Preparation of zeolites using organic template and amine

Crystalline zeolites are prepared using a small quantity of an organic templating compound and a larger quantity of an amine component containing at least one amine having from one to eight carbon atoms, ammonium hydroxide, or mixtures thereof.

BACKGROUND OF THE INVENTION 
Natural and synthetic zeolitic crystalline aluminosilicates are useful as 
catalysts and adsorbents. These aluminosilicates have distinct crystal 
structures which are demonstrated by X-ray diffraction. The crystal 
structure defines cavities and pores which are characteristic of the 
different species. The adsorptive and catalytic properties of each 
crystalline aluminosilicate are determined in part by the dimensions of 
its pores and cavities. Thus, the utility of a particular zeolite in a 
particular application depends at least partly on its crystal structure. 
Because of their unique molecular sieving characteristics, as well as their 
catalytic properties, crystalline aluminosilicates are especially useful 
in such applications as gas drying and separation and hydrocarbon 
conversion. Although many different crystalline aluminosilicates and 
silicates have been disclosed, there is a continuing need for new zeolites 
and silicates with desirable properties for gas separation and drying, 
hydrocarbon and chemical conversions, and other applications. 
Crystalline aluminosilicates are usually prepared from aqueous reaction 
mixtures containing alkali or alkaline earth metal oxides, silica, and 
alumina. "Nitrogenous zeolites" have been prepared from reaction mixtures 
containing an organic templating agent, usually a nitrogen-containing 
organic cation. Use of adamantane materials as the templates for making 
molecular sieves, particularly zeolites, is disclosed in U.S. Pat. No. 
4,665,110, issued May 12, 1987 to Zones which is hereby incorporated by 
reference. Adamantane materials are used as the templates in making a 
particular zeolite, SSZ-25, as disclosed in U.S. Pat. No. 4,826,667, 
issued May 2, 1989 to Zones et al., and co-pending application Ser. No. 
788,656 filed Nov. 6, 1991, which is a continuation of U.S. Ser. No. 
333,666 filed Apr. 5, 1989, both of which are hereby incorporated by 
reference. Use of hexamethyleneimine as the sole template in making 
zeolites similar to SSZ-25 is disclosed in U.S. Pats. No. 4,439,409, 
issued Mar. 27, 1984 to Puppe et al., and 4,954,325, issued Sep. 4, 1990 
to Rubin et al., while use of hexamethyleneimine and piperidine as the 
template in making a zeolite similar to SSZ-25 is disclosed in European 
Patent Application No. 0,293,032 A2, dated May 11, 1988. Use of 
adamantanamine materials in making a zeolite other than SSZ-25 is 
disclosed in U.K. Pat. Application GB 2,193,202 A, dated Feb. 3, 1988. 
Another zeolite utilizing amines in its manufacture is the intermediate 
pore-size zeolite ZSM-5. U.S. Pat. No. 4,495,166, issued Jan. 22, 1985 to 
Calvert et al., discloses use of a small amount of a quaternary ammonium 
compound such as tetrapropyl ammonium in conjunction with other amines to 
make ZSM-5. 
U.S. Pat. No. 5,057,296, issued Oct. 15, 1991 to Beck, discloses a process 
for producing ultra-large pore (sometimes called "mesoporous") crystalline 
materials using a two component system containing an organic template and 
an amine. These mesoporous materials have uniformly sized pores with a 
maximum perpendicular cross section of at least about 13 .ANG.. The second 
component of the system (the amine) is used to expand the pore size of 
these materials to the required 13 .ANG. or greater size by expanding the 
micelle created to form these mesoporous materials. 
The mesoporous materials of the Beck patent are considered very different 
from microporous materials, such as zeolites, and are not currently 
considered to be zeolites. 
SUMMARY OF THE INVENTION 
Crystalline, microporous aluminosilicate molecular sieves have been 
prepared in accordance with this invention using a highly effective new 
method. 
In accordance with this invention there is provided a method for preparing 
a zeolite selected from the group consisting of large pore zeolites, 
medium pore zeolites having unidimensional channels, and small pore 
zeolites, said method comprising: 
A. forming an aqueous reaction mixture comprising (1) a source of an oxide 
selected from silicon oxide, germanium oxide and mixtures thereof; (2) a 
source of an oxide selected from aluminum oxide, gallium oxide, iron 
oxide, boron oxide, titanium oxide and mixtures thereof; (3) a source of 
an alkali metal oxide; (4) an amine component comprising at least one 
amine containing one to eight carbon atoms, ammonium hydroxide, and 
mixtures thereof, and (5) an organic templating compound capable of 
forming said zeolite in the presence of said amine, wherein said amine is 
smaller than said organic templating compound; and 
B. maintaining said aqueous mixture under sufficient crystallization 
conditions until crystals are formed. 
There is further provided in accordance with this invention an improved 
method for preparing a zeolite selected from the group consisting of large 
pore zeolites, medium pore zeolites having unidimensional channels, and 
small pore zeolites from source materials for said zeolite and an organic 
templating compound, the improvement comprising employing a mixture of (1) 
said organic templating compound, and (2) an amine component comprising at 
least one amine containing one to eight carbon atoms, ammonium hydroxide, 
and mixtures thereof, said amine being smaller than said organic 
templating compound and said organic templating compound being capable of 
forming said zeolite in the presence of said amine. 
The present invention also provides these processes wherein the organic 
templating compound is selected from the group consisting of quaternary 
ammonium ions, cyclic amines and polar adamantyl derivatives. 
In a preferred embodiment, the present invention provides these processes 
wherein the organic templating compound is used in an amount less than 
that required to fill all of the micropore volume of the zeolite, i.e., an 
amount less than that required to crystallize the zeolite in the absence 
of the amines of this invention. 
In accordance with this invention, there is also provided a zeolite having 
an as-synthesized molar composition in an anhydrous state of (0.02 to 2.0) 
Q: (0.02 to 1.0) Z: (0.1 to 2.0) M.sub.2 O:W.sub.2O.sub.3 : (10 to 200) 
YO.sub.2, wherein M is an alkali metal cation; W is selected from 
aluminum, gallium, iron, boron, titanium and mixtures thereof; Y is 
selected from silicon, germanium, and mixtures thereof; Z is an amine 
component comprising at least one amine containing from one to eight 
carbon atoms, ammonium hydroxide, and mixtures thereof; and Q is an 
organic templating compound capable of forming the zeolite in the presence 
of the amine. 
Among other factors, the present invention is based on the discovery that 
amines which could be used in the synthesis of small and medium pore-sized 
zeolites can be used to synthesize the large-pore zeolites, such as the 
zeolite known as "Zeolite SSZ-25" or simply "SSZ-25", when used in 
conjunction with a small amount of an organic templating compound, such as 
an adamantane compound for SSZ-25. For example, ZSM-5, a medium pore size, 
multidimensional zeolite, was produced when the amine piperidine or 
cyclopentylamine was used alone (see Table 4, Examples 7 and 9) as the 
templating compound. However, when a small amount of an adamantyl 
quaternary ammonium ion was used in combination with piperidine or 
cyclopentylamine, the large-pore zeolite SSZ-25 resulted (see Table 4, 
Examples 6 and 8). This is particularly surprising since the amount of the 
adamantyl quaternary ammonium ion that was used was insufficient to cause 
significant growth of SSZ-25 if used without other amines present. 
