Molecular sieve abstract
The present invention relates to new crystalline molecular sieve
SSZ-65 prepared using 1-[1-(4-chlorophenyl)-cyclopropylmethyl]-1-ethyl-pyrrolidi-
nium 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 process for converting hydrocarbons comprising contacting
a hydrocarbonaceous feed at hydrocarbon converting conditions with
a catalyst comprising a zeolite 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. The process of claim 1 wherein the zeolite is predominantly
in the hydrogen form.
3. The process of claim 1 wherein the zeolite is substantially
free of acidity.
4. The process of claim 1 wherein the process is a hydrocracking
process comprising contacting the catalyst with a hydrocarbon feedstock
under hydrocracking conditions.
5. The process of claim 4 wherein the zeolite is predominantly
in the hydrogen form.
6. The process of claim 1 wherein the process is a dewaxing process
comprising contacting the catalyst with a hydrocarbon feedstock
under dewaxing conditions.
7. The process of claim 6 wherein the zeolite is predominantly
in the hydrogen form.
8. The process of claim 1 wherein the process is a process for
improving the viscosity index of a dewaxed product of waxy hydrocarbon
feeds comprising contacting the catalyst with a waxy hydrocarbon
feed under isomerization dewaxing conditions.
9. The process of claim 8 wherein the zeolite is predominantly
in the hydrogen form.
10. The process of claim 1 wherein the process is a process for
producing a C.sub.20+ lube oil from a C.sub.20+ olefin feed comprising
isomerizing said olefin feed under isomerization conditions over
the catalyst.
11. The process of claim 10 wherein the zeolite is predominantly
in the hydrogen form.
12. The process of claim 10 wherein the catalyst further comprises
at least one Group VIII metal.
13. The process of claim 1 wherein the process is a process for
catalytically dewaxing a hydrocarbon oil feedstock boiling above
about 350.degree. F. (177.degree. C.) and containing straight chain
and slightly branched chain hydrocarbons comprising contacting said
hydrocarbon oil feedstock in the presence of added hydrogen gas
at a hydrogen pressure of about 15-3000 psi (0.103-20.7 MPa) under
dewaxing conditions with the catalyst.
14. The process of claim 13 wherein the zeolite is predominantly
in the hydrogen form.
15. The process of claim 13 wherein the catalyst further comprises
at least one Group VIII metal.
16. The process of claim 13 wherein said catalyst comprises a layered
catalyst comprising a first layer comprising the zeolite and at
least one Group VIII metal, and a second layer comprising an aluminosilicate
zeolite which is more shape selective than the zeolite of said first
layer.
17. The process of claim 1 wherein the process is a process for
preparing a lubricating oil which comprises: hydrocracking in a
hydrocracking zone a hydrocarbonaceous feedstock to obtain an effluent
comprising a hydrocracked oil; and catalytically dewaxing said effluent
comprising hydrocracked oil at a temperature of at least about 400.degree.
F. (204.degree. C.) and at a pressure of from about 15 psig to about
3000 psig (0.103 to 20.7 MPa gauge) in the presence of added hydrogen
gas with the catalyst.
18. The process of claim 17 wherein the zeolite is predominantly
in the hydrogen form.
19. The process of claim 17 wherein the catalyst further comprises
at least one Group VIII metal.
20. The process of claim 1 wherein the process is a process for
isomerization dewaxing a raffinate comprising contacting said raffinate
in the presence of added hydrogen under isomerization dewaxing conditions
with the catalyst.
21. The process of claim 20 wherein the zeolite is predominantly
in the hydrogen form.
22. The process of claim 20 wherein the catalyst further comprises
at least one Group VIII metal.
23. The process of claim 20 wherein the raffinate is bright stock.
24. The process of claim 1 wherein the process is a process for
increasing the octane of a hydrocarbon feedstock to produce a product
having an increased aromatics content comprising contacting a hydrocarbonaceous
feedstock which comprises normal and slightly branched hydrocarbons
having a boiling range above about 40.degree. C. and less than about
200.degree. C. under aromatic conversion conditions with the catalyst.
25. The process of claim 24 wherein the zeolite is substantially
free of acid.
26. The process of claim 24 wherein the zeolite contains a Group
VIII metal component.
27. The process of claim 1 wherein the process is a catalytic cracking
process comprising contacting a hydrocarbon feedstock in a reaction
zone under catalytic cracking conditions in the absence of added
hydrogen with the catalyst.
28. The process of claim 27 wherein the zeolite is predominantly
in the hydrogen form.
29. The process of claim 27 wherein the catalyst additionally comprises
a large pore crystalline cracking component.
30. The process of claim 1 wherein the process is an isomerization
process for isomerizing C.sub.4 to C.sub.7 hydrocarbons, comprising
contacting a feed having normal and slightly branched C.sub.4 to
C.sub.7 hydrocarbons under isomerizing conditions with the catalyst.
31. The process of claim 30 wherein the zeolite is predominantly
in the hydrogen form.
32. The process of claim 30 wherein the zeolite has been impregnated
with at least one Group VIII metal.
33. The process of claim 30 wherein the catalyst has been calcined
in a steam/air mixture at an elevated temperature after impregnation
of the Group VIII metal.
34. The process of claim 32 wherein the Group VIII metal is platinum.
35. The process of claim 1 wherein the process is a process for
alkylating an aromatic hydrocarbon which comprises contacting under
alkylation conditions at least a molar excess of an aromatic hydrocarbon
with a C.sub.2 to C.sub.20 olefin under at least partial liquid
phase conditions and in the presence of the catalyst.
36. The process of claim 35 wherein the zeolite is predominantly
in the hydrogen form.
37. The process of claim 35 wherein the olefin is a C.sub.2 to
C.sub.4 olefin.
38. The process of claim 37 wherein the aromatic hydrocarbon and
olefin are present in a molar ratio of about 4:1 to about 20:1
respectively.
39. The process of claim 37 wherein the aromatic hydrocarbon is
selected from the group consisting of benzene, toluene, ethylbenzene,
xylene, naphthalene, naphthalene derivatives, dimethylnaphthalene
or mixtures thereof.
40. The process of claim 1 wherein the process is a process for
transalkylating an aromatic hydrocarbon which comprises contacting
under transalkylating conditions an aromatic hydrocarbon with a
polyalkyl aromatic hydrocarbon under at least partial liquid phase
conditions and in the presence of the catalyst.
41. The process of claim 40 wherein the zeolite is predominantly
in the hydrogen form.
42. The process of claim 40 wherein the aromatic hydrocarbon and
the polyalkyl aromatic hydrocarbon are present in a molar ratio
of from about 1:1 to about 25:1 respectively.
43. The process of claim 40 wherein the aromatic hydrocarbon is
selected from the group consisting of benzene, toluene, ethylbenzene,
xylene, or mixtures thereof.
44. The process of claim 40 wherein the polyalkyl aromatic hydrocarbon
is a dialkylbenzene.
45. The process of claim 1 wherein the process is a process to
convert paraffins to aromatics which comprises contacting paraffins
under conditions which cause paraffins to convert to aromatics with
a catalyst comprising the zeolite and gallium, zinc, or a compound
of gallium or zinc.
46. The process of claim 1 wherein the process is a process for
isomerizing olefins comprising contacting said olefin under conditions
which cause isomerization of the olefin with the catalyst.
47. The process of claim 1 wherein the process is a process for
isomerizing an isomerization feed comprising an aromatic C.sub.8
stream of xylene isomers or mixtures of xylene isomers and ethylbenzene,
wherein a more nearly equilibrium ratio of ortho-, meta and para-xylenes
is obtained, said process comprising contacting said feed under
isomerization conditions with the catalyst.
48. The process of claim 1 wherein the process is a process for
oligomerizing olefins comprising contacting an olefin feed under
oligomerization conditions with the catalyst.
49. A process for converting oxygenated hydrocarbons comprising
contacting said oxygenated hydrocarbon under conditions to produce
liquid products with a catalyst comprising a zeolite having a mole
ratio greater than about 15 of an oxide of a first tetravalent element
to an oxide of a second tetravalent element which is different from
said first tetravalent element, trivalent element, pentavalent element
or mixture thereof and having, after calcination, the X-ray diffraction
lines of Table II.
50. The process of claim 49 wherein the oxygenated hydrocarbon
is a lower alcohol.
51. The process of claim 50 wherein the lower alcohol is methanol.
52. The process of claim 1 wherein the process is a process for
the production of higher molecular weight hydrocarbons from lower
molecular weight hydrocarbons comprising the steps of: (a) introducing
into a reaction zone a lower molecular weight hydrocarbon containing
gas and contacting said gas in said zone under C.sub.2+ hydrocarbon
synthesis conditions with the catalyst and a metal or metal compound
capable of converting the lower molecular weight hydrocarbon to
a higher molecular weight hydrocarbon; and (b) withdrawing from
said reaction zone a higher molecular weight hydrocarbon-containing
stream.
