Note: Descriptions are shown in the official language in which they were submitted.
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1 MOLECULAR SIEVE SSZ-65
2 BACKGROUND OF THE INVENTION
3 Field of the Invention
4 The present invention relates to new crystalline molecular sieve SSZ-65, a
method for preparing SSZ-65 using a 1-[1-(4-chlorophenyl)-cyclopropylmethyl]-l-
6 ethyl-pyrrolidinium or 1-ethyl-l-(1-phenyl-cyclopropylmethyl)-pyrrolidinium
cation
7 as a structure directing agent and the use of SSZ-65 in catalysts for, e.g.,
hydrocarbon
8 conversion reactions.
9 State of the Art
Because of their unique sieving characteristics, as well as their catalytic
11 properties, crystalline molecular sieves and molecular sieves are
especially useful in
12 applications such as hydrocarbon conversion, gas drying and separation.
Although
13 many different crystalline molecular sieves have been disclosed, there is a
continuing
14 need for new molecular sieves with desirable properties for gas separation
and drying,
hydrocarbon and chemical conversions, and other applications. New molecular
sieves
16 may contain novel internal pore architectures, providing enhanced
selectivities in
17 these processes.
18 Crystalline aluminosilicates are usually prepared from aqueous reaction
19 mixtures containing alkali or alkaline earth metal oxides, silica, and
alumina.
Crystalline borosilicates are usually prepared under similar reaction
conditions except
21 that boron is used in place of aluminum. By varying the synthesis
conditions and the
22 composition of the reaction mixture, different molecular sieves can often
be formed.
23 SUMMARY OF THE INVENTION
24 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
26 "SSZ-65". Preferably, SSZ-65 is obtained in its silicate, aluminosilicate,
27 titanosilicate, germanosilicate, vanadosilicate or borosilicate form. The
term
28 "silicate" refers to a molecular sieve having a high mole ratio of silicon
oxide relative
29 to aluminum oxide, preferably a mole ratio greater than 100, including
molecular
sieves comprised entirely of silicon oxide. As used herein, the term
"aluminosilicate"
31 refers to a molecular sieve containing both aluminum oxide and silicon
oxide and the
1
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1 term "borosilicate" refers to a molecular sieve containing oxides of both
boron and
2 silicon.
3 In accordance with this invention, there is provided a molecular sieve
having a
4 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
6 from said first tetravalent element or mixture thereof and having, after
calcination, the
7 X-ray diffraction lines of Table II.
8 Further, in accordance with this invention, there is provided a molecular
sieve
9 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,
11 gallium oxide, iron oxide, boron oxide, titanium oxide, indium oxide,
vanadium oxide
12 and mixtures thereof and having, after calcination, the X-ray diffraction
lines of Table
13 II below. It should be noted that the mole ratio of the first oxide or
mixture of first
14 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
16 a germanosilicate.
17 The present invention also includes this molecular sieve which is
18 predominantly in the hydrogen form, which hydrogen form is prepared by ion
19 exchanging with an acid or with a solution of an ammonium salt followed by
a second
calcination. If the molecular sieve is synthesized with a high enough ratio of
SDA
21 cation to sodium ion, calcination alone may be sufficient. For high
catalytic activity,
22 the SSZ-65 molecular sieve should be predominantly in its hydrogen ion
form. It is
23 preferred that, after calcination, at least 80% of the cation sites are
occupied by
24 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
26 hydrogen ions and/or rare earth ions.
27 In accordance with the present invention there is further provided a
process for
28 converting hydrocarbons comprising contacting a hydrocarbonaceous feed at
29 hydrocarbon converting conditions with a catalyst comprising the molecular
sieve of
this invention. The molecular sieve may be predominantly in the hydrogen form.
It
31 may also be substantially free of acidity.
2
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1 Further provided by the present invention is a hydrocracking process
2 comprising contacting a hydrocarbon feedstock under hydrocracking conditions
with
3 a catalyst comprising the molecular sieve of this invention, preferably
predominantly
4 in the hydrogen form.
This invention also includes a dewaxing process comprising contacting a
6 hydrocarbon feedstock under dewaxing conditions with a catalyst comprising
the
7 molecular sieve of this invention, preferably predominantly in the hydrogen
form.
8 The present invention also includes a process for improving the viscosity
9 index of a dewaxed product of waxy hydrocarbon feeds comprising contacting
the
waxy hydrocarbon feed under isomerization dewaxing conditions with a catalyst
11 comprising the molecular sieve of this invention, preferably predominantly
in the
12 hydrogen form.
13 The present invention further includes a process for producing a C20+ lube
oil
14 from a C20+ olefin feed comprising isomerizing said olefin feed under
isomerization
conditions over a catalyst comprising the molecular sieve of this invention.
The
16 molecular sieve may be predominantly in the hydrogen form. The catalyst may
17 contain at least one Group VIII metal.
18 In accordance with this invention, there is also provided a process for
19 catalytically dewaxing a hydrocarbon oil feedstock boiling above about 350
F
(177 C) and containing straight chain and slightly branched chain hydrocarbons
21 comprising contacting said hydrocarbon oil feedstock in the presence of
added
22 hydrogen gas at a hydrogen,pressure of about 15-3000 psi (0.103 - 20.7 MPa)
with a
23 catalyst comprising the molecular sieve of this invention, preferably
predominantly in
24 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
molecular
26 sieve of this invention, and a second layer comprising an aluminosilicate
molecular
27 sieve which is more shape selective than the molecular sieve of said first
layer. The
28 first layer may contain at least one Group VIII metal.
29 Also included in the present invention is a process for preparing a
lubricating
oil which comprises hydrocracking in a hydrocracking zone a hydrocarbonaceous
31 feedstock to obtain an effluent comprising a hydrocracked oil, and
catalytically
32 dewaxing said effluent comprising hydrocracked oil at a temperature of at
least about
3
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1 400 F (204 C) and at a pressure of from about 15 psig to about 3000 psig
(0.103 -
2 20.7 MPa gauge)in the presence of added hydrogen gas with a catalyst
comprising the
3 molecular sieve of this invention. The molecular sieve may be predominantly
in the
4 hydrogen form. The catalyst may contain at least one Group VIII metal.
Further included in this invention is a process for isomerization dewaxing a
6 raffinate comprising contacting said raffinate in the presence of added
hydrogen with
7 a catalyst comprising the molecular sieve of this invention. The raffinate
may be
8 bright stock, and the molecular sieve may be predominantly in the hydrogen
form.
9 The catalyst may contain at least one Group VIII metal.
Also included in this invention is a process for increasing the octane of a
11 hydrocarbon feedstock to produce a product having an increased aromatics
content
12 comprising contacting a hydrocarbonaceous feedstock which comprises normal
and
13 slightly branched hydrocarbons having a boiling range above about 40 C and
less
14 than about 200 C, under aromatic conversion conditions with a catalyst,
comprising
the molecular sieve of this invention made substantially free of acidity by
neutralizing
16 said molecular sieve with a basic metal. Also provided in this invention is
such a
17 process wherein the molecular sieve contains a Group VIII metal component.
18 Also provided by the present invention is a catalytic cracking process
19 comprising contacting a hydrocarbon feedstock in a reaction zone under
catalytic
cracking conditions in the absence of added hydrogen with a catalyst
comprising the
21 molecular sieve of this invention, preferably predominantly in the hydrogen
form.
22 Also included in this invention is such a catalytic cracking process
wherein the
23 catalyst additionally comprises a large pore crystalline cracking
component.
24 This invention further provides an isomerization process for isomerizing C4
to
C7 hydrocarbons, comprising contacting a feed having normal and slightly
branched
26 C4 to C7 hydrocarbons under isomerizing conditions with a catalyst
comprising the
27 molecular sieve of this invention, preferably predominantly in the hydrogen
form.
28 The molecular sieve may be impregnated with at least one Group VIII metal,
29 preferably platinum. The catalyst may be calcined in a steam/air mixture at
an
3o elevated temperature after impregnation of the Group VIII metal.
31 Also provided by the present invention is a process for alkylating an
aromatic
32 hydrocarbon which comprises contacting under alkylation conditions at least
a molar
4
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1 excess of an aromatic hydrocarbon with a C2 to C20 olefin under at least
partial liquid
2 phase conditions and in the presence of a catalyst comprising the molecular
sieve of
3 this invention, preferably predominantly in the hydrogen form. The olefin
may be a
4 C2 to C4 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
6 selected from the group consisting of benzene, toluene, ethylbenzene,
xylene,
7 naphthalene, naphthalene derivatives, dimethylnaphthalene or mixtures
thereof.
8 Further provided in accordance with this invention is a process for
9 transalkylating an aromatic hydrocarbon which comprises contacting under
transalkylating conditions an aromatic hydrocarbon with a polyalkyl aromatic
11 hydrocarbon under at least partial liquid phase conditions and in the
presence of a
12 catalyst comprising the molecular sieve of this invention, preferably
predominantly.in
13 the hydrogen form. The aromatic hydrocarbon and the polyalkyl aromatic
14 hydrocarbon may be present in a molar ratio of from about 1:1 to about
25:1,
respectively.
16 The aromatic hydrocarbon may be selected from the group consisting of
17 benzene, toluene, ethylbenzene, xylene, or mixtures thereof, and the
polyalkyl
18 aromatic hydrocarbon may be a dialkylbenzene.