It was wholly unexpected that amines such as isobutyl, neopentyl, or 
monomethyl amine could be used in relatively large quantities to produce 
zeolites such as SSZ-25 (see Table 3, Examples 3 and 4). Use of amines 
containing from one to eight carbon atoms provides significant cost 
savings over the method of using, e.g., an adamantyl quaternary ammonium 
ion as the sole source of organic component. Additional manufacturing 
flexibility can be obtained, since the process no longer depends on the 
availability of large quantities of one particular amine. 
In addition to these discoveries, it was found that polar adamantyl 
derivatives could be substituted for the more costly adamantyl quaternary 
ammonium ions being used in combination with the amine component to 
prepare SSZ-25 (see Examples 4, 5, 11, and 12), even though these polar 
adamantyl derivatives do not result in crystallization of SSZ-25 when used 
alone. Therefore, the cost of making SSZ-25 is further reduced. 
Substantial reductions in growth time also occurred unexpectedly when using 
the organic component mixture comprising an amine component and an organic 
templating compound. Growth times improved by a factor of from 
approximately two to approximately five in some examples. The commercial 
benefits of reduced plant construction cost for a given production rate 
will be substantial. 
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS 
The zeolites prepared in accordance with this invention are microporous, 
crystalline materials which have a mole ratio of an oxide selected from 
silicon oxide, germanium oxide, and mixtures thereof to an oxide selected 
from aluminum oxide, gallium oxide, iron oxide, boron oxide, titanium 
oxide and mixtures thereof in the range of 10 to 200. These zeolites 
further have a composition, as synthesized and in the anhydrous state, in 
terms of mole ratios as follows: (0.02 to 2.0)Q:(0.02 to l.0)Z:(0.1 to 
2.0)M.sub.2 O:W.sub.2 O.sub.3 :(10 to 200)YO.sub.2, wherein M is an alkali 
metal cation; W is selected from aluminum, gallium, iron, boron, titanium 
and mixtures thereof; Y is selected from silicon, germanium, and mixtures 
thereof; Z is an amine component comprising at least one amine containing 
from one to eight carbon atoms, ammonium hydroxide, and mixtures thereof; 
and Q is an organic templating agent capable of forming the zeolite in the 
presence of the amine. 
The present invention involves a novel method for preparing zeolites, 
comprising the preparation of an aqueous mixture that contains sources of 
a minor quantity of an organic templating compound capable of forming the 
desired zeolite, a larger quantity of an amine component containing at 
least one small amine ranging from 1 to 8 carbons, and/or ammonium 
hydroxide, and preferably seeds of the desired zeolite. Preferably, the 
amine component is an aliphatic or cycloaliphatic amine containing no more 
than 8 carbon atoms or mixtures of such compounds. 
This invention provides considerable cost improvement and flexibility in 
choice of organic components, and most surprisingly, faster 
crystallization rates. 
The present invention is useful in preparing large pore zeolites having 
unidimensional channels, large pore zeolites having multidimensional 
channels, medium pore zeolites having unidimensional channels, small pore 
zeolites having unidimensional channels and small pore zeolites having 
multidimensional channels. As used herein, the term "large pore zeolite" 
refers to zeolites which have .gtoreq.12-ring openings in their framework 
structure, the term "medium pore zeolites" refers to zeolites which have 
10-ring openings in their framework structure, and the term "small pore 
zeolites" refers to zeolites which have .ltoreq.8-ring openings in their 
framework structure. In addition, 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, and the 
term "multidimensional" or "multidimensional channels" refers to the fact 
that the pores in the zeolite form channels which do intersect each other. 
The reaction mixtures used to prepare the zeolites by the method of this 
invention may have a composition, in terms of mole ratios, falling within 
the following ranges: YO.sub.2 :W.sub.2 O.sub.3, 10:1 to 200:1; M:YO.sub.2 
0.01:1 to 0.50:1; OH.sup.- :YO.sub.2 0.01:1 to 0.60:1; Q/YO.sub.2 0.02:1 
to 1.00:1 and Z/YO.sub.2 0.02:1 to 1.00:1, where Y is selected from 
silicon, germanium, and mixtures thereof; W is selected from aluminum, 
gallium, iron, boron, titanium and mixtures thereof; M is an alkali metal 
cation; Z is an amine component comprising at least one amine containing 
from one to eight carbon atoms, ammonium hydroxide, or mixtures thereof; 
and Q is an organic templating compound capable of forming the zeolite in 
the presence of the amine. 
In some instances, the alkali metal cation level in the reaction mixture 
should be carefully controlled. It has now been discovered that alkali 
metal cation:SiO.sub.2 mole ratios much above 0.40 can favor the formation 
of the zeolites ZSM-5 and mordenite. Indeed, it has been found that at 
high alkali metal cation:SiO.sub.2 mole ratios, these two zeolites can be 
produced even in the absence of any organic templating compound. Thus, in 
order to ensure that the desired zeolite is produced, it is advisable to 
carefully control the alkali metal cation content in the reaction mixture. 
To this end, it may also be advisable to avoid using reagents such as 
sodium and potassium silicates. 
The present invention will now be described with respect to one of the 
zeolites, SSZ-25, which can be made using the method of this invention. It 
is understood that the other zeolites which can be made using this method 
are made in substantially the same way. SSZ-25 has a mole ratio of an 
oxide selected from silicon oxide, germanium oxide, and mixtures thereof 
to an oxide selected from aluminum oxide, gallium oxide, iron oxide, boron 
oxide, titanium oxide and mixtures thereof in the range of 10 to 200, and 
having the X-ray diffraction lines of Table 2 below. The zeolite further 
has a composition, as synthesized and in the anhydrous state, in terms of 
mole ratios of oxides as follows: (0.02 to 2.0)Q: (0.20 to 1.0)Z: (0.1 to 
2.0)M.sub.2 O:W.sub.2 O.sub.3 : (10 to 200)YO.sub.2, wherein M is an 
alkali metal cation; W is selected from aluminum, gallium, iron, boron, 
titanium and mixtures thereof; Y is selected from silicon, germanium, and 
mixtures thereof; and Q is an adamantane compound comprising at least one 
compound chosen from the group consisting of adamantane quaternary 
ammonium ions and polar adamantyl derivatives, and Z is an amine component 
comprising at least one amine chosen from amines containing from one to 
eight carbon atoms. SSZ-25 zeolites can have a YO.sub.2 :W.sub.2 O.sub.3 
mole ratio in the range of about 10 to 200. As prepared, the silica to 
alumina mole ratio is typically in the range of about 15:1 to about 100:1. 
Higher mole ratios can be obtained by treating the zeolite with chelating 
agents or acids to extract aluminum from the zeolite lattice. The silica 
to alumina mole ratio can also be increased by using silicon and carbon 
halides and other similar compounds. Preferably, SSZ-25 is an 
aluminosilicate wherein W is aluminum and Y is silicon. 
SSZ-25 zeolites, as synthesized in the presence of adamantyl compounds, 
have crystalline structures with the X-ray powder diffraction patterns 
containing the following characteristic lines: 
TABLE 1(a) 
______________________________________ 
2.theta. d/n Int. 
______________________________________ 
5.0 17.7 2 Br 
6.92 12.77 28 
7.06 12.52 26 
7.87 11.23 21 
8.78 10.07 1 
9.31 9.5 5 
9.93 8.91 42 
12.47 7.10 2 
12.79 6.92 7 
14.00 6.33 22 
14.21 6.23 24 
14.67 6.04 10 
15.87 5.58 15 
17.65 5.02 2 
18.89 4.70 5 
20.02 4.44 13 
20.15 4.41 12 
21.02 4.23 9 
21.48 4.14 11 
21.75 4.09 16 
22.28 3.99 14 
22.60 3.93 33 
23.60 3.77 25 
24.60 3.62 6 
24.84 3.58 10 
25.10 3.55 11 
25.88 3.44 67 
26.83 3.32 15 
27.64 3.23 20 
28.47 3.14 16 
29.00 3.08 1 
29.54 3.02 3 
31.42 2.85 3 
32.15 2.78 4 
33.23 2.70 7 
34.22 2.62 3 
______________________________________ 
TABLE 1(b) 
______________________________________ 
2.theta. d/n Int. 
