Molecular sieve abstract
The present invention relates to new crystalline molecular sieve
SSZ-47B prepared using a N-cyclopentyl-14-diazabicyclo[2.2.2] octane
cation as a structure-directing agent and an amine too large to
fit in the pores of the molecular sieve nonasil, methods for synthesizing
SSZ-47B and processes employing SSZ-47B in a catalyst.
Molecular sieve claims
What is claimed is:
1. A process for converting hydrocarbons comprising contacting
a hydrocarbonaceous feed at hydrocarbon converting conditions with
a catalyst comprising a molecular sieve having a mole ratio greater
than about 15 of (1) an oxide of a first tetravalent element to
(2) an oxide of a trivalent element, pentavalent element, second
tetravalent element different from said first tetravalent element
or mixture thereof having, after calcination, the X-ray diffraction
lines of Table II.
2. The process of claim 1 wherein the molecular sieve has a mole
ratio greater than about 15 of (1) an oxide of silicon, germanium
or mixtures thereof to (2) an oxide of aluminum, gallium, iron,
boron, titanium, indium, vanadium or mixtures thereof.
3. The process of claim 2 wherein the molecular sieve comprises
an oxide of silicon and an oxide of aluminum.
4. The process of claim 2 wherein the molecule sieve has a micropore
volume of at least 0.10.
5. The process of claim 2 wherein the molecular sieve has a Constraint
Index of less than or equal to 2.0.
6. The process of claim 1 wherein the molecular sieve is predominantly
in the hydrogen form.
7. The process of claim 1 wherein the molecular sieve is substantially
free of acidity.
8. The process of claim 1 wherein the process is a hydrocracking
process comprising contacting the catalyst with a hydrocarbon feedstock
under hydrocracking conditions.
9. The process of claim 8 wherein the molecular sieve is predominantly
in the hydrogen form.
10. The process of claim 1 wherein the process is a dewaxing process
comprising contacting the catalyst with a hydrocarbon feedstock
under dewaxing conditions.
11. The process of claim 10 wherein the molecular sieve is predominantly
in the hydrogen form.
12. The process of claim 1 wherein the process is a process for
improving the viscosity index of a dewaxed product of waxy hydrocarbon
feeds comprising contacting the catalyst with a waxy hydrocarbon
feed under isomerization dewaxing conditions.
13. The process of claim 12 wherein the molecular sieve is predominantly
in the hydrogen form.
14. The process of claim 1 wherein the process is a process for
producing a C.sub.20+ lube oil from a C.sub.20+ olefin feed comprising
isomerizing said olefin feed under isomerization conditions over
the catalyst.
15. The process of claim 14 wherein the molecular sieve is predominantly
in the hydrogen form.
16. The process of claim 14 wherein the catalyst further comprises
at least one Group VIII metal.
17. The process of claim 1 wherein the process is a process for
catalytically dewaxing a hydrocarbon oil feedstock boiling above
about 350.degree. F. (177.degree. C.) and containing straight chain
and slightly branched chain hydrocarbons comprising contacting said
hydrocarbon oil feedstock in the presence of added hydrogen gas
at a hydrogen pressure of about 15-3000 psi (0.103-20.7 MPa) under
dewaxing conditions with the catalyst.
18. The process of claim 17 wherein the molecular sieve is predominantly
in the hydrogen form.
19. The process of claim 17 wherein the catalyst further comprises
at least one Group VIII metal.
20. The process of claim 17 wherein said catalyst comprises a layered
catalyst comprising a first layer comprising the molecular sieve
and at least one Group VIII metal, and a second layer comprising
an aluminosilicate molecular sieve which is more shape selective
than the molecular sieve of said first layer.
21. The process of claim 1 wherein the process is a process for
preparing a lubricating oil which comprises: hydrocracking in a
hydrocracking zone a hydrocarbonaceous feedstock to obtain an effluent
comprising a hydrocracked oil; and catalytically dewaxing said effluent
comprising hydrocracked oil at a temperature of at least about 400.degree.
F. (204.degree. C.) and at a pressure of from about 15 psig to about
3000 psig (0.103 to 20.7 MPa gauge) in the presence of added hydrogen
gas with the catalyst.
22. The process of claim 21 wherein the molecular sieve is predominantly
in the hydrogen form.
23. The process of claim 21 wherein the catalyst further comprises
at least one Group VIII metal.
24. The process of claim 1 wherein the process is a process for
isomerization dewaxing a raffinate comprising contacting said raffinate
in the presence of added hydrogen under isomerization dewaxing conditions
with the catalyst.
25. The process of claim 24 wherein the molecular sieve is predominantly
in the hydrogen form.
26. The process of claim 24 wherein the catalyst further comprises
at least one Group VIII metal.
27. The process of claim 24 wherein the raffinate is bright stock.
28. The process of claim 1 wherein the process is a process for
increasing the octane of a hydrocarbon feedstock to produce a product
having an increased aromatics content comprising contacting a hydrocarbonaceous
feedstock which comprises normal and slightly branched hydrocarbons
having a boiling range above about 40.degree. C. and less than about
200.degree. C. under aromatic conversion conditions with the catalyst.
29. The process of claim 28 wherein the molecular sieve is substantially
free of acid.
30. The process of claim 28 wherein the molecular sieve contains
a Group VIII metal component.
31. The process of claim 1 wherein the process is a catalytic cracking
process comprising contacting a hydrocarbon feedstock in a reaction
zone under catalytic cracking conditions in the absence of added
hydrogen with the catalyst.
32. The process of claim 31 wherein the molecular sieve is predominantly
in the hydrogen form.
33. The process of claim 31 wherein the catalyst additionally comprises
a large pore crystalline cracking component.
34. The process of claim 1 wherein the process is an isomerization
process for isomerizing C.sub.4 to C.sub.7 hydrocarbons, comprising
contacting a feed having normal and slightly branched C.sub.4 to
C.sub.7 hydrocarbons under isomerizing conditions with the catalyst.
35. The process of claim 34 wherein the molecular sieve is predominantly
in the hydrogen form.
36. The process of claim 34 wherein the molecular sieve has been
impregnated with at least one Group VIII metal.
37. The process of claim 34 wherein the catalyst has been calcined
in a steam/air mixture at an elevated temperature after impregnation
of the Group VIII metal.
38. The process of claim 36 wherein the Group VIII metal is platinum.
39. The process of claim 1 wherein the process is a process for
alkylating an aromatic hydrocarbon which comprises contacting under
alkylation conditions at least a molar excess of an aromatic hydrocarbon
with a C.sub.2 to C.sub.20 olefin under at least partial liquid
phase conditions and in the presence of the catalyst.
40. The process of claim 39 wherein the molecular sieve is predominantly
in the hydrogen form.
41. The process of claim 39 wherein the olefin is a C.sub.2 to
C.sub.4 olefin.
42. The process of claim 41 wherein the aromatic hydrocarbon and
olefin are present in a molar ratio of about 4:1 to about 20:1
respectively.
43. The process of claim 41 wherein the aromatic hydrocarbon is
selected from the group consisting of benzene, toluene, ethylbenzene,
xylene, naphthalene, naphthalene derivatives, dimethylnaphthalene
or mixtures thereof.
44. The process of claim 1 wherein the process is a process for
alkylating an aromatic hydrocarbon which comprises contacting under
alkylation conditions an aromatic hydrocarbon with a C.sub.20+ olefin
under at least partial liquid phase conditions and in the presence
of the catalyst.
45. The process of claim 44 wherein the molecular sieve is predominantly
in the hydrogen form.
46. The process of claim 45 wherein the aromatic hydrocarbon and
olefin are present in a molar ratio of about 1:15 to about 25:1
respectively.
47. The process of claim 45 wherein the aromatic hydrocarbon is
selected from the group consisting of benzene, toluene, ethylbenzene,
xylene, naphthalene, naphthalene derivatives, dimethylnaphthalene
or mixtures thereof.
48. The process of claim 1 wherein the process is a process for
transalkylating an aromatic hydrocarbon which comprises contacting
under transalkylating conditions an aromatic hydrocarbon with a
polyalkyl aromatic hydrocarbon under at least partial liquid phase
conditions and in the presence of the catalyst.
49. The process of claim 48 wherein the molecular sieve is predominantly
in the hydrogen form.
50. The process of claim 48 wherein the aromatic hydrocarbon and
the polyalkyl aromatic hydrocarbon are present in a molar ratio
of from about 1:1 to about 25:1 respectively.
51. The process of claim 48 wherein the aromatic hydrocarbon is
selected from the group consisting of benzene, toluene, ethylbenzene,
xylene, or mixtures thereof.
52. The process of claim 44 wherein the polyalkyl aromatic hydrocarbon
is a dialkylbenzene.
53. The process of claim 1 wherein the process is a process to
convert paraffins to 5 aromatics which comprises contacting paraffins
under conditions which cause paraffins to convert to aromatics with
a catalyst comprising the molecular sieve and gallium, zinc, or
a compound of gallium or zinc.
54. The process of claim 1 wherein the process is a process for
isomerizing olefins comprising contacting said olefin under conditions
which cause isomerization of the olefin with the catalyst.
55. The process of claim 1 wherein the process is a process for
isomerizing an isomerization feed comprising an aromatic C.sub.8
stream of xylene isomers or mixtures of xylene isomers and ethylbenzene,
wherein a more nearly equilibrium ratio of ortho-, meta and para-xylenes
is obtained, said process comprising contacting said feed under
isomerization conditions with the catalyst.
56. The process of claim 1 wherein the process is a process for
oligomerizing olefins comprising contacting an olefin feed under
oligomerization conditions with the catalyst.
57. The process of claim 1 wherein the process is a process for
the production of higher molecular weight hydrocarbons from lower
molecular weight hydrocarbons comprising the steps of: (a) introducing
into a reaction zone a lower molecular weight hydrocarbon-containing
gas and contacting said gas in said zone under C.sub.2+ hydrocarbon
synthesis conditions with the catalyst and a metal or metal compound
capable of converting the lower molecular weight hydrocarbon to
a higher molecular weight hydrocarbon; and (b) withdrawing from
said reaction zone a higher molecular weight hydrocarbon-containing
stream.
