and 
cations of metals such as rare earth, Mn, Ca, Mg, Zn, Cd, Pt, Pd, Ni, Co, 
Ti, Al, Sn, Ga, In and Fe are particularly preferred. 
The zeolite products were identified by their X-ray diffraction (XRD) 
pattern. The X-ray powder diffraction patterns were determined by standard 
techniques. The radiation was the K-alpha/doublet of copper. The peak 
heights I and the positions, as a function of 2P where P is the Bragg 
angle, were read from the relative intensities, 100.times.I/I.sub.o where 
I.sub.o is the intensity of the strongest line or peak, and d, the 
interplanar spacing in Angstroms corresponding to the recorded lines, can 
be calculated. 
The X-ray diffraction pattern of Table I is representative of a calcined 
medium pore size, unidimensional SSZ-32 zeolite made in accordance with 
this invention. Minor variations in the diffraction pattern can result 
from variations in the silica-to-alumina mole ratio of the particular 
sample due to changes in lattice constants. In addition, sufficiently 
small crystals will affect the shape and intensity of peaks, leading to 
significant peak broadening. The variation in the scattering angle (two 
theta) measurements, due to instrument error and to differences between 
individual samples, is estimated at .+-.0.20 degrees. 
TABLE I 
______________________________________ 
CALCINED SSZ-32 (MADE WITH ISOBUTYLAMINE) 
2Theta d Rel I.sup.a 
______________________________________ 
7.90.sup.b 11.18 VS 
8.12.sup.b 10.88 VS 
8.86 9.97 M 
11.38 7.76 S 
14.60 6.06 W 
15.86 5.58 W 
16.32 5.43 W 
18.12 4.89 W 
19.72 4.50 VS 
20.96 4.24 VS 
22.86 3.89 VS 
24.02 3.70 VS 
24.62 3.61 S-VS 
25.28 3.52 M 
25.98 3.43 S 
28.26 3.16 W 
31.60 2.83 W 
35.52 2.52 S 
______________________________________ 
.sup.a The Xray patterns provided are based on a relative intensity scale 
in which the strongest line in the Xray pattern is assigned a value of 
100: W(weak) is less than 20; M(medium) is between 20 and 40; S(strong) i 
between 40 and 60; VS(very strong) is greater than 60. 
.sup.b These two peaks may have significant overlap, and are sometimes 
treated as a single peak. 
Table IA below shows a typical X-ray diffraction pattern for a calcined 
SSZ-32 zeolite made in accordance with this invention. In Table IA, the 
intensity (I) of the peaks or lines is expressed as the intensity relative 
to the strongest peak or line in the pattern, i.e., I/I.sub.o .times.100 
TABLE IA 
______________________________________ 
CALCINED SSZ-32 (MADE WITH ISOBUTYLAMINE) 
2Theta d I/I.sub.o .times. 100 
______________________________________ 
7.90 11.18 71.8 
8.12 10.88 86.1 
8.86 9.97 32.6 
11.38 7.76 49.3 
14.60 6.06 6.4 
15.86 5.58 11.4 
16.32 5.43 14.6 
18.12 4.89 10.2 
19.72 4.50 100.0 
20.96 4.24 73.9 
22.86 3.89 92.1 
24.02 3.70 92.1 
24.62 3.61 65.4 
25.28 3.52 35.7 
25.98 3.43 46.0 
28.26 3.16 13.3 
31.60 2.83 16.2 
35.52 2.52 50.4 
______________________________________ 
A representative X-ray diffraction pattern for the medium pore size, 
unidimensional ZSM-23 zeolite may be found in U.S. Pat. No. 4,076,842, 
issued Feb. 28, 1978 to Plank et al. The X-ray diffraction pattern for 
ZSM-23 made in accordance with this invention does not differ 
significantly from that shown by Plank et al. 
A representative X-ray diffraction pattern for medium pore size, 
multidimensional ZSM-5 zeolite may be found in U.S. Pat. No. 3,702,886, 
issued in 1972. The X-ray diffraction pattern of Table II is that of a 
ZSM-5 zeolite made in accordance with this invention. 