______________________________________ 
7.08 12.49 40 
7.89 11.21 25 
8.89 9.95 6 
9.91 8.93 46 
11.43 7.74 1 
12.80 6.92 9 
14.00 6.33 Sh 
14.22 6.23 35 
14.68 6.03 13 
15.87 5.58 17 
17.75 5.00 2 
18.95 4.68 6 
19.38 4.58 10 
19.58 4.53 9 
20.05 4.43 13 
20.15 4.41 Sh 
21.00 4.23 5 
21.49 4.13 10 
21.78 4.08 17 
22.30 3.99 Sh 
22.58 3.94 35 
23.59 3.77 25 
24.55 3.63 Sh 
24.82 3.59 10 
25.07 3.55 5 
25.85 3.45 68 
26.48 3.37 3 
26.85 3.32 16 
27.64 3.23 19 
28.46 3.14 14 
28.98 3.08 3 
29.60 3.02 4 
31.42 2.85 4 
32.18 2.78 5 
33.21 2.70 7 
34.22 2.62 2 
______________________________________ 
As can be seen in Tables 1(a) and l(b), X-ray diffraction patterns of the 
as synthesized SSZ-25 will vary. 
After calcination, the SSZ-25 zeolites have a crystalline structure whose 
X-ray powder diffraction pattern shows the following characteristic lines 
as indicated in Table 2 below: 
TABLE 2 
______________________________________ 
2.theta. d/n I/I.sub.o 
______________________________________ 
3.4 25.5 17 
7.19 12.30 100 
8.04 11.00 55 
10.06 8.78 63 
14.35 6.17 40 
16.06 5.51 17 
22.77 3.90 38 
23.80 3.74 20 
26.08 3.417 65 
______________________________________ 
The X-ray powder diffraction patterns were determined by standard 
techniques. The radiation was the K-alpha/doublet of copper and a 
scintillation counter spectrometer with a strip-chart pen recorder was 
used. The peak heights I and the positions, as a function of 2.theta. 
where .theta. is the Bragg angle, were read from the spectrometer chart. 
From these measured values, the relative intensities, 100I/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. Variations in the diffraction pattern can result from 
variations in the organic component used in the preparation and from 
variations in the silica-to-alumina mole ratio from sample to sample. The 
zeolite produced by exchanging the metal or other cations present in the 
zeolite with various other cations yields a similar diffraction pattern, 
although there can be shifts in interplanar spacing as well as variations 
in relative intensity. Calcination can also cause shifts in the X-ray 
diffraction pattern. Notwithstanding these perturbations, the basic 
crystal lattice structure remains unchanged. 
Zeolites can be suitably prepared from an aqueous solution containing 
sources of an alkali metal oxide, an organic component mixture, an oxide 
of aluminum, gallium, iron, boron, titanium or mixtures thereof, and an 
oxide of silicon or germanium, or mixture of the two. The reaction mixture 
should have a composition in terms of mole ratios falling within the 
following ranges: 
______________________________________ 
Broad Preferred 
______________________________________ 
M/YO.sub.2 0.01-0.50 
0.10-0.20 
OH.sup.- /YO.sub.2 
0.01-0.60 
0.10-0.30 
H.sub.2 O/YO.sub.2 
10-120 20-50 
Q/YO.sub.2 0.02-1.00 
0.02-0.10 
YO.sub.2 /W.sub.2 O.sub.3 
10-200 15-120 
Z/YO.sub.2 0.05-1.00 
0.20-0.40 
______________________________________ 
where M is an alkali metal, preferably sodium or potassium; Y is silicon, 
germanium, or both; Q is an adamantane component comprising at least one 
compound chosen from the group consisting of adamantane quaternary 
ammonium ions and polar adamantyl derivatives, Z is an amine component 
comprising at least one amine chosen from amines containing from one to 
eight carbon atoms, ammonium hydroxide and mixtures thereof; and W is 
aluminum, gallium, iron, boron, titanium or mixtures thereof. 
The reaction mixture can also be seeded with as-made zeolite crystals both 
to direct and accelerate the crystallization, as well as to minimize the 
formation of undesired aluminosilicate contaminants. 
By "polar adamantyl derivative" is meant adamantyl compounds which contain 
either (a) a nitrogen atom that can bear a lone pair of electrons or an 
electropositive charge, or (b) an hydroxyl substituent. By "adamantane 
quaternary ammonium ions" is meant adamantane materials containing a 
nitrogen atom which is chemically bonded to four substituents, at least 
three of which are methyl groups and at least one of which is an adamantyl 
compound. By an "adamantane compound" or "adamantane component" is meant a 
composition comprising at least one compound chosen from the group 
consisting of adamantane quaternary ammonium ions and polar adamantyl 
derivatives. By "amine component" is meant at least one amine chosen from 
the group of amines having from one to eight carbon atoms, ammonium 
hydroxide or mixtures thereof. Preferably, the amine is an aliphatic or 
cycloaliphatic amine containing no more than 8 carbon atoms and mixtures 
thereof. By "organic component mixture" is meant a mixture comprising the 
organic templating compound and the amine component. By "seed material" is 
meant a material which reduces growth times of the zeolite crystals. 
One example of a seed material for SSZ-25 is as-made SSZ-25. By "SSZ-25" is 
meant a material consisting substantially of the crystalline material with 
an X-ray diffraction pattern corresponding substantially to that of Table 
2 after calcination of the as-made material. 
The reaction mixture is prepared using standard zeolitic preparation 
techniques. 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, boron, titanium 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 organic component mixture used to prepare SSZ-25 may contain adamantane 
quaternary ammonium ions. The adamantane quaternary ammonium ions are 
derived from a compound of the formula: 
##STR1## 
wherein each of Z.sup.1, Z.sup.2 and Z.sup.3 independently is lower alkyl 
and most preferably methyl; A.theta. is an anion which is not detrimental 
to the formation of the zeolite; and each of R.sup.1, R.sup.2 and R.sup.3 
independently is hydrogen, or lower alkyl and most preferably hydrogen; 
and 
##STR2## 
wherein each of R.sup.4, R.sup.5 and R.sup.6 independently is hydrogen or 
lower alkyl; and most preferably hydrogen; each of Z.sup.4, Z.sup.5 and 
Z.sup.6 independently is lower alkyl and most preferably methyl; and 
A.sup.- is an anion which is not detrimental to the formation of the 
zeolite. Mixtures of compounds having formula (I) and/or (II) can also be 
used. By "lower alkyl" is meant alkyl of from about 1 to 5 carbon atoms. 
A.sup.- is an anion which is not detrimental to the formation of the 
zeolite. Representative of the anions include halide, e.g., fluoride, 
chloride, bromide and iodide, hydroxide, acetate, sulfate, carboxylate, 
etc. Hydroxide is the most preferred anion. It may be beneficial, for 
example, to ion-exchange the halide for hydroxide ion, thereby reducing 
the alkali metal hydroxide quantity required. 
The adamantane quaternary ammonium compounds are prepared by methods known 
in the art. 