53. The process of claim 52 wherein the metal or metal compound
comprises a lanthanide or actinide metal or metal compound.
54. The process of claim 52 wherein the lower molecular weight
hydrocarbon is methane.
Molecular sieve description
[0001] This application is a continuation-in-part of application
Ser. No. 10/401618 filed Mar. 26 2003.
BACKGROUND OF THE INVENTION
[0002] 1. Field of the Invention
[0003] The present invention relates to new crystalline molecular
sieve SSZ-65 a method for preparing SSZ-65 using a 1-[1-(4-chlorophenyl)-cyclo-
propylmethyl]-1-ethyl-pyrrolidinium or 1-ethyl-1-(1-phenyl-cyclopropylmeth-
yl)-pyrrolidinium cation as a structure directing agent and the
use of SSZ-65 in catalysts for, e.g., hydrocarbon conversion reactions.
[0004] 2. State of the Art
[0005] 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.
[0006] 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
[0007] 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.
[0008] In accordance with the present invention there is provided
a process for converting hydrocarbons comprising contacting a hydrocarbonaceous
feed at hydrocarbon converting conditions with a catalyst comprising
the zeolite of this invention. The zeolite may be predominantly
in the hydrogen form. It may also be substantially free of acidity.
[0009] Further provided by the present invention is a hydrocracking
process comprising contacting a hydrocarbon feedstock under hydrocracking
conditions with a catalyst comprising the zeolite of this invention,
preferably predominantly in the hydrogen form.
[0010] This invention also includes a dewaxing process comprising
contacting a hydrocarbon feedstock under dewaxing conditions with
a catalyst comprising the zeolite of this invention, preferably
predominantly in the hydrogen form.
[0011] The present invention also includes a process for improving
the viscosity index of a dewaxed product of waxy hydrocarbon feeds
comprising contacting the waxy hydrocarbon feed under isomerization
dewaxing conditions with a catalyst comprising the zeolite of this
invention, preferably predominantly in the hydrogen form.
[0012] The present invention further includes a process for producing
a C.sub.20+ lube oil from a C.sub.20+ olefin feed comprising isomerizing
said olefin feed under isomerization conditions over a catalyst
comprising the zeolite of this invention. The zeolite may be predominantly
in the hydrogen form. The catalyst may contain at least one Group
VIII metal.
[0013] In accordance with this invention, there is also provided
a process for catalytically dewaxing a hydrocarbon oil feedstock
boiling above about 350.degree. F. (177.degree. C.) and containing
straight chain and slightly branched chain hydrocarbons comprising
contacting said hydrocarbon oil feedstock in the presence of added
hydrogen gas at a hydrogen pressure of about 15-3000 psi (0.103-20.7
MPa) with a catalyst comprising the zeolite of this invention, preferably
predominantly in the hydrogen form. The catalyst may contain at
least one Group VIII metal. The catalyst may be a layered catalyst
comprising a first layer comprising the zeolite of this invention,
and a second layer comprising an aluminosilicate zeolite which is
more shape selective than the zeolite of said first layer. The first
layer may contain at least one Group VIII metal.
[0014] Also included in the present invention is a process for
preparing a lubricating oil which comprises hydrocracking in a hydrocracking
zone a hydrocarbonaceous feedstock to obtain an effluent comprising
a hydrocracked oil, and catalytically dewaxing said effluent comprising
hydrocracked oil at a temperature of at least about 400.degree.
F. (204.degree. C.) and at a pressure of from about 15 psig to about
3000 psig (0.103-20.7 MPa gauge)in the presence of added hydrogen
gas with a catalyst comprising the zeolite of this invention. The
zeolite may be predominantly in the hydrogen form. The catalyst
may contain at least one Group VIII metal.
[0015] Further included in this invention is a process for isomerization
dewaxing a raffinate comprising contacting said raffinate in the
presence of added hydrogen with a catalyst comprising the zeolite
of this invention. The raffinate may be bright stock, and the zeolite
may be predominantly in the hydrogen form. The catalyst may contain
at least one Group VIII metal.
[0016] Also included in this invention is a process for increasing
the octane of a hydrocarbon feedstock to produce a product having
an increased aromatics content comprising contacting a hydrocarbonaceous
feedstock which comprises normal and slightly branched hydrocarbons
having a boiling range above about 40.degree. C. and less than about
200.degree. C., under aromatic conversion conditions with a catalyst
comprising the zeolite of this invention made substantially free
of acidity by neutralizing said zeolite with a basic metal. Also
provided in this invention is such a process wherein the zeolite
contains a Group VIII metal component.
[0017] Also provided by the present invention is a catalytic cracking
process comprising contacting a hydrocarbon feedstock in a reaction
zone under catalytic cracking conditions in the absence of added
hydrogen with a catalyst comprising the zeolite of this invention,
preferably predominantly in the hydrogen form. Also included in
this invention is such a catalytic cracking process wherein the
catalyst additionally comprises a large pore crystalline cracking
component.
[0018] This invention further provides an isomerization process
for isomerizing C.sub.4 to C.sub.7 hydrocarbons, comprising contacting
a feed having normal and slightly branched C.sub.4 to C.sub.7 hydrocarbons
under isomerizing conditions with a catalyst comprising the zeolite
of this invention, preferably predominantly in the hydrogen form.
The zeolite may be impregnated with at least one Group VIII metal,
preferably platinum. The catalyst may be calcined in a steam/air
mixture at an elevated temperature after impregnation of the Group
VIII metal.
[0019] Also provided by the present invention is a process for
alkylating an aromatic hydrocarbon which comprises contacting under
alkylation conditions at least a molar excess of an aromatic hydrocarbon
with a C.sub.2 to C.sub.20 olefin under at least partial liquid
phase conditions and in the presence of a catalyst comprising the
zeolite of this invention, preferably predominantly in the hydrogen
form. The olefin may be a C.sub.2 to C.sub.4 olefin, and the aromatic
hydrocarbon and olefin may be present in a molar ratio of about
4:1 to about 20: 1 respectively. The aromatic hydrocarbon may be
selected from the group consisting of benzene, toluene, ethylbenzene,
xylene, naphthalene, naphthalene derivatives, dimethylnaphthalene
or mixtures thereof.
[0020] Further provided in accordance with this invention is a
process for transalkylating an aromatic hydrocarbon which comprises
contacting under transalkylating conditions an aromatic hydrocarbon
with a polyalkyl aromatic hydrocarbon under at least partial liquid
phase conditions and in the presence of a catalyst comprising the
zeolite of this invention, preferably predominantly in the hydrogen
form. The aromatic hydrocarbon and the polyalkyl aromatic hydrocarbon
may be present in a molar ratio of from about 1:1 to about 25:1
respectively.
[0021] The aromatic hydrocarbon may be selected from the group
consisting of benzene, toluene, ethylbenzene, xylene, or mixtures
thereof, and the polyalkyl aromatic hydrocarbon may be a dialkylbenzene.
[0022] Further provided by this invention is a process to convert
paraffins to aromatics which comprises contacting paraffins under
conditions which cause paraffins to convert to aromatics with a
catalyst comprising the zeolite of this invention, said catalyst
comprising gallium, zinc, or a compound of gallium or zinc.
[0023] In accordance with this invention there is also provided
a process for isomerizing olefins comprising contacting said olefin
under conditions which cause isomerization of the olefin with a
catalyst comprising the zeolite of this invention.
[0024] Further provided in accordance with this invention is a
process for isomerizing an isomerization feed comprising an aromatic
C.sub.8 stream of xylene isomers or mixtures of xylene isomers and
ethylbenzene, wherein a more nearly equilibrium ratio of ortho-,
meta- and para-xylenes is obtained, said process comprising contacting
said feed under isomerization conditions with a catalyst comprising
the zeolite of this invention.
[0025] The present invention further provides a process for oligomerizing
olefins comprising contacting an olefin feed under oligomerization
conditions with a catalyst comprising the zeolite of this invention.
[0026] This invention also provides a process for converting oxygenated
hydrocarbons comprising contacting said oxygenated hydrocarbon with
a catalyst comprising the zeolite of this invention under conditions
to produce liquid products. The oxygenated hydrocarbon may be a
lower alcohol.
[0027] Further provided in accordance with the present invention
is a process for the production of higher molecular weight hydrocarbons
from lower molecular weight hydrocarbons comprising the steps of:
[0028] (a) introducing into a reaction zone a lower molecular weight
hydrocarbon-containing gas and contacting said gas in said zone
under C.sub.2+ hydrocarbon synthesis conditions with the catalyst
and a metal or metal compound capable of converting the lower molecular
weight hydrocarbon to a higher molecular weight hydrocarbon; and
[0029] (b) withdrawing from said reaction zone a higher molecular
weight hydrocarbon-containing stream.