19 Further provided by this invention is a process to convert paraffins to
aromatics which comprises contacting paraffins under conditions which cause
21 paraffins to convert to aromatics with a catalyst comprising the molecular
sieve of this
22 invention, said catalyst comprising gallium, zinc, or a compound of gallium
or zinc.
23 In accordance with this invention there is also provided a process for
24 isomerizing olefins comprising contacting said olefin under conditions
which cause
isomerization of the olefin with a catalyst comprising the molecular sieve of
this
26 invention.
27 Further provided in accordance with this invention is a process for
isomerizing
28 an isomerization feed comprising an aromatic C8 stream of xylene isomers or
29 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
31 feed under isomerization conditions with a catalyst comprising the
molecular sieve of
32 this invention.
5
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1 The present invention further provides a process for oligomerizing olefins
2 comprising contacting an olefin feed under oligomerization conditions with a
catalyst
3 comprising the molecular sieve of this invention.
4 This invention also provides a process for converting oxygenated
hydrocarbons comprising contacting said oxygenated hydrocarbon with a catalyst
6 comprising the molecular sieve of this invention under conditions to produce
liquid
7 products. The oxygenated hydrocarbon may be a lower alcohol.
8 Further provided in accordance with the present invention is a process for
the
9 production of higher molecular weight hydrocarbons from lower molecular
weight
hydrocarbons comprising the steps of:
11 (a) introducing into a reaction zone a lower molecular weight hydrocarbon-
12 containing gas and contacting said gas in said zone under C2+ hydrocarbon
13 synthesis conditions with the catalyst and a metal or metal compound
capable of
14 converting the lower molecular weight hydrocarbon to a higher molecular
weight hydrocarbon; and
16 (b) withdrawing from said reaction zone a higher molecular weight
17 hydrocarbon-containing stream.
18 In accordance with this invention, there is also provided a process for the
19 reduction of oxides of nitrogen contained in a gas stream in the presence
of oxygen
wherein said process comprises contacting the gas stream with a molecular
sieve
21 having a mole ratio greater than about 15 of (1) an oxide of a first
tetravalent element
22 to (2) an oxide of a second tetravalent element different from said first
tetravalent
23 element, trivalent element, pentavalent element or mixture thereof and
having, after
24 calcination, the X-ray diffraction lines of Table II. The molecular sieve
may contain a
metal or metal ions (such as cobalt, copper, platinum, iron, chromium,
manganese,
26 nickel, zinc, lanthanum, palladium, rhodium or mixtures thereof) capable of
27 catalyzing the reduction of the oxides of nitrogen, and the process may be
conducted
28 in the presence of a stoichiometric excess of oxygen. In a preferred
embodiment, the
29 gas stream is the exhaust stream of an internal combustion engine.
DETAILED DESCRIPTION OF THE INVENTION
31 The present invention comprises a family of crystalline, large pore
molecular
32 sieves designated herein "molecular sieve SSZ-65" or simply "SSZ-65". As
used
6
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1 herein, the term "large pore" means having an average pore size diameter
greater than
2 about 6.0 Angstroms, preferably from about 6.5 Angstroms to about 7.5
Angstroms.
3 In preparing SSZ-65, a 1-[1-(4-chlorophenyl)-cyclopropylmethyl]-1-ethyl-
4 pyrrolidinium or 1-ethyl-l-(1-phenyl-cyclopropylmethyl)-pyrrolidinium cation
is used
as a structure directing agent ("SDA"), also known as a crystallization
template. The
6 SDA's useful for making SSZ-65 have the following structures:
7
N
J
"zz~
CI Me
1-[ 1-(4-Chloro-phenyl)-cyclopropylmethyl]-1-ethyl-
8 pyrrolidinium
9
7 N~
Me
11 1-Ethyl-1 -(1-phenyl-cyclopropylmethyl)-pyrrolidinium
12
13 The SDA cation is associated with an anion (X-) which may be any anion that
14 is not detrimental to the formation of the molecular sieve. Representative
anions
include halogen, e.g., fluoride, chloride, bromide and iodide, hydroxide,
acetate,
16 sulfate, tetrafluoroborate, carboxylate, and the like. Hydroxide is the
most preferred
17 anion.
18 In general, SSZ-65 is prepared by contacting an active source of one or
more
19 oxides selected from the group consisting of monovalent element oxides,
divalent
element oxides, trivalent element oxides, tetravalent element oxides and/or
21 pentavalent elements with the 1-[ 1 -(4-chlorophenyl)-cyclopropylmethyl]- 1
-ethyl-
22 pyrrolidinium or 1-ethyl-l-(1-phenyl-cyclopropylmethyl)-pyrrolidinium
cation SDA.
23 SSZ-65 is prepared from a reaction mixture having the composition shown in
24 Table A below.
7
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1 TABLE A
2 Reaction Mixture
3 Typical Preferred
4 YOZ/WaOb > 15 30 - 70
OH-/YO2 0.10 - 0.50 0.20 - 0.30
6 Q/YOZ 0.05 - 0.50 0.10 - 0.20
7 M21"/YO2 0.02 - 0.40 0.10 - 0.25
8 H20/YOZ 30 - 80 35 - 45
9 wherein 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, and b is 2
when a
11 is 1(i.e., W is tetravalent) and b is 3 when a is 2 (i.e., W is trivalent);
M is an alkali
12 metal cation, alkaline earth metal cation or mixtures thereof; n is the
valence of M
13 (i.e., 1 or 2); and Q is a 1-[1-(4-chlorophenyl)-cyclopropylmethyl]-1-ethyl-
14 pyrrolidinium or 1-ethyl-l-(1-phenyl-cyclopropylmethyl)-pyrrolidinium
cation.
In practice, SSZ-65 is prepared by a process comprising:
16 (a) preparing an aqueous solution containing sources of at least one
17 oxide capable of forming a crystalline molecular sieve and a 1-[1-(4-
chlorophenyl)-
18 cyclopropylmethyl]-1-ethyl-pyrrolidinium or 1-ethyl-l-(1-phenyl-
19 cyclopropylmethyl)-pyrrolidinium cation having an anionic counterion which
is not
detrimental to the formation of SSZ-65;
21 (b) maintaining the aqueous solution under conditions sufficient to
22 form crystals of SSZ-65; and
23 (c) recovering the crystals of SSZ-65.
24 Accordingly, SSZ-65 may comprise the crystalline material and the SDA in
combination with metallic and non-metallic oxides bonded in tetrahedral
coordination
26 through shared oxygen atoms to form a cross-linked three dimensional
crystal
27 structure. The metallic and non-metallic oxides comprise one or a
combination of
28 oxides of a first tetravalent element(s), and one or a combination of a
trivalent
29 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
31 preferably selected from the group consisting of silicon, germanium and
combinations
32 thereof. More preferably, the first tetravalent element is silicon. The
trivalent
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1 element, pentavalent element and second tetravalent element (which is
different from
2 the first tetravalent element) is preferably selected from the group
consisting of
3 aluminum, gallium, iron, boron, titanium, indium, vanadium and combinations
4 thereof. More preferably, the second trivalent or tetravalent element is
aluminum or
boron.
6 Typical sources of aluminum oxide for the reaction mixture include
7 aluminates, alumina, aluminum colloids, aluminum oxide coated on silica sol,
8 hydrated alumina gels such as Al(OH)3 and aluminum compounds such as A1C13
and
9 A12(SO4)3. Typical sources of silicon oxide include silicates, silica
hydrogel, silicic
acid, fumed silica, colloidal silica, tetra-alkyl orthosilicates, and silica
hydroxides.
11 Boron, as well as gallium, germanium, titanium, indium, vanadium and iron,
can be
12 added in forms corresponding to their aluminum and silicon counterparts.
13 A source molecular sieve reagent may provide a source of aluminum or boron.
14 In most cases, the source molecular sieve also provides a source of silica.
The source
molecular sieve in its dealuminated or deboronated form may also be used as a
source
16 of silica, with additional silicon added using, for example, the
conventional sources
17 listed above. Use of a source molecular sieve reagent as a source of
alumina for the
18 present process is more completely described in U.S. Patent No. 5,225,179,
issued
19 July 6, 1993 to Nakagawa entitled "Method of Making Molecular Sieves", the
disclosure of which is incorporated herein by reference.
21 Typically, an alkali metal hydroxide and/or an alkaline earth metal
hydroxide,
22 such as the hydroxide of sodium, potassium, lithium, cesium, rubidium,
calcium, and
23 magnesium, is used in the reaction mixture; however, this component can be
omitted
24 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
26 hydroxide ion, thereby reducing or eliminating the alkali metal hydroxide
quantity
27 required. The alkali metal cation or alkaline earth cation may be part of
the
28 as-synthesized crystalline oxide material, in order to balance valence
electron charges
29 therein.
The reaction mixture is maintained at an elevated temperature until the
31 crystals of the SSZ-65 are formed. The hydrothermal crystallization is
usually
32 conducted under autogenous pressure, at a temperature between 100 C and 200
C,
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1 preferably between 135 C and 160 C. The crystallization period is typically
greater
2 than 1 day and preferably from about 3 days to about 20 days.
3 Preferably, the molecular sieve is prepared using mild stirring or
agitation.