The organic component mixture used to prepare SSZ-25 may contain a polar 
adamantyl derivative. The polar adamantyl derivative is commercially 
available and includes compounds such as 1-adamantanamine, 
2-adamantanamine, 1-aminomethyl adamantane, 1-adamantanol, 2-adamantanol 
and mixtures of such compounds. Use of the polar adamantyl derivative 
instead of adamantane quaternary ammonium ions permits a reduction of 
production cost when making SSZ-25. 
The organic component mixture used to prepare SSZ-25 also contains an amine 
component comprising at least one amine chosen from amines containing from 
one to eight carbon atoms, ammonium hydroxide and mixtures thereof. These 
amines are smaller than the organic templating compound used to prepare 
the zeolite. As used herein, the term "smaller", when used with respect to 
the amine component, means that the amine is lower in molecular weight 
than the organic templating compound and typically is no larger physically 
than the organic templating compound. Non-exclusive examples of these 
amines include isopropylamine, isobutyl amine, n-butylamine, piperidine, 
4-methylpiperidine, cyclohexylamine, 1,1,3,3-tetramethyl butyl amine and 
cyclopentylamine and mixtures of such amines. 
Use of these amines permits a reduction in the amount of the adamantane 
compound (or other organic templating compound) used, and significant cost 
savings result. In fact, it has quite surprisingly been found that, by 
using the amine component of the present invention, the amount of organic 
templating compound can be reduced to a level below that which is required 
to fill the micropore volume of the zeolite, i.e., an amount less than 
that required to crystallize the zeolite in the absence of the amines of 
this invention. In addition, use of these amines unexpectedly promotes 
faster growth times when used in combination with seed material. 
In the previous SSZ-25 synthesis that relied completely on the quaternized 
adamantammonium derivative in larger quantity, a minimum of usually 160 
hours was required to obtain the crystallized SSZ-25. By using an 
adamantane compound in conjunction with an amine component and seed 
material, crystallization periods of approximately 50 hours have been 
observed. A significant cost reduction in commercial use will occur as a 
result of the substantial reduction in crystallization period, since less 
equipment time is needed to grow SSZ-25 for a given production rate. 
The reaction mixture used to prepare SSZ-25 can be seeded with material 
such as SSZ-25 crystals both to direct, and accelerate the 
crystallization, as well as to minimize the formation of undesired 
aluminosilicate contaminants. 
The preferred reaction mixture for making SSZ-25 comprises 
1-adamantanamine, isobutylamine, and SSZ-25 seeds as formulated in Example 
17. 
The reaction mixture is maintained at an elevated temperature until the 
crystals of the zeolite are formed. The temperatures during the 
hydrothermal crystallization step are typically maintained from about 
140.degree. C. to about 200.degree. C., preferably from about 160.degree. 
C. to about 180.degree. C., and most preferably from about 170.degree. C. 
to about 180.degree. C. The crystallization period is typically greater 
than 1 day and preferably from about 2 days to about 5 days. 
The hydrothermal crystallization is conducted under pressure and usually in 
an autoclave so that the reaction mixture is subject to autogenous 
pressure. The reaction mixture can be stirred during crystallization. 
During the hydrothermal crystallization step, the zeolite crystals can be 
allowed to nucleate spontaneously from the reaction mixture. 
Once the zeolite 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 120.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. 
The synthetic zeolites can be used as synthesized or can be thermally 
treated. By "thermal treatment" is meant heating to a temperature from 
about 200.degree. C. to about 820.degree. C., either with or without the 
presence of steam. Usually, it is desirable to remove the alkali metal 
cation by ion exchange and replace it with hydrogen, ammonium, or any 
desired metal ion. Thermal treatment including steam helps to stabilize 
the crystalline lattice from attack by acids. 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 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 metal cations, e.g., rare earth, Group IIA 
and Group VIII metals, as well as their mixtures. Of the replacing 
metallic cations, cations of metals such as rare earth, Mn, Ca, Mg, Zn, 
Cd, Pt, Pd, Ni, Co, Ti, Al, Sn, Fe and Co are particularly preferred. 
The hydrogen, ammonium, and metal components can be exchanged into the 
zeolite. The zeolite can also be impregnated with the metals, or the 
metals can be physically intimately admixed with the zeolite using 
standard methods known to the art. Also, the metals can be occluded in the 
crystal lattice by having the desired metals present as ions in the 
reaction mixture from which the zeolite is prepared. 
Typical ion exchange techniques involve contacting the synthetic zeolite 
with a solution containing a salt of the desired replacing cation or 
cations. Although a wide variety of salts can be employed, chlorides and 
other halides, nitrates, acetates, and sulfates are particularly 
preferred. Representative ion exchange techniques are disclosed in a wide 
variety of patents including U.S. Pat. Nos. 3,140,249, issued Jul. 7, 1964 
to Plank et al., 3,140,251, issued Jul. 7, 1964 to Plank et al., and 
3,140,253, issued Jul. 7, 1964 to Plank et al. Ion exchange can take place 
either before or after the zeolite is calcined. 
Following contact with the salt solution of the desired replacing cation, 
the zeolite is typically washed with water and dried at temperatures 
ranging from 65.degree. C. to about 315.degree. C. After washing, the 
zeolite can be calcined in air or inert gas at temperatures ranging from 
about 200.degree. C. to 820.degree. C. for periods of time ranging from 1 
to 48 hours, or more, to produce a catalytically active product especially 
useful in hydrocarbon conversion processes. 
Regardless of cations present in the synthesized form of the zeolite, the 
spatial arrangement of the atoms which form the basic crystal lattice of 
the zeolite remains essentially unchanged. The exchange of cations has 
little, if any, effect on the zeolite lattice structures. 
The zeolites can be formed into a wide variety of physical shapes. 
Generally speaking, the zeolite can be in the form of a powder, a granule, 
or a molded product, such as extrudate having particle size sufficient to 
pass through a 2-mesh (Tyler) screen and be retained on a 400-mesh (Tyler) 
screen. In cases where the catalyst is molded, such as by extrusion with 
an organic binder, the aluminosilicate can be extruded before drying, or 
dried or partially dried and then extruded. The zeolite can be composited 
with other materials resistant to the temperatures and other conditions 
employed in organic conversion processes. By "matrix material" is meant 
other materials with which the zeolite is combined to make catalyst 
particles. Such matrix materials may include active and inactive materials 
and synthetic or naturally occurring zeolites as well as inorganic 
materials such as clays, silica and metal oxides. The latter may occur 
naturally or may be in the form of gelatinous precipitates, sols, or gels, 
including mixtures of silica and metal oxides. Use of an active material 
in conjunction with the synthetic zeolite, i.e., combined with it, tends 
to improve the conversion and selectivity of the catalyst in certain 
organic conversion processes. Inactive materials can suitably serve as 
diluents to control the amount of conversion in a given process so that 
products can be obtained economically without using other means for 
controlling the rate of reaction. Catalysts produced with zeolites or 
other components incorporated therein may be subject to further ion 
exchange steps, metal inclusion, thermal treatment, and other processing 
steps as previously discussed for the zeolite alone. 
Frequently, zeolite materials have been incorporated into naturally 
occurring clays, e.g., bentonite and kaolin. These materials, i.e., clays, 
oxides, etc., function, in part, as binders for the catalyst. It is 
desirable to provide a catalyst having good crush strength, because in 
petroleum refining the catalyst is often subjected to rough handling. This 
tends to break the catalyst down into powders which cause problems in 
processing. 
