Molecular sieve abstract
The present invention relates to new crystalline molecular sieve
SSZ-65 prepared using 1-[1-(4-chlorophenyl)-cyclopropylmethyl]-1-ethyl-pyrrolidinium
or 1-ethyl-1-(1-phenyl-cyclopropylmethyl)-pyrrolidinium cation as
a structure-directing agent, methods for synthesizing SSZ-65 and
processes employing SSZ-65 in a catalyst.
Molecular sieve claims
What is claimed is:
1. A molecular sieve having a mole ratio greater than about 15
of (1) an oxide of a first tetravalent element to (2) an oxide of
a trivalent element, pentavalent element, second tetravalent element
which is different from said first tetravalent element or mixture
thereof and having, after calcination, the X-ray diffraction lines
of Table II.
2. A molecular sieve having a mole ratio greater than about 15
of (1) an oxide selected from the group consisting of silicon oxide,
germanium oxide and mixtures thereof to (2) an oxide selected from
aluminum oxide, gallium oxide, iron oxide, boron oxide, titanium
oxide, indium oxide, vanadium oxide and mixtures thereof, and having,
after calcination, the X-ray diffraction lines of Table II.
3. A molecular sieve according to claim 2 wherein the oxides comprise
silicon oxide and aluminum oxide.
4. A molecular sieve according to claim 2 wherein the oxides comprise
silicon oxide and boron oxide.
5. A molecular sieve according to claim 2 wherein the oxide comprises
silicon oxide.
6. A molecular sieve according to claim 1 wherein said molecular
sieve is predominantly in the hydrogen form.
7. A molecular sieve according to claim 1 wherein said molecular
sieve is substantially free of acidity.
8. A molecular sieve according to claim 2 wherein said molecular
sieve is predominantly in the hydrogen form.
9. A molecular sieve according to claim 2 wherein said molecular
sieve is substantially free of acidity.
10. A molecular sieve having a composition, as synthesized and
in the anhydrous state, in terms of mole ratios as follows: TABLE-US-00012
YO.sub.2/W.sub.cO.sub.d >15 M.sub.2/n/YO.sub.2 0.01 0.03 Q/YO.sub.2
0.02 0.05
wherein Y is silicon, germanium or a mixture thereof; W is aluminum,
gallium, iron, boron, titanium, indium, vanadium or mixtures thereof;
c is 1 or 2; d is 2 when c is 1 or d is 3 or 5 when c is 2; M is
an alkali metal cation, alkaline earth metal cation or mixtures
thereof; n is the valence of M; and Q is a 1-[1-(4-chlorophenyl)-cyclopropylmethyl]-1-ethyl-pyrrolidinium
or 1-ethyl-1-(1-phenyl-cyclopropylmethyl)-pyrrolidinium cation.
11. A molecular sieve according to claim 10 wherein W is aluminum
and Y is silicon.
12. A molecular sieve according to claim 11 wherein W is boron
and Y is silicon.
13. A molecular sieve according to claim 11 wherein Q is a 1-[1-(4-chlorophenyl)-cyclopropylmethyl]-1-ethyl-pyrrolidinium
cation.
14. A molecular sieve according to claim 11 wherein Q is a 1-ethyl-1-(1-phenyl-cyclopropylmethyl)-pyrrolidinium
cation.
15. A method of preparing a crystalline material comprising (1)
an oxide of a first tetravalent element and (2) an oxide of a trivalent
element, pentavalent element, second tetravalent element which is
different from said first tetravalent element or mixture thereof
and having mole ratio of the first oxide to the second oxide greater
than 15 said method comprising contacting under crystallization
conditions sources of said oxides and a structure directing agent
comprising a 1-[1-(4-chlorophenyl)-cyclopropylmethyl]-1-ethyl-pyrrolidinium
or 1-ethyl-1-(1-phenyl-cyclopropylmethyl)-pyrrolidium cation.
16. The method according to claim 15 wherein the first tetravalent
element is selected from the group consisting of silicon, germanium
and combinations thereof.
17. The method according to claim 15 wherein the trivalent element,
pentavalent element or second tetravalent element is selected from
the group consisting of aluminum, gallium, iron, boron, titanium,
indium, vanadium and combinations thereof.
18. The method according to claim 17 wherein the trivalent element,
pentavalent element or second tetravalent element is selected from
the group consisting of aluminum, boron, titanium and combinations
thereof.
