Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
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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]-1-
6 ethyl-pyrrolidinium or 1-ethyl-1-(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
to 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
3o 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,
to 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
i3 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 further provides such a molecular sieve having a
18 composition, as synthesized and in the anhydrous state, in terms of mole
ratios as
19 follows:
YOz/W~Oa 15 - 00
21 M2~nn.'O2 0.01- 0.03
22 Q/YOz 0.02 - 0.05
23 wherein Y is silicon, germanium or a mixture thereof; W is aluminum,
gallium, iron,
24 boron, titanium, indium, vanadium or mixtures thereof; c is 1 or 2; d is 2
when c is 1
(i.e., W is tetravalent) or d is 3 or 5 when c is 2 (i.e., d is 3 when W is
trivalent or 5
26 when W is pentavalent); M is an alkali metal cation, alkaline earth metal
cation or
27 mixtures thereof; n is the valence of M (i.e., 1 or 2); and Q is a 1-[1-(4-
chlorophenyl)-
28 cyclopropyhnethyl]-1-ethyl-pyrrolidinium or 1-ethyl-1-(1-phenyl-
29 cyclopropylmethyl)-pyrrolidinium cation.
3o In accordance with this invention, there is also provided a molecular
31 sieve prepared by thermally treating a molecular sieve having a mole ratio
of an oxide
32 selected from silicon oxide, germanium oxide and mixtures thereof to an
oxide
2
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1 selected from aluminum oxide, gallium oxide, iron oxide, boron oxide,
titanium
2 oxide, indium oxide, vanadium oxide and mixtures thereof greater than about
15 at a
3 temperature of from about 200°C to about 800°C, the thus-
prepared molecular sieve
4 having the X-ray diffraction lines of Table II. The present invention also
includes this
thus-prepared molecular sieve which is predominantly in the hydrogen form,
which
6 hydrogen form is prepared by ion exchanging with an acid or with a solution
of an
7 ammonium salt followed by a second calcination. If the molecular sieve is
8 synthesized with a high enough ratio of SDA cation to sodium ion,
calcination alone
9 may be sufficient. For high catalytic activity, the SSZ-65 molecular sieve
should be
l0 predominantly in its hydrogen ion form. It is preferred that, after
calcination, at least
1 l 80% of the cation sites are occupied by hydrogen ions and/or rare earth
ions. As used
12 herein, "predominantly in the hydrogen form" means that, after calcination,
at least
i3 80% of the cation sites are occupied by hydrogen ions and/or rare earth
ions.
14 Also provided in accordance with the present invention is a method of
preparing a crystalline material comprising (1) an oxide of a first
tetravalent element
16 and (2) an oxide of a trivalent element, pentavalent element, second
tetravalent
17 element which is different from said first tetravalent element, or mixture
thereof and
18 having a mole ratio of the first oxide to the second oxide greater than 15,
said method
19 comprising contacting under crystallization conditions sources of said
oxides and a
structure directing agent comprising a 1-[1-(4-chlorophenyl)-
cyclopropylmethyl]-1-
21 ethyl-pyrrolidinium or 1-ethyl-1-(1-phenyl-cyclopropylmethyl)-pyrrolidinium
cation.
22 In accordance with the present invention there is further provided a
process for
23 converting hydrocarbons comprising contacting a hydrocarbonaceous feed at
24 hydrocarbon converting conditions with a catalyst comprising the molecular
sieve of
this invention. The molecular sieve may be predominantly in the hydrogen form.
It
26 may also be substantially free of acidity.
27 Further provided by the present invention is a hydrocracl~ing process
28 comprising contacting a hydrocarbon feedstock under hydrocraclcing
conditions with
29 a catalyst comprising the molecular sieve of this invention, preferably
predominantly
in the hydrogen form.
3
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1 This invention also includes a dewaxing process comprising contacting a
2 hydrocarbon feedstock under dewaxing conditions with a catalyst comprising
the
3 molecular sieve of this invention, preferably predominantly in the hydrogen
form.
4 The present invention also includes a process for improving the viscosity
index of a dewaxed product of waxy hydrocarbon feeds comprising contacting the
6 waxy hydrocarbon feed under isomerization dewaxing conditions with a
catalyst
7 comprising the molecular sieve of this invention, preferably predominantly
in the
8 hydrogen form.
9 The present invention further includes a process for producing a Cao+ lube
oil
to from a C2o+ olefin feed comprising isomerizing said olefin feed under
isomerization
11 conditions over a catalyst comprising the molecular sieve of this
invention. The
12 molecular sieve may be predominantly in the hydrogen form. The catalyst may
13 contain at least one Group VIII metal.
14 In accordance with this invention, there is also provided a process for
catalytically dewaxing a hydrocarbon oil feedstock boiling above about
350°F
16 (177°C) and containing straight chain and slightly branched chain
hydrocarbons
17 comprising contacting said hydrocarbon oil feedstock in the presence of
added
18 hydrogen gas at a hydrogen pressure of about 15-3000 psi (0.103 - 20.7 MPa)
with a
19 catalyst comprising the molecular sieve of this invention, preferably
predominantly in
the hydrogen form. The catalyst may contain at least one Group VIII metal. The
21 catalyst may be a layered catalyst comprising a first layer comprising the
molecular
22 sieve of this invention, and a second layer comprising an aluminosilicate
molecular
23 sieve which is more shape selective than the molecular sieve of said first
layer. The
24 first layer may contain at least one Group VIII metal.
Also included in the present invention is a process for preparing a
lubricating
26 oil which comprises hydrocracking in a hydrocracking zone a
hydrocarbonaceous
27 feedstoclc to obtain an effluent comprising a hydrocracked oil, and
catalytically
28 dewaxing said effluent comprising hydrocraclced oil at a temperature of at
least about
29 400°F (204°C) arid 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
31 molecular sieve of this invention. The molecular sieve may be predominantly
in the
32 hydrogen form. The catalyst may contain at least one Group VIII metal.
4
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1 Further included in this invention is a process for isomerization dewaxing a
2 raffinate comprising contacting said raffinate in the presence of added
hydrogen with
3 a catalyst comprising the molecular sieve of this invention. The raffinate
may be
4 bright stock, and the molecular sieve may be predominantly in the hydrogen
form.
The catalyst may contain at least one Group VIII metal.
6 Also included in this invention is a process for increasing the octane of a
7 hydrocarbon feedstock to produce a product having an increased aromatics
content
8 comprising contacting a hydrocarbonaceous feedstock which comprises normal
and
9 slightly branched hydrocarbons having a boiling range above about
40°C and less
1o than about 200°C, under aromatic conversion conditions with a
catalyst comprising
1 1 the molecular sieve of this invention made substantially free of acidity
by neutralizing
12 said molecular sieve with a basic metal. Also provided in this invention is
such a
13 process wherein the molecular sieve contains a Group VIII metal component.
14 Also provided by the present invention is a catalytic cracl~ing process
comprising contacting a hydrocarbon feedstoclc in a reaction zone under
catalytic
16 cracking conditions in the absence of added hydrogen with a catalyst
comprising the
17 molecular sieve of this invention, preferably predominantly in the hydrogen
form.
18 Also included in this invention is such a catalytic cracking process
wherein the
19 catalyst additionally comprises a large pore crystalline cracl~ing
component.
2o This invention further provides an isomerization process for isomerizing C4
to
21 C~ hydrocarbons, comprising contacting a feed having normal and slightly
branched
22 C4 to C~ hydrocarbons under isomerizing conditions with a catalyst
comprising the
23 molecular sieve of this invention, preferably predominantly in the hydrogen
form.
24 The molecular sieve may be impregnated with at least one Group VIII metal,
preferably platinum. The catalyst may be calcined in a steam/air mixture at an
26 elevated temperature after impregnation of the Group VIII metal.
27 Also provided by the present invention is a process for allcylating an
aromatic
28 hydrocarbon which comprises contacting under alkylation conditions at least
a molar
29 excess of an aromatic hydrocarbon with a Ca to CZO olefin under at least
partial liquid
3o phase conditions and in the presence of a catalyst comprising the molecular
sieve of
31 this invention, preferably predominantly in the hydrogen form. The olefin
may be a
32 CZ to C4 olefin, and the aromatic hydrocarbon and olefin may be present in
a molar
5
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1 ratio of about 4:1 to about 20:1, respectively. The aromatic hydrocarbon may
be
2 selected from the group consisting of benzene, toluene, ethylbenzene,
xylene,
3 naphthalene, naphthalene derivatives, dimethylnaphthalene or mixtures
thereof.
4 Further provided in accordance with this invention is a process for
transalkylating an aromatic hydrocarbon which comprises contacting under
6 transalkylating conditions an aromatic hydrocarbon with a polyalkyl aromatic
7 hydrocarbon under at least partial liquid phase conditions and in the
presence of a
8 catalyst comprising the molecular sieve of this invention, preferably
predominantly in
9 the hydrogen form. The aromatic hydrocarbon and the polyallcyl aromatic
hydrocarbon may be present in a molar ratio of from about 1:1 to about 25:1,
11 respectively.
12 The aromatic hydrocarbon may be selected from the group consisting of
13 benzene, toluene, ethylbenzene, xylene, or mixtures thereof, and the
polyalkyl
14 aromatic hydrocarbon may be a dialkylbenzene.
Further provided by this invention is a process to convert paraffins to
16 aromatics which comprises contacting paraffins under conditions which cause
17 paraffins to convert to aromatics with a catalyst comprising the molecular
sieve of this
18 invention, said catalyst comprising gallium, zinc, or a compound of gallium
or zinc.
19 In accordance with this invention there is also provided a process for
2o isomerizing olefins comprising contacting said olefin under conditions
which cause
21 isomerization of the olefin with a catalyst comprising the molecular sieve
of this
22 invention.