Naturally occurring clays which can be composited with the synthetic 
zeolites of this invention include the montmorillonite and kaolin 
families, which families include the sub-bentonites and the kaolins 
commonly known as Dixie, McNamee, Georgia and Florida clays or others in 
which the main mineral constituent is halloysite, kaolinite, dickite, 
nacrite, or anauxite. Fibrous clays such as sepiolite and attapulgite can 
also be used as supports. Such clays can be used in the raw state as 
originally mined or can be initially subjected to calcination, acid 
treatment or chemical modification. 
In addition to the foregoing materials, the zeolites can be composited with 
porous matrix materials and mixtures of matrix materials such as silica, 
alumina, titania, magnesia, silica:alumina, silica-magnesia, 
silica-zirconia, silica-thoria, silica-beryllia, silica-titania, 
titania-zirconia as well as ternary compositions such as 
silica-alumina-thoria, silica-alumina-zirconia, silica-alumina-magnesia 
and silica-magnesia-zirconia. The matrix can be in the form of a cogel. 
The zeolites can also be composited with other zeolites such as synthetic 
and natural faujasites (e.g., X and Y), erionites, and mordenites. They 
can also be composited with purely synthetic zeolites such as those of the 
ZSM series. The combination of zeolites can also be composited in a porous 
inorganic matrix. Zeolites are useful in hydrocarbon conversion reactions. 
Examples of these uses are described in U.S. Pat. No. 4,826,667, issued 
May 2, 1989 to Zones et al., which is incorporated herein by reference. 
While the foregoing description has involved primarily the preparation of 
SSZ-25, it should be emphasized that other zeolites can be prepared using 
the method of this invention. For example, the zeolites known as SSZ-32, 
SSZ-28, EU-1, SSZ-35, ferrierite, ZSM-12 and ZSM-22 type structures have 
been successfully prepared in accordance with this invention. When it is 
desired to prepare these or other zeolites by the method of this 
invention, an organic templating compound capable of producing the desired 
zeolite in the presence of the amine component is employed. 
In general, the mole ratios of the components of the reaction mixtures used 
to prepare these zeolites will be the same as, or very similar to, those 
described above with respect to SSZ-25, except, of course that the 
structure of the organic templating compound (Q) used will depend upon the 
zeolite desired to be made. Also, the composition of the reaction mixture 
may vary slightly depending upon the zeolite desired to be made. 
Zeolite SSZ-32 
To prepare SSZ-32, an N-lower alkyl-N'-isopropylimidazolium cation may be 
used as the organic templating compound. These compounds have the general 
formula: 
##STR3## 
wherein R is lower alkyl containing 1 to 5 carbon atoms (preferably methyl 
or isopropyl) and A.sup.- is an anion which is not detrimental to the 
formation of the zeolite. Representative anions include halogens, e.g., 
fluoride, chloride, bromide and iodide, hydroxide, acetate, sulfate, 
carboxylate, and the like. Hydroxide is the most preferred anion. 
The preferred N-lower alkyl-N'-isopropylimidazolium cations are 
N,N'-diisopropylimidazolium cation and N-methyl-N'-isopropylimidazolium 
cation. 
Another type of organic template which can be employed to prepare SSZ-32 
are N,N,N-trialkyl-1,1,3,3-tetraalkylbutyl ammonium cations, which have 
the general formula: 
##STR4## 
where R and A are as defined above for formula III. 
Preferably, R is methyl. 
The as-made SSZ-32 zeolites have a crystalline structure whose X-ray powder 
diffraction pattern shows the following characteristic lines as indicated 
in Table A below: 
TABLE A 
______________________________________ 
2Theta d/n I/I.sub.o 
______________________________________ 
8.04 10.99 30.2 
8.81 10.03 12.6 
11.30 7.82 23.1 
18.08 4.90 8.0 
19.56 4.53 61.2 
20.81 4.26 65.1 
22.75 3.90 100.0 
23.89 3.72 85.6 
24.59 3.62 34.9 
25.16 3.53 21.9 
25.91 3.43 41.8 
26.89 3.31 7.2 
28.13 3.17 11.5 
29.30 3.04 5.9 
31.48 2.84 6.0 
______________________________________ 
ZSM-22 type zeolite 
The organic templating compounds which may be used to prepare ZSM-22 type 
structures include imidazole salts characterized by the following formula: 
##STR5## 
wherein X.sup.1 and X.sup.2 independently represent a linear alkyl group 
containing from 1 to about 10 carbon atoms and A.sup.- represents an 
anion which is not detrimental to the formation of the desired molecular 
sieve, such as those described above for formula (III). 
The alkyl substitutions on the nitrogen atoms of the imidazole ring are any 
straight chain alkyl group having from 1 to about 10 carbon atoms. Thus, 
this moiety includes methyl, ethyl, propyl, n-butyl, as well as linear 
pentyl, hexyl, heptyl, octyl, nonyl, and decyl groups. 
ZSM-22 type zeolites can also be prepared using piperidine derivatives as 
the organic templating compound. A preferred piperidine derivative is 
2,6-dimethylpiperidine. 
The as-made ZSM-22 zeolites have a crystalline structure whose X-ray powder 
diffraction pattern shows the following characteristic lines as indicated 
in Table B below: 
TABLE B 
______________________________________ 
2Theta d/n I/I.sub.o 
______________________________________ 
8.13 10.87 37.7 
10.15 8.70 4.0 
12.72 6.95 18.6 
16.51 5.36 2.6 
19.36 4.58 3.0 
20.28 4.38 100.0 
24.11 3.69 75.3 
24.53 3.63 75.2 
25.64 3.47 63.9 
______________________________________ 
Zeolite SSZ-28 
To prepare SSZ-28, sources of an N,N-dimethyl-tropinium or 
N,N-dimethyl-3-azonium bicyclo3.2.2!nonane cation may be used as the 
organic templating compound. 
The as-made SSZ-28 zeolites have a crystalline structure whose X-ray powder 
diffraction pattern shows the following characteristic lines as indicated 
in Table C below: 
TABLE C 
______________________________________ 
2Theta d/n I/I.sub.o 
______________________________________ 
7.62 11.58 11.0 
11.28 7.83 7.1 
12.94 6.84 9.6 
15.36 5.76 64.7 
17.09 5.18 100.0 
18.24 4.86 32.0 
18.80 4.71 31.8 
19.66 4.51 40.1 
21.40 4.14 26.0 
24.85 3.58 12.1 
26.18 3.40 64.5 
26.49 3.40 28.0 
26.85 3.32 28.6 
28.14 3.17 13.7 
29.75 3.00 13.0 
______________________________________ 
Zeolite EU-1 
The organic templating compounds useful in preparing EU-1 are alkylated 
derivatives of a polymethylene .alpha.-.omega. diamine having the formula: 
##STR6## 
wherein n is in the range from 3 to 12 and R.sup.7 to R.sup.12 which may 
be the same or different, can be alkyl or hydroxyalkyl groups, containing 
from 1 to 8 carbon atoms and up to five of the groups R.sup.7 -R.sup.12 
can be hydrogen, and A.sup.- represents an anion which is not detrimental 
to the formation of the desired zeolite, such as those described above for 
formula (III). 
Preferred alkylated polymethylene diamine derivatives include alkylated 
hexamethylene diamines, especially methylated hexamethylene diamines, for 
example 1,6-N,N,N,N',N',N'-hexamethyl hexamethylene diammonium salts 
(e.g., halide, hydroxide, sulphate, silicate, aluminate). 
Other organic templating compounds which can be used to prepare EU-1 in 
accordance with the present invention are 
4-benzyl-N,N-dimethylpiperidinium compounds, which have the following 
structure: 
##STR7## 
where A.sup.- represents an anion which is not detrimental to the 
formation of the desired molecular sieve, such as those described above 
for formula (III). 