19. The method according to claim 16 wherein the first tetravalent
element is silicon.
20. The method according to claim 15 wherein the structure directing
agent comprises a 1-[1-(4-chlorophenyl)-cyclopropylmethyl]-1-ethyl-pyrrolidinium
cation.
21. The method according to claim 15 wherein the structure directing
agent comprises a 1-ethyl-1-(1-phenyl-cyclopropylmethyl)-pyrrolidinium
cation.
22. The method of claim 15 wherein the crystalline material has,
after calcination, the X-ray diffraction lines of Table II.
Molecular sieve description
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to new crystalline molecular sieve
SSZ-65 a method for preparing SSZ-65 using a 1-[1-(4-chlorophenyl)-cyclopropylmethyl]-1-ethyl-pyrrolidinium
or 1-ethyl-1-(1-phenyl-cyclopropylmethyl)-pyrrolidinium cation as
a structure directing agent and the use of SSZ-65 in catalysts for,
e.g., hydrocarbon conversion reactions.
2. State of the Art
Because of their unique sieving characteristics, as well as their
catalytic properties, crystalline molecular sieves and zeolites
are especially useful in applications such as hydrocarbon conversion,
gas drying and separation. Although many different crystalline molecular
sieves have been disclosed, there is a continuing need for new zeolites
with desirable properties for gas separation and drying, hydrocarbon
and chemical conversions, and other applications. New zeolites may
contain novel internal pore architectures, providing enhanced selectivities
in these processes.
Crystalline aluminosilicates are usually prepared from aqueous
reaction mixtures containing alkali or alkaline earth metal oxides,
silica, and alumina. Crystalline borosilicates are usually prepared
under similar reaction conditions except that boron is used in place
of aluminum. By varying the synthesis conditions and the composition
of the reaction mixture, different zeolites can often be formed.
SUMMARY OF THE INVENTION
The present invention is directed to a family of crystalline molecular
sieves with unique properties, referred to herein as "molecular
sieve SSZ-65" or simply "SSZ-65". Preferably, SSZ-65
is obtained in its silicate, aluminosilicate, titanosilicate, germanosilicate,
vanadosilicate or borosilicate form. The term "silicate"
refers to a molecular sieve having a high mole ratio of silicon
oxide relative to aluminum oxide, preferably a mole ratio greater
than 100 including molecular sieves comprised entirely of silicon
oxide. As used herein, the term "aluminosilicate" refers
to a molecular sieve containing both aluminum oxide and silicon
oxide and the term "borosilicate" refers to a molecular
sieve containing oxides of both boron and silicon.
In accordance with this invention, there is provided a molecular
sieve having a mole ratio greater than about 15 of (1) an oxide
of a first tetravalent element to (2) an oxide of a trivalent element,
pentavalent element, second tetravalent element different from said
first tetravalent element or mixture thereof and having, after calcination,
the X-ray diffraction lines of Table II.
Further, in accordance with this invention, there is provided a
molecular sieve having a mole ratio greater than about 15 of (1)
an oxide selected from silicon oxide, germanium oxide and mixtures
thereof to (2) an oxide selected from aluminum oxide, gallium oxide,
iron oxide, boron oxide, titanium oxide, indium oxide, vanadium
oxide and mixtures thereof and having, after calcination, the X-ray
diffraction lines of Table II below. It should be noted that the
mole ratio of the first oxide or mixture of first oxides to the
second oxide can be infinity, i.e., there is no second oxide in
the molecular sieve. In these cases, the molecular sieve is an all-silica
molecular sieve or a germanosilicate.
The present invention further provides such a molecular sieve having
a composition, as synthesized and in the anhydrous state, in terms
of mole ratios as follows:
TABLE-US-00001 YO.sub.2/W.sub.cO.sub.d 15 .infin. M.sub.2/n/YO.sub.2
0.01 0.03 Q/YO.sub.2 0.02 0.05
wherein Y is silicon, germanium or a mixture thereof; W is aluminum,
gallium, iron, boron, titanium, indium, vanadium or mixtures thereof;
c is 1 or 2; d is 2 when c is 1 (i.e., W is tetravalent) or d is
3 or 5 when c is 2 (i.e., d is 3 when W is trivalent or 5 when W
is pentavalent); M is an alkali metal cation, alkaline earth metal
cation or mixtures thereof; n is the valence of M (i.e., 1 or 2);
and Q is a 1-[1-(4-chlorophenyl)-cyclopropylmethyl]-1-ethyl-pyrrolidinium
or 1-ethyl-1-(1-phenyl-cycloproylmethyl)-pyrrolidinium cation.