4 During the hydrothermal crystallization step, the SSZ-65 crystals can be
allowed to nucleate spontaneously from the reaction mixture. The use of SSZ-65
6 crystals as seed material can be advantageous in decreasing the time
necessary for
7 complete crystallization to occur. In addition, seeding can lead to an
increased purity
8 of the product obtained by promoting the nucleation and/or formation of SSZ-
65 over
9 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
11 in the reaction mixture.
12 Once the molecular sieve crystals have formed, the solid product is
separated
13 from the reaction mixture by standard mechanical separation techniques such
as
14 filtration. The crystals are water-washed and then dried, e.g., at 90 C to
150 C for
from 8 to 24 hours, to obtain the as-synthesized SSZ-65 crystals. The drying
step can
16 be performed at atmospheric pressure or under vacuum.
17 SSZ-65 as prepared has a mole ratio of an oxide selected from silicon
oxide,
18 germanium oxide and mixtures thereof to an oxide selected from aluminum
oxide,
19 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
21 diffraction lines of Table II below. SSZ-65 further has a composition, as
synthesized
22 (i.e., prior to removal of the SDA from the SSZ-65) and in the anhydrous
state, in
23 terms of mole ratios, shown in Table B below.
24 TABLE B
As-Synthesized SSZ-65
26 YO2/WcOd > 15
27 M2/n/YO2 0.01 - 0.03
28 Q/Y02 0.02 - 0.05
29 wherein Y is silicon, germanium or a mixture thereof; W is aluminum,
gallium, iron,
3o boron, titanium, indium, vanadium or mixtures thereof; c is 1 or 2; d is 2
when c is 1
31 (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
32 when W is pentavalent); M is an alkali metal cation, alkaline earth metal
cation or
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1 mixtures thereof; n is the valence of M(i.e., 1 or 2); and Q is a 1- [ 1 -(4-
chlorophenyl)-
2 cyclopropylmethyl]-1-ethyl-pyrrolidinium or 1-ethyl-l-(1-phenyl-
3 cyclopropylmethyl)-pyrrolidinium cation.
4 SSZ-65 can be made with a mole ratio of YO2/W,Oa of oo, i.e., there is
essentially no W,Odpresent in the SSZ-65. In this case, the SSZ-65 would be an
all-
6 silica material or a germanosilicate. Thus, in a typical case where oxides
of silicon
7 and aluminum are used, SSZ-65 can be made essentially aluminum free, i.e.,
having a
8 silica to alumina mole ratio of oo. A method of increasing the mole ratio of
silica to
9 alumina is by using standard acid leaching or chelating treatments. However,
essentially aluminum-free SSZ-65 can be synthesized using essentially aluminum-
free
11 silicon sources as the main tetrahedral metal oxide component, if boron is
also
12 present. The boron can then be removed, if desired, by treating the
borosilicate SSZ-
13 65 with acetic acid at elevated temperature ( as described in Jones et al.,
Chem.
14 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
16 described above and replaced with metal atoms by techniques known in the
art to
17 make, e.g., an aluminosilicate version of SSZ-65. SSZ-65 can also be
prepared
18 directly as an aluminosilicate.
19 Lower silica to alumina ratios may also be obtained by using methods which
insert aluminum into the crystalline framework. For example, aluminum
insertion
21 may occur by thermal treatment of the molecular sieve in combination with
an
22 alumina binder or dissolved source of alumina. Such procedures are
described in U.S.
23 Patent No. 4,559,315, issued on December 17, 1985 to Chang et al.
24 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,
26 as-synthesized, has a crystalline structure whose X-ray powder diffraction
pattern
27 exhibit the characteristic lines shown in Table I and is thereby
distinguished from
28 other molecular sieves.
11
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1 TABLE I
2 As-Synthesized SSZ-65
3
2 Theta(a) d-spacing (Angstroms) Relative Intensity (%)2)
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
4 (a) f 0.1
(b) The X-ray patterns provided are based on a relative intensity scale in
6 which the strongest line in the X-ray pattern is assigned a value of 100:
7 W(weak) is less than 20; M(medium) is between 20 and 40; S(strong)
8 is between 40 and 60; VS(very strong) is greater than 60.
9 Table IA below shows the X-ray powder diffraction lines for as-synthesized
SSZ-65 including actual relative intensities.
11 TABLE IA
12
2 Theta(a) d-spacing (Angstroms) Relative Intensity (%)
7.17 12.32 5.1
7.46 11.84 13.5
7.86 11.24 10.2
8.32 10.62 4.7
13.38 6.61 1.7
17.20 5.15 1.4
18.21 4.87 2.0
19.29 4.60 1.5
21.42 4.15 15.7
22.46 3.96 100.0
22.85 3.89 6.9
25.38 3.51 6.7
26.02 3.42 1.8
27.08 3.29 12.3
28.80 3.10 3.2
29.62 3.01 - 8.5
30.50 2.93 2.9
32.88 2.72 1.4
33.48 2.67 5.7
12
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34.76 2.58 1.8
36.29 2.47 1.6
37.46 2.40 1.3
1 (a) f 0.1
2 After calcination, the SSZ-65 molecular sieves have a crystalline structure
3 whose X-ray powder diffraction pattern include the characteristic lines
shown in
4 Table II:
TABLE II
6 Calcined SSZ-65
2 Theta(a) d-sj2acing (Angstroms) Relative 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
7 (a) f 0.1
8 Table IIA below shows the X-ray powder diffraction lines for calcined SSZ-65
9 including actual relative intensities.
TABLE IIA
11
2 Theta(a) d-spacing (Angstroms) Relative 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
13
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23.14 3.84 28.3
26.68 3.34 20.4
28.10 3.18 26.8
1 (a) f0.1
2
3 The X-ray powder diffraction patterns were determined by standard
4 techniques. The radiation was the K-alpha/doublet of copper. The peak
heights and
the positions, as a function of 20 where 0 is the Bragg angle, were read from
the
6 relative intensities of the peaks, and d, the interplanar spacing in
Angstroms
7 corresponding to the recorded lines, can be calculated.
8 The variation in the scattering angle (two theta) measurements, due to
9 instrument error and to differences between individual samples, is estimated
at
f 0.1 degrees.
11 The X-ray diffraction pattern of Table I is representative of "as-
synthesized"
12 or "as-made" SSZ-65 molecular sieves. Minor variations in the diffraction
pattern
13 can result from variations in the silica-to-alumina or silica-to-boron mole
ratio of the
14 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
16 broadening.
17 Representative peaks from the X-ray diffraction pattern of calcined SSZ-65
18 are shown in Table II. Calcination can also result in changes in the
intensities of the
19 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
21 cations present in the molecular sieve with various other cations (such as
H or NH4)
22 yields essentially the same diffraction pattern, although again, there may
be minor
23 shifts in the interplanar spacing and variations in the relative
intensities of the peaks.
24 Notwithstanding these minor perturbations, the basic crystal lattice
remains
unchanged by these treatments.
26 Crystalline SSZ-65 can be used as-synthesized, but preferably will be
27 thermally treated (calcined). Usually, it is desirable to remove the alkali
metal cation
28 by ion exchange and replace it with hydrogen, ammonium, or any desired
metal ion.
29 The molecular sieve can be leached with chelating agents, e.g., EDTA or
dilute acid
14
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1 solutions, to increase the silica to alumina mole ratio. The molecular sieve
can also
2 be steamed; steaming helps stabilize the crystalline lattice to attack from
acids.
3 The molecular sieve can be used in intimate combination with hydrogenating
4 components, such as tungsten, vanadium, molybdenum, rhenium, nickel, cobalt,
chromium, manganese, or a noble metal, such as palladium or platinum, for
those
6 applications in which a hydrogenation-dehydrogenation function is desired.
7 Metals may also be introduced into the molecular sieve by replacing some of
8 the cations in the molecular sieve with metal cations via standard ion
exchange
9 techniques (see, for example, U.S. Patent Nos. 3,140,249 issued July 7, 1964
to Plank
et al.; 3,140,251 issued July 7, 1964 to Plank et al.; and 3,140,253 issued
July 7, 1964
11 to Plank et al.). Typical replacing cations can include metal cations,
e.g., rare earth,
12 Group IA, Group IIA and Group VIII metals, as well as their mixtures. Of
the
13 replacing metallic cations, cations of metals such as rare earth, Mn, Ca,
Mg, Zn, Cd,
14 Pt, Pd, Ni, Co, Ti, Al, Sn, and Fe are particularly preferred.
The hydrogen, ammonium, and metal components can be ion-exchanged into
16 the SSZ-65. The SSZ-65 can also be impregnated with the metals, or the
metals can
17 be physically and intimately admixed with the SSZ-65 using standard methods
known
18 to the art.
19 Typical ion-exchange techniques involve contacting the synthetic molecular,
sieve with a solution containing a salt of the desired replacing cation or
cations.
21 Although a wide variety of salts can be employed, chlorides and other
halides,
22 acetates, nitrates, and sulfates are particularly preferred. The molecular
sieve is
23 usually calcined prior to the ion-exchange procedure to remove the organic
matter
24 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
26 patents including U.S. Patent Nos. 3,140,249 issued on July 7, 1964 to
Plank et al.;
27 3,140,251 issued on July 7, 1964 to Plank et al.; and 3,140,253 issued on
July 7, 1964
28 to Plank et al.