58. The process of claim 57 wherein the metal or metal compound
comprises a lanthanide or actinide metal or metal compound.
59. The process of claim 57 wherein the lower molecular weight
hydrocarbon is methane.
60. A process for converting oxygenated hydrocarbons comprising
contacting said oxygenated hydrocarbon under conditions to produce
liquid products with a catalyst comprising a molecular sieve having
a mole ratio greater than about 15 of (1) an oxide of a first tetravalent
element to (2) an oxide of a trivalent element, pentavalent element,
second tetravalent element different from said first tetravalent
element or mixture thereof having, after calcination, the X-ray
diffraction lines of Table II.
61. The process of claim 1 wherein the molecular sieve has a mole
ratio greater than about 15 of (1) an oxide of silicon, germanium
or mixtures thereof to (2) an oxide of aluminum, gallium, iron,
boron, titanium, indium, vanadium or mixtures thereof.
62. The process of claim 61 wherein the molecule sieve has a micropore
volume of at least 0.10.
63. The process of claim 61 wherein the molecular sieve has a Constraint
Index of less than or equal to 2.0.
64. The process of claim 61 wherein the oxygenated hydrocarbon
is a lower alcohol.
65. The process of claim 64 wherein the lower alcohol is methanol.
Molecular sieve descriptionBACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] The present invention relates to crystalline molecular sieve
SSZ-47B having high micropore volume and high catalytic activity,
and a method for preparing such high micropore volume, highly active
SSZ-47B using N-cyclopentyl-14-diazabicyclo[2.2.2] octane cation
(referred to herein as "N-cyclopentyl DABCO cation") structure
directing agent (SDA) in the presence of an amine too large to fit
in the pores of the molecular sieve nonasil, a clathrasil material.
[0003] 2. State of the Art
[0004] Because of their unique sieving characteristics, as well
as their catalytic properties, crystalline molecular sieves and
zeolites are especially useful in applications such as hydrocarbon
conversion, gas drying and separation. Although many different crystalline
molecular sieves have been disclosed, there is a continuing need
for new zeolites with desirable properties for gas separation and
drying, hydrocarbon and chemical conversions, and other applications.
New zeolites may contain novel internal pore architectures, providing
enhanced selectivities in these processes.
SUMMARY OF THE INVENTION
[0005] The present invention is directed to a family of crystalline
molecular sieves with unique properties, referred to herein as "molecular
sieve SSZ-47B" or simply "SSZ-47B". Preferably, SSZ-47B
is obtained in its silicate, aluminosilicate, titanosilicate, germanosilicate,
vanadosilicate or borosilicate form. The term "silicate"
refers to a molecular sieve having a high mole ratio of silicon
oxide relative to aluminum oxide (or other metal oxide), preferably
a mole ratio greater than 100 including molecular sieves comprised
entirely of silicon oxide. As used herein, the term "aluminosilicate"
refers to a molecular sieve containing both aluminum oxide and silicon
oxide and the term "borosilicate" refers to a molecular
sieve containing oxides of both boron and silicon.
[0006] Molecular sieves, including zeolites, are typically synthesized
by using a structure directing agent ("SDA", sometimes
called a templating agent) in the reaction mixture used to make
the molecular sieve. The SDA is believed to "direct" the
formation of the molecular sieve's crystal structure as the pores
of the molecular sieve form. As such, the SDA must be small enough
to fit within the pores of the desired molecular sieve.
[0007] U.S. Pat. No. 6156290 issued Dec. 5 2000 to Lee et al.,
discloses zeolite SSZ-47 and a method of making it using a 3(trimethylammonium)-bicyclo[3.2.1]octane
ammonium cation or N,N-dimethyl-3-azoniabicyclo[4.2.1]nonane cation
as an SDA. However, when each of these cations alone is used as
the SDA, significant amounts of nonasil can form as an intergrowth
in the crystal structure of the SSZ-47.
[0008] U.S. Pat. No. 5785947 issued Jul. 28 1998 to Zones et
al., discloses the preparation of zeolites using a small quantity
of an SDA and a larger quantity of an amine component containing
at least one amine having from one to eight carbon atoms, ammonium
hydroxide or mixtures thereof. It is believed that the amines disclosed
in U.S. Pat. No. 5785947 are all small enough to fit in the pores
of nonasil and, therefore, would not prevent the intergrowth of
nonasil during the preparation of SSZ-47B.
[0009] It has now been found that SSZ-47B can be synthesized while
preventing the formation of nonasil intergrowth. This is accomplished
by including in the reaction mixture, along with the SDA, a neutral
amine that is too large to fit in the pores of nonasil. Preferably,
the amine is also small enough to fit in the pores of SSZ-47B. In
addition to preventing the formation of nonasil intergrowth, it
has been discovered that the SSZ-47B made in accordance with this
invention has a micropore volume and catalytic activity approximately
double that of the SSZ-47 disclosed in Lee et al.
[0010] The diffraction patterns of SSZ-47 and SSZ-47B share similar
features with those of the NON/EUO/NES family of zeolites. The powder
diffraction patterns of SSZ-47 possess a combination of sharp and
broad peaks that are often observed in the powder XRD patterns of
disordered or intergrown materials. The diffraction patterns of
SSZ-47 exhibit a peak at about 9.5.degree. 2.theta. which is very
close to the 111 peak of nonasil (NON), a clathrasil material with
no accessible micropore volume. The intensity and position of this
peak vary among different preparations of SSZ-47. However, in contrast
with nonasil-type materials, these samples of SSZ-47 possess micropore
volumes of 0.06-0.08. This measured micropore volume is lower than
those typically measured for medium or large pore zeolites. As the
relative intensity of the peak near 9.5.degree. 2.theta. increases,
the measured micropore volume (among different preparations) of
the SSZ-47 material decreases. These data are consistent with an
increase in the fraction of nonasil or other clathrasil-like domains
within the zeolite. These data suggest SSZ-47 may contain clathrasil-like
domains intergrown with EUO- and/or NES-type domains or with domains
of other 10-ring and/or 12-ring pore zeolites.
[0011] The samples of SSZ-47 are prepared using a combination of
a quaternary ammonium compound and isobutylamine as structure directing
agents. When these samples are calcined in the presence of oxygen,
the resulting materials are often discolored. This result indicates
there may be organic molecules occluded within cage structures that
do not allow access to small molecules such as oxygen. The largest
dimensions of the nonasil cage parallel to the orthorhombic axes
of the crystal structure are 8.9 (y-axis).times.8.4 (x-axis).times.6.5
.ANG. (z-axis). These dimensions are determined by subtracting the
ionic radii of the oxygen atoms (1.35 .ANG.) from the distances
between the centers of opposing oxygen atoms. Since the dimensions
of the quaternary ammonium compounds are too large to allow their
occlusion within nonasil-type cages, it is likely that the smaller
isobutylamine molecules are occluded within these small cages. This
suggests that amines too large to fit within a nonasil cage may
prevent the creation of these cage structures if they are used in
place of isobutylamine in the zeolite syntheses. Since the nonasil
cages are not accessible to adsorbing molecules, elimination of
the nonasil domains might improve the adsorption or catalytic properties
of the material.
[0012] It has been found that molecular sieves can be synthesized
using a combination of quaternary ammonium compounds with a large,
neutral amine. Although the diffraction patterns of these materials
are similar to those of SSZ-47 they do not possess the 111 peak
of nonasil and the measured micropore volumes of these materials
are appreciably greater than those of SSZ-47. These improved materials
collectively are referred to herein as "SSZ-47B."
[0013] In accordance with the present invention, there is provided
a molecular sieve having a mole ratio greater than about 15 of (1)
an oxide of a first tetravalent element to (2) an oxide of a trivalent
element, pentavalent element, second tetravalent element different
from said first tetravalent element or mixture thereof having, after
calcination, the X-ray diffraction lines of Table II.
[0014] The present invention further provides a molecular sieve
having a mole ratio greater than about 15 of (1) an oxide of silicon,
germanium or mixtures thereof to (2) an oxide of aluminum, gallium,
iron, boron, titanium, indium, vanadium or mixtures thereof having,
after calcination, the X-ray diffraction lines of Table II. The
present invention also provides such a molecule sieve having a micropore
volume of at least 0.10. Further provided is such a molecular sieve
having a Constraint Index of less than or equal to 2.0.
[0015] For high catalytic activity, the SSZ-47B molecular sieve
should be predominantly in its hydrogen ion form. It is preferred
that, after calcination, at least 80% of the cation sites are occupied
by hydrogen ions and/or rare earth ions. As used herein, "predominantly
in the hydrogen form" means that, after calcination, at least
80% of the cation sites are occupied by hydrogen ions and/or rare
earth ions.
[0016] In accordance with the present invention there is provided
a process for converting hydrocarbons comprising contacting a hydrocarbonaceous
feed at hydrocarbon converting conditions with a catalyst comprising
the molecular sieve of this invention. The molecular sieve may be
predominantly in the hydrogen form. It may also be substantially
free of acidity.
[0017] Further provided by the present invention is a hydrocracking
process comprising contacting a hydrocarbon feedstock under hydrocracking
conditions with a catalyst comprising the molecular sieve of this
invention, preferably predominantly in the hydrogen form.
[0018] This invention also includes a dewaxing process comprising
contacting a hydrocarbon feedstock under dewaxing conditions with
a catalyst comprising the molecular sieve of this invention, preferably
predominantly in the hydrogen form.
[0019] The present invention also includes a process for improving
the viscosity index of a dewaxed product of waxy hydrocarbon feeds
comprising contacting the waxy hydrocarbon feed under isomerization
dewaxing conditions with a catalyst comprising the molecular sieve
of this invention, preferably predominantly in the hydrogen form.