In accordance with this invention, there is also provided a molecular
sieve prepared by thermally treating a zeolite having 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, indium oxide, vanadium
oxide and mixtures thereof greater than about 15 at a temperature
of from about 200.degree. C. to about 800.degree. C., the thus-prepared
zeolite having the X-ray diffraction lines of Table II. The present
invention also includes this thus-prepared molecular sieve which
is predominantly in the hydrogen form, which hydrogen form is prepared
by ion exchanging with an acid or with a solution of an ammonium
salt followed by a second calcination. If the zeolite is synthesized
with a high enough ratio of SDA cation to sodium ion, calcination
alone may be sufficient. For high catalytic activity, the SSZ-65
zeolite should be predominantly in its hydrogen ion form. It is
preferred that, after calcination, at least 80% of the cation sites
are occupied by hydrogen ions and/or rare earth ions. As used herein,
"predominantly in the hydrogen form" means that, after
calcination, at least 80% of the cation sites are occupied by hydrogen
ions and/or rare earth ions.
Also provided in accordance with the present invention is a method
of preparing a crystalline material comprising (1) an oxide of a
first tetravalent element and (2) an oxide of a trivalent element,
pentavalent element, second tetravalent element which is different
from said first tetravalent element, or mixture thereof and having
a mole ratio of the first oxide to the second oxide greater than
15 said method comprising contacting under crystallization conditions
sources of said oxides and a structure directing agent comprising
a 1-[1-(4-chlorophenyl)-cyclopropylmethyl]-1-ethyl-pyrrolidinium
or 1-ethyl-1-(1-phenyl-cyclopropylnethyl)-pyrrolidinium cation.
DETAILED DESCRIPTION OF THE INVENTION
The present invention comprises a family of crystalline, large
pore molecular sieves designated herein "molecular sieve SSZ-65"
or simply "SSZ-65". As used herein, the term "large
pore" means having an average pore size diameter greater than
about 6.0 Angstroms, preferably from about 6.5 Angstroms to about
7.5 Angstroms.
In preparing SSZ-65 a 1-[1-(4-chlorophenyl)-cyclopropylmethyl]-1-ethyl-pyrrolidinium
or 1-ethyl-1-(1-phenyl-cyclopropylmethyl)-pyrrolidinium cation is
used as a structure directing agent ("SDA"), also known
as a crystallization template. The SDA's useful for making SSZ-65
have the following structures: ##STR00001## ##STR00002##
The SDA cation is associated with an anion (X.sup.-) which may
be any anion that is not detrimental to the formation of the zeolite.
Representative anions include halogen, e.g., fluoride, chloride,
bromide and iodide, hydroxide, acetate, sulfate, tetrafluoroborate,
carboxylate, and the like. Hydroxide is the most preferred anion.
In general, SSZ-65 is prepared by contacting an active source of
one or more oxides selected from the group consisting of monovalent
element oxides, divalent element oxides, trivalent element oxides,
tetravalent element oxides and/or pentavalent elements with the
1-[1-(4-chlorophenyl)-cyclopropylmethyl]-1-ethyl-pyrrolidinium or
1-ethyl-1-(1-phenyl-cyclopropylmethyl)-pyrrolidinium cation SDA.
SSZ-65 is prepared from a reaction mixture having the composition
shown in Table A below.
TABLE-US-00002 TABLE A Reaction Mixture Typical Preferred YO.sub.2/W.sub.aO.sub.b
>15 30 70 OH--/YO.sub.2 0.10 0.50 0.20 0.30 Q/YO.sub.2 0.05 0.50
0.10 0.20 M.sub.2/n/YO.sub.2 0.02 0.40 0.10 0.25 H.sub.2O/YO.sub.2
30 80 35 45 where Y, W, Q, M and n are as defined above, and a is
1 or 2 and b is 2 when a is 1 (i.e., W is tetravalent) and b is
3 when a is 2 (i.e., W is trivalent).
In practice, SSZ-65 is prepared by a process comprising: (a) preparing
an aqueous solution containing sources of at least one oxide capable
of forming a crystalline molecular sieve and a 1-[1-(4-chlorophenyl)-cyclopropylmethyl]-1-ethyl-pyrrolidinium
or 1-ethyl-1-(1-phenyl-cyclopropylmethyl)-pyrrolidinium cation having
an anionic counterion which is not detrimental to the formation
of SSZ-65; (b) maintaining the aqueous solution under conditions
sufficient to form crystals of SSZ-65; and (c) recovering the crystals
of SSZ-65.