29 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
31 65 C to about 200 C. After washing, the molecular sieve can be calcined in
air or
32 inert gas at temperatures ranging from about 200 C to about 800 C for
periods of
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1 time ranging from 1 to 48 hours, or more, to produce a catalytically active
product
2 especially useful in hydrocarbon conversion processes.
3 Regardless of the cations present in the synthesized form of SSZ-65, the
4 spatial arrangement of the atoms which form the basic crystal lattice of the
molecular
sieve remains essentially unchanged.
6 SSZ-65 can be formed into a wide variety of physical shapes. Generally
7 speaking, the molecular sieve can be in the form of a powder, a granule, or
a molded
8 product, such as extrudate having a particle size sufficient to pass through
a 2-mesh
9 (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
11 extruded before drying, or, dried or partially dried and then extruded.
12 SSZ-65 can be composited with other materials resistant to the temperatures
13 and other conditions employed in organic conversion processes. Such matrix
14 materials include active and inactive materials and synthetic or naturally
occurring,
molecular sieves as well as inorganic materials such as clays, silica and
metal oxides.
16 Examples of such materials and the manner in which they can be used are
disclosed in
17 U.S. Patent No. 4,910,006, issued May 20, 1990 to Zones et al., and U.S.
Patent
18 No. 5,316,753, issued May 31, 1994 to Nakagawa, both of which are
incorporated by
19 reference herein in their entirety.
SSZ-65 molecular sieves are useful in hydrocarbon conversion reactions.
21 Hydrocarbon conversion reactions are chemical and catalytic processes in
which
22 carbon containing compounds are changed to different carbon containing
compounds.
23 Examples of hydrocarbon conversion reactions in which SSZ-65 are expected
to be
24 useful include hydrocracking, dewaxing, catalytic cracking and olefin and
aromatics
formation reactions. The catalysts are also expected to be useful in other
petroleum
26 refining and hydrocarbon conversion reactions such as isomerizing n-
paraffins and
27 naphthenes, polymerizing and oligomerizing olefinic or acetylenic compounds
such as
28 isobutylene and butene-1, reforming, isomerizing polyalkyl substituted
aromatics
29 (e.g., m-xylene), and disproportionating aromatics (e.g., toluene) to
provide mixtures
of benzene, xylenes and higher methylbenzenes and oxidation reactions. Also
31 included are rearrangement reactions to make various naphthalene
derivatives, and
16
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1 forming higher molecular weight hydrocarbons from lower molecular weight
2 hydrocarbons (e.g., methane upgrading).
3 The SSZ-65 catalysts may have high selectivity, and under hydrocarbon
conversion
4 conditions can provide a high percentage of desired products relative to
total products.
For high catalytic activity, the SSZ-65 molecular sieve should be
6 predominantly in its hydrogen ion form. Generally, the molecular sieve is
converted
7 to its hydrogen form by ammonium exchange followed by calcination. If the
8 molecular sieve is synthesized with a high enough ratio of SDA cation to
sodium ion,
9 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
11 herein, "predominantly in the hydrogen form" means that, after calcination,
at least
12 80% of the cation sites are occupied by hydrogen ions and/or rare earth
ions.
13 SSZ-65 molecular sieves can be used in processing hydrocarbonaceous
14 feedstocks. Hydrocarbonaceous feedstocks contain carbon compounds and can
be
from many different sources, such as virgin petroleum fractions, recycle
petroleum
16 fractions, shale oil, liquefied coal, tar sand oil, synthetic paraffins
from NAO,
17 recycled plastic feedstocks and, in general, can be any carbon containing
feedstock
18 susceptible to zeolitic catalytic reactions. Depending on the type of
processing the
19 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,
21 however, that in general processing will be more efficient (and the
catalyst more
22 active) the lower the metal, nitrogen, and sulfur content of the feedstock.
23 The conversion of hydrocarbonaceous feeds can take place in any convenient
24 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
26 depending on the conversion process and method of operation.
27 Other reactions which can be performed using the catalyst of this invention
28 containing a metal, e.g., a Group VIII metal such platinum, include
29 hydrogenation-dehydrogenation reactions, denitrogenation and
desulfurization
reactions.
17
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1 The following table indicates typical reaction conditions which may be
2 employed when using catalysts comprising SSZ-65 in the hydrocarbon
conversion
3 reactions of this invention. Preferred conditions are indicated in
parentheses.
4
Process Tem ., C Pressure LHSV
H drocrackin 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.- 0.5-50
(atm.-5 atm.)
Oligomerization 232-649 0.1-50 atm. ' 0.2-50
10-2324 - 0.05-205
(27-204)4 - (0.1-10)5
Paraffins to 100-700 0-1000 psig 0.5-40
aromatics
Condensation of 260-538 0.5-1000 psig, 0:5-50
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 260-593 0.5-50 atm. 0.1-100
isomerization (315-566)2 (1-5 atm)2 (0.5-50)5
38-3714 1-200 atm.4 0.5-50
6
7 1 Several hundred atmospheres
8 2 Gas phase reaction
9 3 Hydrocarbon partial pressure
4 Liquid phase reaction
11 5 WHSV
12 Other reaction conditions and parameters are provided below.
13 Hydrocracking
14 Using a catalyst which comprises SSZ-65, preferably predominantly in the
hydrogen form, and a hydrogenation promoter, heavy petroleum residual
feedstocks,
16 cyclic stocks and other hydrocrackate charge stocks can be hydrocracked
using the
18
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I process conditions and catalyst components disclosed in the aforementioned
U.S.
2 Patent No. 4,910,006 and U.S. Patent No. 5,316,753.
3 The hydrocracking catalysts contain an effective amount of at least one
4 hydrogenation component of the type commonly employed in hydrocracking
catalysts. The hydrogenation component is generally selected from the group of
6 hydrogenation catalysts consisting of one or more metals of Group VIB and
7 Group VIII, including the salts, complexes and solutions containing such.
The
8 hydrogenation catalyst is preferably selected from the group of metals,
salts and
9 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
11 one of nickel, molybdenum, cobalt, tungsten, titanium, chromium and
mixtures
12 thereof. Reference to the catalytically active metal or metals is intended
to encompass
13 such metal or metals in the elemental state or in some form such as an
oxide, sulfide,
14 halide, carboxylate and the like. The hydrogenation catalyst is present in
an effective
amount to provide the hydrogenation function of the hydrocracking catalyst,
and
16 preferably in the range of from 0.05 to 25% by weight.
17 Dewaxin~
18 SSZ-65, preferably predominantly in the hydrogen form, can be used to dewax
19 hydrocarbonaceous feeds by selectively removing straight chain paraffins.
Typically,
the viscosity index of the dewaxed product is improved (compared to the waxy
feed)
21 when the waxy feed is contacted with SSZ-65 under isomerization dewaxing
22 conditions.
23 The catalytic dewaxing conditions are dependent in large measure on the
feed
24 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
26 between about 500 and about 30,000 SCF/bbl (standard cubic feet per barrel)
(0.089
27 to 5.34 SCM/liter (standard cubic meters/liter)), preferably about 1000 to
about
28 20,000 SCF/bbl (0.178 to 3.56 SCM/liter). Generally, hydrogen will be
separated
29 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 F (177 C).
31 A typical dewaxing process is the catalytic dewaxing of a hydrocarbon oil
32 feedstock boiling above about 350 F (177 C) and containing straight chain
and
19
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1 slightly branched chain hydrocarbons by contacting the hydrocarbon oil
feedstock in
2 the presence of added hydrogen gas at a hydrogen pressure of about 15-3000
psi
3 (0.103-20.7 MPa) with a catalyst comprising SSZ-65 and at least one Group
VIII
4 metal.
The SSZ-65 hydrodewaxing catalyst may optionally contain a hydrogenation
6 component of the type commonly employed in dewaxing catalysts. See the
7 aforementioned U.S. Patent No. 4,910,006 and U.S. Patent No. 5,316,753 for
8 examples of these hydrogenation components.
9 The hydrogenation component is present in an effective amount to provide an
effective hydrodewaxing and hydroisomerization catalyst preferably in the
range of
11 from about 0.05 to 5% by weight. The catalyst may be run in such a mode
to.increase
12 isomerization dewaxing at the expense of cracking reactions.
13 The feed may be hydrocracked, followed by dewaxing. This type of two stage
14 process and typical hydrocracking conditions are described in U.S. Patent
No. 4,921,594, issued May 1, 1990 to Miller, which is incorporated herein by
16 reference in its entirety.
17 SSZ-65 may also be utilized as a dewaxing catalyst in the form of a layered
18 catalyst. That is, the catalyst comprises a first layer comprising
molecular sieve SSZ-
19 65 and at least one Group VIII metal, and a second layer comprising an
aluminosilicate molecular sieve which is more shape selective than molecular
sieve
21 SSZ-65. The use of layered catalysts is disclosed in U.S. Patent No.
5,149,421, issued
22 September 22, 1992 to Miller, which is incorporated by reference herein in
its
23 entirety. The layering may also include a bed of SSZ-65 layered with a non-
zeolitic
24 component designed for either hydrocracking or hydrofinishing.