[0020] The present invention further includes a process for producing
a C.sub.20+ lube oil from a C.sub.20+ olefin feed comprising isomerizing
said olefin feed under isomerization conditions over a catalyst
comprising the molecular sieve of this invention. The molecular
sieve may be predominantly in the hydrogen form. The catalyst may
contain at least one Group VIII metal.
[0021] In accordance with this invention, there is also provided
a process for catalytically dewaxing a hydrocarbon oil feedstock
boiling above about 350.degree. F. (177.degree. C.) and containing
straight chain and slightly branched chain hydrocarbons comprising
contacting said hydrocarbon oil feedstock in the presence of added
hydrogen gas at a hydrogen pressure of about 15-3000 psi (0.103-20.7
MPa) with a catalyst comprising the molecular sieve of this invention,
preferably predominantly in the hydrogen form. The catalyst may
contain at least one Group VIII metal. The catalyst may be a layered
catalyst comprising a first layer comprising the molecular sieve
of this invention, and a second layer comprising an aluminosilicate
molecular sieve which is more shape selective than the molecular
sieve of said first layer. The first layer may contain at least
one Group VIII metal.
[0022] Also included in the present invention is a process for
preparing a lubricating oil which comprises hydrocracking in a hydrocracking
zone a hydrocarbonaceous feedstock to obtain an effluent comprising
a hydrocracked oil, and catalytically dewaxing said effluent comprising
hydrocracked oil at a temperature of at least about 400.degree.
F. (204.degree. C.) and at a pressure of from about 15 psig to about
3000 psig (0.103-20.7 Mpa gauge)in the presence of added hydrogen
gas with a catalyst comprising the molecular sieve of this invention.
The molecular sieve may be predominantly in the hydrogen form. The
catalyst may contain at least one Group VIII metal.
[0023] Further included in this invention is a process for isomerization
dewaxing a raffinate comprising contacting said raffinate in the
presence of added hydrogen with a catalyst comprising the molecular
sieve of this invention. The raffinate may be bright stock, and
the molecular sieve may be predominantly in the hydrogen form. The
catalyst may contain at least one Group VIII metal.
[0024] Also included in this invention is a process for increasing
the octane of a hydrocarbon feedstock to produce a product having
an increased aromatics content comprising contacting a hydrocarbonaceous
feedstock which comprises normal and slightly branched hydrocarbons
having a boiling range above about 40.degree. C. and less than about
200.degree. C., under aromatic conversion conditions with a catalyst
comprising the molecular sieve of this invention made substantially
free of acidity by neutralizing said molecular sieve with a basic
metal. Also provided in this invention is such a process wherein
the molecular sieve contains a Group VIII metal component.
[0025] Also provided by the present invention is a catalytic cracking
process comprising contacting a hydrocarbon feedstock in a reaction
zone under catalytic cracking conditions in the absence of added
hydrogen with a catalyst comprising the molecular sieve of this
invention, preferably predominantly in the hydrogen form. Also included
in this invention is such a catalytic cracking process wherein the
catalyst additionally comprises a large pore crystalline cracking
component.
[0026] This invention further provides an isomerization process
for isomerizing C.sub.4 to C.sub.7 hydrocarbons, comprising contacting
a feed having normal and slightly branched C.sub.4 to C.sub.7 hydrocarbons
under isomerizing conditions with a catalyst comprising the molecular
sieve of this invention, preferably predominantly in the hydrogen
form. 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 elevated temperature after impregnation
of the Group VIII metal.
[0027] Also provided by the present invention is a process for
alkylating an aromatic hydrocarbon which comprises contacting under
alkylation conditions at least a molar excess of an aromatic hydrocarbon
with a C.sub.2 to C.sub.20 olefin under at least partial liquid
phase conditions and in the presence of a catalyst comprising the
molecular sieve of this invention, preferably predominantly in the
hydrogen form. The olefin may be a C.sub.2 to C.sub.4 olefin, and
the aromatic hydrocarbon and olefin may be present in a molar ratio
of about 4:1 to about 20:1 respectively. The aromatic hydrocarbon
may be selected from the group consisting of benzene, toluene, ethylbenzene,
xylene, naphthalene, naphthalene derivatives, dimethylnaphthalene
or mixtures thereof.
[0028] The present invention also provides a process for alkylating
an aromatic hydrocarbon which comprises contacting under alkylation
conditions an aromatic hydrocarbon with a C.sub.20+ olefin under
at least partial liquid phase conditions and in the presence of
a catalyst comprising the molecular sieve of this invention, preferably
predominantly in the hydrogen form. The aromatic hydrocarbon and
olefin are present in a molar ratio of about 1:15 to about 25:1
respectively. The aromatic hydrocarbon is selected from the group
consisting of benzene, toluene, ethylbenzene, xylene, naphthalene,
naphthalene derivatives, dimethylnaphthalene or mixtures thereof.
[0029] Further provided in accordance with this invention is a
process for transalkylating an aromatic hydrocarbon which comprises
contacting under transalkylating conditions an aromatic hydrocarbon
with a polyalkyl aromatic hydrocarbon under at least partial liquid
phase conditions and in the presence of a catalyst comprising the
molecular sieve of this invention, preferably predominantly in the
hydrogen form. The aromatic hydrocarbon and the polyalkyl aromatic
hydrocarbon may be present in a molar ratio of from about 1:1 to
about 25:1 respectively.
[0030] The aromatic hydrocarbon may be selected from the group
consisting of benzene, toluene, ethylbenzene, xylene, or mixtures
thereof, and the polyalkyl aromatic hydrocarbon may be a dialkylbenzene.
[0031] Further provided by this invention is a process to convert
paraffins to aromatics which comprises contacting paraffins under
conditions which cause paraffins to convert to aromatics with a
catalyst comprising the molecular sieve of this invention, said
catalyst comprising gallium, zinc, or a compound of gallium or zinc.
[0032] In accordance with this invention there is also provided
a process for isomerizing olefins comprising contacting said olefin
under conditions which cause isomerization of the olefin with a
catalyst comprising the molecular sieve of this invention.
[0033] Further provided in accordance with this invention is a
process for isomerizing an isomerization feed comprising an aromatic
C.sub.8 stream of xylene isomers or mixtures of xylene isomers and
ethylbenzene, wherein a more nearly equilibrium ratio of ortho-,
meta- and para-xylenes is obtained, said process comprising contacting
said feed under isomerization conditions with a catalyst comprising
the molecular sieve of this invention.
[0034] The present invention further provides a process for oligomerizing
olefins comprising contacting an olefin feed under oligomerization
conditions with a catalyst comprising the molecular sieve of this
invention.
[0035] This invention also provides a process for converting oxygenated
hydrocarbons comprising contacting said oxygenated hydrocarbon with
a catalyst comprising the molecular sieve of this invention under
conditions to produce liquid products. The oxygenated hydrocarbon
may be a lower alcohol.
[0036] Further provided in accordance with the present invention
is a process for the production of higher molecular weight hydrocarbons
from lower molecular weight hydrocarbons comprising the steps of:
[0037] (a) introducing into a reaction zone a lower molecular weight
hydrocarbon-containing gas and contacting said gas in said zone
under C.sub.2+ hydrocarbon synthesis conditions with the catalyst
and a metal or metal compound capable of converting the lower molecular
weight hydrocarbon to a higher molecular weight hydrocarbon; and
[0038] (b) withdrawing from said reaction zone a higher molecular
weight hydrocarbon-containing stream.
BRIEF DESCRIPTION OF THE DRAWINGS
[0039] FIG. 1 is an X-ray diffraction pattern of SSZ-47B after
it has been calcined.
[0040] FIG. 2 is an X-ray diffraction pattern of SSZ-47B in the
as-made form, i.e., prior to removal of the SDA from SSZ-47B.
[0041] FIG. 3 shows two X-ray diffraction patterns, the top one
being SSZ-47 and the bottom one being SSZ-47B.
DETAILED DESCRIPTION OF THE INVENTION
[0042] The present invention comprises a family of crystalline,
large pore molecular sieves designated herein "molecular sieve
SSZ-47B" or simply "SSZ-47B". As used herein, the
term "large pore" means having an average pore size diameter
greater than about 6.0 Angstroms, preferably from about 6.5 Angstroms
to about 7.5 Angstroms.
[0043] In preparing SSZ-47B, a N-cyclopentyl DABCO cation is used
as a structure directing agent ("SDA"), also known as
a crystallization template. The N-cyclopentyl DABCO cation has the
following structure: 1
[0044] N-cyclopentyl DABCO cation can be prepared as described
in U.S. Pat. No. 6033643 issued Mar. 7 2000 to Yuen et al.,
which is incorporated by reference in its entirety.
[0045] The SDA cation is associated with an anion (X.sup.-) which
may be any anion that is not detrimental to the formation of the
zeolite. Representative anions include halogen, e.g., fluoride,
chloride, bromide and iodide, hydroxide, acetate, sulfate, tetrafluoroborate,
carboxylate, and the like. Hydroxide is the most preferred anion.
[0046] The amine used in combination with the N-cyclopentyl DABCO
SDA is large enough that it will not fit in the pores of the molecular
sieve nonasil. Preferably, it is also small enough that it does
fit in the pores of SSZ-47B. An example of such an amine is 44'-trimethylene
dipiperidine which has the structure 2
[0047] In general, SSZ-47B is prepared by contacting an active
source of one or more oxides selected from the group consisting
of monovalent element oxides, divalent element oxides, trivalent
element oxides, tetravalent element oxides and/or pentavalent elements
with the SDA and amine.
[0048] SSZ-47B is prepared from a reaction mixture having the composition
shown in Table A below.