DETAILED DESCRIPTION OF THE INVENTION
[0030] 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.
[0031] In preparing SSZ-65 a 1-[1-(4-chlorophenyl)-cyclopropylmethyl]-1-e-
thyl-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: 1
1-[1-(4-Chloro-phenyl)-cyclopropylmethyl]- 1-ethyl-pyrrolidinium
[0032] 2
1-Ethyl-1-(1-phenyl-cyclopropylmethyl)-pyrrolidinium
[0033] 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.
[0034] 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.
[0035] SSZ-65 is prepared from a reaction mixture having the composition
shown in Table A below.
1TABLE 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
[0036] where Y is silicon, germanium or a mixture thereof; W is
aluminum, gallium, iron, boron, titanium, indium, vanadium or mixtures
thereof, a is 1 or 2 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), 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-cyclopropylmethyl)-pyrrolidinium cation.
[0037] In practice, SSZ-65 is prepared by a process comprising:
[0038] (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;
[0039] (b) maintaining the aqueous solution under conditions sufficient
to form crystals of SSZ-65; and
[0040] (c) recovering the crystals of SSZ-65.
[0041] 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.
[0042] 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.
[0043] 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.
[0044] 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.
[0045] 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.
[0046] Preferably, the molecular sieve is prepared using mild stirring
or agitation.
[0047] 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.
[0048] 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.
[0049] 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.
2TABLE 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
[0050] where Y, W, M, n and Q are as defined above, c is 1 or 2
and 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).
[0051] SSZ-65 can be made with a mole ratio of YO2W.sub.cO.sub.d
of .infin., i.e., there is essentially no W.sub.cO.sub.d present
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., Chem. Mater., 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.
[0052] 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.
[0053] 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.
3TABLE 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.
[0054] Table IA below shows the X-ray powder diffraction lines
for as-synthesized SSZ-65 including actual relative intensities.
4TABLE 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
[0055] 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:
5TABLE 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
[0056] Table IIA below shows the X-ray powder diffraction lines
for calcined SSZ-65 including actual relative intensities.
6TABLE 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
[0057] 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.
[0058] 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.
[0059] 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.
[0060] 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.
[0061] 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.
[0062] 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.
[0063] 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. Nos. 3140249 issued Jul. 7 1964 to Plank et al.; 3140251
issued Jul. 7 1964 to Plank et al.; and 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.
[0064] 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.
[0065] 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. Nos.
3140249 issued on Jul. 7 1964 to Plank et al.; 3140251 issued
on Jul. 7 1964 to Plank et al.; and 3140253 issued on Jul. 7
1964 to Plank et al.
[0066] 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.
[0067] 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.
[0068] 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.
[0069] 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.
Hydrocarbon Conversion Processes
[0070] SSZ-65 zeolites 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
in which SSZ-65 are expected to be useful include hydrocracking,
dewaxing, catalytic cracking and olefin and aromatics formation
reactions. The catalysts are also expected to be useful in other
petroleum refining and hydrocarbon conversion reactions such as
isomerizing n-paraffins and naphthenes, polymerizing and oligomerizing
olefinic or acetylenic compounds such as isobutylene and butene-1
reforming, isomerizing polyalkyl substituted aromatics (e.g., m-xylene),
and disproportionating aromatics (e.g., toluene) to provide mixtures
of benzene, xylenes and higher methylbenzenes and oxidation reactions.
Also included are rearrangement reactions to make various naphthalene
derivatives, and forming higher molecular weight hydrocarbons from
lower molecular weight hydrocarbons (e.g., methane upgrading). The
SSZ-65 catalysts may have high selectivity, and under hydrocarbon
conversion conditions can provide a high percentage of desired products
relative to total products.
[0071] For high catalytic activity, the SSZ-65 zeolite should be
predominantly in its hydrogen ion form. Generally, the zeolite is
converted to its hydrogen form by ammonium exchange followed by
calcination. If the zeolite is synthesized with a high enough ratio
of SDA cation to sodium ion, calcination alone may be sufficient.
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.
[0072] SSZ-65 zeolites can be used in processing hydrocarbonaceous
feedstocks. Hydrocarbonaceous feedstocks contain carbon compounds
and can be from many different sources, such as virgin petroleum
fractions, recycle petroleum fractions, shale oil, liquefied coal,
tar sand oil, synthetic paraffins from NAO, recycled plastic feedstocks
and, in general, can be any carbon containing feedstock susceptible
to zeolitic catalytic reactions. Depending on the type of processing
the hydrocarbonaceous feed is to undergo, the feed can contain metal
or be free of metals, it can also have high or low nitrogen or sulfur
impurities. It can be appreciated, however, that in general processing
will be more efficient (and the catalyst more active) the lower
the metal, nitrogen, and sulfur content of the feedstock.
[0073] The conversion of hydrocarbonaceous feeds can take place
in any convenient mode, for example, in fluidized bed, moving bed,
or fixed bed reactors depending on the types of process desired.
The formulation of the catalyst particles will vary depending on
the conversion process and method of operation.
[0074] Other reactions which can be performed using the catalyst
of this invention containing a metal, e.g., a Group VIII metal such
platinum, include hydrogenation-dehydrogenation reactions, denitrogenation
and desulfurization reactions.
[0075] The following table indicates typical reaction conditions
which may be employed when using catalysts comprising SSZ-65 in
the hydrocarbon conversion reactions of this invention. Preferred
conditions are indicated in parentheses.
7 Process Temp., .degree. C. Pressure LHSV Hydrocracking 175-485
0.5-350 bar 0.1-30 Dewaxing 200-475 15-3000 psig, 0.1-20 (250-450)
0.103-20.7 MPa (0.2-10) gauge (200-3000 1.38-20.7 MPa gauge) Aromatics
400-600 atm.-10 bar 0.1-15 formation (480-550) Cat. cracking 127-885
subatm.-.sup.1 0.5-50 (atm.-5 atm.) Oligomerization .sup. 232-649.sup.2
0.1-50 atm..sup.23 .sup. 0.2-50.sup.2 .sup. 10-232.sup.4 -- .sup.
0.05-20.sup.5 .sup. (27-204).sup.4 -- .sup. (0.1-10).sup.5 Paraffins
to 100-700 0-1000 psig .sup. 0.5-40.sup.5 aromatics Condensation
of 260-538 0.5-1000 psig, 0.5-50.sup.5 alcohols 0.00345-6.89 MPa
gauge Isomerization 93-538 50-1000 psig, 1-10 (204-315) 0.345-6.89
MPa (1-4) gauge Xylene .sup. 260-593.sup.2 0.5-50 atm..sup.2 .sup.
0.1-100.sup.5 isomerization .sup. (315-566).sup.2 (1-5 atm).sup.2
.sup. (0.5-50).sup.5 .sup. 38-371.sup.4 1-200 atm..sup.4 0.5-50
.sup.1Several hundred atmospheres .sup.2Gas phase reaction .sup.3Hydrocarbon
partial pressure .sup.4Liquid phase reaction .sup.5WHSV
[0076] Other reaction conditions and parameters are provided below.
Hydrocracking
[0077] Using a catalyst which comprises SSZ-65 preferably predominantly
in the hydrogen form, and a hydrogenation promoter, heavy petroleum
residual feedstocks, cyclic stocks and other hydrocrackate charge
stocks can be hydrocracked using the process conditions and catalyst
components disclosed in the aforementioned U.S. Pat. No. 4910006
and U.S. Pat. No. 5316753.
[0078] The hydrocracking catalysts contain an effective amount
of at least one hydrogenation component of the type commonly employed
in hydrocracking catalysts. The hydrogenation component is generally
selected from the group of hydrogenation catalysts consisting of
one or more metals of Group VIB and Group VIII, including the salts,
complexes and solutions containing such. The hydrogenation catalyst
is preferably selected from the group of metals, salts and complexes
thereof of the group consisting of at least one of platinum, palladium,
rhodium, iridium, ruthenium and mixtures thereof or the group consisting
of at least one of nickel, molybdenum, cobalt, tungsten, titanium,
chromium and mixtures thereof. Reference to the catalytically active
metal or metals is intended to encompass such metal or metals in
the elemental state or in some form such as an oxide, sulfide, halide,
carboxylate and the like. The hydrogenation catalyst is present
in an effective amount to provide the hydrogenation function of
the hydrocracking catalyst, and preferably in the range of from
0.05 to 25% by weight.
Dewaxing
[0079] SSZ-65 preferably predominantly in the hydrogen form, can
be used to dewax hydrocarbonaceous feeds by selectively removing
straight chain paraffins. Typically, the viscosity index of the
dewaxed product is improved (compared to the waxy feed) when the
waxy feed is contacted with SSZ-65 under isomerization dewaxing
conditions.