23 Further provided in accordance with this invention is a process for
isomerizing
24 an isomerization feed comprising an aromatic C$ stream of xylene isomers or
mixtures of xylene isomers and ethylbenzene, wherein a more nearly equilibrium
ratio
26 of ortho-, meta- and para-xylenes is obtained, said process comprising
contacting said
27 feed under isomerization conditions with a catalyst comprising the
molecular sieve of
28 this invention.
29 The present invention further provides a process for oligomerizing olefins
3o comprising contacting an olefin feed under oligomerization conditions with
a catalyst
31 comprising the molecular sieve of this invention.
6
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1 This invention also provides a process for converting oxygenated
2 hydrocarbons comprising contacting said oxygenated hydrocarbon with a
catalyst
3 comprising the molecular sieve of this invention under conditions to produce
liquid
4 products. The oxygenated hydrocarbon may be a lower alcohol.
Further provided in accordance with the present invention is a process for the
6 production of higher molecular weight hydrocarbons from lower molecular
weight
7 hydrocarbons comprising the steps of:
8 (a) introducing into a reaction zone a lower molecular weight hydrocarbon-
9 containing gas and contacting said gas in said zone under CZ+ hydrocarbon
to synthesis conditions with the catalyst and a metal or metal compound
capable of
11 converting the lower molecular weight hydrocarbon to a higher molecular
12 weight hydrocarbon; and
13 (b) withdrawing from said reaction zone a higher molecular weight
14 hydrocarbon-containing stream.
In accordance with this invention, there is also provided a process for the
16 reduction of oxides of nitrogen contained in a gas stream in the presence
of oxygen
17 wherein said process comprises contacting the gas stream with a molecular
sieve
18 having a mole ratio greater than about 15 of (1) an oxide of a first
tetravalent element
19 to (2) an oxide of a second tetravalent element different from said first
tetravalent
2o element, trivalent element, pentavalent element or mixture thereof and
having, after
21 calcination, the X-ray diffraction lines of Table II. The molecular sieve
may contain a
22 metal or metal ions (such as cobalt, copper, platinum, iron, chromium,
manganese,
23 nickel, zinc, lanthanum, palladium, rhodium or mixtures thereof) capable of
24 catalyzing the reduction of the oxides of nitrogen, and the process may be
conducted
in the presence of a stoichiometric excess of oxygen. In a preferred
embodiment, the
26 gas stream is the exhaust stream of an internal combustion engine.
27 DETAILED DESCRIPTION OF THE INVENTION
28 The present invention comprises a family of crystalline, large pore
molecular
29 sieves designated herein "molecular sieve SSZ-65" or simply "SSZ-65". As
used
3o herein, the term "large pore" means having an average pore size diameter
greater than
31 about 6.0 Angstroms, preferably from about 6.5 Angstroms to about 7.5
Angstroms.
7
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1 In preparing SSZ-65, a 1-[1-(4-chlorophenyl)-cyclopropylmethyl]-1-ethyl-
2 pyrrolidinium or 1-ethyl-1-(1-phenyl-cyclopropylmethyl)-pyrrolidinium canon
is used
3 as a structure directing agent ("SDA"), also known as a crystallization
template. The
4 SDA's useful for making SSZ-65 have the following structures:
NJ
CI ~ Me
1-[ 1-(4-Chloro-phenyl)-cyclopropylmethyl]-1-ethyl-
6 pyrrolidinium
8
i , ~~
9 1-Ethyl-1-( 1-phenyl-cyclopropylmethyl)-pyrrolidinium
11 The SDA cation is associated with an anion (X-) which may be any aiuon that
12 is not detrimental to the formation of the molecular sieve. Representative
anions
13 include halogen, e.g., fluoride, chloride, bromide and iodide, hydroxide,
acetate,
14 sulfate, tetrafluoroborate, carboxylate, and the like. Hydroxide is the
most preferred
anion.
16 In general, SSZ-65 is prepared by contacting an active source of one or
more
17 oxides selected from the group consisting of monovalent element oxides,
divalent
18 element oxides, trivalent element oxides, tetravalent element oxides and/or
19 pentavalent elements with the 1-[1-(4-chlorophenyl)-cyclopropylmethyl]-1-
ethyl-
2o pyrrolidinium or 1-ethyl-1-(1-phenyl-cyclopropylmethyl)-pyrrolidinium
cation SDA.
21 SSZ-65 is prepared from a reaction mixture having the composition shown in
22 Table A below.
8
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1 TABLE A
2 Reaction Mixture
3 Typical Preferred
4 Y02/WaOb > 15 30 - 70
s OH-/Y02 0.10 - 0.50 0.20 - 0.30
6 Q/Y02 0.05 - 0.50 0.10 - 0.20
7 M2i"/YO2 0.02 - 0.40 0.10 - 0.25
8 HZO/YOa 30 - 80 35 - 45
9 where Y, W, Q, M and n are as defined above, and a is 1 or 2, and b is 2
when a is 1
1o (i.e., W is tetravalent) and b is 3 when a is 2 (i.e., W is trivalent).
11 In practice, SSZ-65 is prepared by a process comprising:
12 (a) preparing an aqueous solution containing sources of at least one
13 oxide capable of forming a crystalline molecular sieve and a 1-[1-(4-
chlorophenyl)-
14 cyclopropylmethyl]-1-ethyl-pyrrolidinium or 1-ethyl-1-(1-phenyl-
15 cyclopropylinethyl)-pyrrolidinium cation having an anionic counterion which
is not
16 detrimental to the formation of SSZ-65;
17 (b) maintaining the aqueous solution under conditions sufficient to
18 form crystals of SSZ-65; and
19 (c) recovering the crystals of SSZ-65.
2o Accordingly, SSZ-65 may comprise the crystalline material and the SDA in
21 combination with metallic and non-metallic oxides bonded in tetrahedral
coordination
22 through shared oxygen atoms to form a cross-linked three dimensional
crystal
23 structure. The metallic and non-metallic oxides comprise one or a
combination of
24 oxides of a first tetravalent element(s), and one or a combination of a
trivalent
25 element(s), pentavalent element(s), second tetravalent elements) different
from the
26 first tetravalent elements) or mixture thereof. The first tetravalent
elements) is
2'7 preferably selected from the group consisting of silicon, germanium and
combinations
28 thereof. More preferably, the first tetravalent element is silicon. The
trivalent
29 element, pentavalent element and second tetravalent element (which is
different from
3o the first tetravalent element) is preferably selected from the group
consisting of
31 aluminum, gallium, iron, boron, titanium, indium, vanadium and combinations
9
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1 thereof. More preferably, the second trivalent or tetravalent element is
aluminum or
2 boron.
3 Typical sources of aluminum oxide for the reaction mixture include
4 aluminates, alumina, aluminum colloids, aluminum oxide coated on silica sol,
hydrated alumina gels such as Al(OH)3 and aluminum compounds such as AlCl3 and
6 A12(S04)3. Typical sources of silicon oxide include silicates, silica
hydrogel, silicic
7 acid, Earned silica, colloidal silica, tetra-alkyl orthosilicates, and
silica hydroxides.
8 Boron, as well as gallium, germanium, titanium, indium, vanadium and iron,
can be
9 added in forms corresponding to their aluminum and silicon counterparts.
to A source molecular sieve reagent may provide a source of aluminum or boron.
11 In most cases, the source molecular sieve also provides a source of silica.
The source
12 molecular sieve in its dealuminated or deboronated form may also be used as
a source
13 of silica, with additional silicon added using, for example, the
conventional sources
14 listed above. Use of a source molecular sieve reagent as a source of
alumina for the
present process is more completely described in U.S. Patent No. 5,225,179,
issued
16 July 6, 1993 to Nakagawa entitled "Method of Making Molecular Sieves", the
17 disclosure of which is incorporated herein by reference.
1 s Typically, an alkali metal hydroxide and/or an alkaline earth metal
hydroxide,
19 such as the hydroxide of sodium, potassium, lithium, cesium, rubidium,
calcium, and
2o magnesium, is used in the reaction mixture; however, this component can be
omitted
21 so long as the equivalent basicity is maintained. The SDA may be used to
provide
22 hydroxide ion. Thus, it may be beneficial to ion exchange, for example, the
halide to
23 hydroxide ion, thereby reducing or eliminating the alkali metal hydroxide
quantity
24 required. The alkali metal canon or alkaline earth cation may be part of
the
as-synthesized crystalline oxide material, in order to balance valence
electron charges
26 therein.
27 The reaction mixture is maintained at an elevated temperature until the
28 crystals of the SSZ-65 are formed. The hydrothermal crystallization is
usually
29 conducted under autogenous pressure, at a temperature between 100°C
and 200°C,
3o preferably between 135°C and 160°C. The crystallization
period is typically greater
31 than 1 day and preferably from about 3 days to about 20 days.
32 Preferably, the molecular sieve is prepared using mild stirring or
agitation.
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1 During the hydrothermal crystallization step, the SSZ-65 crystals can be
2 allowed to nucleate spontaneously from the reaction mixture. The use of SSZ-
65
3 crystals as seed material can be advantageous in decreasing the time
necessary for
4 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
6 any undesired phases. When used as seeds, SSZ-65 crystals are added in an
amount
7 between 0.1 and 10% of the weight of first tetravalent element oxide, e.g.
silica, used
8 in the reaction mixture.
9 Once the molecular sieve crystals have formed, the solid product is
separated
1 o from the reaction mixture by standard mechanical separation techniques
such as
11 filtration. The crystals are water-washed and then dried, e.g., at
90°C to 150°C for
12 from 8 to 24 hours, to obtain the as-synthesized SSZ-65 crystals. The
drying step can
13 be performed at atmospheric pressure or under vacuum.