1TABLE A Reaction Mixture Typical Preferred YO.sub.2/W.sub.aO.sub.b
>15 30-70 OH--/YO.sub.2 0.10-0.50 0.20-0.30 Q/YO.sub.2 0.05-0.50
0.10-0.20 M.sub.2/n/YO.sub.2 0.02-0.40 0.10-0.25 H.sub.2O/YO.sub.2
30-80 35-45 Amine/YO.sub.2 0.05-0.50 0.10-0.20
[0049] where Y, W, Q, M, n and Amine are as defined above, and
a is 1 or 2 and b is 2 when a is 1 (i.e., W is tetravalent) and
b is 3 when a is 2 (i.e., W is trivalent).
[0050] In practice, SSZ-47B is prepared by a process comprising:
[0051] (a) preparing an aqueous solution containing sources of
at least one oxide capable of forming a crystalline molecular sieve,
a N-cyclopentyl DABCO cation having an anionic counterion which
is not detrimental to the formation of SSZ-47B, and an amine too
large to fit in the pores of the molecular sieve nonasil;
[0052] (b) maintaining the aqueous solution under conditions sufficient
to form crystals of SSZ-47B; and
[0053] (c) recovering the crystals of SSZ-47B.
[0054] Accordingly, SSZ-47B may comprise the crystalline material,
the SDA and the amine in combination with metallic and non-metallic
oxides bonded in tetrahedral coordination through shared oxygen
atoms to form a cross-linked three dimensional crystal structure.
The metallic and non-metallic oxides comprise one or a combination
of oxides of a first tetravalent element(s), and one or a combination
of a trivalent element(s), pentavalent element(s), second tetravalent
element(s) different from the first tetravalent element(s) or mixture
thereof. The first tetravalent element(s) is preferably selected
from the group consisting of silicon, germanium and combinations
thereof. More preferably, the first tetravalent element is silicon.
The trivalent element, pentavalent element and second tetravalent
element (which is different from the first tetravalent element)
is preferably selected from the group consisting of aluminum, gallium,
iron, boron, titanium, indium, vanadium and combinations thereof.
More preferably, the second trivalent or tetravalent element is
aluminum or boron.
[0055] Typical sources of aluminum oxide for the reaction mixture
include aluminates, alumina, aluminum colloids, aluminum oxide coated
on silica sol, hydrated alumina gels such as Al(OH).sub.3 and aluminum
compounds such as AlCl.sub.3 and Al.sub.2(SO.sub.4).sub.3. Typical
sources of silicon oxide include silicates, silica hydrogel, silicic
acid, fumed silica, colloidal silica, tetra-alkyl orthosilicates,
and silica hydroxides. Boron, as well as gallium, germanium, titanium,
indium, vanadium and iron, can be added in forms corresponding to
their aluminum and silicon counterparts.
[0056] A source zeolite reagent may provide a source of aluminum
or boron. In most cases, the source zeolite also provides a source
of silica. The source zeolite in its dealuminated or deboronated
form may also be used as a source of silica, with additional silicon
added using, for example, the conventional sources listed above.
Use of a source zeolite reagent as a source of alumina for the present
process is more completely described in U.S. Pat. No. 5225179
issued Jul. 6 1993 to Nakagawa entitled "Method of Making
Molecular Sieves", the disclosure of which is incorporated
herein by reference.
[0057] Typically, an alkali metal hydroxide and/or an alkaline
earth metal hydroxide, such as the hydroxide of sodium, potassium,
lithium, cesium, rubidium, calcium, and magnesium, is used in the
reaction mixture; however, this component can be omitted so long
as the equivalent basicity is maintained. The SDA may be used to
provide hydroxide ion. Thus, it may be beneficial to ion exchange,
for example, the halide to hydroxide ion, thereby reducing or eliminating
the alkali metal hydroxide quantity required. The alkali metal cation
or alkaline earth cation may be part of the as-synthesized crystalline
oxide material, in order to balance valence electron charges therein.
[0058] The reaction mixture is maintained at an elevated temperature
until the crystals of the SSZ-47B are formed. The hydrothermal crystallization
is usually conducted under autogenous pressure, at a temperature
between 100.degree. C. and 200.degree. C., preferably between 135.degree.
C. and 160.degree. C. The crystallization period is typically greater
than 1 day and preferably from about 3 days to about 20 days.
[0059] Preferably, the molecular sieve is prepared using mild stirring
or agitation.
[0060] During the hydrothermal crystallization step, the SSZ-47B
crystals can be allowed to nucleate spontaneously from the reaction
mixture. The use of SSZ-47B crystals as seed material can be advantageous
in decreasing the time necessary for complete crystallization to
occur. In addition, seeding can lead to an increased purity of the
product obtained by promoting the nucleation and/or formation of
SSZ-47B over any undesired phases. When used as seeds, SSZ-47B crystals
are added in an amount between 0.1 and 10% of the weight of first
tetravalent element oxide, e.g. silica, used in the reaction mixture.
[0061] Once the molecular sieve crystals have formed, the solid
product is separated from the reaction mixture by standard mechanical
separation techniques such as filtration. The crystals are water-washed
and then dried, e.g., at 90.degree. C. to 150.degree. C. for from
8 to 24 hours, to obtain the as-synthesized SSZ-47B crystals. The
drying step can be performed at atmospheric pressure or under vacuum.
[0062] SSZ-47B as prepared has a mole ratio of an oxide selected
from silicon oxide, germanium oxide and mixtures thereof to an oxide
selected from aluminum oxide, gallium oxide, iron oxide, boron oxide,
titanium oxide, indium oxide, vanadium oxide and mixtures thereof
greater than about 15 and has, after calcination, the X-ray diffraction
lines of Table II below. SSZ-47B further has a composition, as synthesized
(i.e., prior to removal of the SDA from the SSZ-47B) and in the
anhydrous state, in terms of mole ratios, shown in Table B below.
2TABLE B As-Synthesized SSZ-47B YO.sub.2/W.sub.cO.sub.d >15
M.sub.2/n/YO.sub.2 0.01-0.03 Q/YO.sub.2 0.02-0.05 Amine/YO.sub.2
0.01-0.05
[0063] where Y, W, c, d, M, n, Q and Amine are as defined above.
[0064] .sup.13C MASNMR analysis of as-synthesized SSZ-47B provides
evidence that the as-synthesized SSZ-47B contains both the N-cyclopentyl
DABCO SDA and the amine inside the molecular sieve. This is also
evidence that the amine is small enough to fit in the pores of SSZ-47B.
[0065] SSZ-47B can be made with a mole ratio of YO.sub.2/W.sub.cO.sub.d
of .infin., i.e., there is essentially no W.sub.cO.sub.d present
in the SSZ-47B. In this case, the SSZ-47B would be an all-silica
material or a germanosilicate. Thus, in a typical case where oxides
of silicon and aluminum are used, SSZ-47B can be made essentially
aluminum free, i.e., having a silica to alumina mole ratio of .infin..
A method of increasing the mole ratio of silica to alumina is by
using standard acid leaching or chelating treatments. Essentially
aluminum-free SSZ-47B can be synthesized using essentially aluminum-free
silicon sources as the main tetrahedral metal oxide component in
the presence of boron. The boron can then be removed, if desired,
by treating the borosilicate SSZ-47B with acetic acid at elevated
temperature ( as described in Jones et al., Chem. Mater., 2001
13 1041-1050) to produce an all-silica version of SSZ-47B. SSZ-47B
can also be prepared directly as a borosilicate. If desired, the
boron can be removed as described above and replaced with metal
atoms by techniques known in the art to make, e.g., an aluminosilicate
version of SSZ-47B. SSZ-47B can also be prepared directly as an
aluminosilicate.
[0066] Lower silica to alumina ratios may also be obtained by using
methods which insert aluminum into the crystalline framework. For
example, aluminum insertion may occur by thermal treatment of the
zeolite in combination with an alumina binder or dissolved source
of alumina. Such procedures are described in U.S. Pat. No. 4559315
issued on Dec. 17 1985 to Chang et al.
[0067] SSZ-47B, as-synthesized, has a crystalline structure whose
X-ray powder diffraction pattern exhibit the characteristic lines
shown in Table I and is thereby distinguished from other molecular
sieves.
3TABLE I As-Synthesized SSZ-47B 2 Theta.sup.(a) d-spacing (Angstroms)
Relative Intensity (%).sup.(b) 7.80 11.3 S 8.54 10.4 W-M 19.02 4.67
M 20.36 4.36 VS 22.10 4.02 S-VS 23.06 3.86 M 23.74 3.75 M 25.92
3.44 W-M 26.46 3.37 W 27.10 3.29 S .sup.(a).+-.0.1 .sup.(b)The X-ray
patterns provided are based on a relative intensity scale in which
the strongest line in the X-ray pattern is assigned a value of 100:
W(weak) is less than 20; M(medium) is between 20 and 40; S(strong)
is between 40 and 60; VS(very strong) is greater than 60.
[0068] Table IA below shows the X-ray powder diffraction lines
for as-synthesized SSZ-47B including actual relative intensities.
4TABLE IA 2 Theta.sup.(a) d-spacing (Angstroms) Relative Intensity
(%) 7.80 11.3 49 8.54 10.4 19 12.82 6.91 11 15.74 5.63 8 19.02 4.67
30 20.36 4.36 100 22.10 4.02 59 23.06 3.86 22 23.74 3.75 24 25.92
3.44 20 26.46 3.37 18 27.10 3.29 48 28.10 3.18 7 28.76 3.10 9 30.22
2.96 6 32.98 2.72 6 35.42 2.53 7 36.22 2.48 5 36.99 2.43 2 37.34
2.41 5 38.72 2.33 5 39.08 2.30 4 .sup.(a).+-.0.1
[0069] After calcination, the SSZ-47B molecular sieves have a crystalline
structure whose X-ray powder diffraction pattern include the characteristic
lines shown in Table II:
5TABLE II Calcined SSZ-47B 2 Theta.sup.(a) d-spacing (Angstroms)
Relative Intensity (%) 7.91 11.18 S 8.68 10.19 M 19.14 4.64 M-S
20.51 4.33 VS 22.23 4.00 S 23.27 3.82 M 23.9 3.72 W 26 3.43 W 26.62
3.35 M 27.26 3.27 S .sup.(a).+-.0.1
[0070] Table IIA below shows the X-ray powder diffraction lines
for calcined SSZ-47B including actual relative intensities.