The as-made EU-1 zeolites have a crystalline structure whose X-ray powder 
diffraction pattern shows the following characteristic lines as indicated 
in Table D below: 
TABLE D 
______________________________________ 
2Theta d/n I/I.sub.o 
______________________________________ 
7.92 11.15 48.3 
8.70 10.15 21.5 
9.06 9.75 6.0 
12.87 6.87 2.3 
19.04 4.65 39.7 
20.53 4.32 100.0 
22.15 4.01 61.8 
23.26 3.82 31.8 
23.94 3.71 20.0 
25.97 3.43 9.3 
26.52 3.36 9.4 
27.29 3.26 34.8 
______________________________________ 
Zeolite SSZ-35 
SSZ-35 can be prepared in accordance with the present invention using a 
polycyclic compound having the following formula as the organic templating 
compound: 
##STR8## 
where A.sup.- is an anion which is not detrimental to the formation of 
the desired zeolite, such as those described above for formula (III). 
Another organic templating compound which may be used to prepare SSZ-35 in 
accordance with this invention is 
N-ethyl-N-methyl-9-azoniabicyclo3.3.1!nonane which has the following 
structure: 
##STR9## 
where L.sup.- is an anion which is not detrimental to the production of 
the molecular sieve, such as those described above for formula (III). 
The anion for the salt may be essentially any anion such as halide or 
hydroxide which is not detrimental to the formation of the molecular 
sieve. As used herein, "halide" refers to the halogen anions particularly 
fluorine, chlorine, bromine, iodine, and combinations thereof. Thus, 
representative anions include hydroxide, acetate, sulfate, carboxylate, 
tetrafluoroborate, and halides, such as fluoride, chloride, bromide and 
iodide. Hydroxide and iodide are particularly preferred as anions. 
The N-ethyl-N-methyl-9-azabicyclo3.3.1!nonane templating compound used in 
making SSZ-35 is a conformationally constrained organic molecule. Altering 
the structure of this relatively rigid molecule can lead to a change in 
the molecular sieve obtained, presumably due to the differing steric 
demands of each template. However, increasing the steric requirements of 
the template may lead to a decrease in crystallization rate as well as a 
decrease in template solubility in the reaction mixture. If the template 
is not sufficiently soluble, or if the template has particularly bulky 
substituent groups, it may be difficult to form crystals in the reaction 
mixture. Addition of a surfactant to the reaction mixture may help to 
solubilize the template. 
The N-ethyl-N-methyl-9-azabicyclo3.3.1!nonane templating compound may be 
synthesized by conventional techniques. In general, this template can be 
prepared in an efficient manner by condensing glutardialdehyde with a 
primary amine and acetone-dicarboxylic acid, all of which are readily 
available, inexpensive reagents. The intermediate formed is the 
2,4-dicarboxy-3-keto-9-aza-bicyclononane, a di-.beta.-ketoester which is 
easily decarboxylated upon treatment with acid. The 3-keto-moiety is 
removed by a classic Wolff-Kishner reduction (hydrazine, triethylene 
glycol, potassium hydroxide), and the desired quaternary ammonium salt is 
obtained by reaction of the resulting amine with an alkyl halide. 
Following purification by recrystallization, the halide salt can be 
ion-exchanged to the corresponding hydroxide salt using an ion-exchange 
resin. 
The as-made SSZ-35 zeolites have a crystalline structure whose X-ray powder 
diffraction pattern shows the following characteristic lines as indicated 
in Table E below: 
TABLE E 
______________________________________ 
2Theta d/n I/I.sub.o 
______________________________________ 
7.99 11.05 100.0 
9.65 9.16 7.4 
15.37 5.76 17.0 
18.88 4.69 43.7 
19.32 4.59 62.6 
19.82 4.48 30.1 
21.60 4.11 17.8 
22.80 3.89 20.8 
25.68 3.47 29.6 
27.41 3.25 27.3 
29.20 3.06 17.6 
______________________________________ 
Zeolite ZSM-12 
Zeolite ZSM-12 can be prepared in accordance with this invention using a 
heterocyclic compound having the following formula as the organic 
templating compound: 
##STR10## 
wherein L.sup.- is an anion which is not detrimental to the formation of 
the ZSM-12. 
The as-made ZSM-12 zeolite has a crystalline structure whose X-ray powder 
diffraction pattern shows the following characteristic lines as indicated 
in Table F below: 
TABLE F 
______________________________________ 
2Theta d I/I.sub.o .times. 100 
______________________________________ 
7.43 11.05 24.4 
8.70 10.15 9.5 
18.87 4.70 15.6 
19.90 4.46 6.9 
20.75 4.28 100.0 
22.93 3.88 52.8 
26.26 3.39 13.3 
27.82 3.20 4.8 
35.41 2.53 11.4 
______________________________________ 
Another surprising aspect of this invention is that, when some organic 
templating compounds are used in combination with the amine component of 
this invention, a different zeolite structure is made than that which 
would be obtained in the absence of the amine component. For example, 
SSZ-35 has been made from organic templating compounds which are salts of 
1,3,3,8,8-pentamethyl-3-azonia3.2.1!octane. These compounds have a 
molecular structure of the general formula: 
##STR11## 
wherein L.sup.- is an anion which is not detrimental to the formation of 
the zeolite. However, when these organic templating compounds are used in 
combination with the amine component of this invention, the resulting 
zeolite is SSZ-25. 
Each organocation of this 1,3,3,8,8-pentamethyl-3-azonia3.2.1!octane 
family has a charged quaternary ammonium heteroatom and two rings, one of 
which includes the quaternary ammonium heteroatom as a bridging unit. The 
anion for the salt may be essentially any anion such as halide or 
hydroxide which is not detrimental to the formation of the molecular 
sieve. As used herein, "halide" refers to the halogen anions particularly 
fluorine, chlorine, bromine, iodine, and combinations thereof. Thus, 
representative anions include hydroxide, acetate, sulfate, carboxylate, 
tetrafluoroborate, and halides such as fluoride, chloride, bromide, and 
iodide. Hydroxide and iodide are particularly preferred as anions. 
Many of the organocation salts which have been disclosed in the prior art 
for use as templates for molecular sieve synthesis are conformationally 
flexible. These molecules can adopt many conformations in aqueous 
solution, and several templates can give rise to a single crystalline 
product. In contrast, the 
1,3,3,8,8-pentamethyl-3-azoniabicyclo3.2.1!octane templating compounds 
described above used to make SSZ-25 are conformationally constrained 
organic molecules. 
These 1,3,3,8,8-pentamethyl-3-azoniabicyclo3.2.1!octane compounds can be 
prepared by converting camphoric anhydride to the corresponding N-methyl 
imide using methyl amine. The imide can be reduced to N-methylcamphidine 
upon reduction with lithium aluminum hydride in ether, and the desired 
quaternary ammonium salt obtained by treatment with methyl iodide. 
Following purification by recrystallization, the halide salt can be 
ion-exchanged to the corresponding hydroxide salt using an ion-exchange 
resin.

EXAMPLES 
EXAMPLE 1 
Preparation of N,N,N-Trimethyl-1-adamantanammonium Hydroxide 
(Template A) 
Ten (10) grams of 1-adamantanamine (Aldrich) was dissolved in a mixture of 
29 gms tributylamine and 60 mls dimethylformamide. The mixture was chilled 
in an ice bath. 
28.4 Grams of methyl iodide were added dropwise to the chilled solution 
with continuous stirring. After several hours, crystals appear. The 
reaction was continued overnight and allowed to come to room temperature. 