TABLE II 
______________________________________ 
AS-SYNTHESIZED ZSM-5 
2Theta d Rel I 
______________________________________ 
7.94 11.13 M 
8.84 10.00 S 
14.79 5.98 W 
20.86 4.25 W 
23.09 3.85 VS 
23.69 3.75 M 
______________________________________ 
Table IIA below shows the X-ray diffraction pattern of as-synthesized ZSM-5 
made in accordance with this invention, including the intensities of the 
peaks or lines. 
TABLE IIA 
______________________________________ 
AS-SYNTHESIZED ZSM-5 
2Theta d I/I.sub.0 .times. 100 
______________________________________ 
7.94 11.13 28.4 
8.84 10.00 52.6 
14.79 5.98 9.0 
20.86 4.25 11.3 
23.09 3.85 100.0 
23.69 3.75 22.9 
______________________________________ 
The X-ray diffraction pattern of Table III is representative of a medium 
pore size, unidimensional theta-1 zeolite made in accordance with the 
present invention. 
TABLE III 
______________________________________ 
AS-SYNTHESIZED THETA-1 
2Theta d Rel I 
______________________________________ 
8.15 10.84 VS 
10.16 8.70 W 
12.77 6.93 W 
16.32 5.43 W 
19.40 4.57 W 
20.34 4.36 VS 
24.56 3.62 VS 
24.67 3.47 M 
35.58 2.52 M 
______________________________________ 
Table IIIA below shows an X-ray diffraction pattern representative of 
as-synthesized theta-1 made in accordance with this invention, including 
the intensities of the peaks or lines. 
TABLE IIIA 
______________________________________ 
AS-SYNTHESIZED THETA-1 
2Theta d I/I.sub.o .times. 100 
______________________________________ 
8.15 10.84 63.8 
10.16 8.70 14.6 
12.77 6.93 19.1 
16.32 5.43 7.0 
19.40 4.57 9.0 
20.34 4.36 100.0 
24.56 3.62 65.1 
24.67 3.47 35.8 
35.58 2.52 21.1 
______________________________________ 
Calcination can also result in changes in the intensities of the peaks as 
well as minor shifts in the diffraction pattern. The zeolite produced by 
exchanging the metal or other cations present in the zeolite with various 
other cations (such as H.sup.+ or NH.sub.4.sup.+) yields essentially the 
same diffraction pattern, although again, there may be minor shifts in the 
interplanar spacing and variations in the relative intensities of the 
peaks. Notwithstanding these minor perturbations, the basic crystal 
lattice remains unchanged by these treatments. 
The medium pore size zeolites prepared by the present process are useful in 
hydrocarbon conversion reactions. Hydrocarbon conversion reactions are 
chemical and catalytic processes in which carbon-containing compounds are 
changed to different carbon-containing compounds. Examples of hydrocarbon 
conversion reactions include catalytic cracking, hydrocracking, dewaxing, 
alkylation, isomerization, olefin and aromatics formation reactions, and 
aromatics isomerization.

The following examples demonstrate, but do not limit, the present 
invention. 
EXAMPLES 
There are numerous variations on the embodiments of the present invention 
illustrated in the Examples which are possible in light of the teachings 
supporting the present invention. It is therefore understood that within 
the scope of the following claims, the invention may be practiced 
otherwise than as specifically described or exemplified. 
Example 1 
Preparation of SSZ-32 Using Isobutylamine and 2.5 Wt % Seed Crystals 
In a 23 ml Teflon cup for a Parr 4745 reactor were added 3.0 ml of a 1.0N 
KOH solution, 6.3 grams of water, and 0.088 gram of Reheis F2000 hydrated 
alumina. After all the solids had dissolved, 2.25 grams of Nyacol 
2040-NH.sub.4 colloidal silica was added, followed by 0.22 gram of 
isobutylamine and 0.022 gram of SSZ-32 seeds. The reactor was closed and 
heated at 170.degree. C. in a Blue M oven while tumbling at 43 rpm for 
seven days. The resulting solids were collected by filtration and 
determined by X-ray diffraction ("XRD") to be SSZ-32. The XRD pattern had 
broad lines, indicative of small crystallites. 