6TABLE IIA 2 Theta.sup.(a) d-spacing (Angstroms) Relative Intensity
(%) 7.91 11.18 57.4 8.68 10.19 34.1 9.025 9.80 6.9 11.42 7.75 5.6
12.91 6.86 9.9 14.2 6..24 3.4 15.22 5.82 4.2 15.77 5.62 5.2 19.14
4.64 40.6 20.51 4.33 100.0 22.23 4.00 47.2 23.27 3.82 22.2 23.9
3.72 18.4 26 3.43 10.8 26.62 3.35 25.9 27.26 3.27 60.8 28.26 3.16
4.7 28.97 3.08 6.2 30.33 2.95 8.8 30.95 2.89 0.8 33.18 2.70 4.2
34.63 2.59 6.4 35.56 2.52 8.3 36.51 2.46 3.4 37.42 2.40 8.8 .sup.(a).+-.0.1
[0071] The X-ray powder diffraction patterns were determined by
standard techniques. The radiation was the K-alpha/doublet of copper.
The peak heights and the positions, as a function of 20 where .theta.
is the Bragg angle, were read from the relative intensities of the
peaks, and d, the interplanar spacing in Angstroms corresponding
to the recorded lines, can be calculated.
[0072] The variation in the scattering angle (two theta) measurements,
due to instrument error and to differences between individual samples,
is estimated at .+-.0.1 degrees.
[0073] The X-ray diffraction pattern of Table I is representative
of "as-synthesized" or "as-made" SSZ-47B molecular
sieves. Minor variations in the diffraction pattern can result from
variations in the silica-to-alumina or silica-to-boron mole ratio
of the particular sample due to changes in lattice constants. In
addition, sufficiently small crystals will affect the shape and
intensity of peaks, leading to significant peak broadening.
[0074] Representative peaks from the X-ray diffraction pattern
of calcined SSZ-47B are shown in Table II. Calcination can also
result in changes in the intensities of the peaks as compared to
patterns of the "as-made" material, as well as minor shifts
in the diffraction pattern. The molecular sieve produced by exchanging
the metal or other cations present in the molecular sieve with various
other cations (such as H.sup.+ or NH.sub.4.sup.+) yields essentially
the same diffraction pattern, although again, there may be minor
shifts in the interplanar spacing and variations in the relative
intensities of the peaks. Notwithstanding these minor perturbations,
the basic crystal lattice remains unchanged by these treatments.
[0075] Crystalline SSZ-47B can be used as-synthesized, but preferably
will be thermally treated (calcined). Usually, it is desirable to
remove the alkali metal cation by ion exchange and replace it with
hydrogen, ammonium, or any desired metal ion. The molecular sieve
can be leached with chelating agents, e.g., EDTA or dilute acid
solutions, to increase the silica to alumina mole ratio. The molecular
sieve can also be steamed; steaming helps stabilize the crystalline
lattice to attack from acids.
[0076] The molecular sieve can be used in intimate combination
with hydrogenating components, such as tungsten, vanadium, molybdenum,
rhenium, nickel, cobalt, chromium, manganese, or a noble metal,
such as palladium or platinum, for those applications in which a
hydrogenation-dehydrogenation function is desired.
[0077] Metals may also be introduced into the molecular sieve by
replacing some of the cations in the molecular sieve with metal
cations via standard ion exchange techniques (see, for example,
U.S. Pat. No. 3140249 issued Jul. 7 1964 to Plank et al.; U.S.
Pat. No. 3140251 issued Jul. 7 1964 to Plank et al.; and U.S.
Pat. No. 3140253 issued Jul. 7 1964 to Plank et al.). Typical
replacing cations can include metal cations, e.g., rare earth, Group
IA, Group IIA and Group VIII metals, as well as their mixtures.
Of the replacing metallic cations, cations of metals such as rare
earth, Mn, Ca, Mg, Zn, Cd, Pt, Pd, Ni, Co, Ti, Al, Sn, and Fe are
particularly preferred.
[0078] The hydrogen, ammonium, and metal components can be ion-exchanged
into the SSZ-47B. The SSZ-47B can also be impregnated with the metals,
or the metals can be physically and intimately admixed with the
SSZ-47B using standard methods known to the art.
[0079] Typical ion-exchange techniques involve contacting the synthetic
molecular sieve with a solution containing a salt of the desired
replacing cation or cations. Although a wide variety of salts can
be employed, chlorides and other halides, acetates, nitrates, and
sulfates are particularly preferred. The molecular sieve is usually
calcined prior to the ion-exchange procedure to remove the organic
matter present in the channels and on the surface, since this results
in a more effective ion exchange. Representative ion exchange techniques
are disclosed in a wide variety of patents including U.S. Pat. No.
3140249 issued on Jul. 7 1964 to Plank et al.; U.S. Pat. No.
3140251 issued on Jul. 7 1964 to Plank et al.; and U.S. Pat.
No. 3140253 issued on Jul. 7 1964 to Plank et al.
[0080] Following contact with the salt solution of the desired
replacing cation, the molecular sieve is typically washed with water
and dried at temperatures ranging from 65.degree. C. to about 200.degree.
C. After washing, the molecular sieve can be calcined in air or
inert gas at temperatures ranging from about 200.degree. C. to about
800.degree. C. for periods of time ranging from 1 to 48 hours, or
more, to produce a catalytically active product especially useful
in hydrocarbon conversion processes.
[0081] Regardless of the cations present in the synthesized form
of SSZ-47B, the spatial arrangement of the atoms which form the
basic crystal lattice of the molecular sieve remains essentially
unchanged.
[0082] SSZ-47B can be formed into a wide variety of physical shapes.
Generally speaking, the molecular sieve can be in the form of a
powder, a granule, or a molded product, such as extrudate having
a particle size sufficient to pass through a 2-mesh (Tyler) screen
and be retained on a 400-mesh (Tyler) screen. In cases where the
catalyst is molded, such as by extrusion with an organic binder,
the SSZ-47B can be extruded before drying, or, dried or partially
dried and then extruded.
[0083] SSZ-47B can be composited with other materials resistant
to the temperatures and other conditions employed in organic conversion
processes. Such matrix materials include active and inactive materials
and synthetic or naturally occurring zeolites as well as inorganic
materials such as clays, silica and metal oxides. Examples of such
materials and the manner in which they can be used are disclosed
in U.S. Pat. No. 4910006 issued May 20 1990 to Zones et al.,
and U.S. Pat. No. 5316753 issued May 31 1994 to Nakagawa, both
of which are incorporated by reference herein in their entirety.
Hydrocarbon Conversion Processes
[0084] SSZ-47B molecular sieves are useful in hydrocarbon conversion
reactions. Hydrocarbon conversion reactions are chemical and catalytic
processes in which carbon containing compounds are changed to different
carbon containing compounds. Examples of hydrocarbon conversion
reactions in which SSZ-47B are expected to be useful include hydrocracking,
dewaxing, catalytic cracking and olefin and aromatics formation
reactions. The catalysts are also expected to be useful in other
petroleum refining and hydrocarbon conversion reactions such as
isomerizing n-paraffins and naphthenes, polymerizing and oligomerizing
olefinic or acetylenic compounds such as isobutylene and butene-1
reforming, isomerizing polyalkyl substituted aromatics (e.g., m-xylene),
and disproportionating aromatics (e.g., toluene) to provide mixtures
of benzene, xylenes and higher methylbenzenes and oxidation reactions.
Also included are rearrangement reactions to make various naphthalene
derivatives, and forming higher molecular weight hydrocarbons from
lower molecular weight hydrocarbons (e.g., methane upgrading).
[0085] The SSZ-47B catalysts may have high selectivity, and under
hydrocarbon conversion conditions can provide a high percentage
of desired products relative to total products.
[0086] For high catalytic activity, the SSZ-47B molecular sieve
should be predominantly in its hydrogen ion form. Generally, the
molecular sieve is converted to its hydrogen form by ammonium exchange
followed by calcination. If the molecular sieve is synthesized with
a high enough ratio of SDA cation to sodium ion, calcination alone
may be sufficient. It is preferred that, after calcination, at least
80% of the cation sites are occupied by hydrogen ions and/or rare
earth ions. As used herein, "predominantly in the hydrogen
form" means that, after calcination, at least 80% of the cation
sites are occupied by hydrogen ions and/or rare earth ions.
[0087] SSZ-47B molecular sieves can be used in processing hydrocarbonaceous
feedstocks. Hydrocarbonaceous feedstocks contain carbon compounds
and can be from many different sources, such as virgin petroleum
fractions, recycle petroleum fractions, shale oil, liquefied coal,
tar sand oil, synthetic paraffins from NAO, recycled plastic feedstocks
and, in general, can be any carbon containing feedstock susceptible
to zeolitic catalytic reactions. Depending on the type of processing
the hydrocarbonaceous feed is to undergo, the feed can contain metal
or be free of metals, it can also have high or low nitrogen or sulfur
impurities. It can be appreciated, however, that in general processing
will be more efficient (and the catalyst more active) the lower
the metal, nitrogen, and sulfur content of the feedstock.
[0088] The conversion of hydrocarbonaceous feeds can take place
in any convenient mode, for example, in fluidized bed, moving bed,
or fixed bed reactors depending on the types of process desired.
The formulation of the catalyst particles will vary depending on
the conversion process and method of operation.
[0089] Other reactions which can be performed using the catalyst
of this invention containing a metal, e.g., a Group VIII metal such
platinum, include hydrogenation-dehydrogenation reactions, denitrogenation
and desulfurization reactions.
[0090] The following table indicates typical reaction conditions
which may be employed when using catalysts comprising SSZ-47B in
the hydrocarbon conversion reactions of this invention. Preferred
conditions are indicated in parentheses.