14 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,
16 gallium oxide, iron oxide, boron oxide, titanium oxide, indium oxide,
vanadium oxide
17 and mixtures thereof greater than about 15; arid has, after calcination,
the X-ray
18 diffraction lines of Table II below. SSZ-65 further has a composition, as
synthesized
19 (i.e., prior to removal of the SDA from the SSZ-65) and in the anhydrous
state, in
r
2o terms of mole ratios, shown in Table B below.
21 TABLE B
22 As-Synthesized SSZ-65
23 YOz/W~Od > 15
24 M2~n~'Oz 0.01- 0.03
Q/YOz 0.02 - 0.05
26 where Y, W, c, d, M, n and Q are as defined above.
27 SSZ-65 can be made with a mole ratio of YOz/W~Oa of °o, i.e., there
is
28 essentially no W~Od present in the SSZ-65. In this case, the SSZ-65 would
be an all-
29 silica material or a germanosilicate. Thus, in a typical case where oxides
of silicon
3o and aluminum are used, SSZ-65 can be made essentially aluminum free, i.e.,
having a
31 silica to alumina mole ratio of °o. A method of increasing the mole
ratio of silica to
32 alumina is by using standard acid leaching or chelating treatments.
However,
11
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1 essentially aluminum-free SSZ-65 can be synthesized using essentially
aluminum-free
2 silicon sources as the main tetrahedral metal oxide component, if boron is
also
3 ~ present. The boron can then be removed, if desired, by treating the
borosilicate SSZ-
4 65 with acetic acid at elevated temperature ( as described in Jones et al.,
Chem.
MateY., 2001, 13, 1041-1050) to produce an all-silica version of SSZ-65. SSZ-
65 can
6 also be prepared directly as a borosilicate. If desired, the boron can be
removed as
7 described above and replaced with metal atoms by techniques known in the art
to
8 make, e.g., an aluminosilicate version of SSZ-65. SSZ-65 can also be
prepared
9 directly as an aluminosilicate.
to Lower silica to alumina ratios may also be obtained by using methods which
1 1 insert aluminum into the crystalline framework. For example, aluminum
insertion
12 may occur by thermal treatment of the molecular sieve in combination with
an
13 alumina binder or dissolved source of alumina. Such procedures are
described in U.S.
14 Patent No. 4,559,315, issued on December 17, 1985 to Chang et al.
It is believed that SSZ-65 is comprised of a new framework structure or
16 topology which is characterized by its X-ray diffraction pattern. SSZ-65,
17 as-synthesized, has a crystalline structure whose X-ray powder diffraction
pattern
18 exhibit the characteristic lines shown in Table I and is thereby
distinguished from
19 other molecular sieves.
2o TABLE I
21 As-Synthesized SSZ-65
22
2 Theta~a) d-spacing-(Angstroms)Relative Intensity
(%)~'~
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
23 ~a~ ~ 0.1
12
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1 ~'~ The X-ray patterns provided are based on a relative intensity scale in
2 which the strongest line in the X-ray pattern is assigned a value of 100:
3 W(weak) is less than 20; M(medium) is between 20 and 40; S(strong)
4 is between 40 and 60; VS(very strong) is greater than 60.
Table IA below shows the X-ray powder diffraction lines for as-synthesized
6 SSZ-65 including actual relative intensities.
7 TABLE IA
8
2 Theta~a~ d-spacin~(An~stroms) Relative Iutensit~(%)
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,g
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
34.76 2.58 1.8
36.29 2.47 1.6
37.46 2.40 1.3
9 ~a~ ~ 0.1
to After calcination, the SSZ-65 molecular sieves have a crystalline structure
11 whose X-ray powder diffraction pattern include the characteristic lines
shown in
12 Table II:
13 TABLE II
14 Calcined SSZ-65
2 Theta~a~ d-spacing-(An stroms) Relative Intensity (%)
7.19 12.29 M
7.42 11.91 VS
7.82 11.30 VS
8.30 10.64 M
13
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13.40 6.60 - M
21.46 4.14 W
22.50 3.95 VS
22.81 3.90 W
27.14 3.28 M
29.70 3.06 W
1 Via) ~ 0.1
2 Table IIA below shows the X-ray powder
diffraction lines for calcined SSZ-65
3 including actual relative intensities.
4 TABLE IIA
2 Theta~a~ d-spacing (An strums) Relative Intensity
(%)
7.19 12.29 27.7
7.42 11.91 68.5
7.82 11.29 67.0
8.30 10.64 40.1
10.46 8:45 3.1
11.31 7.82 6.7
13.40 6.60 25.1
14.38 6.16 5.3
14.60 6.06 6.5
21.46 4.14 11.2
22.50 3.95 - 100.0
22.81 3.90 13.0
25.42 3:50 9.2
27.14 3.28 19.6
28.80 3.10 8.2
29.70 3.01 11.0
30.48 2.93 3.3
33.56 2.67 3.9
34.86 2.57 3.3
36.29 2.47 3.2
37.64 2.39 2,g
6 ~a~ ~ 0.1
7 The X-ray powder diffraction patterns were
determined by standard
8 techniques. The radiation was the K-alpha/doubletThe peak heights
of copper. and
9 the positions, as a function of 2~ where
8 is the Bragg angle, were read from the
1o relative intensities of the peaks, and in Angstroms
d, the interplanar spacing
1 corresponding to the recorded lines, can
1 be calculated.
12 The variation in the scattering angle (two
theta) measurements, due to
13 instrument error and to differences between individual samples, is
estimated at
14 ~ 0.1 degrees.
14
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1 The X-ray diffraction pattern of Table I is representative of "as-
synthesized"
2 or "as-made" SSZ-65 molecular sieves. Minor variations in the diffraction
pattern
3 can result from variations in the silica-to-alumina or silica-to-boron mole
ratio of the
4 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
6 broadening.
7 Representative peaks from the X-ray diffraction pattern of calcined SSZ-65
8 are shown in Table II. Calcination can also result in changes in the
intensities of the
9 peaks as compared to patterns of the "as-made" material, as well as minor
shifts in the
1o diffraction pattern. The molecular sieve produced by exchanging the metal
or other
11 cations present in the molecular sieve with various other cations (such as
H+ or NH4+)
12 yields essentially the same diffraction pattern, although again, there may
be minor
13 shifts in the interplanar spacing and variations in the relative
intensities of the peaks.
14 Notwithstanding these minor perturbations, the basic crystal lattice
remains
unchanged by these treatments.
16 Crystalline SSZ-65 can be used as-synthesized, but preferably will be
17 thermally treated (calcined). Usually, it is desirable to remove the alkali
metal cation
18 by ion exchange and replace it with hydrogen, ammonium, or any desired
metal ion.
19 The molecular sieve can be leached with chelating agents, e.g., EDTA or
dilute acid
~2o solutions, to increase the silica to alumina mole ratio. The molecular
sieve can also
21 be steamed; steaming helps stabilize the crystalline lattice to attack from
acids.
22 The molecular sieve can be used in intimate combination with hydrogenating
23 components, such as tungsten, vanadiuan, molybdenum, rhenium, nickel,
cobalt,
24. chromium, manganese, or a noble metal, such as palladium or platinum, for
those
applications in which a hydrogenation-dehydrogenation function is desired.
26 Metals may also be introduced into the molecular sieve by replacing some of
27 the cations in the molecular sieve with metal cations via standard ion
exchange
28 techniques (see, for example, U.S. Patent Nos. 3,140,249 issued July 7,
1964 to Plank
29 et al.; 3,140,251 issued July 7, 1964 to Plank et al.; and 3,140,253 issued
July 7, 1964
3o to Plank et al.). Typical replacing cations can include metal cations,
e.g., rare earth,
31 Group IA, Group IIA and Group VIII metals, as well as their mixtures. Of
the
CA 02520856 2005-09-26
WO 2004/094347 PCT/US2004/007754
1 replacing metallic cations, cations of metals such as rare earth, Mn, Ca,
Mg, Zn, Cd,
2 Pt, Pd, Ni, Co, Ti, Al, Sn, and Fe are particularly preferred.
3 The hydrogen, ammonium, and metal components can be ion-exchanged into
4 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
6 to the art.
7 Typical ion-exchange techniques involve contacting the synthetic molecular
8 sieve with a solution containing a salt of the desired replacing cation or
cations.
9 Although a wide variety of salts can be employed, chlorides and other
halides,
l0 acetates, nitrates, and sulfates are particularly preferred. The molecular
sieve is
11 usually calcined prior to the ion-exchange procedure to remove the organic
matter
12 present in the channels and on the surface, since this results in a more
effective ion
13 exchange. Representative ion exchange techniques are disclosed in a wide
variety of
14 patents including IJ.S. Patent Nos. 3,140,249 issued on July 7, 1964 to
Plank et al.;
3,140,251 issued on July 7, 1964 to Plank et al.; and 3,140,253 issued on July
7, 1964
16 to Plank et al.
17 Following contact with the salt solution of the desired replacing cation,
the
1 s molecular sieve is typically washed with water and dried at temperatures
ranging from
19 65°C to about 200°C. After waslung, the molecular sieve can
be calcined in air or
2o inert gas at temperatures ranging from about 200°C to about
800°C for periods of
21 time ranging from 1 to 48 hours, or more, to produce a catalytically active
product
22 especially useful in hydrocarbon conversion processes.
23 Regardless of the cations present in the synthesized form of SSZ-65, the
24 spatial arrangement of the atoms which form the basic crystal lattice of
the molecular
sieve remains essentially unchanged.