[0080] The catalytic dewaxing conditions are dependent in large
measure on the feed used and upon the desired pour point. Hydrogen
is preferably present in the reaction zone during the catalytic
dewaxing process. The hydrogen to feed ratio is typically between
about 500 and about 30000 SCF/bbl (standard cubic feet per barrel)
(0.089 to 5.34 SCM/liter (standard cubic meters/liter)), preferably
about 1000 to about 20000 SCF/bbl (0.178 to 3.56 SCM/liter). Generally,
hydrogen will be separated from the product and recycled to the
reaction zone. Typical feedstocks include light gas oil, heavy gas
oils and reduced crudes boiling above about 350.degree. F. (177.degree.
C.).
[0081] A typical dewaxing process is the catalytic dewaxing of
a hydrocarbon oil feedstock boiling above about 350.degree. F. (177.degree.
C.) and containing straight chain and slightly branched chain hydrocarbons
by contacting the hydrocarbon oil feedstock in the presence of added
hydrogen gas at a hydrogen pressure of about 15-3000 psi (0.103-20.7
MPa) with a catalyst comprising SSZ-65 and at least one Group VIII
metal.
[0082] The SSZ-65 hydrodewaxing catalyst may optionally contain
a hydrogenation component of the type commonly employed in dewaxing
catalysts. See the aforementioned U.S. Pat. No. 4910006 and U.S.
Pat. No. 5316753 for examples of these hydrogenation components.
[0083] The hydrogenation component is present in an effective amount
to provide an effective hydrodewaxing and hydroisomerization catalyst
preferably in the range of from about 0.05 to 5% by weight. The
catalyst may be run in such a mode to increase isomerization dewaxing
at the expense of cracking reactions.
[0084] The feed may be hydrocracked, followed by dewaxing. This
type of two stage process and typical hydrocracking conditions are
described in U.S. Pat. No. 4921594 issued May 1 1990 to Miller,
which is incorporated herein by reference in its entirety.
[0085] SSZ-65 may also be utilized as a dewaxing catalyst in the
form of a layered catalyst. That is, the catalyst comprises a first
layer comprising zeolite SSZ-65 and at least one Group VIII metal,
and a second layer comprising an aluminosilicate zeolite which is
more shape selective than zeolite SSZ-65. The use of layered catalysts
is disclosed in U.S. Pat. No. 5149421 issued Sep. 22 1992 to
Miller, which is incorporated by reference herein in its entirety.
The layering may also include a bed of SSZ-65 layered with a non-zeolitic
component designed for either hydrocracking or hydrofinishing.
[0086] SSZ-65 may also be used to dewax raffinates, including bright
stock, under conditions such as those disclosed in U.S. Pat. No.
4181598 issued Jan. 1 1980 to Gillespie et al., which is incorporated
by reference herein in its entirety.
[0087] It is often desirable to use mild hydrogenation (sometimes
referred to as hydrofinishing) to produce more stable dewaxed products.
The hydrofinishing step can be performed either before or after
the dewaxing step, and preferably after. Hydrofinishing is typically
conducted at temperatures ranging from about 190.degree. C. to about
340.degree. C. at pressures from about 400 psig to about 3000 psig
(2.76 to 20.7 MPa gauge) at space velocities (LHSV) between about
0.1 and 20 and a hydrogen recycle rate of about 400 to 1500 SCF/bbl
(0.071 to 0.27 SCM/liter). The hydrogenation catalyst employed must
be active enough not only to hydrogenate the olefins, diolefins
and color bodies which may be present, but also to reduce the aromatic
content. Suitable hydrogenation catalyst are disclosed in U.S. Pat.
No. 4921594 issued May 1 1990 to Miller, which is incorporated
by reference herein in its entirety. The hydrofinishing step is
beneficial in preparing an acceptably stable product (e.g., a lubricating
oil) since dewaxed products prepared from hydrocracked stocks tend
to be unstable to air and light and tend to form sludges spontaneously
and quickly.
[0088] Lube oil may be prepared using SSZ-65. For example, a C.sub.20+
lube oil may be made by isomerizing a C.sub.20+ olefin feed over
a catalyst comprising SSZ-65 in the hydrogen form and at least one
Group VIII metal. Alternatively, the lubricating oil may be made
by hydrocracking in a hydrocracking zone a hydrocarbonaceous feedstock
to obtain an effluent comprising a hydrocracked oil, and catalytically
dewaxing the effluent at a temperature of at least about 400.degree.
F. (204.degree. C.) and at a pressure of from about 15 psig to about
3000 psig (0.103-20.7 MPa gauge) in the presence of added hydrogen
gas with a catalyst comprising SSZ-65 in the hydrogen form and at
least one Group VIII metal.
Aromatics Formation
[0089] SSZ-65 can be used to convert light straight run naphthas
and similar mixtures to highly aromatic mixtures. Thus, normal and
slightly branched chained hydrocarbons, preferably having a boiling
range above about 40.degree. C. and less than about 200.degree.
C., can be converted to products having a substantial higher octane
aromatics content by contacting the hydrocarbon feed with a catalyst
comprising SSZ-65. It is also possible to convert heavier feeds
into BTX or naphthalene derivatives of value using a catalyst comprising
SSZ-65.
[0090] The conversion catalyst preferably contains a Group VIII
metal compound to have sufficient activity for commercial use. By
Group vm metal compound as used herein is meant the metal itself
or a compound thereof. The Group VIII noble metals and their compounds,
platinum, palladium, and iridium, or combinations thereof can be
used. Rhenium or tin or a mixture thereof may also be used in conjunction
with the Group VIII metal compound and preferably a noble metal
compound. The most preferred metal is platinum. The amount of Group
VIII metal present in the conversion catalyst should be within the
normal range of use in reforming catalysts, from about 0.05 to 2.0
weight percent, preferably 0.2 to 0.8 weight percent.
[0091] It is critical to the selective production of aromatics
in useful quantities that the conversion catalyst be substantially
free of acidity, for example, by neutralizing the zeolite with a
basic metal, e.g., alkali metal, compound. Methods for rendering
the catalyst free of acidity are known in the art. See the aforementioned
U.S. Pat. No. 4910006 and U.S. Pat. No. 5316753 for a description
of such methods.
[0092] The preferred alkali metals are sodium, potassium, rubidium
and cesium. The zeolite itself can be substantially free of acidity
only at very high silica:alumina mole ratios.
Catalytic Cracking
[0093] Hydrocarbon cracking stocks can be catalytically cracked
in the absence of hydrogen using SSZ-65 preferably predominantly
in the hydrogen form.
[0094] When SSZ-65 is used as a catalytic cracking catalyst in
the absence of hydrogen, the catalyst may be employed in conjunction
with traditional cracking catalysts, e.g., any aluminosilicate heretofore
employed as a component in cracking catalysts. Typically, these
are large pore, crystalline aluminosilicates. Examples of these
traditional cracking catalysts are disclosed in the aforementioned
U.S. Pat. No. 4910006 and U.S. Pat. No 5316753. When a traditional
cracking catalyst (TC) component is employed, the relative weight
ratio of the TC to the SSZ-65 is generally between about 1:10 and
about 500:1 desirably between about 1:10 and about 200:1 preferably
between about 1:2 and about 50:1 and most preferably is between
about 1:1 and about 20:1. The novel zeolite and/or the traditional
cracking component may be further ion exchanged with rare earth
ions to modify selectivity.
[0095] The cracking catalysts are typically employed with an inorganic
oxide matrix component. See the aforementioned U.S. Pat. No. 4910006
and U.S. Pat. No. 5316753 for examples of such matrix components.
Isomerization
[0096] The present catalyst is highly active and highly selective
for isomerizing C.sub.4 to C.sub.7 hydrocarbons. The activity means
that the catalyst can operate at relatively low temperature which
thermodynamically favors highly branched paraffins. Consequently,
the catalyst can produce a high octane product. The high selectivity
means that a relatively high liquid yield can be achieved when the
catalyst is run at a high octane.
[0097] The present process comprises contacting the isomerization
catalyst, i.e., a catalyst comprising SSZ-65 in the hydrogen form,
with a hydrocarbon feed under isomerization conditions. The feed
is preferably a light straight run fraction, boiling within the
range of 30.degree. F. to 250.degree. F. (-1.degree. C. to 121.degree.
C.) and preferably from 60.degree. F. to 200.degree. F. (16.degree.
C. to 93.degree. C.). Preferably, the hydrocarbon feed for the process
comprises a substantial amount of C.sub.4 to C.sub.7 normal and
slightly branched low octane hydrocarbons, more preferably C.sub.5
and C.sub.6 hydrocarbons.
[0098] It is preferable to carry out the isomerization reaction
in the presence of hydrogen. Preferably, hydrogen is added to give
a hydrogen to hydrocarbon ratio (H.sub.2/HC) of between 0.5 and
10 H.sub.2/HC, more preferably between 1 and 8 H.sub.2/HC. See the
aforementioned U.S. Pat. No. 4910006 and U.S. Pat. No. 5316753
for a further discussion of isomerization process conditions.