SSZ-65 may also be used to dewax raffinates, including bright stock, under
26 conditions such as those disclosed in U. S. Patent No. 4,181,598, issued
January 1,
27 1980 to Gillespie et al., which is incorporated by reference herein in its
entirety.
28 It is often desirable to use mild hydrogenation (sometimes referred to as
29 hydrofinishing) to produce more stable dewaxed products. The hydrofinishing
step
can be performed either before or after the dewaxing step, and preferably
after.
31 Hydrofinishing is typically conducted at temperatures ranging from about
190 C to
32 about 340 C at pressures from about 400 psig to about 3000 psig (2.76 to
20.7 MPa
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1 gauge) at space velocities (LHSV) between about 0.1 and 20 and a hydrogen
recycle
2 rate of about 400 to 1500 SCF/bbl (0.071 to 0.27 SCM/liter). The
hydrogenation
3 catalyst employed must be active enough not only to hydrogenate the olefins,
4 diolefins and color bodies which may be present, but also to reduce the
aromatic
content. Suitable hydrogenation catalyst are disclosed in U. S. Patent No.
4,921,594,
6 issued May 1, 1990 to Miller, which is incorporated by reference herein in
its entirety.
7 The hydrofinishing step is beneficial in preparing an acceptably stable
product (e.g., a
8 lubricating oil) since dewaxed products prepared from hydrocracked stocks
tend to be
9 unstable to air and light and tend to form sludges spontaneously and
quickly.
Lube oil may be prepared using SSZ-65. For example, a C20+ lube oil may be
11 made by isomerizing a CZO+ olefin feed over a catalyst comprising SSZ-65 in
the
12 hydrogen form and at least one Group VIII metal. Alternatively, the
lubricating oil
13 may be made by hydrocracking in a hydrocracking zone a hydrocarbonaceous
14 feedstock to obtain an effluent comprising a hydrocracked oil, and
catalytically
dewaxing the effluent at a temperature of at least about 400 F (204 C) and at
a
16 pressure of from about 15 psig to about 3000 psig (0.103-20.7 MPa gauge) in
the
17 presence of added hydrogen gas with a catalyst comprising SSZ-65 in the
hydrogen
18 form and at least one Group VIII metal.
19 Aromatics Formation
SSZ-65 can be used to convert light straight run naphthas and similar mixtures
21 to highly aromatic mixtures. Thus, normal and slightly branched chained
22 hydrocarbons, preferably having a boiling range above about 40 C and less
than about
23 200 C, can be converted to products having a substantial higher octane
aromatics
24 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
26 using a catalyst comprising SSZ-65.
27 The conversion catalyst preferably contains a Group VIII metal compound to
28 have sufficient activity for commercial use. By Group VIII metal compound
as used
29 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
31 be used. Rhenium or tin or a mixture thereof may also be used in
conjunction with
32 the Group VIII metal compound and preferably a noble metal compound. The
most
21
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1 preferred metal is platinum. The amount of Group VIII metal present in the
2 conversion catalyst should be within the normal range of use in reforming
catalysts,
3 from about 0.05 to 2.0 weight percent, preferably 0.2 to 0.8 weight percent.
4 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
6 the molecular sieve with a basic metal, e.g., alkali metal, compound.
Methods for
7 rendering the catalyst free of acidity are known in the art. See the
aforementioned
8 U.S. Patent No. 4,910,006 and U.S. Patent No. 5,316,753 for a description of
such
9 methods.
The preferred alkali metals are sodium, potassium, rubidium and cesium. The
11 molecular sieve itself can be substantially free of acidity only at very
high.
12 silica:alumina mole ratios.
13 Catalytic Cracking
14 Hydrocarbon cracking stocks can be catalytically cracked in the absence of
hydrogen using SSZ-65, preferably predominantly in the hydrogen form.
16 When SSZ-65 is used as a catalytic cracking catalyst in the absence of
17 hydrogen, the catalyst may be employed in conjunction with traditional
cracking
18 catalysts, e.g., any aluminosilicate heretofore employed as a component in
cracking
19 catalysts. Typically, these are large pore, crystalline aluminosilicates.
Examples of
these traditional cracking catalysts are disclosed in the aforementioned U.S.
Patent
21 No. 4,910,006 and U.S. Patent No 5,316,753. When a traditional cracking
catalyst
22 (TC) component is employed, the relative weight ratio of the TC to the SSZ-
65 is
23 generally between about 1:10 and about 500:1, desirably between about 1:10
and
24 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 molecular sieve and/or the
traditional
26 cracking component may be further ion exchanged with rare earth ions to
modify
27 selectivity.
28 The cracking catalysts are typically employed with an inorganic oxide
matrix
29 component. See the aforementioned U.S. Patent No. 4,910,006 and U.S. Patent
3o No. 5,316,753 for examples of such matrix components.
22
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1 Isomerization
2 The present catalyst is highly active and highly selective for isomerizing
C4 to
3 C7 hydrocarbons. The activity means that the catalyst can operate at
relatively low
4 temperature which thermodynamically favors highly branched paraffins.
Consequently, the catalyst can produce a high octane product. The high
selectivity
6 means that a relatively high liquid yield can be achieved when the catalyst
is run at a
7 high octane.
8 The present process comprises contacting the isomerization catalyst, i.e., a
9 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
11 within the range of 30 F to 250 F (-1 C to 121 C) and preferably from 60 F
to 200 F
12 (16 C to 93 C). Preferably, the hydrocarbon feed for the process comprises
a
13 substantial amount of C4 to C7 normal and slightly branched low octane
14 hydrocarbons, more preferably C5 and C6 hydrocarbons.
It is preferable to carry out the isomerization reaction in the presence of
16 hydrogen. Preferably, hydrogen is added to give a hydrogen to hydrocarbon
ratio
17 (H2/HC) of between 0.5 and 10 H2/HC, more preferably between 1 and 8 HZ/HC.
See
18 the aforementioned U.S. Patent No. 4,910,006 and U.S. Patent No. 5,316,753
for a
19 further discussion of isomerization process conditions.
A low sulfur feed is especially preferred in the present process. The feed
21 preferably contains less than 10 ppm, more preferably less than 1 ppm, and
most
22 preferably less than 0.1 ppm sulfur. In the case of a feed which is not
already low in
23 sulfur, acceptable levels can be reached by hydrogenating the feed in a
presaturation
24 zone with a hydrogenating catalyst which is resistant to sulfur poisoning.
See the
aforementioned U.S. Patent No. 4,910,006 and U.S. Patent No. 5,316,753 for a
further
26 discussion of this hydrodesulfurization process.
27 It is preferable to limit the nitrogen level and the water content of the
feed.
28 Catalysts and processes which are suitable for these purposes are known to
those
29 skilled in the art.
After a period of operation, the catalyst can become deactivated by sulfur or
31 coke. See the aforementioned U.S. Patent No. 4,910,006 and U.S. Patent
32 No. 5,316,753 for a further discussion of methods of removing this sulfur
and coke,
33 and of regenerating the catalyst.
34 The conversion catalyst preferably contains a Group VIII metal compound to
have sufficient activity for commercial use. By Group VIII metal compound as
used
23
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1 herein is meant the metal itself or a compound thereof. The Group VIII noble
metals
2 and their compounds, platinum, palladium, and iridium, or combinations
thereof can
3 be used. Rhenium and tin may also be used in conjunction with the noble
metal. The
4 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,
6 from about 0.05 to 2.0 weight percent, preferably 0.2 to 0.8 weight percent.
7 Alkylation and Transalkylation
8 SSZ-65 can be used in a process for the alkylation or transalkylation of an
9 aromatic hydrocarbon. The process comprises contacting the aromatic
hydrocarbon
with a C2 to C16 olefin alkylating agent or a polyalkyl aromatic hydrocarbon
11 transalkylating agent, under at least partial liquid phase conditions, and
in the
12 presence of a catalyst comprising SSZ-65.
13 SSZ-65 can also be used for removing benzene from gasoline by alkylating
the
14 benzene as described above and removing the alkylated product from the
gasoline.
For high catalytic activity, the SSZ-65 molecular sieve should be
16 predominantly in its hydrogen ion form. It is preferred that, after
calcination, at least
17 80% of the cation sites are occupied by hydrogen ions and/or rare earth
ions.
18 Examples of suitable aromatic hydrocarbon feedstocks which may be
19 alkylated or transalkylated by the process of the invention include
aromatic
compounds such as benzene, toluene and xylene. The preferred aromatic
21 hydrocarbon is benzene. There may be occasions where naphthalene or
naphthalene
22 derivatives such as dimethylnaphthalene may be desirable. Mixtures of
aromatic
23 hydrocarbons may also be employed.
24: 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,
26 butene-1, trans-butene-2 and cis-butene-2, or mixtures thereof. There may
be
27 instances where pentenes are desirable. The preferred olefins are ethylene
and
28 propylene. Longer chain alpha olefins may be used as well.
29 When transalkylation is desired, the transalkylating agent is a polyalkyl
3o aromatic hydrocarbon containing two or more alkyl groups that each may have
from 2
31 to about 4 carbon atoms. For example, suitable polyalkyl aromatic
hydrocarbons
32 include di-, tri- and tetra-alkyl aromatic hydrocarbons, such as
diethylbenzene,
33 triethylbenzene, diethylmethylbenzene (diethyltoluene), di-
isopropylbenzeneõ
34 di-isopropyltoluene, dibutylbenzene, and the like. Preferred polyalkyl
aromatic
24
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1 hydrocarbons are the dialkyl benzenes. A particularly preferred polyalkyl
aromatic
2 hydrocarbon is di-isopropylbenzene.