26 SSZ-65 can be formed into a wide variety of physical shapes. Generally
27 speaking, the molecular sieve can be in the form of a powder, a granule, or
a molded
28 product, such as extrudate having a particle size sufficient to pass
through a 2-mesh
29 (Tyler) screen and be retained on a 400-mesh (Tyler) screen. In cases where
the
3o catalyst is molded, such as by extrusion with an organic binder, the SSZ-65
can be
31 extruded before drying, or, dried or partially dried and then extruded.
16
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1 SSZ-65 can be composited with other materials resistant to the temperatures
2 and other conditions employed in organic conversion processes. Such matrix
3 materials include active and inactive materials and synthetic or naturally
occurring
4 molecular sieves as well as inorganic materials such as clays, silica and
metal oxides.
Examples of such materials and the maimer in which they can be used are
disclosed in
6 U.S. Patent No. 4,910,006, issued May 20, 1990 to Zones et al., and U.S.
Patent
7 No. 5,316,753, issued May 31, 1994 to Nakagawa, both of which are
incorporated by
8 reference herein in their entirety.
9 SSZ-65 molecular sieves are useful in hydrocarbon conversion reactions.
to Hydrocarbon conversion reactions are chemical and catalytic processes in
which
1 1 carbon containing compounds are changed to different carbon containing
compounds.
12 Examples of hydrocarbon conversion reactions in which SSZ-65 are expected
to be
13 useful include hydrocracking, dewaxing, catalytic cracking and olefin and
aromatics
14 formation reactions. The catalysts are also expected to be useful in other
petroleum
refining and hydrocarbon conversion reactions such as isomerizing n-paraffins
and
16 naphthenes, polymerizing and oligomerizing olefinic or acetylenic compounds
such as
17 isobutylene and butene-l, reforming, isomerizing polyallcyl substituted
aromatics
18 (e.g., m-xylene), and disproportionating aromatics (e.g., toluene) to
provide mixtures
19 of benzene, xylenes and higher methylbenzenes and oxidation reactions. Also
2o included are rearrangement reactions to make various naphthalene
derivatives, and
21 forming higher molecular weight hydrocarbons from lower molecular weight
22 hydrocarbons (e.g., methane upgrading).
23 The SSZ-65 catalysts may have high selectivity, and under hydrocarbon
conversion
24 conditions can provide a high percentage of desired products relative to
total products.
For high catalytic activity, the SSZ-65 molecular sieve should be
26 predominantly in its hydrogen ion form. Generally, the molecular sieve is
converted
27 to its hydrogen form by ammonium exchange followed by calcination. If the
28 molecular sieve is synthesized with a high enough ratio of SDA cation to
sodium ion,
29 calcination alone may be sufficient. It is preferred that, after
calcination, at least 80%
of the cation sites axe occupied by hydrogen ions and/or rare earth ions. As
used
31 herein, "predominantly in the hydrogen form" means that, after calcination,
at least
32 80% of the cation sites are occupied by hydrogen ions and/or rare earth
ions.
17
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1 SSZ-65 molecular sieves can be used in processing hydrocarbonaceous
2 feedstoclcs. Hydrocarbonaceous feedstocks contain caxbon compounds and can
be
3 from many different sources, such as virgin petroleum fractions, recycle
petroleum
4 fractions, shale oil, liquefied coal, tar sand oil, synthetic paraffins from
NAO,
recycled plastic feedstocks and, in general, can be any carbon containing
feedstock
6 susceptible to zeolitic catalytic reactions. Depending on the type of
processing the
7 hydrocarbonaceous feed is to undergo, the feed can contain metal or be free
of metals,
8 it can also have high or low nitrogen or sulfur impurities. It can be
appreciated,
9 however, that in general processing will be more efficient (and the catalyst
more
to active) the lower the metal, nitrogen, and sulfur content of the feedstock.
11 The conversion of hydrocarbonaceous feeds can take place in any convenient
12 mode, fox example, in fluidized bed, moving bed, or fixed bed reactors
depending on
13 the types of process desired. The formulation of the catalyst particles
will vary
14 depending on the conversion process and method of operation.
Other reactions which can be performed using the catalyst of this invention
16 containing a metal, e.g., a Group VIII metal such platinum, include
17 hydrogenation-dehydrogenation reactions, denitrogenation and
desulfurization
18 reactions.
i9 The following table indicates typical reaction conditions which may be
2o employed when using catalysts comprising SSZ-65 in the hydrocarbon
conversion
21 reactions of this invention. Preferred conditions are indicated in
parentheses.
22
Process Temp.,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.-' 0.5-50
(atm.-5 atm.)
Oligomerization232-649' 0.1-50 atm.L' 0.2-50z
10-2324 ' 0.05-205
(27-204)4 ' (0.1-10)5
18
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WO 2004/094347 PCT/US2004/007754
1
2
Paraffins to 100-700 . 0-1000 psig 0.5-40
aromatics
Condensation 260-538 0.5-1000 psig, 0.5-50
of
alcohols 0.00345-6.89
MPa
gauge
Isomerization 93-538 50-1000 prig, 1-10
(204-315) 0.345-6.89 MPa (1-4)
gauge
Xylene 260-593' 0.5-50 atm.2 0.1-100
isomerization (315-566)2 (1-5 atm)2 (0.5-50)5
38-3714 1-200 atm.4 0.5-50
3 1 Several hundred atmospheres
4 2 Gas phase reaction
3 Hydrocarbon partial pressure
6 4 Liquid phase reaction
7 5 WHSV
8 Other reaction conditions and parameters are provided below
Hydrocrackin~
' Using a catalyst which comprises SSZ-65, preferably predominantly in the
11 hydrogen form, and a hydrogenation promoter, heavy petroleum residual
feedstocks,
12 cyclic stocks and other hydrocrackate charge stocks can be hydrocracked
using the
13 process conditions and catalyst components disclosed in the aforementioned
U.S.
14. Patent No. 4,910,006 and U.S. Patent No. 5,316,753.
The hydrocracking catalysts contain an effective amount of at least one
16 hydrogenation component of the type commonly employed in hydrocracl~ing
17 catalysts. The hydrogenation component is generally selected from the group
of
18 hydrogenation catalysts consisting of one or more metals of Group VIB and
19 Group VIII, including the salts, complexes and solutions containing such.
The
2o hydrogenation catalyst is preferably selected from the group of metals,
salts and
21 complexes thereof of the group consisting of at least one of platinum,
palladium,
22 rhodium, iridium, ruthenium and mixtures thereof or the group consisting of
at least
23 one of niclcel, molybdenum, cobalt, tungsten, titanium, chromium and
mixtures
24 ~ 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,
19
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WO 2004/094347 PCT/US2004/007754
1 halide, carboxylate and the like. The hydrogenation catalyst is present in
an effective
2 amount to provide the hydrogenation function of the hydrocracking catalyst,
and
3 preferably in the range of from 0.05 to 25% by weight.
4 Dewaxin~
SSZ-65, preferably predominantly in the hydrogen form, can be used to dewax
6 hydrocarbonaceous feeds by selectively removing straight chain paraffms.
Typically,
7 the viscosity index of the dewaxed product is improved (compared to the waxy
feed)
8 when the waxy feed is contacted with SSZ-65 under isomerization dewaxing
9 conditions.
to The catalytic dewaxing conditions are dependent in large measure on the
feed
11 used and upon the desired pour point. Hydrogen is preferably present in the
reaction
12 zone during the catalytic dewaxing process. The hydrogen to feed ratio is
typically
13 between about 500 and about 30,000 SCF/bbl (standard cubic feet per barrel)
(0.089
14 to 5.34 SCM/liter (standard cubic meters/liter)), preferably about 1000 to
about
20,000 SCF/bbl (0.178 to 3.56 SCM/liter). Generally, hydrogen will be
separated
16 from the product and recycled to the reaction zone. Typical feedstocks
include light
i7 gas oil, heavy gas oils and reduced crudes boiling above about 350°F
(177°C).
18 A typical dewaxing process is the catalytic dewaxing of a hydrocarbon oil
19 feedstock boiling above about 350°F (177°C) and containing
straight chain and
slightly branched chain hydrocarbons by contacting the hydrocarbon oil
feedstock in
21 the presence of added hydrogen gas at a hydrogen pressure of about 15-3000
psi
22 (0.103-20.7 MPa) with a catalyst comprising SSZ-65 and at least one Group
VIII
23 metal.
24 The SSZ-65 hydrodewaxing catalyst may optionally contain a hydrogenation
component of the type cormnonly employed in dewaxing catalysts. See the
26 aforementioned U.S. Patent No. 4,910,006 and U.S. Patent No. 5,316,753 for
27 examples of these hydrogenation components.
28 The hydrogenation component is present in an effective amount to provide an
29 effective hydrodewaxing and hydroisomerization catalyst preferably in the
range of
3o from about 0.05 to 5% by weight. The catalyst may be run in such a mode to
increase
31 isomerization dewaxing at the expense of cracking reactions.
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1 The feed may be hydrocracked, followed by dewaxing. This type of two stage
2 process and typical hydrocracking conditions are described in U.S. Patent
3 No. 4,921,594, issued May 1, 1990 to Miller, which is incorporated herein by
4 reference in its entirety.
SSZ-65 may also be utilized as a dewaxing catalyst in the form of a layered
6 catalyst. That is, the catalyst comprises a first layer comprising molecular
sieve SSZ-
7 65 and at least one Group VIII metal, and a second layer comprising an
8 aluminosilicate molecular sieve which is more shape selective than molecular
sieve
9 SSZ-65. The use of layered catalysts is disclosed in U.S. Patent No.
5,149,421, issued
to September 22, 1992 to Miller, which is incorporated by reference herein in
its
1 1 entirety. The layering may also include a bed of SSZ-65 layered with a non-
zeolitic
12 component designed for either hydrocracking or hydrofinishing.