[0099] A low sulfur feed is especially preferred in the present
process. The feed preferably contains less than 10 ppm, more preferably
less than 1 ppm, and most preferably less than 0.1 ppm sulfur. In
the case of a feed which is not already low in sulfur, acceptable
levels can be reached by hydrogenating the feed in a presaturation
zone with a hydrogenating catalyst which is resistant to sulfur
poisoning. See the aforementioned U.S. Pat. No. 4910006 and U.S.
Pat. No. 5316753 for a further discussion of this hydrodesulfurization
process.
[0100] It is preferable to limit the nitrogen level and the water
content of the feed. Catalysts and processes which are suitable
for these purposes are known to those skilled in the art.
[0101] After a period of operation, the catalyst can become deactivated
by sulfur or coke. See the aforementioned U.S. Pat. No. 4910006
and U.S. Pat. No. 5316753 for a further discussion of methods
of removing this sulfur and coke, and of regenerating the catalyst.
[0102] The conversion catalyst preferably contains a Group VIII
metal compound to have sufficient activity for commercial use. By
Group VIII metal compound as used herein is meant the metal itself
or a compound thereof. The Group VIII noble metals and their compounds,
platinum, palladium, and iridium, or combinations thereof can be
used. Rhenium and tin may also be used in conjunction with the noble
metal. The most preferred metal is platinum. The amount of Group
VIII metal present in the conversion catalyst should be within the
normal range of use in isomerizing catalysts, from about 0.05 to
2.0 weight percent, preferably 0.2 to 0.8 weight percent.
Alkylation and Transalkylation
[0103] SSZ-65 can be used in a process for the alkylation or transalkylation
of an aromatic hydrocarbon. The process comprises contacting the
aromatic hydrocarbon with a C.sub.2 to C.sub.16 olefin alkylating
agent or a polyalkyl aromatic hydrocarbon transalkylating agent,
under at least partial liquid phase conditions, and in the presence
of a catalyst comprising SSZ-65.
[0104] SSZ-65 can also be used for removing benzene from gasoline
by alkylating the benzene as described above and removing the alkylated
product from the gasoline.
[0105] 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.
[0106] Examples of suitable aromatic hydrocarbon feedstocks which
may be alkylated or transalkylated by the process of the invention
include aromatic compounds such as benzene, toluene and xylene.
The preferred aromatic hydrocarbon is benzene. There may be occasions
where naphthalene or naphthalene derivatives such as dimethylnaphthalene
may be desirable. Mixtures of aromatic hydrocarbons may also be
employed.
[0107] Suitable olefins for the alkylation of the aromatic hydrocarbon
are those containing 2 to 20 preferably 2 to 4 carbon atoms, such
as ethylene, propylene, butene-1 trans-butene-2 and cis-butene-2
or mixtures thereof. There may be instances where pentenes are desirable.
The preferred olefins are ethylene and propylene. Longer chain alpha
olefins may be used as well.
[0108] When transalkylation is desired, the transalkylating agent
is a polyalkyl aromatic hydrocarbon containing two or more alkyl
groups that each may have from 2 to about 4 carbon atoms. For example,
suitable polyalkyl aromatic hydrocarbons include di-, tri- and tetra-alkyl
aromatic hydrocarbons, such as diethylbenzene, triethylbenzene,
diethylmethylbenzene (diethyltoluene), di-isopropylbenzene, di-isopropyltoluene,
dibutylbenzene, and the like. Preferred polyalkyl aromatic hydrocarbons
are the dialkyl benzenes. A particularly preferred polyalkyl aromatic
hydrocarbon is di-isopropylbenzene.
[0109] When alkylation is the process conducted, reaction conditions
are as follows. The aromatic hydrocarbon feed should be present
in stoichiometric excess. It is preferred that molar ratio of aromatics
to olefins be greater than four-to-one to prevent rapid catalyst
fouling. The reaction temperature may range from 1 00.degree. F.
to 600.degree. F. (38.degree. C. to 315.degree. C.), preferably
250.degree. F. to 450.degree. F. (121.degree. C. to 232.degree.
C.). The reaction pressure should be sufficient to maintain at least
a partial liquid phase in order to retard catalyst fouling. This
is typically 50 psig to 1000 psig (0.345 to 6.89 MPa gauge) depending
on the feedstock and reaction temperature. Contact time may range
from 10 seconds to 10 hours, but is usually from 5 minutes to an
hour. The weight hourly space velocity (WHSV), in terms of grams
(pounds) of aromatic hydrocarbon and olefin per gram (pound) of
catalyst per hour, is generally within the range of about 0.5 to
50.
[0110] When transalkylation is the process conducted, the molar
ratio of aromatic hydrocarbon will generally range from about 1:1
to 25:1 and preferably from about 2:1 to 20:1. The reaction temperature
may range from about 100.degree. F. to 600.degree. F. (38.degree.
C. to 315.degree. C.), but it is preferably about 250.degree. F.
to 450.degree. F. (121.degree. C. to 232.degree. C.). The reaction
pressure should be sufficient to maintain at least a partial liquid
phase, typically in the range of about 50 psig to 1000 psig (0.345
to 6.89 MPa gauge), preferably 300 psig to 600 psig (2.07 to 4.14
MPa gauge). The weight hourly space velocity will range from about
0.1 to 10. U.S. Pat. No. 5082990 issued on Jan. 21 1992 to Hsieh,
et al. describes such processes and is incorporated herein by reference.
Conversion of Paraffins to Aromatics
[0111] SSZ-65 can be used to convert light gas C.sub.2-C.sub.6
paraffins to higher molecular weight hydrocarbons including aromatic
compounds. Preferably, the zeolite will contain a catalyst metal
or metal oxide wherein said metal is selected from the group consisting
of Groups IB, IIB, VIII and IIIA of the Periodic Table. Preferably,
the metal is gallium, niobium, indium or zinc in the range of from
about 0.05 to 5% by weight.
Isomerization of Olefins
[0112] SSZ-65 can be used to isomerize olefins. The feed stream
is a hydrocarbon stream containing at least one C.sub.4-6 olefin,
preferably a C.sub.4-6 normal olefin, more preferably normal butene.
Normal butene as used in this specification means all forms of normal
butene, e.g., 1-butene, cis-2-butene, and trans-2-butene. Typically,
hydrocarbons other than normal butene or other C.sub.4-.sub.6 normal
olefins will be present in the feed stream. These other hydrocarbons
may include, e.g., alkanes, other olefins, aromatics, hydrogen,
and inert gases.
[0113] The feed stream typically may be the effluent from a fluid
catalytic cracking unit or a methyl-tert-butyl ether unit. A fluid
catalytic cracking unit effluent typically contains about 40-60
weight percent normal butenes. A methyl-tert-butyl ether unit effluent
typically contains 40-100 weight percent normal butene. The feed
stream preferably contains at least about 40 weight percent normal
butene, more preferably at least about 65 weight percent normal
butene. The terms iso-olefin and methyl branched iso-olefin may
be used interchangeably in this specification.
[0114] The process is carried out under isomerization conditions.
The hydrocarbon feed is contacted in a vapor phase with a catalyst
comprising the SSZ-65. The process may be carried out generally
at a temperature from about 625.degree. F. to about 950.degree.
F. (329-510.degree. C.), for butenes, preferably from about 700.degree.
F. to about 900.degree. F. (371-482.degree. C.), and about 350.degree.
F. to about 650.degree. F. (177-343.degree. C.) for pentenes and
hexenes. The pressure ranges from subatmospheric to about 200 psig
(1.38 MPa gauge), preferably from about 15 psig to about 200 psig
(0.103 to 1.38 MPa gauge), and more preferably from about 1 psig
to about 150 psig (0.00689 to 1.03 MPa gauge).
[0115] The liquid hourly space velocity during contacting is generally
from about 0.1 to about 50 hr.sup.-1 based on the hydrocarbon feed,
preferably from about 0.1 to about 20 hr.sup.-1 more preferably
from about 0.2 to about 10 hr.sup.-1 most preferably from about
1 to about 5 hr.sup.-1. A hydrogen/hydrocarbon molar ratio is maintained
from about 0 to about 30 or higher. The hydrogen can be added directly
to the feed stream or directly to the isomerization zone. The reaction
is preferably substantially free of water, typically less than about
two weight percent based on the feed. The process can be carried
out in a packed bed reactor, a fixed bed, fluidized bed reactor,
or a moving bed reactor. The bed of the catalyst can move upward
or downward. The mole percent conversion of, e.g., normal butene
to iso-butene is at least 10 preferably at least 25 and more preferably
at least 35.