Accordingly, SSZ-65 may comprise the crystalline material and the
SDA in combination with metallic and non-metallic oxides bonded
in tetrahedral coordination through shared oxygen atoms to form
a cross-linked three dimensional crystal structure. The metallic
and non-metallic oxides comprise one or a combination of oxides
of a first tetravalent element(s), and one or a combination of a
trivalent element(s), pentavalent element(s), second tetravalent
element(s) different from the first tetravalent element(s) or mixture
thereof. The first tetravalent element(s) is preferably selected
from the group consisting of silicon, germanium and combinations
thereof. More preferably, the first tetravalent element is silicon.
The trivalent element, pentavalent element and second tetravalent
element (which is different from the first tetravalent element)
is preferably selected from the group consisting of aluminum, gallium,
iron, boron, titanium, indium, vanadium and combinations thereof.
More preferably, the second trivalent or tetravalent element is
aluminum or boron.
Typical sources of aluminum oxide for the reaction mixture include
aluminates, alumina, aluminum colloids, aluminum oxide coated on
silica sol, hydrated alumina gels such as Al(OH).sub.3 and aluminum
compounds such as AlCl.sub.3 and Al.sub.2(SO.sub.4).sub.3. Typical
sources of silicon oxide include silicates, silica hydrogel, silicic
acid, fumed silica, colloidal silica, tetra-alkyl orthosilicates,
and silica hydroxides. Boron, as well as gallium, germanium, titanium,
indium, vanadium and iron, can be added in forms corresponding to
their aluminum and silicon counterparts.
A source zeolite reagent may provide a source of aluminum or boron.
In most cases, the source zeolite also provides a source of silica.
The source zeolite in its dealuminated or deboronated form may also
be used as a source of silica, with additional silicon added using,
for example, the conventional sources listed above. Use of a source
zeolite reagent as a source of alumina for the present process is
more completely described in U.S. Pat. No. 5225179 issued Jul.
6 1993 to Nakagawa entitled "Method of Making Molecular Sieves",
the disclosure of which is incorporated herein by reference.
Typically, an alkali metal hydroxide and/or an alkaline earth metal
hydroxide, such as the hydroxide of sodium, potassium, lithium,
cesium, rubidium, calcium, and magnesium, is used in the reaction
mixture; however, this component can be omitted so long as the equivalent
basicity is maintained. The SDA may be used to provide hydroxide
ion. Thus, it may be beneficial to ion exchange, for example, the
halide to hydroxide ion, thereby reducing or eliminating the alkali
metal hydroxide quantity required. The alkali metal cation or alkaline
earth cation may be part of the as-synthesized crystalline oxide
material, in order to balance valence electron charges therein.
The reaction mixture is maintained at an elevated temperature until
the crystals of the SSZ-65 are formed. The hydrothermal crystallization
is usually conducted under autogenous pressure, at a temperature
between 100.degree. C. and 200.degree. C., preferably between 135.degree.
C. and 160.degree. C. The crystallization period is typically greater
than 1 day and preferably from about 3 days to about 20 days.
Preferably, the molecular sieve is prepared using mild stirring
or agitation.
During the hydrothermal crystallization step, the SSZ-65 crystals
can be allowed to nucleate spontaneously from the reaction mixture.
The use of SSZ-65 crystals as seed material can be advantageous
in decreasing the time necessary for complete crystallization to
occur. In addition, seeding can lead to an increased purity of the
product obtained by promoting the nucleation and/or formation of
SSZ-65 over any undesired phases. When used as seeds, SSZ-65 crystals
are added in an amount between 0.1 and 10% of the weight of first
tetravalent element oxide, e.g. silica, used in the reaction mixture.
Once the molecular sieve 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 SSZ-65 crystals. The drying
step can be performed at atmospheric pressure or under vacuum.
SSZ-65 as prepared 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, indium oxide, vanadium oxide and mixtures thereof greater
than about 15; and has, after calcination, the X-ray diffraction
lines of Table II below. SSZ-65 further has a composition, as synthesized
(i.e., prior to removal of the SDA from the SSZ-65) and in the anhydrous
state, in terms of mole ratios, shown in Table B below.