13 SSZ-65 may also be used to dewax raffinates, including bright stock, under
14 conditions such as those disclosed in U. S. Patent No. 4,181,598, issued
January 1,
1980 to Gillespie et al., which is incorporated by reference herein in its
entirety.
16 It is often desirable to use mild hydrogenation (sometimes referred to as
17 hydrofinishing) to produce more stable dewaxed products. The hydrofinishing
step
i8 can be performed either before or after the dewaxing step, and preferably
after.
19 Hydrofinishing is typically conducted at temperatures ranging from about
190°C to
about 340°C at pressures from about 400 psig to about 3000 psig (2.76
to 20.7 MPa
21 gauge) at space velocities (LHSV) between about 0.1 and 20 and a hydrogen
recycle
22 rate of about 400 to 1500 SCF/bbl (0.071 to 0.27 SCM/liter). The
hydrogenation
23 catalyst employed must be active enough not only to hydrogenate the
olefins,
24 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,
26 issued May 1, 1990 to Miller, which is incorporated by reference herein in
its entirety.
27 The hydrofinishing step is beneficial in preparing an acceptably stable
product (e.g., a
28 lubricating oil) since dewaxed products prepared from hydrocracked stocks
tend to be
29 unstable to air and light and tend to form sludges spontaneously and
quickly.
3o Lube oil may be prepared using SSZ-65. For example, a CZO+ Tube oil may be
31 made by isomerizing a C2o+ olefin feed over a catalyst comprising SSZ-65 in
the
32 hydrogen form and at least one Group VIII metal. Alternatively, the
lubricating oil
21
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1 may be made by hydrocracking in a hydrocracking zone a hydrocarbonaceous
2 feedstock to obtain an effluent comprising a hydrocracked oil, and
catalytically
3 dewaxing the effluent at a temperature of at least about 400°F
(204°C) and at a
4 pressure of from about 15 prig 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
6 form and at least one Group VIII metal.
7 Aromatics Formation
8 SSZ-65 can be used to convert light straight run naphthas and similar
mixtures
9 to highly aromatic mixtures. Thus, normal and slightly branched chained
to hydrocarbons, preferably having a boiling range above about 40°C and
less than about
11 200°C, can be converted to products having a substantial higher
octane aromatics
12 content by contacting the hydrocarbon feed with a catalyst comprising SSZ-
65. It is
i3 also possible to convert heavier feeds into BTX or naphthalene derivatives
of value
14 using a catalyst comprising SSZ-65.
The conversion catalyst preferably contains a Group VIII metal compound to
16 have sufficient activity for commercial use. By Group VIII metal compound
as used
17 herein is meant the metal itself or a compound thereof. The Group VIII
noble metals
18 and their compounds, platinum, palladium, and iridium, or combinations
thereof can
19 be used. Rhenium or tin or a mixture thereof may also be used in
conjunction with
2o the Group VIII metal compound and preferably a noble metal compound. The
most
21 preferred metal is platinum. The amount of Group VIII metal present in the
22 conversion catalyst should be within the normal range of use in reforming
catalysts,
23 from about 0.05 to 2.0 weight percent, preferably 0.2 to 0.8 weight
percent.
24 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
26 the molecular sieve with a basic metal, e.g., allcali metal, compound.
Methods for
27 rendering the catalyst free of acidity are known in the art. See the
aforementioned
28 U.S. Patent No. 4,910,006 and U.S. Patent No. 5,316,753 for a description
of such
29 methods.
3o The preferred alkali metals are sodium, potassium, rubidium and cesium. The
31 molecular sieve itself can be substantially free of acidity only at very
high
32 silica:alumina mole ratios.
22
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1 Catalytic Cracking
2 Hydrocarbon cracking stocks can be catalytically cracked in the absence of
3 hydrogen using SSZ-65, preferably predominantly in the hydrogen form.
4 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
6 catalysts, e.g., any aluminosilicate heretofore employed as a component in
cracking
7 catalysts. Typically, these are large pore, crystalline aluminosilicates.
Examples of
8 these traditional cracking catalysts are disclosed in the aforementioned
U.S. Patent
9 No. 4,910,006 and U.S. Patent No 5,316,753. When a traditional cracking
catalyst
to (TC) component is employed, the relative weight ratio of the TC to the SSZ-
65 is
1 1 generally between about 1:10 and about 500:1, desirably between about 1:10
and
12 about 200:1, preferably between about 1:2 and about 50:1, and most
preferably is
13 between about 1:1 and about 20:1. The novel molecular sieve and/or the
traditional
14 cracking component may be further ion exchanged with rare earth ions to
modify
selectivity.
16 The cracking catalysts are typically employed with an inorganic oxide
matrix
17 component. See the aforementioned U.S. Patent No. 4,910,006 and U.S. Patent
i8 No. 5,316,753 for examples of such matrix components.
19 Isomerization
2o The present catalyst is highly active and highly selective for isomerizing
C4 to
21 C~ hydrocarbons. The activity means that the catalyst can operate at
relatively low
22 temperature which thermodynamically favors highly branched paraffins.
23 Consequently, the catalyst can produce a high octane product. The high
selectivity
24 means that a relatively high liquid yield can be achieved when the catalyst
is run at a
high octane.
26 The present process comprises contacting the isomerization catalyst, i.e.,
a
27 catalyst comprising SSZ-65 in the hydrogen form, with a hydrocarbon feed
under
28 isomerization conditions. The feed is preferably a light straight run
fraction, boiling
29 within the range of 30°F to 250°F (-1°C to
121°C) and preferably from 60°F to 200°F
(16°C to 93°C). Preferably, the hydrocarbon feed for the process
comprises a
31 substantial amount of C4 to C~ normal and slightly branched low octane
32 hydrocarbons, more preferably CS and C6 hydrocarbons.
23
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1 It is preferable to carry out the isomerization reaction in the presence of
2 hydrogen. Preferably, hydrogen is added to give a hydrogen to hydrocarbon
ratio
3 (H2/HC) of between 0.5 and 10 HZ/HC, more preferably between 1 and 8 HZ/HC.
See
4 the aforementioned U.S. Patent No. 4,910,006 and U.S. Patent No. 5,316,753
for a
further discussion of isomerization process conditions.
6 A low sulfur feed is especially preferred in the present process. The feed
7 preferably contains less than 10 ppm, more preferably less than 1 ppm, and
most
8 preferably less than 0.1 ppm sulfur. In the case of a feed which is not
already low in
9 sulfur, acceptable levels can be reached by hydrogenating the feed in a
presaturation
1o zone with a hydrogenating catalyst which is resistant to sulfur poisoning.
See the
11 aforementioned U.S. Patent No. 4,910,006 and U.S. Patent No. 5,316,753 for
a further
12 discussion of this hydrodesulfurization process.
13 It is preferable to limit the nitrogen level and the water content of the
feed.
14 Catalysts and processes which are suitable for these purposes are known to
those
slcilled in the art.
16 After a period of operation, the catalyst can become deactivated by sulfux
or
17 coke. See the aforementioned U.S. Patent No. 4,910,006 and U.S. Patent
18 No. 5,316,753 for a further discussion of methods of removing this sulfur
and coke,
19 and of regenerating the catalyst.
2o The conversion catalyst preferably contains a Group VIII metal compound to
21 have sufficient activity for commercial use. By Group VIII metal compound
as used
22 herein is meant the metal itself or a compound thereof. The Group VIII
noble metals
23 and their compounds, platinum, palladium, and iridium, or combinations
thereof can
24 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
26 conversion catalyst should be within the normal range of use in isomerizing
catalysts,
27 from about 0.05 to 2.0 weight percent, preferably 0.2 to 0.8 weight
percent.
28 Allcylation and Transall~ylation
29 SSZ-65 can be used in a process for the alkylation or transalkylation of an
3o aromatic hydrocarbon. The process comprises contacting the aromatic
hydrocarbon
31 with a C2 to C16 olefin alkylating agent or a polyalkyl aromatic
hydrocarbon
32 transalkylating agent, under at least partial liquid phase conditions, and
in the
33 presence of a catalyst comprising SSZ-65.
34 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.
24
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1 For high catalytic activity, the SSZ-65 molecular sieve should be
2 predominantly in its hydrogen ion form. It is preferred that, after
calcination, at least
3 80% of the cation sites are occupied by hydrogen ions and/or rare earth
ions.
4 Examples of suitable aromatic hydrocarbon feedstocks which may be
alkylated or transalkylated by the process of the invention include aromatic
6 compounds such as benzene, toluene and xylene. The preferred aromatic
7 hydrocarbon is benzene. There may be occasions where naphthalene or
naphthalene
8 derivatives such as dimethylnaphthalene may be desirable. Mixtures of
aromatic
9 hydrocarbons may also be employed.
1o Suitable olefins for the alkylation of the aromatic hydrocarbon are those
11 containing 2 to 20, preferably 2 to 4, carbon atoms, such as ethylene,
propylene,
12 butene-1, traps-butene-2 and cis-butene-2, or mixtures thereof. There may
be
13 instances where pentenes are desirable. The preferred olefins are ethylene
and
14 propylene. Longer chain alpha olefins may be used as well.