Xylene Isomerization
[0116] SSZ-65 may also be useful in a process for isomerizing one
or more xylene isomers in a C.sub.8 aromatic feed to obtain ortho-,
meta-, and para-xylene in a ratio approaching the equilibrium value.
In particular, xylene isomerization is used in conjunction with
a separate process to manufacture para-xylene. For example, a portion
of the para-xylene in a mixed C.sub.8 aromatics stream may be recovered
by crystallization and centrifugation. The mother liquor from the
crystallizer is then reacted under xylene isomerization conditions
to restore ortho-, meta- and para-xylenes to a near equilibrium
ratio. At the same time, part of the ethylbenzene in the mother
liquor is converted to xylenes or to products which are easily separated
by filtration. The isomerate is blended with fresh feed and the
combined stream is distilled to remove heavy and light by-products.
The resultant C.sub.8 aromatics stream is then sent to the crystallizer
to repeat the cycle.
[0117] Optionally, isomerization in the vapor phase is conducted
in the presence of 3.0 to 30.0 moles of hydrogen per mole of alkylbenzene
(e.g., ethylbenzene). If hydrogen is used, the catalyst should comprise
about 0.1 to 2.0 wt. % of a hydrogenation/dehydrogenation component
selected from Group VIII (of the Periodic Table) metal component,
especially platinum or nickel. By Group VIII metal component is
meant the metals and their compounds such as oxides and sulfides.
[0118] Optionally, the isomerization feed may contain 10 to 90
wt. of a diluent such as toluene, trimethylbenzene, naphthenes or
paraffins.
Oligomerization
[0119] It is expected that SSZ-65 can also be used to oligomerize
straight and branched chain olefins having from about 2 to 21 and
preferably 2-5 carbon atoms. The oligomers which are the products
of the process are medium to heavy olefins which are useful for
both fuels, i.e., gasoline or a gasoline blending stock and chemicals.
[0120] The oligomerization process comprises contacting the olefin
feedstock in the gaseous or liquid phase with a catalyst comprising
SSZ-65.
[0121] The zeolite can have the original cations associated therewith
replaced by a wide variety of other cations according to techniques
well known in the art. Typical cations would include hydrogen, ammonium
and metal cations including mixtures of the same. Of the replacing
metallic cations, particular preference is given to cations of metals
such as rare earth metals, manganese, calcium, as well as metals
of Group II of the Periodic Table, e.g., zinc, and Group VIII of
the Periodic Table, e.g., nickel. One of the prime requisites is
that the zeolite have a fairly low aromatization activity, i.e.,
in which the amount of aromatics produced is not more than about
20% by weight. This is accomplished by using a zeolite with controlled
acid activity [alpha value] of from about 0.1 to about 120 preferably
from about 0.1 to about 100 as measured by its ability to crack
n-hexane.
[0122] Alpha values are defined by a standard test known in the
art, e.g., as shown in U.S. Pat. No. 3960978 issued on Jun. 1
1976 to Givens et al. which is incorporated totally herein by reference.
If required, such zeolites may be obtained by steaming, by use in
a conversion process or by any other method which may occur to one
skilled in this art.
Condensation of Alcohols
[0123] SSZ-65 can be used to condense lower aliphatic alcohols
having 1 to 10 carbon atoms to a gasoline boiling point hydrocarbon
product comprising mixed aliphatic and aromatic hydrocarbon. The
process disclosed in U.S. Pat. No. 3894107 issued Jul. 8 1975
to Butter et al., describes the process conditions used in this
process, which patent is incorporated totally herein by reference.
[0124] The catalyst may be in the hydrogen form or may be base
exchanged or impregnated to contain ammonium or a metal cation complement,
preferably in the range of from about 0.05 to 5% by weight. The
metal cations that may be present include any of the metals of the
Groups I through VIII of the Periodic Table. However, in the case
of Group IA metals, the cation content should in no case be so large
as to effectively inactivate the catalyst, nor should the exchange
be such as to eliminate all acidity. There may be other processes
involving treatment of oxygenated substrates where a basic catalyst
is desired.
Methane Upgrading
[0125] Higher molecular weight hydrocarbons can be formed from
lower molecular weight hydrocarbons by contacting the lower molecular
weight hydrocarbon with a catalyst comprising SSZ-65 and a metal
or metal compound capable of converting the lower molecular weight
hydrocarbon to a higher molecular weight hydrocarbon. Examples of
such reactions include the conversion of methane to C.sub.2+ hydrocarbons
such as ethylene or benzene or both. Examples of useful metals and
metal compounds include lanthanide and or actinide metals or metal
compounds.
[0126] These reactions, the metals or metal compounds employed
and the conditions under which they can be run are disclosed in
U.S. Patents Nos. 4734537 issued Mar. 29 1988 to Devries et
al.; 4939311 issued Jul. 3 1990 to Washechecket al.; 4962261
issued Oct. 9 1990 to Abrevaya et al.; 5095161 issued Mar. 10
1992 to Abrevaya et al.; 5105044 issued Apr. 14 1992 to Han
et al.; 5105046 issued Apr. 14 1992 to Washecheck; 5238898
issued Aug. 24 1993 to Han et al.; 5321185 issued Jun. 14 1994
to van der Vaart; and 5336825 issued Aug. 9 1994 to Choudhary
et al., each of which is incorporated herein by reference in its
entirety.
EXAMPLES
[0127] The following examples demonstrate but do not limit the
present invention.
Example 1
Synthesis of SDA 1-[1-(4-chlorophenyl)-cyclopropylmethyl]-1-ethyl-pyrrolid-
inium Cation
[0128] 3
1-[1-(4-Chloro-phenyl)-cyclopropylmethyl]-1-ethyl-pyrrolidinium
[0129] The structure directing agent is synthesized according to
the synthetic scheme shown below (Scheme 1).
[0130] 1-[1-(4-chloro-phenyl)-cyclopropylmethyl]-1-ethyl-pyrrolidinium
iodide is prepared from the reaction of the parent amine 1-[1-(4-chloro-phenyl)-cyclopropylmethyl]-pyrrolidine
with ethyl iodide. A 100 gm (0.42 mole) of the amine, 1-[1-(4-chloro-phenyl)-cyclopropylmeth-
yl]-pyrrolidine, is dissolved in 1000 ml anhydrous methanol in a
3-litre 3-necked reaction flask (equipped with a mechanical stirrer
and a reflux condenser). To this solution, 98 gm (0.62 mole) of
ethyl iodide is added, and the mixture is stirred at room temperature
for 72 hours. Then, 39 gm (0.25 mol.) of ethyl iodide is added and
the mixture is heated at reflux for 3 hours. The reaction mixture
is cooled down and excess ethyl iodide and the solvent are removed
at reduced pressure on a rotary evaporator. The obtained dark tan-colored
solids (162 gm) are further purified by dissolving in acetone (500
ml) followed by precipitation by adding diethyl ether. Filtration
and air-drying the obtained solids gives 153 gm (93% yield) of the
desired 1-[1-(4-chloro-phenyl)-cyclopropylmethyl]-1-et- hyl-pyrrolidinium
iodide as a white powder. The product is pure by .sup.1H and .sup.13C-NMR
analysis.
[0131] The hydroxide form of 1-[1-(4-chloro-phenyl)-cyclopropyhnethyl]-1-e-
thyl-pyrrolidinium cation is obtained by an ion exchange treatment
of the iodide salt with Ion-Exchange Resin-OH (BIO RAD.RTM. AH1-X8).
In a 1-liter volume plastic bottle, 100 gm (255 mmol) of 1-[1-(4-chloro-phenyl)-cyclopropylmethyl]-1-ethyl-pyrrolidinium
iodide is dissolved in 300 ml de-ionized water. Then, 320 gm of
the ion exchange resin is added and the solution is allowed to gently
stir overnight. The mixture is then filtered, and the resin cake
is rinsed with minimal amount of de-ionized water. The filtrate
is analyzed for hydroxide concentration by titration analysis on
a small sample of the solution with 0.1N HCl. The reaction yields
96% of (245 mmol) of the desired 1-[1-(4-chloro-phenyl)-cyclopropylmethyl]-1-ethyl-pyrrolidinium
hydroxide (hydroxide concentration of 0.6 M).
[0132] The parent amine 1-[1-(4-chloro-phenyl)-cyclopropylmethyl]-pyrrolid-
ine is obtained from the LiAlH.sub.4-reduction of the precursor
amide [1-(4-chloro-phenyl)-cyclopropyl]-pyrrolidin-1-yl-methanone.