7 Process Temp., .degree. C. Pressure LHSV Hydrocracking 175-485
0.5-350 bar 0.1-30 Dewaxing 200-475 15-3000 psig, 0.1-20 (250-450)
0.103-20.7 Mpa gauge (0.2-10) (200-3000 1.38-20.7 Mpa gauge) Aromatics
400-600 atm.-10 bar 0.1-15 formation (480-550) Cat. Cracking 127-885
subatm.-.sup.1 0.5-50 (atm.-5 atm.) Oligomerization .sup. 232-649.sup.2
0.1-50 atm..sup.23 .sup. 0.2-50.sup.2 .sup. 10-232.sup.4 -- .sup.
0.05-20.sup.5 .sup. (27-204).sup.4 -- .sup. (0.1-10).sup.5 Paraffins
to 100-700 0-1000 psig .sup. 0.5-40.sup.5 aromatics Condensation
of 260-538 0.5-1000 psig, .sup. 0.5-50.sup.5 alcohols 0.00345-6.89
Mpa gauge Isomerization 93-538 50-1000 psig, 1-10 (204-315) 0.345-6.89
Mpa gauge (1-4) Xylene .sup. 260-593.sup.2 0.5-50 atm..sup.2 .sup.
0.1-100.sup.5 isomerization .sup. (315-566).sup.2 (1-5 atm).sup.2
.sup. (0.5-50).sup.5 .sup. 38-371.sup.4 1-200 atm..sup.4 0.5-50
.sup.1Several hundred atmospheres .sup.2Gas phase reaction .sup.3Hydrocarbon
partial pressure .sup.4Liquid phase reaction .sup.5WHSV Other reaction
conditions and parameters are provided below.
Hydrocracking
[0091] Using a catalyst which comprises SSZ-47B, preferably predominantly
in the hydrogen form, and a hydrogenation promoter, heavy petroleum
residual feedstocks, cyclic stocks and other hydrocrackate charge
stocks can be hydrocracked using the process conditions and catalyst
components disclosed in the aforementioned U.S. Pat. No. 4910006
and U.S. Pat. No. 5316753.
[0092] The hydrocracking catalysts contain an effective amount
of at least one hydrogenation component of the type commonly employed
in hydrocracking catalysts. The hydrogenation component is generally
selected from the group of hydrogenation catalysts consisting of
one or more metals of Group VIB and Group VIII, including the salts,
complexes and solutions containing such. The hydrogenation catalyst
is preferably selected from the group of metals, salts and complexes
thereof of the group consisting of at least one of platinum, palladium,
rhodium, iridium, ruthenium and mixtures thereof or the group consisting
of at least one of nickel, molybdenum, cobalt, tungsten, titanium,
chromium and mixtures thereof. Reference to the catalytically active
metal or metals is intended to encompass such metal or metals in
the elemental state or in some form such as an oxide, sulfide, halide,
carboxylate and the like. The hydrogenation catalyst is present
in an effective amount to provide the hydrogenation function of
the hydrocracking catalyst, and preferably in the range of from
0.05 to 25% by weight.
Dewaxing
[0093] SSZ-47B, preferably predominantly in the hydrogen form,
can be used to dewax hydrocarbonaceous feeds by selectively removing
straight chain paraffins. Typically, the viscosity index of the
dewaxed product is improved (compared to the waxy feed) when the
waxy feed is contacted with SSZ-47B under isomerization dewaxing
conditions.
[0094] The catalytic dewaxing conditions are dependent in large
measure on the feed used and upon the desired pour point. Hydrogen
is preferably present in the reaction zone during the catalytic
dewaxing process. The hydrogen to feed ratio is typically between
about 500 and about 30000 SCF/bbl (standard cubic feet per barrel)
(0.089 to 5.34 SCM/liter (standard cubic meters/liter)), preferably
about 1000 to about 20000 SCF/bbl (0.178 to 3.56 SCM/liter). Generally,
hydrogen will be separated from the product and recycled to the
reaction zone. Typical feedstocks include light gas oil, heavy gas
oils and reduced crudes boiling above about 350.degree. F. (177.degree.
C.).
[0095] A typical dewaxing process is the catalytic dewaxing of
a hydrocarbon oil feedstock boiling above about 350.degree. F. (177.degree.
C.) and containing straight chain and slightly branched chain hydrocarbons
by contacting the hydrocarbon oil feedstock in the presence of added
hydrogen gas at a hydrogen pressure of about 15-3000 psi (0.103-20.7
Mpa) with a catalyst comprising SSZ-47B and at least one Group VIII
metal.
[0096] The SSZ-47B hydrodewaxing catalyst may optionally contain
a hydrogenation component of the type commonly employed in dewaxing
catalysts. See the aforementioned U.S. Pat. No. 4910006 and U.S.
Pat. No. 5316753 for examples of these hydrogenation components.
[0097] The hydrogenation component is present in an effective amount
to provide an effective hydrodewaxing and hydroisomerization catalyst
preferably in the range of from about 0.05 to 5% by weight. The
catalyst may be run in such a mode to increase isomerization dewaxing
at the expense of cracking reactions.
[0098] The feed may be hydrocracked, followed by dewaxing. This
type of two stage process and typical hydrocracking conditions are
described in U.S. Pat. No. 4921594 issued May 1 1990 to Miller,
which is incorporated herein by reference in its entirety.
[0099] SSZ-47B may also be utilized as a dewaxing catalyst in the
form of a layered catalyst. That is, the catalyst comprises a first
layer comprising molecular sieve SSZ-47B and at least one Group
VIII metal, and a second layer comprising an aluminosilicate molecular
sieve which is more shape selective than molecular sieve SSZ-47B.
The use of layered catalysts is disclosed in U.S. Pat. No. 5149421
issued Sep. 22 1992 to Miller, which is incorporated by reference
herein in its entirety. The layering may also include a bed of SSZ-47B
layered with a non-zeolitic component designed for either hydrocracking
or hydrofinishing.
[0100] SSZ-47B may also be used to dewax raffinates, including
bright stock, under conditions such as those disclosed in U.S. Pat.
No. 4181598 issued Jan. 1 1980 to Gillespie et al., which is
incorporated by reference herein in its entirety.
[0101] It is often desirable to use mild hydrogenation (sometimes
referred to as hydrofinishing) to produce more stable dewaxed products.
The hydrofinishing step can be performed either before or after
the dewaxing step, and preferably after. Hydrofinishing is typically
conducted at temperatures ranging from about 190.degree. C. to about
340.degree. C. at pressures from about 400 psig to about 3000 psig
(2.76 to 20.7 Mpa gauge) at space velocities (LHSV) between about
0.1 and 20 and a hydrogen recycle rate of about 400 to 1500 SCF/bbl
(0.071 to 0.27 SCM/liter). The hydrogenation catalyst employed must
be active enough not only to hydrogenate the olefins, diolefins
and color bodies which may be present, but also to reduce the aromatic
content. Suitable hydrogenation catalyst are disclosed in U.S. Pat.
No. 4921594 issued May 1 1990 to Miller, which is incorporated
by reference herein in its entirety. The hydrofinishing step is
beneficial in preparing an acceptably stable product (e.g., a lubricating
oil) since dewaxed products prepared from hydrocracked stocks tend
to be unstable to air and light and tend to form sludges spontaneously
and quickly.
[0102] Lube oil may be prepared using SSZ-47B. For example, a C.sub.20+
lube oil may be made by isomerizing a C.sub.20+ olefin feed over
a catalyst comprising SSZ-47B in the hydrogen form and at least
one Group VIII metal. Alternatively, the lubricating oil may be
made by hydrocracking in a hydrocracking zone a hydrocarbonaceous
feedstock to obtain an effluent comprising a hydrocracked oil, and
catalytically dewaxing the effluent at a temperature of at least
about 400.degree. F. (204.degree. C.) and at a pressure of from
about 15 psig to about 3000 psig (0.103-20.7 Mpa gauge) in the presence
of added hydrogen gas with a catalyst comprising SSZ-47B in the
hydrogen form and at least one Group VIII metal.
Aromatics Formation
[0103] SSZ-47B can be used to convert light straight run naphthas
and similar mixtures to highly aromatic mixtures. Thus, normal and
slightly branched chained hydrocarbons, preferably having a boiling
range above about 40.degree. C. and less than about 200.degree.
C., can be converted to products having a substantial higher octane
aromatics content by contacting the hydrocarbon feed with a catalyst
comprising SSZ-47B. It is also possible to convert heavier feeds
into BTX or naphthalene derivatives of value using a catalyst comprising
SSZ-47B.
[0104] The conversion catalyst preferably contains a Group VIII
metal compound to have sufficient activity for commercial use. By
Group VIII metal compound as used herein is meant the metal itself
or a compound thereof. The Group VIII noble metals and their compounds,
platinum, palladium, and iridium, or combinations thereof can be
used. Rhenium or tin or a mixture thereof may also be used in conjunction
with the Group VIII metal compound and preferably a noble metal
compound. The most preferred metal is platinum. The amount of Group
VIII metal present in the conversion catalyst should be within the
normal range of use in reforming catalysts, from about 0.05 to 2.0
weight percent, preferably 0.2 to 0.8 weight percent.
[0105] It is critical to the selective production of aromatics
in useful quantities that the conversion catalyst be substantially
free of acidity, for example, by neutralizing the molecular sieve
with a basic metal, e.g., alkali metal, compound. Methods for rendering
the catalyst free of acidity are known in the art. See the aforementioned
U.S. Pat. No. 4910006 and U.S. Pat. No. 5316753 for a description
of such methods.
[0106] The preferred alkali metals are sodium, potassium, rubidium
and cesium. The molecular sieve itself can be substantially free
of acidity only at very high silica:alumina mole ratios.
Catalytic Cracking
[0107] Hydrocarbon cracking stocks can be catalytically cracked
in the absence of hydrogen using SSZ-47B, preferably predominantly
in the hydrogen form.