TABLE-US-00003 TABLE B As-Synthesized SSZ-65 YO.sub.2/W.sub.cO.sub.d
>15 M.sub.2/n/YO.sub.2 0.01 0.03 Q/YO.sub.2 0.02 0.05 where Y,
W, c, d, M, n and Q are as defined above.
SSZ-65 can be made with a mole ratio of YO.sub.2/W.sub.cO.sub.d
of .infin., i.e., there is essentially no W.sub.cO.sub.dpresent
in the SSZ-65. In this case, the SSZ-65 would be an all-silica material
or a germanosilicate. Thus, in a typical case where oxides of silicon
and aluminum are used, SSZ-65 can be made essentially aluminum free,
i.e., having a silica to alumina mole ratio of .infin.. A method
of increasing the mole ratio of silica to alumina is by using standard
acid leaching or chelating treatments. However, essentially aluminum-free
SSZ-65 can be synthesized using essentially aluminum-free silicon
sources as the main tetrahedral metal oxide component, if boron
is also present. The boron can then be removed, if desired, by treating
the borosilicate SSZ-65 with acetic acid at elevated temperature
(as described in Jones et al., 2001 13 1041 1050) to produce an
all-silica version of SSZ-65. SSZ-65 can also be prepared directly
as a borosilicate. If desired, the boron can be removed as described
above and replaced with metal atoms by techniques known in the art
to make, e.g., an aluminosilicate version of SSZ-65. SSZ-65 can
also be prepared directly as an aluminosilicate.
Lower silica to alumina ratios may also be obtained by using methods
which insert aluminum into the crystalline framework. For example,
aluminum insertion may occur by thermal treatment of the zeolite
in combination with an alumina binder or dissolved source of alumina.
Such procedures are described in U.S. Pat. No. 4559315 issued
on Dec. 17 1985 to Chang et al.
It is believed that SSZ-65 is comprised of a new framework structure
or topology which is characterized by its X-ray diffraction pattern.
SSZ-65 as-synthesized, has a crystalline structure whose X-ray
powder diffraction pattern exhibit the characteristic lines shown
in Table I and is thereby distinguished from other molecular sieves.
TABLE-US-00004 TABLE I As-Synthesized SSZ-65 d-spacing Relative
2 Theta.sup.(a) (Angstroms) Intensity (%).sup.(b) 6.94 12.74 M 9.18
9.63 M 16.00 5.54 W 17.48 5.07 M 21.02 4.23 VS 21.88 4.06 S 22.20
4.00 M 23.02 3.86 M 26.56 3.36 M 28.00 3.19 M .sup.(a).+-.0.1 .sup.(b)The
X-ray patterns provided are based on a relative intensity scale
in which the strongest line in the X-ray pattern is assigned a value
of 100:W(weak) is less than 20; M(medium) is between 20 and 40;
S(strong) is between 40 and 60; VS(very strong) is greater than
60.
Table IA below shows the X-ray powder diffraction lines for as-synthesized
SSZ-65 including actual relative intensities.
TABLE-US-00005 TABLE IA d-spacing Relative 2 Theta.sup.(a) (Angstroms)
Intensity (%) 6.94 12.74 26.7 9.18 9.63 22.7 16.00 5.54 14.2 17.48
5.07 25.8 21.02 4.23 100.0 21.88 4.06 47.8 22.20 4.00 27.0 23.02
3.86 36.8 26.56 3.36 21.9 28.00 3.19 27.0 .sup.(a).+-.0.1
After calcination, the SSZ-65 molecular sieves have a crystalline
structure whose X-ray powder diffraction pattern include the characteristic
lines shown in Table II:
TABLE-US-00006 TABLE II Calcined SSZ-65 d-spacing Relative 2 Theta.sup.(a)
(Angstroms) Intensity (%) 6.08 14.54 M 6.98 12.66 VS 9.28 9.53 S
17.58 5.04 M 21.14 4.20 VS 21.98 4.04 S 22.26 3.99 M 23.14 3.84
M 26.68 3.34 M 28.10 3.18 M .sup.(a).+-.0.1
Table IIA below shows the X-ray powder diffraction lines for calcined
SSZ-65 including actual relative intensities.