3 When alkylation is the process conducted, reaction conditions are as
follows.
4 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
6 rapid catalyst fouling. The reaction temperature may range from 100 F to 600
F
7 (38 C to 315 C), preferably 250 F to 450 F (121 C to 232 C). The reaction
pressure
8 should be sufficient to maintain at least a partial liquid phase in order to
retard
9 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
11 10 seconds to 10 hours, but is usually from 5 minutes to an hour. The
weight hourly
12 space velocity (WHSV), in terms of grams (pounds) of aromatic hydrocarbon
and
13 olefin per gram (pound) of catalyst per hour, is generally within the range
of about 0.5
14 to 50.
When transalkylation is the process conducted, the molar ratio of aromatic
16 hydrocarbon will generally range from about 1:1 to 25:1, and preferably
from about
17 2:1 to 20:1. The reaction temperature may range from about 100 F to 600 F
(38 C to
18 315 C), but it is preferably about 250 F. to 450 F (121 C to 232 C). The
reaction
19 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
21 600 psig (2.07 to 4.14 MPa gauge). The weight hourly space velocity will
range from
22 about 0.1 to 10. U.S. Patent No. 5,082,990 issued on January 21, 1992 to
Hsieh, et al.
23 describes such processes and is incorporated herein by reference.
24 Conversion of Paraffins to Aromatics
SSZ-65 can be used to convert light gas C2-C6 paraffins to higher molecular
26 weight hydrocarbons including aromatic compounds. Preferably, the molecular
sieve
27 will contain a catalyst metal or metal oxide wherein said metal is selected
from the
28 group consisting of Groups IB, IIB, VIII and IIIA of the Periodic Table.
Preferably,
29 the metal is gallium, niobium, indium or zinc in the range of from about
0.05 to 5%
3o by weight.
31 Isomerization of Olefins
32 SSZ-65 can be used to isomerize olefins. The feed stream is a hydrocarbon
33 stream containing at least one C4-6 olefin, preferably a C4_6 normal
olefin, more
34 preferably normal butene. Normal butene as used in this specification means
all
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1 forms of normal butene, e.g., 1-butene, cis-2-butene, and trans-2-butene.
Typically,
2 hydrocarbons other than normal butene or other C4_6 normal olefins will be
present in
3 the feed stream. These other hydrocarbons may include, e.g., alkanes, other
olefins,
4 aromatics, hydrogen, and inert gases.
The feed stream typically may be the effluent from a fluid catalytic cracking
6 unit or a methyl-tert-butyl ether unit. A fluid catalytic cracking unit
effluent typically
7 contains about 40-60 weight percent normal butenes. A methyl-tert-butyl
ether unit
8 effluent typically contains 40-100 weight percent normal butene. The feed
stream
9 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
11 branched iso-olefin may be used interchangeably in this specification.
12 The process is carried out under isomerization conditions. The hydrocarbon
13 feed is contacted in a vapor phase with a catalyst comprising the SSZ-65.
The
14 process may be carried out generally at a temperature from about 625 F to
about
950 F (329-510 C), for butenes, preferably from about 700 F to about 900 F
(371-.
16 482 C), and about 350 F to about 650 F (177-343 C) for pentenes and
hexenes. The
17 pressure ranges from subatmospheric to about 200 psig (1.38 MPa gauge),
preferably
18 from about 15 psig to about 200 psig (0.103 to 1.38 MPa gauge), and more
preferably
19 from about 1 psig to about 150 psig (0.00689 to 1.03 MPa gauge).
The liquid hourly space velocity during contacting is generally from about 0.1
21 to about 50 hr-1, based on the hydrocarbon feed, preferably from about 0.1
to about
22 20 hr-1, more preferably from about 0.2 to about 10 hr"1, most preferably
from about 1
23 to about 5 hr-1. A hydrogen/hydrocarbon molar ratio is maintained from
about 0 to
24 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,
26 typically less than about two weight percent based on the feed. The process
can be
27 carried out in a packed bed reactor, a fixed bed, fluidized bed reactor, or
a moving bed
28 reactor. The bed of the catalyst can move upward or downward. The mole
percent
29 conversion of, e.g., normal butene to iso-butene is at least 10, preferably
at least 25,
and more preferably at least 35.
26
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1 Xylene Isomerization
2 SSZ-65 may also be useful in a process for isomerizing one or more xylene
3 isomers in a C8 aromatic feed to obtain ortho-, meta-, and para-xylene in a
ratio
4 approaching the equilibrium value. In particular, xylene isomerization is
used in
conjunction with a separate process to manufacture para-xylene. For example, a
6 portion of the para-xylene in a mixed C8 aromatics stream may be recovered
by
7 crystallization and centrifugation. The mother liquor from the crystallizer
is then
8 reacted under xylene isomerization conditions to restore ortho-, meta- and
9 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
11 filtration. The isomerate is blended with fresh feed and the combined
stream is
12 distilled to remove heavy and light by-products. The resultant C8 aromatics
stream is
13 then sent to the crystallizer to repeat the cycle.
14 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
16 hydrogen is used, the catalyst should comprise about 0.1 to 2.0 wt.% of a
17 hydrogenation/dehydrogenation component selected from Group VIII (of the
Periodic
18 Table) metal component, especially platinum or nickel. By Group VIII metal
19 component is meant the metals and their compounds such as oxides and
sulfides.
Optionally, the isomerization feed may contain 10 to 90 wt. of a diluent such
21 as toluene, trimethylbenzene, naphthene,s or paraffins.
22 Oligomerization .
23 It is expected that SSZ-65 can also be used to oligomerize straight and
24 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
26 which are useful for both fuels, i.e., gasoline or a gasoline blending
stock and
27 chemicals.
28 The oligomerization process comprises contacting the olefin feedstock in
the
29 gaseous or liquid phase with a catalyst comprising SSZ-65.
The molecular sieve can have the original cations associated therewith
31 replaced by a wide variety of other cations according to techniques well
known in the
32 art. Typical cations would include hydrogen, ammonium and metal cations
including
27
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I mixtures of the same. Of the replacing metallic cations, particular
preference is given
2 to cations of metals such as rare earth metals, manganese, calcium, as well
as metals
3 of Group II of the Periodic Table, e.g., zinc, and Group VIII of the
Periodic Table,
4 e.g., nickel. One of the prime requisites is that the molecular sieve have a
fairly low
aromatization activity, i.e., in which the amount of aromatics produced is not
more
6 than about 20% by weight. This is accomplished by using a molecular sieve
with
7 controlled acid activity [alpha value] of from about 0.1 to about 120,
preferably from
8 about 0.1 to about 100, as measured by its ability to crack n-hexane.
9 Alpha values are defined by a standard test known in the art, e.g., as shown
in
U.S. Patent No. 3,960,978 issued on June 1, 1976 to Givens et al. which is
11 incorporated totally herein by reference. If required, such molecular
sieves may be
12 obtained by steaming, by use in a conversion process or by any other method
which
13 may occur to one skilled in this art.
14 Condensation of Alcohols
SSZ-65 can be used to condense lower aliphatic alcohols having 1 to
16 10 carbon atoms to a gasoline boiling point hydrocarbon product comprising
mixed
17 aliphatic and aromatic hydrocarbon. The process disclosed in U.S. Patent
18 No. 3,894,107, issued July 8, 1975 to Butter et al., describes the process
conditions
19 used in this process, which patent is incorporated totally herein by
reference.
The catalyst may be in the hydrogen form or may be base exchanged or
21 impregnated to contain ammonium or a metal cation complement, preferably in
the
22 range of from about 0.05 to 5% by weight. The metal cations that may be
present
23 include any of the metals of the Groups I through VIII of the Periodic
Table.
24 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
26 eliminate all acidity. There may be other processes involving treatment of
27 oxygenated substrates where a basic catalyst is desired.
28 Methane Up ading
29 Higher molecular weight hydrocarbons can be formed from lower molecular
weight hydrocarbons by contacting the lower molecular weight hydrocarbon with
a
31 catalyst comprising SSZ-65 and a metal or metal compound capable of
converting the
32 lower molecular weight hydrocarbon to a higher molecular weight
hydrocarbon.
33 Examples of such reactions include the conversion of methane to CZ+
hydrocarbons
28
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1 such as ethylene or benzene or both. Examples of useful metals and metal
2 compounds include lanthanide and or actinide metals or metal compounds.
3 These reactions, the metals or metal compounds employed and the conditions
4 under which they can be run are disclosed in U.S. Patents No. 4,734,537,
issued
March 29, 1988 to Devries et al.; 4,939,311, issued July 3, 1990 to Washecheck
et al.;
6 4,962,261, issued October 9, 1990 to Abrevaya et al.; 5,095,161, issued
March 10,
7 1992 to Abrevaya et al.; 5,105,044, issued April 14, 1992 to Han et al.;
5,105,046,
8 issued April 14, 1992 to Washecheck; 5,238,898, issued August 24, 1993 to
Han et
9 al.; 5,321,185, issued June 14, 1994 to van der Vaart; and 5,336,825, issued
August 9,
1994 to Choudhary et al., each of which is incorporated herein by reference in
its
11 entirety.