[0108] When SSZ-47B is used as a catalytic cracking catalyst in
the absence of hydrogen, the catalyst may be employed in conjunction
with traditional cracking catalysts, e.g., any aluminosilicate heretofore
employed as a component in cracking catalysts. Typically, these
are large pore, crystalline aluminosilicates. Examples of these
traditional cracking catalysts are disclosed in the aforementioned
U.S. Pat. No. 4910006 and U.S. Pat. No 5316753. When a traditional
cracking catalyst (TC) component is employed, the relative weight
ratio of the TC to the SSZ-47B is generally between about 1:10 and
about 500:1 desirably between about 1:10 and about 200:1 preferably
between about 1:2 and about 50:1 and most preferably is between
about 1:1 and about 20:1. The novel molecular sieve and/or the traditional
cracking component may be further ion exchanged with rare earth
ions to modify selectivity.
[0109] The cracking catalysts are typically employed with an inorganic
oxide matrix component. See the aforementioned U.S. Pat. No. 4910006
and U.S. Pat. No. 5316753 for examples of such matrix components.
Isomerization
[0110] The present catalyst is highly active and highly selective
for isomerizing C.sub.4 to C.sub.7 hydrocarbons. The activity means
that the catalyst can operate at relatively low temperature which
thermodynamically favors highly branched paraffins. Consequently,
the catalyst can produce a high octane product. The high selectivity
means that a relatively high liquid yield can be achieved when the
catalyst is run at a high octane.
[0111] The present process comprises contacting the isomerization
catalyst, i.e., a catalyst comprising SSZ-47B in the hydrogen form,
with a hydrocarbon feed under isomerization conditions. The feed
is preferably a light straight run fraction, boiling within the
range of 30.degree. F. to 250.degree. F. (-1.degree. C. to 121.degree.
C.) and preferably from 60.degree. F. to (16.degree. C. to 93.degree.
C.). Preferably, the hydrocarbon feed for the process comprises
a substantial amount of C.sub.4 to C.sub.7 normal and slightly branched
low octane hydrocarbons, more preferably C.sub.5 and C.sub.6 hydrocarbons.
[0112] It is preferable to carry out the isomerization reaction
in the presence of hydrogen. Preferably, hydrogen is added to give
a hydrogen to hydrocarbon ratio (H.sub.2/HC) of between 0.5 and
10 H.sub.2/HC, more preferably between 1 and 8 H.sub.2/HC. See the
aforementioned U.S. Pat. No. 4910006 and U.S. Pat. No. 5316753
for a further discussion of isomerization process conditions.
[0113] A low sulfur feed is especially preferred in the present
process. The feed preferably contains less than 10 ppm, more preferably
less than 1 ppm, and most preferably less than 0.1 ppm sulfur. In
the case of a feed which is not already low in sulfur, acceptable
levels can be reached by hydrogenating the feed in a presaturation
zone with a hydrogenating catalyst which is resistant to sulfur
poisoning. See the aforementioned U.S. Pat. No. 4910006 and U.S.
Pat. No. 5316753 for a further discussion of this hydrodesulfurization
process.
[0114] It is preferable to limit the nitrogen level and the water
content of the feed. Catalysts and processes which are suitable
for these purposes are known to those skilled in the art.
[0115] After a period of operation, the catalyst can become deactivated
by sulfur or coke. See the aforementioned U.S. Pat. No. 4910006
and U.S. Pat. No. 5316753 for a further discussion of methods
of removing this sulfur and coke, and of regenerating the catalyst.
[0116] The conversion catalyst preferably contains a Group VIII
metal compound to have sufficient activity for commercial use. By
Group VIII metal compound as used herein is meant the metal itself
or a compound thereof. The Group VIII noble metals and their compounds,
platinum, palladium, and iridium, or combinations thereof can be
used. Rhenium and tin may also be used in conjunction with the noble
metal. The most preferred metal is platinum. The amount of Group
VIII metal present in the conversion catalyst should be within the
normal range of use in isomerizing catalysts, from about 0.05 to
2.0 weight percent, preferably 0.2 to 0.8 weight percent.
Alkylation and Transalkylation
[0117] SSZ-47B can be used in a process for the alkylation or transalkylation
of an aromatic hydrocarbon. The process comprises contacting the
aromatic hydrocarbon with a C.sub.2 to C.sub.16 olefin alkylating
agent or a polyalkyl aromatic hydrocarbon transalkylating agent,
under at least partial liquid phase conditions, and in the presence
of a catalyst comprising SSZ-47B.
[0118] SSZ-47B can also be used for removing benzene from gasoline
by alkylating the benzene as described above and removing the alkylated
product from the gasoline.
[0119] For high catalytic activity, the SSZ-47B molecular sieve
should be predominantly in its hydrogen ion form. It is preferred
that, after calcination, at least 80% of the cation sites are occupied
by hydrogen ions and/or rare earth ions.
[0120] Examples of suitable aromatic hydrocarbon feedstocks which
may be alkylated or transalkylated by the process of the invention
include aromatic compounds such as benzene, toluene and xylene.
The preferred aromatic hydrocarbon is benzene. There may be occasions
where naphthalene or naphthalene derivatives such as dimethylnaphthalene
may be desirable. Mixtures of aromatic hydrocarbons may also be
employed.
[0121] Suitable olefins for the alkylation of the aromatic hydrocarbon
are those containing 2 to 20 preferably 2 to 4 carbon atoms, such
as ethylene, propylene, butene-1 trans-butene-2 and cis-butene-2
or mixtures thereof. There may be instances where pentenes are desirable.
The preferred olefins are ethylene and propylene. Longer chain alpha
olefins may be used as well.
[0122] When transalkylation is desired, the transalkylating agent
is a polyalkyl aromatic hydrocarbon containing two or more alkyl
groups that each may have from 2 to about 4 carbon atoms. For example,
suitable polyalkyl aromatic hydrocarbons include di-, tri- and tetra-alkyl
aromatic hydrocarbons, such as diethylbenzene, triethylbenzene,
diethylmethylbenzene (diethyltoluene), di-isopropylbenzene, di-isopropyltoluene,
dibutylbenzene, and the like. Preferred polyalkyl aromatic hydrocarbons
are the dialkyl benzenes. A particularly preferred polyalkyl aromatic
hydrocarbon is di-isopropylbenzene.
[0123] When alkylation is the process conducted, reaction conditions
are as follows. The aromatic hydrocarbon feed should be present
in stoichiometric excess. It is preferred that molar ratio of aromatics
to olefins be greater than four-to-one to prevent rapid catalyst
fouling. The reaction temperature may range from 100.degree. F.
to 600.degree. F. (38.degree. C. to 315.degree. C.), preferably
250.degree. F. to 450.degree. F. (121.degree. C. to 232.degree.
C.). The reaction pressure should be sufficient to maintain at least
a partial liquid phase in order to retard catalyst fouling. This
is typically 50 psig to 1000 psig (0.345 to 6.89 Mpa gauge) depending
on the feedstock and reaction temperature. Contact time may range
from 10 seconds to 10 hours, but is usually from 5 minutes to an
hour. The weight hourly space velocity (WHSV), in terms of grams
(pounds) of aromatic hydrocarbon and olefin per gram (pound) of
catalyst per hour, is generally within the range of about 0.5 to
50.
[0124] When transalkylation is the process conducted, the molar
ratio of aromatic hydrocarbon will generally range from about 1:1
to 25:1 and preferably from about 2:1 to 20:1. The reaction temperature
may range from about 100.degree. F. to 600.degree. F. (38.degree.
C. to 315.degree. C.), but it is preferably about 250.degree. F.
to 450.degree. F. (121.degree. C. to 232.degree. C.). The reaction
pressure should be sufficient to maintain at least a partial liquid
phase, typically in the range of about 50 psig to 1000 psig (0.345
to 6.89 Mpa gauge), preferably 300 psig to 600 psig (2.07 to 4.14
Mpa gauge). The weight hourly space velocity will range from about
0.1 to 10. U.S. Pat. No. 5082990 issued on January 21 1992 to
Hsieh, et al. describes such processes and is incorporated herein
by reference.
[0125] SSZ-47B can also be used to alkylate aromatics compounds
using C.sub.20+ olefins. These alkylated aromatics can then be converted
to sulfonic acids or sulfonates and used as additives in lubricating
oils. Such an alkylation process is disclosed in U.S. Pat. No. 5922922
issued Jul. 13 1999 to Harris et al., which is incorporated by
reference in its entirety.
[0126] The aromatic hydrocarbon that is alkylated in this process
is preferably benzene or toluene, but a higher molecular weight
hydrocarbon may also be used. The feed aromatic hydrocarbon may,
therefore be benzene, toluene, xylene, naphthalene, etc. Preferably
it is benzene or toluene, because the resulting alkylates are more
easily processed into the corresponding sulfonic acids or LOB or
HOB sulfonates.
[0127] The olefinic hydrocarbons that are consumed in the process
are normal alpha-olefins (NAO) that may have from about six to thirty
carbon atoms per molecule. Preferably, they have about fourteen
to thirty carbon atoms per molecule. Most preferably, they are predominantly
alpha olefins having from twenty to twenty-eight carbon atoms per
molecule.
[0128] The NAO is isomerized with an acidic catalyst prior to alkylation.
Preferably, the catalyst is a molecular sieve with a one-dimensional
pore system such as SM-3 MAPO-11 SAPO-11 SSZ-32 ZSM-23 MAPO-39
SAPO-39 ZSM-22 and SSZ-20. Other possible solid acidic catalysts
include ZSM-35 SUZ-4 NU-23 NU-87 and natural or synthetic ferrierites.
[0129] The isomerization process conditions are well known in the
art. See, for example, aforementioned U.S. Pat. No. 5922922.
[0130] SSZ-47B, in acidic form, is used as the alkylation catalyst.