The crystals were filtered and washed with tetrahydrofuran and then 
diethyl ether before vacuum drying. Additional product was obtained by 
adding enough diethyl ether to the reaction filtrate to produce two phases 
and then with vigorous stirring acetone was added until the solution just 
became one phase. Continued stirring produced crystallization at which 
time the solution can be chilled to induce further crystallization. The 
product has a melting point near 300.degree. C. (decomp.) and the 
elemental analyses and NMR are consistent with the known structure. The 
vacuum-dried iodide salt was then ion-exchanged with ion-exchange resin AG 
1X8 (in molar excess) to the hydroxide form. The exchange was performed 
over a column or more preferably by overnight stirring of the resin beads 
and the iodide salt in an aqueous solution designed to give about a 0.5 
molar solution of the organic hydroxide. This produces Template A. 
EXAMPLE 2 
Preparation of N,N,N-Trimethyl-2-adamantanammonium Hydroxide 
(Template B) 
Five (5) grams of 2-adamantanone (Aldrich Chemical Co.) was mixed with 2.63 
gms of formic acid (88%) and 4.5 gms of dimethyl formamide. The mixture 
was then heated in a pressure vessel for 16 hours at 190.degree. C. Care 
should be taken to anticipate the increase in pressure the reaction 
experiences due to CO.sub.2 evolution. The reaction was conveniently 
carried out in a Parr 4748 reactor with teflon liner. The workup consists 
of extracting N,N-dimethyl-2-adamantanamine from a basic (pH=12) aqueous 
solution with diethyl ether. The various extracts were dried with Na.sub.2 
SO.sub.4, the solvent removed and the product taken up in ethyl acetate. 
An excess of methyl iodide was added to a cooled solution which was then 
stirred at room temperature for several days. The crystals were collected 
and washed with diethyl ether to give N,N,N-trimethyl-2-adamantammonium 
iodide. The product is checked by microanalysis for C, H, and N. The 
conversion to the hydroxide form was carried out analogously to Template A 
above. 
EXAMPLE 3 
Synthesis of SSZ-25 
0.50 Grams of a 0.55 molar solution of Template B and 0.22 gms of isobutyl 
amine and 0.03 gms.of SSZ-25 seeds were mixed with 0.20 gms KOH(s), 0.083 
gms of Reheis F-2000 hydrated alumina (50-56 wt% aluminum oxide), and 11.4 
Ml H.sub.2 O. After thorough mixing, 0.90 gms of Cabosil M5 was blended in 
as silica source. The reaction mixture was heated in the Teflon cup of a 
Parr 4745 reactor at 170.degree. C. at 43 rpm for 4 days. Workup produced 
crystalline SSZ-25. 
EXAMPLE 4 
Synthesis of SSZ-25 
In this example, the use of a nonquaternized amine is demonstrated. The 
same experiment was run as in Example 3, millimole of 1-adamantanamine 
(Aldrich) replaced late B. The product was again SSZ-25. 
EXAMPLE 5 
Synthesis of SSZ-25 
This example also demonstrates the use of a nonquaternized amine. 12.5 
Grams of Reheis F-2000 was dissolved in 30 gms of kOH(s) and 1500 Ml 
H.sub.2 O 7.5 gms of 1-adamantanamine (Aldrich Chemical Co.), and 75 gms 
of 4-methylpiperidine (Aldrich Chemical Co.). 3 Grams of SSZ-25 seed 
crystals and 437 of Ludox AS-30 were added last. The reaction was run in a 
1-gallon autoclave with Hastelloy C liner at 170.degree. C. and 75 rpm. 
After 6 days, the product was crystalline SSZ-25 
Refer to Table 3 for a summary of Examples 3-5. 
TABLE 3 
______________________________________ 
Adamantyl 
Ex. No. 
Component Amine Product 
______________________________________ 
3 Template B Isobutyl Amine 
SSZ-25 
4 1-adamantanamine 
Isobutyl Amine 
SSZ-25 
5 1-adamantanamine 
4-methylpiperidine 
SSZ-25 
______________________________________ 
EXAMPLES 6-9 
Synthesis of SSZ-25 
In these examples, the effectiveness or necessity of the adamantyl 
quaternary ammonium ion is demonstrated by comparison of reaction products 
with and without such a component at only a 0.02 molar ratio to silica. 
This quantity of adamantyl component is insufficient to fill the micropore 
volume of the growing SSZ-25 and additional organic is needed, and was 
subsequently found in the micropore system. Table 4 shows the comparative 
examples. 
TABLE 4 
______________________________________ 
SSZ-25 Syntheses With and Without Adamantyl 
Quaternary Ammonium Ion Synthesis Promoters.sup.(a) 
Adamantyl SiO.sub.2 / 
Ex. No. 
Component Amine.sup.(b) 
Al.sub.2 O.sub.3 
KOH/SiO.sub.2 
Product 
______________________________________ 
6 B Piperidine 35 0.20 SSZ-25 
7 -- Piperidine 35 0.20 ZSM-5 
8 B Cyclopentylamine 
35 0.20 SSZ-25 
9 -- Cyclopentylamine 
35 0.20 ZSM-5 
______________________________________ 
.sup.(a) Experiments carried out as in Example 3. 
.sup.(b) Experiments carried out using amine/SiO.sub.2 ratio of 0.20. 
B = Template B (Example 2). 
EXAMPLES 10-12 
Synthesis of SSZ-25 
In these experiments, the variation of the adamantane compound is 
demonstrated. The experiments are carried out as in Example 3. Recall that 
in Example 7, the use of piperidine alone, even in the presence of SSZ-25 
seeds, produced ZSM-5. 
Refer to Table 5 for the variations of the adamantane compound. 
TABLE 5 
______________________________________ 
Adamantyl SiO.sub.2 / 
Ex. No. 
Component* 
Piperidine/SiO.sub.2 
Al.sub.2 O.sub.3 
KOH/SiO.sub.2 
Product 
______________________________________ 
10 A 0.20 35 0.20 SSZ-25 
11 C 0.20 35 0.20 SSZ-25 
12 D 0.20 35 0.20 SSZ-25 
______________________________________ 
*At a level of 0.02 relative to SiO.sub.2. 
A = Template A (Example 1). 
C = Quaternized derivative of 1aminomethyl-adamantane. 
D = 1adamantanol. 
EXAMPLES 13-20 
Synthesis of SSZ-25 
In these examples, SSZ-25 was formulated, using SSZ-25 as a seed material 
in two examples and using no seed in two examples to determine whether 
seed material was necessary to produce SSZ-25. The final product was 
SSZ-25 in all cases. In the examples where 4-methylpiperidine was used as 
the amine component, improvement in growth time was observed at three days 
for the example utilizing seed material. In the examples where 
isobutylamine was used as the amine component, the growth time was 
improved by at least a factor of two for the example utilizing seed 
material. 
In these examples, 1 millimole of 1-adamantanamine was mixed with 15 
millimoles of silica as SiO.sub.2 and 3 millimoles of the smaller amine. 
All of the remaining ratios of reactants and run conditions were as in 
Example 3. In Examples 13-16, the major amine was 4-methylpiperidine. For 
Examples 17-20, the major amine was isobutylamine. Reaction conditions 
were substantially the same as those in Example 3. Results are summarized 
in Table 6. 
TABLE 6 
______________________________________ 
Effect of seed on type of zeolite produced and growth time 
for SSZ-25 
Ex. No. 