12 SSZ-65 may be used for the catalytic reduction of the oxides of nitrogen in
a
13 gas stream. Typically, the gas stream also contains oxygen, often a
stoichiometric
14 excess thereof. Also, the SSZ-65 may contain a metal or metal ions within
or on it
which are capable of catalyzing the reduction of the nitrogen oxides. Examples
of
16 such metals or metal ions include copper, cobalt, platinum, iron, chromium,
17 manganese, nickel, zinc, lanthanum, palladium, rhodium and mixtures
thereof.
18 One example of such a process for the catalytic reduction of oxides of
nitrogen
19 in the presence of a molecular sieve is disclosed in U.S. Patent No.
4,297,328, issued
October 27, 1981 to Ritscher et al., which is incorporated by reference
herein. There,
21 the catalytic process is the combustion of carbon monoxide and hydrocarbons
and the
22 catalytic reduction of the oxides of nitrogen contained in a gas stream,
such as the
23 exhaust gas from an internal combustion engine. The molecular sieve used is
metal
24 ion-exchanged, doped or loaded sufficiently so as to provide an effective
amount of
catalytic copper metal or copper ions within or on the molecular sieve. In
addition,
26 the process is conducted in an excess of oxidant, e.g., oxygen.
27 EXAMPLES
28 The following examples demonstrate but do not limit the present invention.
29
29
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1 Example 1
2 Synthesis of SDA 1-L-(4-chlorophenyl)-cycloprop l~methyl]-1-ethyl-
pyrrolidinium
3 Cation
4
CI ~ N~
~
Me
1-[ 1 -(4-Chloro-phenyl)-
cyclopropylmethyl]-1-ethyl-pyrrolidinium
6 The structure directing agent is synthesized according to the synthetic
scheme
7 shown below (Scheme 1).
8 1-[1-(4-chloro-phenyl)-cyclopropylmethyl]-1-ethyl-pyrrolidinium iodide is
9 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
11 amine, 1-[1-(4-chloro-phenyl)-cyclopropylmethyl]-pyrrolidine, is dissolved
in 1000
12 ml anhydrous methanol in a 3-litre 3-necked reaction flask (equipped with a
13 mechanical stirrer and a reflux condenser). To this solution, 98 gm (0.62
mole) of
14 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
16 for 3 hours. The reaction mixture is cooled down and excess ethyl iodide
and the
17 solvent are removed at reduced pressure on a rotary evaporator. The
obtained dark
18 tan-colored solids (162 gm) are further purified by dissolving in acetone
(500 ml)
19 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)-
21 cyclopropylmethyl]-I-ethyl-pyrrolidinium iodide as a white powder. The
product is
22 pure by 'H and 13C-NMR analysis.
23 The hydroxide form of 1-[ 1-(4-chloro-phenyl)-cyclopropylmethyl]-1-ethyl-
24 pyrrolidinium cation is obtained by an ion exchange treatment of the iodide
salt with
Ion-Exchange Resin-OH (BIO RAD AH1-X8). In a 1-liter volume plastic bottle,
26 100 gm (255 mmol) of 1-[1-(4-chloro-phenyl)-cyclopropylmethyl]-1-ethyl-
27 pyrrolidinium iodide is dissolved in 300 ml de-ionized water. Then, 320 gm
of the
28 ion exchange resin is added and the solution is allowed to gently stir
overnight. The
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1 mixture is then filtered, and the resin cake is rinsed with minimal amount
of de-
2 ionized water. The filtrate is analyzed for hydroxide concentration by
titration
3 analysis on a small sample of the solution with 0.1N HCI. The reaction
yields 96% of
4 (245 mmol) of the desired 1-[1-(4-chloro-phenyl)-cyclopropylmethyl]-1-ethyl-
pyrrolidinium hydroxide (hydroxide concentration of 0.6 M).
6 The parent amine 1-[1-(4-chloro-phenyl)-cyclopropylmethyl]-pyrrolidine is
7 obtained from the LiA1H4-reduction of the precursor amide [1-(4-chloro-
phenyl)-
8 cyclopropyl]-pyrrolidin-1-yl-methanone. In a 3-neck 3-liter reaction flask
equipped
9 with a mechanical stirrer and reflux condenser, 45.5 gm (1.2 mol.) of LiA1H4
is
suspended in 750 ml anhydrous tetrahydrofuran (THF). The suspension is cooled
11 down to 0 C (ice-bath), and 120 gm (0.48 mole) of [ 1-(4-chloro-phenyl)-
12 cyclopropyl]-pyrrolidin-1-yl-methanone dissolved in 250 ml THF is added (to
the
13 suspension) drop-wise via an addition funnel. Once all the amide solution
is added,
14 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 C (the
heating
16 mantle was replaced withan ice-bath), and the mixture is diluted with 500
ml diethyl
17 ether. The reaction is worked up by adding 160 ml of 15% wt. of an aqueous
NaOH
18 solution drop-wise (via an addition funnel) with vigorous stirring. The
starting gray
19 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.
21 Filtration and concentration of the filtrate gives 106 gm (94% yield) of
the desired
22 amine 1-[1-(4-chloro-phenyl)-cyclopropylmethyl]-pyrrolidine as a pale
yellow oily
23 substance. The amine is pure as indicated by the clean 1H and 13C-NMR
spec.tral
24 analysis.
The parent amide [1-(4-chloro-phenyl)-cyclopropyl]-pyrrolidin-l-yl-
26 methanone is prepared by reacting pyrrolidine with 1-(4-chloro-phenyl)-
27 cyclopropanecarbonyl chloride. A 2-Liter reaction flask equipped with a
mechanical
28 stirrer is charged with 1000 ml of dry benzene, 53.5 gm (0.75 mol.) of
pyrrolidine and
29 76 gm (0.75 mol.) of triethyl amine. To this mixture (at 0 C), 108 1-(4-
chloro-
phenyl)-cyclopropanecarbonyl chloride gm (0.502 mol.) of (dissolved 100.m1
31 benzene) is added drop-wise (via an addition funnel). Once the addition is
completed,
32 the resulting mixture is allowed to stir at room temperature overnight. The
reaction
31
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1 mixture (a biphasic mixture: liquid and tan-colored precipitate) is
concentrated on a
2 rotary evaporator at reduced pressure to strip off excess pyrrolidine and
the solvent
3 (usually hexane or benzene). The remaining residue is diluted with 750 ml
water and
4 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
6 anhydrous sodium sulfate, filtered and concentrated on a rotary evaporator
at reduced
7 pressure to give 122 gm (0.49 mol, 97% yield) of the amide as a tan-colored
solid
8 substance.
9 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)-
11 cyclopropanecarboxylic acid with thionyl chloride (SOCIz) as described
below. To
12 200 gms of thionyl chloride and 200 ml dichloromethane in a 3-necked
reaction flask,
13 equipped with a mechanical stirrer and a reflux condenser, 100 gm (0.51
mol) of the
14 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
16 then heated at reflux. The reaction vessel is equipped with a trap (filled
with water) to
17 collect and trap the acidic gaseous byproducts, and used in monitoring the
reaction.
18 The reaction is usually done once the evolution of the gaseous byproducts
is ceased.
19 The reaction mixture is then cooled down and concentrated on a rotary
evaporator at
reduced pressure to remove excess thionyl chloride and dichloromethane. The
21 reaction yields 109 gm (98%) of the desired 1-(4-chloro-phenyl)-
22 cyclopropanecarbonyl chloride as reddish viscous oil.
23
32
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1 Scheme I
H
v
~\ OH SOC12 _ ~\ CI Pyr'olidine I~
CI ~ O CI O CI ~ O NU
1-(4-Chloro-phenyl)- 1-(4-Chloro-phenyl)- [ 1-(4-Chloro-phenyl)-cyclopropyl]-
cyclopropanecarboxylic acid cyclopropanecarbonyl chloride pyrrolidin-1-yl-
methanone
N A
LiA 1H4 I~ 1)EtI _ ez
CI ~ N 2) Ion-Exchange-OH CI ~JMe
1-[ 1-(4-Chloro-phenyl)-
cyclopropylmethyl]-pyrrolidine 1-[ 1-(4-Chloro-phenyl)-
2 cyclopropylmethyl]-1-ethyl-pyrrolidinium
3
4 Example 2
Synthesis of SDA 1-ethyl- 1 _(1-phenyl-cyclopropylmethyl)-pyrrolidiniurri
cation
6 SDA 1-ethyl-l-(1-phenyl-cyclopropylmethyl)-pyrrolidinium cation is
7 synthesized using the synthesis procedure of Example 1, except that the
synthesis
8 starts from 1-phenyl-cyclopropanecarbonyl chloride and pyrrolidine.
9 Example 3
Synthesis of SSZ-65
11 A 23 cc Teflon liner is charged with 5.4 gm of 0.6M aqueous solution of 1-
12 ethyl-l-(1-phenyl-cyclopropylmethyl)-pyrrolidinium hydroxide (3 mmol SDA),
1.2
13 gm of 1M aqueous solution of NaOH (1.2 mmol NaOH) and 5.4 gm of de-ionized
14 water. To this mixture, 0.06 gm of sodium borate decahydrate (0.157 mmol of
Na2B4O7.10H20; -0.315 mmol B203) is added and stirred until completely
dissolved.