TABLE-US-00007 TABLE IIA d-spacing Relative 2 Theta.sup.(a) (Angstroms)
Intensity (%) 6.08 14.54 37.7 6.98 12.66 82.8 9.28 9.53 50.7 17.58
5.04 28.2 21.14 4.20 100.0 21.98 4.04 47.8 22.26 3.99 19.6 23.14
3.84 28.3 26.68 3.34 20.4 28.10 3.18 26.8 .sup.(a).+-.0.1
The X-ray powder diffraction patterns were determined by standard
techniques. The radiation was the K-alpha/doublet of copper. The
peak heights and the positions, as a function of 2.theta. where
.theta. is the Bragg angle, were read from the relative intensities
of the peaks, and d, the interplanar spacing in Angstroms corresponding
to the recorded lines, can be calculated.
The variation in the scattering angle (two theta) measurements,
due to instrument error and to differences between individual samples,
is estimated at .+-.0.1 degrees.
The X-ray diffraction pattern of Table I is representative of "as-synthesized"
or "as-made" SSZ-65 molecular sieves. Minor variations
in the diffraction pattern can result from variations in the silica-to-alumina
or silica-to-boron 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.
Representative peaks from the X-ray diffraction pattern of calcined
SSZ-65 are shown in Table II. Calcination can also result in changes
in the intensities of the peaks as compared to patterns of the "as-made"
material, as well as minor shifts in the diffraction pattern. The
molecular sieve produced by exchanging the metal or other cations
present in the molecular sieve 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.
Crystalline SSZ-65 can be used as-synthesized, but preferably will
be thermally treated (calcined). 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 molecular sieve can be leached
with chelating agents, e.g., EDTA or dilute acid solutions, to increase
the silica to alumina mole ratio. The molecular sieve can also be
steamed; steaming helps stabilize the crystalline lattice to attack
from acids.
The molecular sieve 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.
Metals may also be introduced into the molecular sieve by replacing
some of the cations in the molecular sieve with metal cations via
standard ion exchange techniques (see, for example, U.S. Pat. No.
3140249 issued Jul. 7 1964 to Plank et al.; U.S. Pat. No. 3140251
issued Jul. 7 1964 to Plank et al.; and U.S. Pat. No. 3140253
issued Jul. 7 1964 to Plank et al.). Typical replacing cations
can include metal cations, e.g., rare earth, Group IA, 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, and Fe are particularly
preferred.
The hydrogen, ammonium, and metal components can be ion-exchanged
into the SSZ-65. The SSZ-65 can also be impregnated with the metals,
or the metals can be physically and intimately admixed with the
SSZ-65 using standard methods known to the art.
Typical ion-exchange techniques involve contacting the synthetic
molecular sieve 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, acetates, nitrates, and
sulfates are particularly preferred. The molecular sieve is usually
calcined prior to the ion-exchange procedure to remove the organic
matter present in the channels and on the surface, since this results
in a more effective ion exchange. Representative ion exchange techniques
are disclosed in a wide variety of patents including U.S. Pat. No.
3140249 issued on Jul. 7 1964 to Plank et al.; U.S. Pat. No.
3140251 issued on Jul. 7 1964 to Plank et al.; and U.S. Pat.
No. 3140253 issued on Jul. 7 1964 to Plank et al.
Following contact with the salt solution of the desired replacing
cation, the molecular sieve is typically washed with water and dried
at temperatures ranging from 65.degree. C. to about 200.degree.
C. After washing, the molecular sieve can be calcined in air or
inert gas at temperatures ranging from about 200.degree. C. to about
800.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 the cations present in the synthesized form of SSZ-65
the spatial arrangement of the atoms which form the basic crystal
lattice of the molecular sieve remains essentially unchanged.
SSZ-65 can be formed into a wide variety of physical shapes. Generally
speaking, the molecular sieve can be in the form of a powder, a
granule, or a molded product, such as extrudate having a 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 SSZ-65 can be extruded
before drying, or, dried or partially dried and then extruded.
SSZ-65 can be composited with other materials resistant to the
temperatures and other conditions employed in organic conversion
processes. Such matrix materials include active and inactive materials
and synthetic or naturally occurring zeolites as well as inorganic
materials such as clays, silica and metal oxides. Examples of such
materials and the manner in which they can be used are disclosed
in U.S. Pat. No. 4910006 issued May 20 1990 to Zones et al.,
and U.S. Pat. No. 5316753 issued May 31 1994 to Nakagawa, both
of which are incorporated by reference herein in their entirety.
SSZ-65 is useful in catalysts for a variety of hydrocarbon conversion
reactions such as hydrocracking, dewaxing, isomerization and the
like. |