Amine Component 
Seed Used 
Growth Time 
Product 
______________________________________ 
13 4-methylpiperidine 
SSZ-25 3 days SSZ-25 + 
amorphous 
14 4-methylpiperidine 
SSZ-25 6 days SSZ-25 
15 4-methylpiperidine 
none 3 days amorphous 
16 4-methylpiperidine 
none 6 days SSZ-25 
17 isobutylamine 
SSZ-25 3 days SSZ-25 
18 isobutylamine 
SSZ-25 6 days SSZ-25 
19 isobutylamine 
none 3 days SSZ-25 + 
amorphous 
20 isobutylamine 
none 6 days SSZ-25 
______________________________________ 
EXAMPLES 21-28 
Synthesis of SSZ-32 
A basic reaction solution was made by combining 0.50 millimoles of 
N,N'-diisopropylimidazolium hydroxide late E), 0.20 gram of solid KOH, 
0.083 gram of Reheis F-2000 hydrated aluminum hydroxide, and a total of 
11.4 ml of water. To this solution, 0.90 gram of Cabosil M-5 fumed silica 
(98%) was added. Finally, 0.20 gram of isobutyl amine was added. These 
reactants were all combined in the Teflon cup of a Parr 4745 reactor (23 
ml capacity). The reactor was sealed and loaded onto a rotating spit in a 
Blue kM oven and heated at 170.degree. C. for 6 days while rotating at 43 
rpm. After this time period, the reactor was cooled in air, the resulting 
solid product filtered and washed with water in a funnel, and then 
air-dried. The resulting powder was analyzed by X-ray diffraction (XRD) 
and found to be SSZ-32. An elemental analysis showed the SiO.sub.2 
/Al.sub.2 O.sub.3 ratio for this product to be 28. 
This reaction was repeated using each in turn the amines listed in Table 7 
below in the quantities also shown in that table. The product of each 
reaction was SSZ-32. 
TABLE 7 
______________________________________ 
Example No. Amine Amount of Amine 
______________________________________ 
22 methylamine 0.5 g* 
23 NH.sub.4 OH 0.66 g** 
24 butylamine 0.20 g 
25 t-butylamine 0.25 g 
26 dipropylamine 0.22 g 
27 isopropylamine 
0.20 g 
28 cyclopentylamine 
0.26 g 
______________________________________ 
*40% aqueous solution 
**30% aqueous solution 
These examples demonstrate that SSZ-32 can be prepared using very low 
levels of the organic templating compound, in this case a mole ratio of 
Template E/SiO.sub.2 of only 0.033. In fact, his reaction has been 
successfully conducted with this ratio as low as 0.02. Without the 
addition of the small mine (isobutyl amine) the product, SSZ-32, would not 
be achieved at this low level of templating compound. 
EXAMPLE 29-39 
A procedure similar to that described in Examples 21-28 was used to prepare 
the zeolites listed in the table below except that the organic template 
was N,N,N-trimethyl-1,1,3,3-tetramethyl butyl ammonium hydroxide (Template 
E') and the amines were those listed in the table below. 
The reaction mixture contained the following mole ratios: 
Template E'/SiO.sub.2 =0.02 
Amine/SiO.sub.2 =0.20 
Also, the reaction mixture contained 0.6 wt. % SSZ-32 seed crystals. 
______________________________________ 
Ex No. Amine Growth Time Product 
______________________________________ 
29* isobutylamine 
9 days SSZ-32 (plus trace 
amorphous) 
30* cyclopentylamine 
9 days SSZ-32 
31* isopropylamine 
7 days SSZ-32 
32* n-butylamine 7 days ZSM-5 (plus minor 
amount of 
ferrierite) 
33* piperidine 7 days ZSM-5 
34* cyclohexylamine 
18 days ferrierite (plus 
minor amount of 
cristobalite) 
35* 1,1,3,3-tetra- 
7 days SSZ-32 
methylbutyl amine 
36** isobutylamine 
6 days SSZ-32 (plus trace 
cristobalite) 
37** isopropylamine 
7 days SSZ-32 (plus 
cristobalite) 
38** n-butylamine 7 days cristobalite + ZSM- 
5 + quartz 
39** piperidine 7 days ZSM-5 (plus - 
amorphous material) 
______________________________________ 
*Silica source was Nyacol colloidal silica. 
**Silica source was Cabosil fumed silica. 
EXAMPLE 40 
Synthesis of SSZ-28 
The same reaction as described in Example 21 for SSZ-32 was carried out, 
but with the following changes. The organic templating compound was 
N,N-dimethyl-3-azonium bicyclo3.2.2!nonane hydroxide (Template F), and 
the ratio of Template F/SiO.sub.2 was 0.05 (i.e., 0.75 millimoles of 
Template F was used in the reaction). The resulting product was found to 
be SSZ-28 by XRD. 
This example also demonstrates that zeolites can be prepared by the method 
of this invention using very low amounts of organic templating compound. 
EXAMPLE 41 
Synthesis of EU-1 
The same reaction using the same molar quantities described in Example 40 
was carried out with the exception that the organic templating compound 
was the diquaternary ammonium compound 1,6-N,N,N,N',N',N'-hexamethyl 
hexamethylene diammonium hydroxide (Template G). The resulting product was 
analyzed by XRD and found to be zeolite EU-1. 
EXAMPLE 42 
Synthesis of EU-1 
0.62 Gram of a solution of 4-benzyl-N,N-dimethylpiperidinium hydroxide 
(0.485 mmol OH.sup.- /g), 0.08 gram of Reheis F2000 hydrated aluminum 
hydroxide, and 0.20 gram of solid KOH were dissolved in 11.4 grams of 
water. Isobutyl amine (0.22 gram) was added to this solution, followed by 
the addition of 0.90 gram of Cabosil M-5 fumed silica. The resulting 
reaction mixture was mixed thoroughly and sealed in a Parr 4745 reactor 
which was then heated to 170.degree. C. and rotated at 43 rpm. After 16 
days the reaction was complete, and the product which was isolated was 
determined by XRD to be EU-1. 
EXAMPLE 43 
Synthesis of SSZ-35 
The same reaction using the same molar quantities described in Example 40 
was carried out, except that the organic templating compound used was the 
polycyclic compound having formula VI above (Template H). The resulting 
product was determined by XRD to be SSZ-35. 
EXAMPLE 44 
Synthesis of ZSM-22 type structures 
The same reaction described in Example 21 was carried out, except that the 
organic templating compound was 2,6-dimethylpiperidine (Template I) which 
was used in the ratio of Template I/SiO.sub.2 of 0.02. The resulting 
product was determined by XRD to be ZSM-22 type structures. 
EXAMPLE 45 
Using the procedure of Example 21 and the amines and organic templating 
compounds shown in Table 8, the zeolites also shown in Table 8 were 
prepared. 
TABLE 8 
______________________________________ 
Zeolite Amine Amount of Amine 
Template 
______________________________________ 
SSZ-28 cyclopentylamine 
0.26 g F 
SSZ-25 piperidine 0.26 g F 
EU-1 cyclopentylamine 
0.26 g G 
SSZ-35 cyclopentylamine 
0.26 g H 
SSZ-35 piperidine 0.26 g H 
ZSM-22 cyclopentylamine 
0.26 g I 
ZSM-22 piperidine 0.26 g I 
______________________________________ 
EXAMPLE 46 Synthesis of ZSM-12 
The same procedure described in Example 21 was performed, except that a 
piperidine-based templating agent (Template J) having the following 
structure: 
##STR12## 
was used in place of the imidazolium-based template employed in Example 
21. After 23 days of heating at 170.degree. C., the product was isolated 
and identified as ZSM-12. Elemental analysis showed the product to have a 
SiO.sub.2 /Al.sub.2 O.sub.3 mole ratio of 30.