Example 2 
Preparation of SSZ-32 Using Isobutylamine and 5.0 Wt % Seed Crystals 
The procedure of Example 1 was repeated, with the exception that 0.045 gram 
of SSZ-32 seeds was used. After seven days at 170.degree. C., the product 
was isolated and determined to be SSZ-32 with a minor amount of 
Cristobalite. 
Example 3 
Preparation of SSZ-32 Using Isobutylamine and 3.0 Wt % Seed Crystals 
One hundred forty grams of potassium hydroxide (87.2%) were dissolved in 
5834 grams of water. Reheis F2000 hydrated alumina (57.3 grams) was added 
and the mixture was stirred to dissolve all the solids. Nyacol 
2040-NH.sub.4 colloidal silica (1634.2 grams) was then added, followed by 
19.6 grams of SSZ-32 seed crystals. The resulting mixture was stirred as 
270.3 ml of isobutylamine was added to the reaction liner. The liner was 
transferred to a 5-gallon autoclave which was heated to 170.degree. C. and 
stirred at a rate of 75 rpm. After 48 hours, the product was filtered, 
washed with water, dried and determined to be SSZ-32. The product's 
SIO.sub.2 /Al.sub.2 O.sub.3 mole ratio was found to be 31. 
Example 4 
Preparation of SSZ-32 Using Isobutylamine With No Seed Crystals 
Five hundred forty-four ml of 1.0N KOH solution was mixed with 918.8 grams 
of water and 14.3 grams of Reheis F2000 hydrated alumina. The resulting 
mixture was stirred until all the solids had dissolved, and then 408.5 
grams of Nyacol 2040-NH.sub.4 colloidal silica was added, followed by 67.6 
ml of isobutylamine. The reaction liner was transferred to a 1-gallon 
autoclave which was heated to 170.degree. C. and stirred at a rate of 150 
rpm. After 60 hours, the resulting product was isolated and determined by 
XRD to be SSZ-32 with a trace amount of Cristobalite. 
Example 5 
Preparation of SSZ-32 Using Trimethylamine and 5 Wt % Seed Crystals 
In a 23 ml Teflon cup for a Parr 4745 reactor were added 0.75 gram of a 25% 
aqueous solution of trimethylamine, 2.88 ml of a 1.0N KOH solution, 0.085 
gram of Reheis F2000 hydrated alumina and 7.5 grams of water. After the 
solids dissolved, 0.89 gram of Cabosil M-5 fumed silica was added, 
followed by 0.045 gram of SSZ-32 seed crystals. After 12 days at 
170.degree. C. and 43 rpm, the resulting product was isolated and 
determined to be SSZ-32. 
Example 6 
Preparation of SSZ-32 Using Diisobutylamine and 3.0 Wt % Seed Crystals 
The procedure described in Example 4 was repeated with the following 
changes: 118.75 ml of diisobutylamine was used instead of isobutylamine, 
and 4.90 grams of SSZ-32 seed crystals was used. After stirring at 150 rpm 
at 170.degree. C. for 49 hours, the resulting product was isolated and 
determined by XRD to be SSZ-32. The SiO.sub.2 /Al.sub.2 O.sub.3 mole ratio 
of the product was 34. 
Example 7 
Preparation of SSZ-32 Using Diisopropylamine and 5 Wt % Seed Crystals 
In a Teflon liner for a Parr 1-liter autoclave were added 70.6 ml of a 1.0N 
KOH solution, 209.4 grams of water, and 2.06 grams of Reheis F2000 
hydrated alumina. The mixture was stirred until all the solids dissolved, 
then 21.8 grams of Cabosil M-5 fumed silica was added. Again, the mixture 
was stirred to dissolve the solids, and 9.9 ml of diisopropylamine was 
added, followed by 1.06 grams of SSZ-32 seed crystals. The resulting 
mixture was heated to 170.degree. C. and stirred at 150 rpm for six days. 