In a 3-neck 3-liter reaction flask equipped with a mechanical stirrer
and reflux condenser, 45.5 gm (1.2 mol.) of LiAlH.sub.4 is suspended
in 750 ml anhydrous tetrahydrofuran (THF). The suspension is cooled
down to 0.degree. C. (ice-bath), and 120 gm (0.48 mole) of [1-(4-chloro-phenyl)-cyclopropyl]-pyrrolidin-1-yl-methanone
dissolved in 250 ml THF is added (to the suspension) drop-wise via
an addition funnel. Once all the amide solution is added, the ice-bath
is replaced with a heating mantle and the reaction mixture is heated
at reflux overnight. Then, the reaction solution is cooled down
to 0.degree. C. (the heating mantle was replaced with an ice-bath),
and the mixture is diluted with 500 ml diethyl ether. The reaction
is worked up by adding 160 ml of 15% wt. of an aqueous NaOH solution
drop-wise (via an addition funnel) with vigorous stirring. The starting
gray reaction solution changes to a colorless liquid with a white
powdery precipitate. The solution mixture is filtered and the filtrate
is dried over anhydrous magnesium sulfate. Filtration and concentration
of the filtrate gives 106 gm (94% yield) of the desired amine 1-[1-(4-chloro-phenyl)-cyclopropylmethyl]-pyrrolidine
as a pale yellow oily substance. The amine is pure as indicated
by the clean .sup.1H and .sup.13C-NMR spectral analysis.
[0133] The parent amide [1-(4-chloro-phenyl)-cyclopropyl]-pyrrolidin-1-yl--
methanone is prepared by reacting pyrrolidine with 1-(4-chloro-phenyl)-cyc-
lopropanecarbonyl chloride. A 2-Liter reaction flask equipped with
a mechanical stirrer is charged with 1000 ml of dry benzene, 53.5
gm (0.75 mol.) of pyrrolidine and 76 gm (0.75 mol.) of triethyl
amine. To this mixture (at 0.degree. C.), 108 1-(4-chloro-phenyl)-cyclopropanecarbonyl
chloride gm (0.502 mol.) of (dissolved 100 ml benzene) is added
drop-wise (via an addition funnel). Once the addition is completed,
the resulting mixture is allowed to stir at room temperature overnight.
The reaction mixture (a biphasic mixture: liquid and tan-colored
precipitate) is concentrated on a rotary evaporator at reduced pressure
to strip off excess pyrrolidine and the solvent (usually hexane
or benzene). The remaining residue is diluted with 750 ml water
and extracted with 750 ml chloroform in a separatory funnel. The
organic layer is washed twice with 500 ml water and once with brine.
Then, the organic layer is dried over anhydrous sodium sulfate,
filtered and concentrated on a rotary evaporator at reduced pressure
to give 122 gm (0.49 mol, 97% yield) of the amide as a tan-colored
solid substance.
[0134] The 1-(4-chloro-phenyl)-cyclopropanecarbonyl chloride used
in the synthesis of the amide is synthesized by treatment of the
parent acid 1-(4-chloro-phenyl)-cyclopropanecarboxylic acid with
thionyl chloride (SOCl.sub.2) as described below. To 200 gms of
thionyl chloride and 200 ml dichloromethane in a 3-necked reaction
flask, equipped with a mechanical stirrer and a reflux condenser,
100 gm (0.51 mol.) of the 1-(4-chloro-phenyl)-cyclopropanecarboxylic
acid is added in small increments (5 gm at a time) over 15 minutes
period. Once all the acid is added, the reaction mixture is then
heated at reflux. The reaction vessel is equipped with a trap (filled
with water) to collect and trap the acidic gaseous byproducts, and
used in monitoring the reaction. The reaction is usually done once
the evolution of the gaseous byproducts is ceased. The reaction
mixture is then cooled down and concentrated on a rotary evaporator
at reduced pressure to remove excess thionyl chloride and dichloromethane.
The reaction yields 109 gm (98%) of the desired 1-(4-chloro-phenyl)-cyclopropanecarbonyl
chloride as reddish viscous oil. 4
Example 2
Synthesis of SDA 1-ethyl-1-(1-phenyl-cyclopropylmethyl)-pyrrolidinium
cation
[0135] SDA 1-ethyl-1-(1-phenyl-cyclopropylmethyl)-pyrrolidinium
cation is synthesized using the synthesis procedure of Example 1
except that the synthesis starts from 1-phenyl-cyclopropanecarbonyl
chloride and pyrrolidine.
Example 3
Synthesis of SSZ-65
[0136] A 23 cc Teflon liner is charged with 5.4 gm of 0.6M aqueous
solution of 1-ethyl-1-(1-phenyl-cyclopropylmethyl)-pyrrolidinium
hydroxide (3 mmol SDA), 1.2 gm of 1M aqueous solution of NaOH (1.2
mmol NaOH) and 5.4 gm of de-ionized water. To this mixture, 0.06
gm of sodium borate decahydrate (0.157 mmol of Na.sub.2B.sub.4O.sub.7.10H.sub.2O;
.about.0.315 mmol B.sub.2O.sub.3) is added and stirred until completely
dissolved. Then, 0.9 gm of CAB-O-SIL.RTM. M-5 fumed silica (.about.14.7
mmol SiO.sub.2) is added to the solution and the mixture is thoroughly
stirred. The resulting gel is capped off and placed in a Parr bomb
steel reactor and heated in an oven at 160.degree. C. while rotating
at 43 rpm. The reaction is monitored by checking the gel's pH, and
by looking for crystal formation using Scanning Electron Microscopy
(SEM). The reaction is usually complete after heating 9-12 days
at the conditions described above. Once the crystallization is completed,
the starting reaction gel turns to a mixture comprised of a clear
liquid and powdery precipitate. The mixture is filtered through
a fritted-glass funnel. The collected solids are thoroughly washed
with water and, then, rinsed with acetone (10 ml) to remove any
organic residues. The solids are allowed to air-dry overnight and,
then, dried in an oven at 120.degree. C. for 1 hour. The reaction
affords 0.85 gram of a very fine powder. SEM shows the presence
of only one crystalline phase. The as-synthesized product is determined
by powder XRD data analysis to be SSZ-65 and has the following XRD
lines:
8 d-spacing Relative 2 Theta.sup.(a) (Angstroms) Intensity (%)
5.98 14.78 10.1 6.94 12.74 26.7 9.18 9.63 22.7 10.44 8.47 9.4 12.10
7.32 9.6 12.56 7.05 8.3 16.00 5.54 14.2 17.48 5.07 25.8 18.14 4.89
6.3 21.02 4.23 100.0 21.88 4.06 47.8 22.20 4.00 27.0 23.02 3.86
36.8 23.54 3.78 8.7 24.34 3.66 14.9 26.06 3.42 9.9 26.56 3.36 21.9
27.52 3.24 6.6 28.00 3.19 27.0 28.88 3.09 8.2 30.12 2.97 5.2 30.54
2.93 8.7 31.42 2.85 15.1
Example 4
Seeded Synthesis of Borosilicate SSZ-65
[0137] The synthesis of borosilicate SSZ-65 (B-SSZ-65) described
in Example 3 above is repeated with the exception of adding 0.04
gm of SSZ-65 as seeds to speed up the crystallization process. The
reaction conditions are exactly the same as for the previous example.
The crystallization is complete in four days and affords 0.9 gm
of B-SSZ-65.
Example 5
Synthesis of Aluminosilicate SSZ-65
[0138] A 23 cc Teflon liner is charged with 4 gm of 0.6M aqueous
solution of 1-ethyl-1-(1-phenyl-cyclopropylmethyl)-pyrrolidinium
hydroxide (2.25 mmol SDA), 1.5 gm of 1M aqueous solution of NaOH
(1.5 mmol NaOH) and 2 gm of de-ionized water. To this mixture, 0.25
gm of Na--Y zeolite (Union Carbide's LZY-52; SiO.sub.2/Al.sub.2O.sub.3=5)
is added and stirred until completely dissolved. Then, 0.85 gm of
CAB-O-SIL.RTM. M-5 fumed silica (.about.14. mmol SiO.sub.2) is added
to the solution and the mixture is thoroughly stirred. The resulting
gel is capped off and placed in a Parr bomb steel reactor and heated
in an oven at 160.degree. C. while rotating at 43 rpm. The reaction
is monitored by checking the gel's pH (increase in the pH usually
results from condensation of the silicate species during crystallization,
and decrease in pH often indicates decomposition of the SDA), and
by checking for crystal formation by scanning electron microscopy.
The reaction is usually complete after heating for 12 days at the
conditions described above. Once the crystallization is completed,
the starting reaction gel turns to a mixture comprised of a liquid
and powdery precipitate. The mixture is filtered through a fritted-glass
funnel. The collected solids are thoroughly washed with water and,
then, rinsed with acetone (10 ml) to remove any organic residues.
The solids are allowed to air-dry overnight and, then, dried in
an oven at 120.degree. C. for 1 hour. The reaction affords 0.8 gram
of SSZ-65.