When transalkylation is desired, the transalkylating agent is a polyalkyl
16 aromatic hydrocarbon containing two or more alkyl groups that each may have
from 2
17 to about 4 carbon atoms. For example, suitable polyalkyl aromatic
hydrocarbons
18 include di-, tri- and tetra-alkyl aromatic hydrocarbons, such as
diethylbenzene,
19 triethylbenzene, diethylmethylbenzene (diethyltoluene), di-
isopropylbenzene,
2o di-isopropyltoluene, dibutylbenzene, and the like. Preferred polyalkyl
aromatic
21 hydrocarbons are the dialkyl benzenes. A particularly preferred polyalkyl
aromatic
22, hydrocarbon is di-isopropylbenzene.
23 When alkylation is the process conducted, reaction conditions are as
follows.
24 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
26 rapid catalyst fouling. The reaction temperature may range from
100°F to 600°F
27 (38°C to 315°C), preferably 250°F to 450°F
(121°C to 232°C). The reaction pressure
28 should be sufficient to maintain at least a partial liquid phase in order
to retard
29 catalyst fouling. This is typically 50 psig to 1000 psig (0.345 to 6.89 MPa
gauge)
3o depending on the feedstock and reaction temperature. Contact time may range
from
31 10 seconds to 10 hours, but is usually from 5 minutes to an hour. The
weight hourly
32 space velocity (WHSV), in terms of grams (pounds) of aromatic hydrocarbon
and
33 olefin per gram (pound) of catalyst per hour, is generally within the range
of about 0.5
34 to 50.
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WO 2004/094347 PCT/US2004/007754
1 When transalkylation is the process conducted, the molar ratio of aromatic
2 hydrocarbon will generally range from about 1:1 to 25: l, and preferably
from about
3 2:1 to 20:1. The reaction temperature may range from about 100°F to
600°F (38°C to
4 315°C), but it is preferably about 250°F to 450°F
(121°C to 232°C). The reaction
pressure should be sufficient to maintain at least a partial liquid phase,
typically in the
6 range of about 50 psig to 1000 psig (0.345 to 6.89 MPa gauge), preferably
300 psig to
7 600 psig (2.07 to 4.14 MPa gauge). The weight hourly space velocity will
range from
8 about 0.1 to 10. U.S. Patent No. 5,082,990 issued on January 21, 1992 to
Hsieh, et al.
9 describes such processes and is incorporated herein by reference.
to Conversion of Paraffms to Aromatics
11 , SSZ-65 can be used to convert light gas C2-C6 paraffins to higher
molecular
12 weight hydrocarbons including aromatic compounds. Preferably, the molecular
sieve
13 will contain a catalyst metal or metal oxide wherein said metal is selected
from the
14 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%
16 by weight.
17 Isomerization of Olefins
18 SSZ-65 can be used to isomerize olefins. The feed stream is a hydrocarbon
19 stream containing at least one C4_6 olefin, preferably a C4_6 normal
olefin, more
2o preferably normal butene. Normal butene as used in this specification means
all
21 forms of normal butene, e.g., 1-butene, cis-2-butene, and trans-2-butene.
Typically,
22 hydrocarbons other than normal butene or other Cø_6 normal olefins will be
present in
23 the feed stream. These other hydrocarbons may include, e.g., alkanes, other
olefins,
24 aromatics, hydrogen, and inert gases.
The feed stream typically may be the effluent from a fluid catalytic cracking
26 unit or a methyl-tert-butyl ether unit. A fluid catalytic cracking unit
effluent typically
27 contains about 40-60 weight percent normal butenes. A methyl-tert-butyl
ether unit
28 effluent typically contains 40-100 weight percent normal butene. The feed
stream
29 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
31 branched iso-olefin may be used interchangeably in this specification.
32 The process is carried out under isomerization conditions. The hydrocarbon
33 feed is contacted in a vapor phase with a catalyst comprising the SSZ-65.
The
26
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1 process may be carried out generally at a temperature from about
625°F to about
2 950°F (329-510°C), for butenes, preferably from about
700°F to about 900°F (371-
3 482°C), and about 350°F to about 650°F (177-
343°C) for pentenes and hexenes. The
4 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
6 from about 1 psig to about 150 psig (0.00689 to 1.03 MPa gauge).
7 The liquid hourly space velocity during contacting is generally from about
0.1
8 to about 50 hr-1, based on the hydrocarbon feed, preferably from about 0.1
to about
9 20 hr-1, more preferably from about 0.2 to about 10 hr-1, most preferably
from about 1
l0 to about 5 hr-1. A hydrogen/hydrocarbon molar ratio is maintained from
about 0 to
1 1 about 30 or higher. The hydrogen can be added directly to the feed stream
or directly
12 to the isomerization zone. The reaction is preferably substantially free of
water,
13 typically less than about two weight percent based on the feed. The process
can be
14 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
16 conversion of, e.g., normal butene to iso-butene is at least 10, preferably
at least 25,
17 and more preferably at least 35.
1 s Xylene Isomerization
i9 SSZ-65 may also be useful in a process for isomerizing one or more xylene
2o isomers in a C8 aromatic feed to obtain ortho-, mete-, and pare-xylene in a
ratio
21 approaching the equilibrium value. In particular, xylene isomerization is
used in
22 conjunction with a separate process to manufacture pare-xylene. For
example, a
23 portion of the pare-xylene in a mixed C8 aromatics stream may be recovered
by
24 crystallization and centrifugation. The mother liquor from the crystallizer
is then
reacted under xylene isomerization conditions to restore ortho-, mete- and
26 pare-xylenes to a near equilibrium ratio. At the same time, part of the
ethylbenzene in
27 the mother liquor is converted to xylenes or to products which are easily
separated by
28 filtration. The isomerate is blended with fresh feed and the combined
stream is
29 distilled to remove heavy and light by-products. The resultant C8 aromatics
stream is
3o then sent to the crystallizes to repeat the cycle.
31 Optionally, isomerization in the vapor phase is conducted in the presence
of
32 3.0 to 30.0 moles of hydrogen per mole of alkylbenzene (e.g.,
ethylbenzene). If
27
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1 hydrogen is used, the catalyst should comprise about 0.1 to 2.0 wt.% of a
2 hydrogenation/dehydrogenation component selected from Group VIII (of the
Periodic
3 Table) metal component, especially platinum or nickel. By Group VIII metal
4 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
6 as toluene, trimethylbenzene, naphthenes or paraffins.
7 Oli~omerization
8 It is expected that SSZ-65 can also be used to oligomerize straight and
9 branched chain olefins having from about 2 to 21 and preferably 2-5 carbon
atoms.
1o The oligomers which are the products of the process are medium to heavy
olefins
1 l which are useful for both fuels, i.e., gasoline or a gasoline blending
stock and
12 chemicals.
13 The oligomerization process comprises contacting the olefin feedstock in
the
14 gaseous or liquid phase with a catalyst comprising SSZ-65.
The molecular sieve can have the original cations associated therewith
16 replaced by a wide variety of other cations according to techniques well
known in the
17 art. Typical cations would include hydrogen, ammonium and metal cations
including
18 mixtures of the same. Of the replacing metallic cations, particular
preference is given
19 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,
21 e.g., nickel. One of the prime requisites is that the molecular sieve have
a fairly low
22 aromatization activity, i.e., in which the amount of aromatics produced is
not more
23 than about 20% by weight. This is accomplished by using a molecular sieve
with
24 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.
26 Alpha values are defined by a standard test known in the art, e.g., as
shovcni in
27 U.S. Patent No. 3,960,978 issued on June 1, 1976 to Givens et al. which is
28 incorporated totally herein by reference. If required, such molecular
sieves may be
29 obtained by steaming, by use in a conversion process or by any other method
which
3o may occur to one slcilled in this art.
31 ' Condensation of Alcohols
32 SSZ-65 can be used to condense lower aliphatic alcohols having 1 to
33 10 carbon atoms to a gasoline boiling point hydrocarbon product comprising
mixed
28
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1 aliphatic and aromatic hydrocarbon. The process disclosed in U.S. Patent
2 No. 3,894,107, issued July 8, 1975 to Butter et al., describes the process
conditions
3 used in this process, which patent is incorporated totally herein by
reference.
4. The catalyst may be in the hydrogen form or may be base exchanged or
impregnated to contain ammouum or a metal cation complement, preferably in the
6 range of from about 0.05 to 5% by weight. The metal cations that may be
present
7 include any of the metals of the Groups I through VIII of the Periodic
Table.
8 However, in the case of Group IA metals, the cation content should in no
case be so
9 large as to effectively inactivate the catalyst, nor should the exchange be
such as to
1o eliminate all acidity. There may be other processes involving treatment of
11 oxygenated substrates where a basic catalyst is desired.
12 Methane Up air ding
13 Higher molecular weight hydrocarbons can be formed from lower molecular
14 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
16 lower molecular weight hydrocarbon to a higher molecular weight
hydrocarbon.
17 Examples of such reactions include the conversion of methane to C2+
hydrocarbons
18 such as ethylene or benzene or both. Examples of useful metals and metal
19 compounds include lanthanide and or actinide metals or metal compounds.
2o These reactions, the metals or metal compounds employed and the conditions
21 under which they can be run are disclosed in U.S. Patents No. 4,734,537,
issued
22 March 29, 1988 to Devries et al.; 4,939,311, issued July 3, 1990 to
Washecheck et al.;
23 4,962,261, issued October 9, 1990 to Abrevaya et al.; 5,095,161, issued
March 10,
24 1992 to Abrevaya et al.; 5,105,044, issued April 14, 1992 to Han et al.;
5,105,046,
issued April 14, 1992 to Washecheck; 5,238,898, issued August 24, 1993 to Han
et
26 al.; 5,321,185, issued June 14, 1994 to van der Vaart; and 5,336,825,
issued August 9,
27 1994 to Choudhary et al., each of which is incorporated herein by reference
in its
28 entirety.