The resulting product was isolated and determined to be SSZ-32 with a 
minor amount of an unknown material. 
Example 8 
Preparation of ZSM-23 Using Isobutylamine 
The procedure described in Example 1 was repeated except that only 0.044 
gram of Reheis F2000 hydrated alumina was used, giving a starting 
SiO.sub.2 /Al.sub.2 O.sub.3 mole ratio of 67. In addition, 0.04 gram of 
SSZ-32 seed crystals was used. After three days at 170.degree. C. at 43 
rpm, the resulting product was isolated and determined to be ZSM-23 with a 
trace amount of Cristobalite. 
Example 9 
Preparation of ZSM-5 Using Cylopentylamine 
In a 23 ml Teflon cup for a Parr 4745 reactor were added 2.88 ml of a 1.0N 
KOH solution, 0.085 gram of Reheis F2000 hydrated alumina and 7.5 grams of 
water. After the solids were dissolved, 0.89 gram of Cabosil M-5 fumed 
silica was added, followed by 0.005 gram of SSZ-32 seed crystals and 0.256 
gram of cyclopentylamine. After 11 days at 170.degree. C. and 43 rpm, the 
resulting product was isolated and determined to be ZSM-5 with a trace 
amount of an unidentified impurity. Tables II and IIA above indicate the 
X-ray diffraction lines used to identify the product of this preparation. 
Example 10 
Preparation of Theta-1 Using Sec-butylamine 
In a 23 ml Teflon cup for a Parr 4745 reactor were added 2.88 grams of a 
1.0N KOH solution, 4.9 grams of water, and 0.084 gram of Reheis F2000 
hydrated alumina. After the solids dissolved, 2.17 grams of Nyacol 
2040-NH.sub.4 colloidal silica was added, followed by 0.29 ml of 
sec-butylamine and 0.04 gram of SSZ-32 seed crystals. After six days at 
170.degree. and 43 rpm, the resulting product was isolated and determined 
to be theta-1 (TON) with a trace amount of Cristobalite. The peaks in the 
XRD pattern for this product were very broad, indicative of very small 
crystallites. 
Example 11 
Preparation of Theta-1 Using Sec-butylamine 
The procedure described in Example 10 was repeated with the following 
changes: 0.056 gram of Reheis F2000 hydrated alumina was used (giving a 
starting SiO.sub.2 /Al.sub.2 O.sub.3 mole ratio of 50 rather than 33) and 
0.03 gram of theta-1 seed crystals was used. After four days at 
170.degree. C. and 43 rpm, the resulting product was isolated and 
determined by XRD to be theta-1 (TON) with a trace amount of Cristobalite. 
This XRD pattern for this product had much sharper peaks than that in 
Example 10. 
Example 12 
Preparation of Theta-1 Using Cis-2,5-dimethylpyrrolidine 
A solution was prepared using 0.083 gram Reheiss F-2000 hydrated alumina, 
0.20 gram solid KOH and 11.40 grams water. Cabosil fumed silica (0.90 
gram) and 3 mmole of cis-2,5-dimethylpyrrolidine were added to the 
reaction mixture which was then sealed and heated for ten days at 
170.degree. C. at 43 rpm. A crystalline product formed which was 
identified as theta-1. 
Example 13 
Preparation of Theta-1 Using Cis-2,6-dimethylpiperidine 
A solution was prepared using 2.58 grams of Reheiss F-2000 hydrated 
alumina, 6.20 grams of solid KOH and 337 grams of water. To this solution 
was added 10.50 grams of cis-2,6-dimethylpiperidine and 28 grams of 
Cabosil fumed silica. The resulting reaction mixture was brought to 
170.degree. C. over eight hours, held at this temperature for six days and 
stirred at 100 rpm over this period. The reaction produced a good quality 
theta-1 crystalline product.