Examples 6-15
Syntheses of SSZ-65 at Varying SiO.sub.2/B.sub.2O.sub.3 Ratios
[0139] SSZ-65 is synthesized at varying SiO.sub.2/B.sub.2O.sub.3
mole ratios in the starting synthesis gel. This is accomplished
using the synthetic conditions described in Example 3 keeping everything
the same while changing the SiO.sub.2/B.sub.2O.sub.3 mole ratios
in the starting gel. This is done by keeping the amount of CAB-O-SIL.RTM.
M-5 (98% SiO.sub.2 and 2% H.sub.2O) the same while varying the amount
of sodium borate in each synthesis. Consequently, varying the amount
of sodium borate leads to varying the SiO.sub.2/Na mole ratios in
the starting gels. Table 1 below shows the results of a number of
syntheses with varying SiO.sub.2/B.sub.2O.sub.3 in the starting
synthesis gel.
9TABLE 1 Example SiO.sub.2/ SiO.sub.2/ Crystallization No. B.sub.2O.sub.3
Na Time(days) Products 6 140 13.3 15 SSZ-65 7 93 12.7 12 SSZ-65
8 70 12.1 12 SSZ-65 9 56 11.6 12 SSZ-65 10 47 11.2 12 SSZ-65 11
40 10.7 12 SSZ-65 12 31 10 12 SSZ-65 13 23 9 12 SSZ-65 14 19 8.2
6 SSZ-65 15 14 7.1 6 SSZ-65 .sup.-OH/SiO.sub.2 = 0.28 R.sup.+/SiO.sub.2
= 0.2 H.sub.2O/SiO.sub.2 = 44 (R.sup.+ = organic cation (SDA))
Example 16
Calcination of SSZ-65
[0140] SSZ-65 as synthesized in Example 3 is calcined to remove
the structure directing agent (SDA) as described below. A thin bed
of SSZ-65 in a calcination dish is heated in a muffle furnace from
room temperature to 120.degree. C. at a rate of 1.degree. C./minute
and held for 2 hours. Then, the temperature is ramped up to 540.degree.
C. at a rate of 1.degree. C./minute and held for 5 hours. The temperature
is ramped up again at 1.degree. C./minute to 595.degree. C. and
held there for 5 hours. A 50/50 mixture of air and nitrogen passes
through the muffle furnace at a rate of 20 standard cubic feet (0.57
standard cubic meters) per minute during the calcination process.
The calcined SSZ-65 has the following XRD lines:
10 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 10.52 8.41 16.4 12.14
7.29 14.3 12.64 7.00 6.2 14.06 6.30 5.0 15.26 5.81 8.1 16.10 5.50
17.5 17.58 5.04 28.2 18.30 4.85 5.3 21.14 4.20 100.0 21.98 4.04
47.8 22.26 3.99 19.6 23.14 3.84 28.3 23.66 3.76 7.7 24.50 3.63 13.1
26.24 3.40 8.6 26.68 3.34 20.4 28.10 3.18 26.8 28.96 3.08 7.0 30.24
2.96 5.6 30.68 2.91 9.7 31.54 2.84 14.6
Example 17
Conversion of Borosilicate-SSZ-65 to Aluminosilicate SSZ-65
[0141] The calcined version of borosilicate SSZ-65 (as synthesized
in Example 3 and calcined in Example 16) is easily converted to
the aluminosilicate SSZ-65 version by suspending borosilicate SSZ-65
in 1M solution of aluminum nitrate nonahydrate (15 ml of 1M Al(NO.sub.3).sub.3.9H.sub.2O
soln./1 gm SSZ-65). The suspension is heated at reflux overnight.
The resulting mixture is then filtered and the collected solids
are thoroughly rinsed with de-ionized water and air-dried overnight.
The solids are further dried in an oven at 120.degree. C. for 2
hours.
Example 18
Ammonium-Ion Exchange of SSZ-65
[0142] The Na.sup.+ form of SSZ-65 (prepared as in Example 3 or
as in Example 5 and calcined as in Example 16) is converted to NH.sub.4+-SSZ-65
form by heating the material in an aqueous solution of NH.sub.4NO.sub.3
(typically 1 gm NH.sub.4NO.sub.3/1 gm SSZ-65 in 20 ml H.sub.2O)
at 90.degree. C. for 2-3 hours. The mixture is then filtered and
the obtained NH.sub.4-exchanged-product is washed with de-ionized
water and dried. The NH.sub.4.sup.+ form of SSZ-65 can be converted
to the H.sup.+ form by calcination (as described in Example 16)
to 540.degree. C.
Example 19
Argon Adsorption Analysis
[0143] SSZ-65 has a micropore volume of 0.16 cc/gm based on argon
adsorption isotherm at 87.5.degree. K (-186.degree. C.) recorded
on ASAP 2010 equipment from Micromerities. The sample is first degassed
at 400.degree. C. for 16 hours prior to argon adsorption. The low-pressure
dose is 6.00 cm.sup.3/g (STP). A maximum of one hour equilibration
time per dose is used and the total run time is 35 hours. The argon
adsorption isotherm is analyzed using the density function theory
(DFT) formalism and parameters developed for activated carbon slits
by Olivier (Porous Mater. 1995 2 9) using the Saito Foley adaptation
of the Horvarth-Kawazoe formalism (Microporous Materials, 1995
3 531) and the conventional t-plot method (J. Catalysis, 1965
4 319).
Example 20
Constraint Index
[0144] The hydrogen form of SSZ-65 of Example 3 (after treatment
according to Examples 16 17 and 18) is pelletized at 3 KPSI, crushed
and granulated to 20-40 mesh. A 0.6 gram sample of the granulated
material is calcined in air at 540.degree. C. for 4 hours and cooled
in a desiccator to ensure dryness. Then, 0.5 gram is packed into
a 3/8 inch stainless steel tube with alundum on both sides of the
molecular sieve bed. A Lindburg furnace is used to heat the reactor
tube. Helium is introduced into the reactor tube at 10 cc/min. and
at atmospheric pressure. The reactor is heated to about 315.degree.
C., and a 50/50 feed of n-hexane and 3-methylpentane is introduced
into the reactor at a rate of 8 .mu.l/min. The feed is delivered
by a Brownlee pump. Direct sampling into a GC begins after 10 minutes
of feed introduction. The Constraint Index (CI) value is calculated
from the GC data using methods known in the art. SSZ-65 has a CI
of 0.67 and a conversion of 92% after 20 minutes on stream. The
material fouls rapidly and at 218 minutes the CI is 0.3 and the
conversion is 15.7%. The data suggests a large pore zeolite with
perhaps large cavities.
Example 21
Hydrocracking of n-Hexadecane
[0145] A 1 gm sample of SSZ-65 (prepared as in Example 3 and treated
as in Examples 16 17 and 18) is suspended in 10 gm de-ionized water.
To this suspension, a solution of Pd(NH.sub.3).sub.4(NO.sub.3).sub.2
at a concentration which would provide 0.5 wt. % Pd with respect
to the dry weight of the molecular sieve sample is added. The pH
of the solution is adjusted to pH of .about.9 by a drop-wise addition
of dilute ammonium hydroxide solution. The mixture is then heated
in an oven at 75.degree. C. for 48 hours. The mixture is then filtered
through a glass frit, washed with de-ionized water, and air-dried.
The collected Pd-SSZ-65 sample is slowly calcined up to 482.degree.
C. in air and held there for three hours.
[0146] The calcined Pd/SSZ-65 catalyst is pelletized in a Carver
Press and granulated to yield particles with a 20/40 mesh size.
Sized catalyst (0.5 g) is packed into a 1/4 inch OD tubing reactor
in a micro unit for n-hexadecane hydroconversion. The table below
gives the run conditions and the products data for the hydrocracking
test on n-hexadecane.
[0147] After the catalyst is tested with n-hexadecane, it is titrated
using a solution of butylamine in hexane. The temperature is increased
and the conversion and product data evaluated again under titrated
conditions. The results shown in the table below show that SSZ-65
is effective as a hydrocracking catalyst.
11 Temperature 260.degree. C. (550.degree. F.) Time-on-Stream (hrs.)
342.4-343.4 WHSV 1.55 PSIG 1200 Titrated? Yes n-16 % Conversion
96.9 Hydrocracking Conv. 47.9 Isomerization Selectivity, % 50.5
Cracking Selectivity, % 49.5 C.sub.4-, % 2.7 C.sub.5/C.sub.4 16.9
C.sub.5+C.sub.6/C.sub.5 % 16.74 DMB/MP 0.06 C.sub.4-C.sub.13 i/n
3.83 C.sub.7-C.sub.13 yield 38.35
Example 22
Synthesis of SSZ-65
[0148] SSZ-65 is synthesized in a manner similar to that of Example
3 using a 1-[1-(4-chlorophenyl)-cyclopropylmethyl]-1-ethyl-pyrrolidinium
cation as the SDA. |