29 SSZ-65 may be used for the catalytic reduction of the oxides of nitrogen in
a
3o gas stream. Typically, the gas stream also contains oxygen, often a
stoichiometric
31 excess thereof. Also, the SSZ-65 may contain a metal or metal ions within
or on it
32 which are capable of catalyzing the reduction of the nitrogen oxides.
Examples of
29
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WO 2004/094347 PCT/US2004/007754
1 such metals or metal ions include copper, cobalt, platinum, iron, chromium,
2 manganese, nickel, zinc, lanthanum, palladium, rhodium and mixtures thereof.
3 One example of such a process for the catalytic reduction of oxides of
nitrogen
4 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,
6 the catalytic process is the combustion of carbon monoxide and hydrocarbons
and the
7 catalytic reduction of the oxides of nitrogen contained in a gas stream,
such as the
8 exhaust gas from an internal combustion engine. The molecular sieve used is
metal
9 ion-exchanged, doped or loaded sufficiently so as to provide an effective
amount of
to catalytic copper metal or copper ions within or on the molecular sieve. In
addition,
11 the process is conducted in an excess of oxidant, e.g., oxygen.
12 EXAMPLES
i3 The following examples demonstrate but do not limit the present invention.
14
Example 1
16 Synthesis of SDA 1-[1-(4-chlorophenyl)-c clo~ro~ylmethyl]-1-eth ~~l-
pyrrolidinum
17 Cation
18
CI
Me
1-[1-(4-Chloro-phenyl)-
1 g cyclopropyhnethyl]-1-ethyl-pyrrolidinium
The structure directing agent is synthesized according to the synthetic scheme
21 shown below (Scheme 1).
22 1-[1-(4-chloro-phenyl)-cyclopropylmethyl]-1-ethyl-pyrrolidinium iodide is
23 prepared from the reaction of the parent amine 1-[1-(4-chloro-phenyl)-
24 cyclopropylmethyl]-pyrrolidine with ethyl iodide. A 100 gm (0.42 mole) of
the
amine, 1-[1-(4-chloro-phenyl)-cyclopropylmethyl]-pyrrolidine, is dissolved in
1000
26 ml anhydrous methanol in a 3-litre 3-necked reaction flaslc (equipped with
a
27 mechanical stirrer and a reflux condenser). To this solution, 98 gm (0.62
mole) of
2s ethyl iodide is added, and the mixture is stirred at room temperature for
72 hours.
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1 Then, 39 gm (0.25 mol.) of ethyl iodide is added and the mixture is heated
at reflux
2 for 3 hours. The reaction mixture is cooled down and excess ethyl iodide and
the
3 solvent are removed at reduced pressure on a rotary evaporator. The obtained
dark
4 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
6 obtained solids gives 153 gm (93% yield) ofthe desired 1-[1-(4-chloro-
phenyl)-
7 cyclopropylmethyl]-1-ethyl-pyrrolidinium iodide as a white powder. The
product is
8 pure by 1H and 13C-NMR analysis.
9 The hydroxide form of 1-[1-(4-chloro-phenyl)-cyclopropylmethyl]-1-ethyl-
to pyrrolidinium cation is obtained by an ion exchange treatment of the iodide
salt with
1 1 Ion-Exchange Resin-OH (BIO RAD~ AH1-X8). In a 1-liter volume plastic
bottle,
12 100 gm (255 rmnol) of 1-[1-(4-chloro-phenyl)-cyclopropylmethyl]-1-ethyl-
13 pyrrolidinium iodide is dissolved in 300 ml de-ionized water. Then, 320 gm
of the
i4 ion exchange resin is added and the solution is allowed to gently stir
overnight. The
mixture is then filtered, and the resin calve is rinsed with minimal amount of
de-
16 ionized water. The filtrate is analyzed for hydroxide concentration by
titration
17 analysis on a small sample of the solution with O.1N HCI. The reaction
yields 96% of
is (245 mmol) of the desired 1-[1-(4-chloro-phenyl)-cyclopropyhnethyl]-1-ethyl-
19 pyrrolidinium hydroxide (hydroxide concentration of 0.6 M).
The parent amine 1-[1-(4-chloro-phenyl)-cyclopropylmethyl]-pyrrolidine is
21 obtained from the LiAlH4-reduction of the precursor amide [1-(4-chloro-
phenyl)
22 cyclopropyl]-pyrrolidin-1-yl-methanone. In a 3-neck 3-liter reaction flask
equipped
23 with a mechanical stirrer and reflux condenser, 45.5 gm (1.2 mol.) of
LiAlH4 is
24 suspended in 750 ml anhydrous tetrahydroftiran (THF). The suspension is
cooled
down to 0°C (ice-bath), and 120 gm (0.48 mole) of [1-(4-chloro-phenyl)-
26 cyclopropyl]-pyrrolidin-1-yl-methanone dissolved in 250 ml THF is added (to
the
27 suspension) drop-wise via an addition funnel. Once all the amide solution
is added,
28 the ice-bath is replaced with a heating mantle and the reaction mixture is
heated at
29 reflux overnight. Then, the reaction solution is cooled down to 0°C
(the heating
3o mantle was replaced with an ice-bath), and the mixture is diluted with 500
ml diethyl
31 ether. The reaction is worked up by adding 160 ml of 15% wt. of an aqueous
NaOH
32 solution drop-wise (via an addition funnel) with vigorous stirring. The
starting gray
31
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1 reaction solution changes to a colorless liquid with a white powdery
precipitate. The
2 solution mixture is filtered and the filtrate is dried over anhydrous
magnesium sulfate.
3 Filtration and concentration of the filtrate gives 106 gm (94% yield) of the
desired
4 amine 1-[1-(4-chloro-phenyl)-cyclopropylrnethyl]-pyrrolidine as a pale
yellow oily
substance. The amine is pure as indicated by the clean 1H and 13C-NMR spectral
6 analysis.
7 The parent amide [1-(4-chloro-phenyl)-cyclopropyl]-pyrrolidin-1-yl-
8 methanone is prepared by reacting pyrrolidine with 1-(4-chloro-phenyl)-
9 cyclopropanecarbonyl 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
11 76 gm (0.75 mol.) of triethyl amine. To this mixture (at 0°C), 108 1-
(4-chloro-
12 phenyl)-cyclopropanecarbonyl chloride gm (0.502 mol.) of (dissolved 100 ml
13 benzene) is added drop-wise (via an addition fumiel). Once the addition is
completed,
14 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
16 rotary evaporator at reduced pressure to strip off excess pyrrolidine and
the solvent
17 (usually hexane or benzene). The remaiiung residue is diluted with 750 ml
water and
i8 extracted with 750 ml chloroform in a separatory funnel. The organic layer
is washed
19 twice with 500 ml water and once with brine. Then, the organic layer is
dried over
2o anhydrous sodium sulfate, filtered and concentrated on a rotary evaporator
at reduced
21 pressure to give 122 gm (0.49 mol, 97% yield) of the amide as a tan-colored
solid
22 substance.
23 The 1-(4-chloro-phenyl)-cyclopropanecarbonyl chloride used in the synthesis
24 of the amide is synthesized by treatment of the parent acid 1-(4-chloro-
phenyl)-
cyclopropanecarboxylic acid with thionyl chloride (SOCl2) as described below.
To
26 200 gins of thionyl chloride and 200 ml dichloromethane in a 3-necked
reaction flask,
27 equipped with a mechanical stirrer and a reflux condenser, 100 gm (0.51
mol.) of the
28 1-(4-chloro-phenyl)-cyclopropanecarboxylic acid is added in small
increments (5 gm
29 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
31 collect and trap the acidic gaseous byproducts, and used in monitoring the
reaction.
32 The reaction is usually done once the evolution of the gaseous byproducts
is ceased.
32
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1 The reaction mixture is then cooled down and concentrated on a rotary
evaporator at
2 reduced pressure to remove excess thionyl chloride and dichloromethane. The
3 reaction yields 109 gm (98%) of the desired 1-(4-chloro-phenyl)-
4 cyclopropanecarbonyl chloride as reddish viscous oil.
6 Scheme 1
H
\ OH SO'~ I \ CI Pyr'i'oh I
CI ~ O CI ~ C CI ~ OWN
1-(4-Chloro-phenyl)- 1-(4-Chloro-phenyl)- [ 1-(4-Chloro-phenyl)-cyclopropyl]-
cyclopropanecarboxylic acid cyclopropanecarbonyl chloride pyrrolidin-1-yl-
methanone
1)EtI
Lip
CI ~ N~ 2) Ion-Exchange-OH CI I i <N~
Me
1-[ 1-(4-Chloro-phenyl)
cyclopropylmethyl]-pyrrolidine 1-[1-(4-Chloro-phenyl)-
cyclopropylmethyl]-1-ethyl-pyrrolidinium
8
9 Example 2
to Synthesis of SDA 1-ethyl-1-(1-phenyl-c~propylmethyl~pyrrolidinium cation
11 SDA 1-ethyl-1-(1-phenyl-cyclopropylinethyl)-pyrrolidinium cation is
12 synthesized using the synthesis procedure of Example 1, except that the
synthesis
13 starts from 1-phenyl-cyclopropanecarbonyl chloride and pyrrolidine.
14 Example 3
Synthesis of SSZ-65
16 A 23 cc Teflon liner is charged with 5.4 gm of 0.6M aqueous solution of 1-
17 ethyl-1-(1-phenyl-cyclopropylmethyl)-pyrrolidinium hydroxide (3 mrnol SDA),
1.2
18 gm of 1M aqueous solution of NaOH (1.2 mmol NaOH) and 5.4 gm of de-ionized
19 water. To this mixture, 0.06 gm of sodium borate decahydrate (0.157 inmol
of
NaZB40~.1OH20; 0.315 mmol Bz03) is added and stirred until completely
dissolved.