16 Then, 0.9 gm of CAB-O-SIL M-5 fumed silica (-14.7 mmol Si02) is added to
the
17 s.olution and the mixture is thoroughly stirred. The resulting gel is
capped off and
18 placed in a Parr bomb steel reactor and heated in an oven at 160 C while
rotating at
19 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
21 usually complete after heating 9-12 days at the conditions described above.
Once the
22 crystallization is completed, the starting reaction gel turns to a mixture
comprised of a
33
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1 clear liquid and powdery precipitate. The mixture is filtered through a
fritted-glass
2 funnel. The collected solids are thoroughly washed with water and, then,
rinsed with
3 acetone (10 ml) to remove: any organic residues. The solids. are allowed to
air-dry
4 overnight and, then, dried in an oven at 120 C for lhour. The reaction
affords 0.85
gram of a very fine powder. SEM shows the presence of only one crystalline
phase.
6 The product is determined by powder XRD data analysis to be SSZ-65.
7 Example 4
8 Seeded Synthesis of Borosilicate SSZ-65
9 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
11 up the, crystallization process. The reaction conditions are exactly the
same as for the
12 previous example. The crystallization is complete in four days and affords
0.9 gm of
13 B-SSZ-65.
14 Example 5
Synthesis of Aluminosilicate SSZ-65
16 A 23 cc Teflon liner is charged with 4 gm of 0.6M aqueous solution of 1-
17 ethyl-l-(1-phenyl-cyclopropylmethyl)-pyrrolidinium hydroxide (2.25 mmol
SDA),
18 1.5 gm of 1M aqueous solution of NaOH (1.5 mmol NaOH) and 2 gm of de-
ionized
19 water. To this mixture, 0.25 gm of Na-Y molecular sieve (Union Carbide's
LZY-52;
Si02/A1203=5) is added and stirred until completely dissolved. Then, 0.85 gm
of
21 CAB-O-SIL M-5 fumed silica (-14. mmol Si02) is added to the solution and
the
22 mixture is thoroughly stirred. The resulting gel is capped off and placed
in a Parr
23 bomb steel reactor and heated in an oven at 160 C while rotating* at 43
rpm. The
24 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
26 often indicates decomposition of the SDA), and by checking for crystal
formation by
27 scanning electron microscopy. The reaction is usually complete after
heating for 12
28 days at the conditions described above. Once the crystallization is
completed, the
29 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
31 thoroughly washed with water and, then, rinsed with acetone (10 ml) to
remove any
34
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1 organic residues. The solids are allowed to air-dry overnight and, then,
dried in an
2 oven at 1200 C for lhour. The reaction affords 0.8 gram of SSZ-65.
3 Examples 6-15
4 Syntheses of SSZ-65 at Varying SiO,B O3 Ratios
SSZ-65 is synthesized at varying SiO2B203 mole ratios in the starting
6 synthesis gel. This is accomplished using the synthetic conditions described
in
7 Example 3 keeping everything the same while changing the Si02/B203 mole
ratios in
8 the starting gel. This is done by keeping the amount of CAB-O-SIL M-5 (98%
Si02
9 and 2% H20) the same while varying the amount of sodium borate in each
synthesis.
Consequently, varying the amount of sodium borate leads to varying the Si02/Na
11 mole ratios in the starting gels. Table 1 below shows the results of a
number of
12 syntheses with varying Si02/B203 in the starting synthesis gel.
13 Table 1
Example No. Si02/B203 Si02/Na Crystallization Products
Time(days)
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
14 7.1 6 SSZ-65
14 "OH/SiO2=0.28, R+/SiO2=0.2, H20/SiO2=44
15 (R+= organic cation (SDA))
16 Example 16
17 Calcination of SSZ-65
18 SSZ-65 as synthesized in Example 3 is calcined to remove the structure
19 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 C at a rate of 1
C/minute
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i and held for 2 hours. Then, the temperature is ramped up to 540 C at a rate
of
2 1 C/minute and held for 5 hours. The temperature is ramped up again at 1
C/minute
3' to 595 C and held there for 5 hours. A 50/50 mixture of air and nitrogen
passes
4 through the muffle furnace at a rate of 20 standard cubic feet (0.57
standard cubic
meters) per minute during the calcination process.
6 Example 17
7 Conversion of Borosilicate-SSZ-65 to Aluminosilicate SSZ-65
8 The calcined version of borosilicate SSZ-65 (as synthesized in Example 3 and
9 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
11 ml of 1M Al(NO3)3.9Hz0 soln./1 gm SSZ-65). The suspension is heated at
reflux
12 overnight. The resulting mixture is then filtered and the collected solids
are
13 thoroughly rinsed with de-ionized water and air-dried overnight. The solids
are
14 further dried in an oven at 120 C for 2 hours.
Example 18
16 Ammonium- Ion Exchange of SSZ-65
17 The Na} form of SSZ-65 (prepared as in Example 3 or as in Example 5 and
18 calcined as in Example 16) is converted to NH4+-SSZ-65 form by heatitig the
material
19 in an aqueous solution of NH4NO3 (typically 1 gm NH4NO3/1 gm SSZ-65 in 20
ml
H20) at 90 C for 2-3 hours. The mixture is then filtered and the obtained NH4-
21 exchanged-product is washed with de-ionized water and dried. The NH4+ form
of
22 SSZ-65 can be converted to the H+ form by calcination (as described in
Example 16)
23 to 540 C.
24 Example 19
Argon Adsorption Analysis
26 SSZ-65 has a micropore volume of 0.16 cc/gm based. on argon adsorption
isotherm at .
27 87.5 K(-186 C) recorded on ASAP 2010 equipment from Micromerities. The
28 sample is first degassed at 400 C for 16 hours prior to argon adsorption.
The low-
29 pressure dose is 6.00 cm3/g (STP). A maximum of one hour equilibration time
per
3o dose is used and the total run time is 35 hours. The argon adsorption
isotherm is
31 analyzed using the density function theory (DFT) formalism and parameters
32 developed for activated carbon slits by Olivier (Porous Mater. 1995, 2, 9)
using the,
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1 Saito Foley adaptation of the Horvarth-Kawazoe formalism (Microporous
Materials,
2 1995, 3, 531) and the conventional t-plot method (J. Catalysis, 1965, 4,
319).
3 Example 20
4 Constraint Index
The hydrogen form of SSZ-65 of Example 3 (after treatment according to
6 Examples 16, 17 and 18) is pelletized at 3 KPSI, crushed and granulated to
20-40
7 mesh. A 0.6 gram sample of the granulated material is calcined in air at 540
C for 4
8 hours and cooled in a desiccator to ensure dryness. Then, 0.5 gram is packed
into a
9 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
11 reactor. tube at 10 cc/min. and at atmospheric pressure. The reactor is
heated to about
12 315 C, and a 50/50 feed of n-hexane and 3-methylpentane is introduced into
the
13 reactor at a rate of 8 l/min. The feed is delivered by a Brownlee pump.
Direct
14 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.
16 SSZ-65 has a CI of 0.67 and a conversion of 92% after 20 minutes on stream.
The
17 material fouls rapidly and at 218 minutes the CI is 0.3 and the conversion
is 15.7%.
18 The data suggests a large pore molecular sieve with perhaps large cavities.
19 Example 21
Hydrocracking of n-Hexadecane
21 A 1 gm sample of SSZ-65 (prepared as in Example 3 and treated as in
22 Examples 16, 17 and 18) is suspended in 10 gm de-ionized water. To this
suspension,
23 a solution of Pd(NH3)4(NO3)2 at a concentration which would provide 0.5 wt.
% Pd
24 with respect to the dry weight of the molecular sieve sample is added. The
pH of the
solution is adjusted to pH of -9 by a drop-wise addition of dilute ammonium
26 hydroxide solution. The mixture is then heated in an oven at 75 C for 48
hours. The
27 mixture is then filtered through a glass frit, washed with de-ionized
water, and air-
28 dried. The collected Pd-SSZ-65 sample is slowly calcined up to 482 C in air
and held
29 there for three hours.
The calcined Pd/SSZ-65 catalyst is pelletized in a Carver Press and granulated
31 to yield particles with a 20/40 mesh size. Sized catalyst (0.5 g) is packed
into a'/4
32 inch OD tubing reactor in a micro unit for n-hexadecane hydroconversion.
The table
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1 below gives the run conditions and the products data for the hydrocracking
test on n-
2 hexadecane.
3 After the catalyst is tested with n-hexadecane, it is titrated using a
solution of
4 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
6 show that SSZ-65 is effective as a hydrocracking catalyst.
7
Temperature 260 C (550 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
C4_, % 2.7
C5/C4 16.9
C5+C6/C5, % 16.74
DMB/MP 0.06
C4-C13 i/n 3.83
C7-C13 yield 38.35
8
9 Example 22
Synthesis of SSZ-65
11 SSZ-65 is synthesized in a manner similar to that of Example 3 using a 1-[1-
12 (4-chlorophenyl)-cyclopropylmethyl]-1-ethyl-pyrrolidinium cation as the
SDA.
38