21 Then, 0.9 gm of CAB-O-SIL~ M-5 fumed silica 014.7 mmol SiOa) is added to
the
22 solution and the mixture is thoroughly stirred. The resulting gel is capped
off and
33
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1 placed in a Parr bomb steel reactor and heated in an oven at 160° C
while rotating at
2 43 rpm. The reaction is monitored by checking the gel's pH, and by looking
for
3 crystal formation using Scanning Electron Microscopy (SEM). The reaction is
4 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
6 clear liquid and powdery precipitate. The mixture is filtered through a
fritted-glass
7 funnel. The collected solids are thoroughly washed with water and, then,
rinsed with
s acetone (10 ml) to remove any organic residues. The solids are allowed to
air-dry
9 overnight and, then, dried in an oven at 120° C for lhour. The
reaction affords 0:85
l0 gram of a very fine powder. SEM shows the presence of only one crystalline
phase.
11 The product is determined by powder XRD data analysis to be SSZ-65.
12 Example 4
13 Seeded Synthesis of Borosilicate SSZ-65
14 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
16 up the crystallization process. The reaction conditions are exactly the
same as for the
17 previous example. The crystallization is complete in four days and affords
0.9 gm of
~8 B-SSZ-65.
19 Example 5
2o Synthesis of Aluminosilicate SSZ-65
21 A 23 cc Teflon liner is charged with 4 gm of 0.6M aqueous solution of 1-
22 ethyl-1-(1-phenyl-cyclopropylmethyl)-pyrrolidinium hydroxide (2.25 mmol
SDA),
23 1.5 gm of 1M aqueous solution of NaOH (1.5 mmol NaOH) and 2 gm of de-
ionized
24 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
26 CAB-O-SIL~ M-5 fumed silica (~14. mmol Si02) is added to the solution and
the
27 mixture is thoroughly stirred. The resulting gel is capped off and placed
in a Parr
28 bomb steel reactor and heated in an oven at 160° C while rotating at
43 rpm. The
29 reaction is monitored by checking the gel's pH (increase in the pH usually
results
3o from condensation of the silicate species during crystallization, and
decrease in pH
31 often indicates decomposition of the SDA), and by checl~ing for crystal
formation by
32 scanning electron microscopy. The reaction is usually complete after
heating for 12
34
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WO 2004/094347 PCT/US2004/007754
1 days at the conditions described above. Once the crystallization is
completed, the
2 starting reaction gel turns to a mixture comprised of a liquid and powdery
precipitate.
3 The mixture is filtered through a fritted-glass funnel. The collected solids
are
4. 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
6 oven at 120° C for lhour. The reaction affords 0.8 gram of SSZ-65.
7 Examples 6-15
8 Syntheses of SSZ-65 at Varying SiO~B 03 Ratios
9 SSZ-65 is synthesized at varying SiO2B203 mole ratios in the starting
to synthesis gel. This is accomplished using the synthetic conditions
described in
1 1 Example 3 keeping everything the same while changing the Si02B2O3 mole
ratios in
12 the starting gel. This is done by keeping the amount of CAB-O-SIL~ M-5 (98%
Si02
13 and 2% H20) the same while varying the amount of sodium borate in each
synthesis.
14 Consequently, varying the amount of sodium borate leads to varying the
Si02/Na
mole ratios in the starting gels. Table 1 below shows the results of a number
of
i6 syntheses with varying Si02B203 in the starting synthesis gel.
17 Table 1
Example Si02Bz03 Si02/Na CrystallizationProducts
No. Time(days)
6 140 13.3 15 SSZ-65
7 93 12.7 12 S SZ-65
8 70 12.1 12 SSZ-65
9 56 11.6 12 SSZ-65
10 47 11.2 12 S SZ-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
18 -UH/Si02=0.28, R' /SiOz=0.2, HZO/Si02=44
19 (R+= organic cation (SDA))
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1 Example 16
2 Calcination of SSZ-65
3 SSZ-65 as synthesized in Example 3 is calcined to remove the structure
4 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
6 and held for 2 hours. Then, the temperature is ramped up to 540°C at
a rate of
7 1°C/minute and held for 5 hours. The temperature is ramped up again
at 1°C/minute
s to 595°C and held there for 5 hours. A 50/50 mixture of air arid
nitrogen passes
9 through the muffle funiace at a rate of 20 standard cubic feet (0.57
standard cubic
meters) per minute during the calcination process.
1 1 Example 17
12 Conversion of Borosilicate-SSZ-65 to Aluminosilicate SSZ-65
13 The calcined version of borosilicate SSZ-65 (as synthesized in Example 3
and
14 calcined in Example 16) is easily converted to the aluminosilicate SSZ-65
version by
is suspending borosilicate SSZ-65 in 1M solution of aluminum nitrate
nonahydrate (15
16 ml of 1M Al(N03)3.9H2O soln./1 gm SSZ-65). The suspension is heated at
reflux
17 overnight. The resulting mixture is then filtered and the collected solids
are
18 thoroughly rinsed with de-ionized water and air-dried overnight. The solids
are
19 fizrther dried in an oven at 120°C for 2 hours.
Example 18
21 Ammonium- Ion Exchange of SSZ-65
22 The Na~ form of SSZ-65 (prepared as in Example 3 or as in Example 5 and
23 calcined as in Example 16) is converted to NH4+-SSZ-65 form by heating the
material
24 in an aqueous solution of NH4N03 (typically lgm NH4N03/1 gm SSZ-65 in 20 ml
H~,O) at 90°C for 2-3 hours. The mixture is then filtered and the
obtained NH4-
26 exchanged-product is washed with de-ionized water and dried. The NH4+ form
of
27 SSZ-65 can be converted to the H+ form by calcination (as described in
Example 16)
2s to 540°C.
29 Example 19
3o Argon Adsorption Analysis
31 SSZ-65 has a micropore volume of 0.16 cc/gm based on argon adsorption
isotherm at
32 87.5° K (-186°C) recorded on ASAP 2010 equipment from
Micromerities. The
36
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WO 2004/094347 PCT/US2004/007754
1 sample is first degassed at 400°C for 16 hours prior to argon
adsorption. The low-
2 pressure dose is 6.00 cm3/g (STP). A maximum of one hour equilibration time
per
3 dose is used and the total run time is 35 hours. The argon adsorption
isotherm is
4 analyzed using the density function theory (DFT) formalism and parameters
developed for activated carbon slits by Olivier (Porous Mate. 1995, 2, 9)
using the
6 Saito Foley adaptation of the Howarth-Kawazoe formalism (Mic~oporous
Materials,
7 1995, 3, 531) and the conventional t-plot method (J. Catalysis, 1965, 4,
319).
8 Example 20
9 Constraint Index
1o The hydrogen form of SSZ-65 of Example 3 (after treatment according to
11 Examples 16, 17 and 18) is pelletized at 3 I~I'SI, crushed and granulated
to 20-40
12 mesh. A 0.6 gram sample of the granulated material is calcined in air at
540°C for 4
13 hours and cooled in a desiccator to ensure dryness. Then, 0.5 gram is
packed into a
14 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
16 reactor tube at 10 cc/min. and at atmospheric pressure. The reactor is
heated to about
17 315°C, and a 50/50 feed of n-hexane and 3-methylpentane is
introduced into the
1s reactor at a rate of 8 ~1/min. The feed is delivered by a Brownlee pump.
Direct
19 sampling into a GC begins after 10 minutes of feed introduction. The
Constraint
2o Index (CI) value is calculated from the GC data using methods known in the
art.
21 SSZ-65 has a CI of 0.67 and a conversion of 92% after 20 minutes on stream.
The
22 material fouls rapidly and at 218 minutes the CI is 0.3 and the conversion
is 15.7%.
23 The data suggests a large pore molecular sieve with perhaps large cavities.
24 Example 21
Hydrocrackin.~ of n-Hexadecane
26 A 1 gm sample of SSZ-65 (prepared as in Example 3 and treated as in
27 Examples 16, 17 and 18) is suspended in 10 gm de-ionized water. To this
suspension,
2s a solution of Pd(NH3)4(N03)2 at a concentration which would provide 0.5 wt.
% Pd
29 with respect to the dry weight of the molecular sieve sample is added. The
pH of the
3o solution is adjusted to pH of ~9 by a drop-wise addition of dilute ammonium
31 hydroxide solution. The mixture is then heated in an oven at 75°C
for 48 hours. The
32 mixture is then filtered through a glass frit, washed with de-ionized
water, and air-
37
CA 02520856 2005-09-26
WO 2004/094347 PCT/US2004/007754
1 dried. The collected Pd-SSZ-65 sample is slowly calcined up to 482°C
in air and held
2 there for three hours.
3 The calcined PdISSZ-65 catalyst is pelletized in a Carver Press and
granulated
4 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
6 below gives the run conditions and the products data for the hydrocracking
test on n-
7 hexadecane.
8 After the catalyst is tested with n-hexadecane, it is titrated using a
solution of
9 butylamine in hexane. The temperature is increased and the conversion and
product
1o data evaluated again under titrated conditions. The results shown in the
table below
11 show that SSZ-65 is effective as a hydrocracking catalyst.
12
Temperature 260C (550F)
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
CS/C4 16.9
Cs+C6/C5, % 16.74
DMB/MP 0.06
C4-C13 i/n 3.83
C~-C13 yield 38.35
13
14 Example 22
Synthesis of SSZ-65
16 SSZ-65 is synthesized in a manner similar to that of Example 3 using a 1-[1-
17 (4-chlorophenyl)-cyclopropylmethyl]-1-ethyl-pyrrolidinium cation as the
SDA.
38