Preferably, it is used predominantly in the hydrogen form.
[0131] The alkylation process conditions are likewise well known
in the art. The alkylation reaction is typical carried out with
an aromatic to olefin mole ratio from 1:15 to 25:1. Process temperatures
can range from 100.degree. C. to 250.degree. C. As the olefins have
a high boiling point, the process is preferably carried out in the
liquid phase.
Conversion of Paraffins to Aromatics
[0132] SSZ-47B can be used to convert light gas C.sub.2-C.sub.6
paraffins to higher molecular weight hydrocarbons including aromatic
compounds. Preferably, the molecular sieve will contain a catalyst
metal or metal oxide wherein said metal is selected from the group
consisting of Groups IB, IIB, VIII and IIIA of the Periodic Table.
Preferably, the metal is gallium, niobium, indium or zinc in the
range of from about 0.05 to 5% by weight.
Isomerization of Olefins
[0133] SSZ-47B can be used to isomerize olefins. The feed stream
is a hydrocarbon stream containing at least one C.sub.4-6 olefin,
preferably a C.sub.4-6 normal olefin, more preferably normal butene.
Normal butene as used in this specification means all forms of normal
butene, e.g., 1-butene, cis-2-butene, and trans-2-butene. Typically,
hydrocarbons other than normal butene or other C.sub.4-6 normal
olefins will be present in the feed stream. These other hydrocarbons
may include, e.g., alkanes, other olefins, aromatics, hydrogen,
and inert gases.
[0134] The feed stream typically may be the effluent from a fluid
catalytic cracking unit or a methyl-tert-butyl ether unit. A fluid
catalytic cracking unit effluent typically contains about 40-60
weight percent normal butenes. A methyl-tert-butyl ether unit effluent
typically contains 40-100 weight percent normal butene. The feed
stream preferably contains at least about 40 weight percent normal
butene, more preferably at least about 65 weight percent normal
butene. The terms iso-olefin and methyl branched iso-olefin may
be used interchangeably in this specification.
[0135] The process is carried out under isomerization conditions.
The hydrocarbon feed is contacted in a vapor phase with a catalyst
comprising the SSZ-47B. The process may be carried out generally
at a temperature from about 625.degree. F. to about 950.degree.
F. (329-510.degree. C.), for butenes, preferably from about 700.degree.
F. to about 900.degree. F. (371-482.degree. C.), and about 350.degree.
F. to about 650.degree. F. (177-343.degree. C.) for pentenes and
hexenes. The pressure ranges from subatmospheric to about 200 psig
(1.38 Mpa gauge), preferably from about 15 psig to about 200 psig
(0.103 to 1.38 Mpa gauge), and more preferably from about 1 psig
to about 150 psig (0.00689 to 1.03 Mpa gauge).
[0136] The liquid hourly space velocity during contacting is generally
from about 0.1 to about 50 hr.sup.-1 based on the hydrocarbon feed,
preferably from about 0.1 to about 20 h.sup.-1 more preferably
from about 0.2 to about 10 hr.sup.-1 most preferably from about
1 to about 5 hr.sup.-1. A hydrogen/hydrocarbon molar ratio is maintained
from about 0 to about 30 or higher. The hydrogen can be added directly
to the feed stream or directly to the isomerization zone. The reaction
is preferably substantially free of water, typically less than about
two weight percent based on the feed. The process can be carried
out in a packed bed reactor, a fixed bed, fluidized bed reactor,
or a moving bed reactor. The bed of the catalyst can move upward
or downward. The mole percent conversion of, e.g., normal butene
to iso-butene is at least 10 preferably at least 25 and more preferably
at least 35.
Xylene Isomerization
[0137] SSZ-47B may also be useful in a process for isomerizing
one or more xylene isomers in a C.sub.8 aromatic feed to obtain
ortho-, meta-, and para-xylene in a ratio approaching the equilibrium
value. In particular, xylene isomerization is used in conjunction
with a separate process to manufacture para-xylene. For example,
a portion of the para-xylene in a mixed C.sub.8 aromatics stream
may be recovered by crystallization and centrifugation. The mother
liquor from the crystallizer is then reacted under xylene isomerization
conditions to restore ortho-, meta- and para-xylenes to a near equilibrium
ratio. At the same time, part of the ethylbenzene in the mother
liquor is converted to xylenes or to products which are easily separated
by filtration. The isomerate is blended with fresh feed and the
combined stream is distilled to remove heavy and light by-products.
The resultant C.sub.8 aromatics stream is then sent to the crystallizer
to repeat the cycle.
[0138] Optionally, isomerization in the vapor phase is conducted
in the presence of 3.0 to 30.0 moles of hydrogen per mole of alkylbenzene
(e.g., ethylbenzene). If hydrogen is used, the catalyst should comprise
about 0.1 to 2.0 wt. % of a hydrogenation/dehydrogenation component
selected from Group VIII (of the Periodic Table) metal component,
especially platinum or nickel. By Group VIII metal component is
meant the metals and their compounds such as oxides and sulfides.
[0139] Optionally, the isomerization feed may contain 10 to 90
wt. of a diluent such as toluene, trimethylbenzene, naphthenes or
paraffins.
Oligomerization
[0140] It is expected that SSZ-47B can also be used to oligomerize
straight and branched chain olefins having from about 2 to 21 and
preferably 2-5 carbon atoms. The oligomers which are the products
of the process are medium to heavy olefins which are useful for
both fuels, i.e., gasoline or a gasoline blending stock and chemicals.
[0141] The oligomerization process comprises contacting the olefin
feedstock in the gaseous or liquid phase with a catalyst comprising
SSZ-47B.
[0142] The molecular sieve can have the original cations associated
therewith replaced by a wide variety of other cations according
to techniques well known in the art. Typical cations would include
hydrogen, ammonium and metal cations including mixtures of the same.
Of the replacing metallic cations, particular preference is given
to cations of metals such as rare earth metals, manganese, calcium,
as well as metals of Group II of the Periodic Table, e.g., zinc,
and Group VIII of the Periodic Table, e.g., nickel. One of the prime
requisites is that the molecular sieve have a fairly low aromatization
activity, i.e., in which the amount of aromatics produced is not
more than about 20% by weight. This is accomplished by using a molecular
sieve with controlled acid activity [alpha value] of from about
0.1 to about 120 preferably from about 0.1 to about 100 as measured
by its ability to crack n-hexane.
[0143] Alpha values are defined by a standard test known in the
art, e.g., as shown in U.S. Pat. No. 3960978 issued on Jun. 1
1976 to Givens et al. which is incorporated totally herein by reference.
If required, such molecular sieves may be obtained by steaming,
by use in a conversion process or by any other method which may
occur to one skilled in this art.
Condensation of Alcohols
[0144] SSZ-47B can be used to condense lower aliphatic alcohols
having 1 to 10 carbon atoms to a gasoline boiling point hydrocarbon
product comprising mixed aliphatic and aromatic hydrocarbon. The
process disclosed in U.S. Pat. No. 3894107 issued Jul. 8 1975
to Butter et al., describes the process conditions used in this
process, which patent is incorporated totally herein by reference.
[0145] The catalyst may be in the hydrogen form or may be base
exchanged or impregnated to contain ammonium or a metal cation complement,
preferably in the range of from about 0.05 to 5% by weight. The
metal cations that may be present include any of the metals of the
Groups I through VIII of the Periodic Table. However, in the case
of Group IA metals, the cation content should in no case be so large
as to effectively inactivate the catalyst, nor should the exchange
be such as to eliminate all acidity. There may be other processes
involving treatment of oxygenated substrates where a basic catalyst
is desired.
Methane Upgrading
[0146] Higher molecular weight hydrocarbons can be formed from
lower molecular weight hydrocarbons by contacting the lower molecular
weight hydrocarbon with a catalyst comprising SSZ-47B and a metal
or metal compound capable of converting the lower molecular weight
hydrocarbon to a higher molecular weight hydrocarbon. Examples of
such reactions include the conversion of methane to C.sub.2+ hydrocarbons
such as ethylene or benzene or both. Examples of useful metals and
metal compounds include lanthanide, actinide, molybdenum and/or
niobium metals or metal compounds.
[0147] These reactions, the metals or metal compounds employed
and the conditions under which they can be run are disclosed in
U.S. Pat. No. 4734537 issued Mar. 29 1988 to Devries et al.;
U.S. Pat. No. 4939311 issued Jul. 3 1990 to Washecheck et al.;
U.S. Pat. No. 4962261 issued Oct. 9 1990 to Abrevaya et al.;
U.S. Pat. No. 5095161 issued Mar. 10 1992 to Abrevaya et al.;
U.S. Pat. No. 5105044 issued Apr. 14 1992 to Han et al.; U.S.
Pat. No. 5105046 issued Apr. 14 1992 to Washecheck; U.S. Pat.
No. 5238898 issued Aug. 24 1993 to Han et al.; U.S. Pat. No.
5321185 issued Jun. 14 1994 to van der Vaart; and U.S. Pat.
No. 5336825 issued Aug. 9 1994 to Choudhary et al., each of
which is incorporated herein by reference in its entirety.
EXAMPLES
[0148] The following examples demonstrate but do not limit the
present invention.
Example 1
[0149] A reaction mixture is prepared in the Teflon cup of a Parr
23 ml reactor by combining the following: 2 millimoles (0.42 gram)
of 44'-trimethylene dipiperidine, 1.0 millimole of N-cyclopentyl
DABCO hydroxide in a total of 9.25 grams of water, 0.088 gram of
Reheis F-2000 alumina (53-56 wt. % Al.sub.2O.sub.3), 3 grams of
1 N KOH and 0.90 gram of Cabosil M-5 fumed silica. The first two
components represent the amine that is too large to form nonasil
and the SDA that forms SSZ-47B, respectively. The reaction mixture
is heated at 170.degree. C. while being tumbled at 43 RPM. The reaction
mixture has a silica/alumina mole ratio (SAR) of 32. The SSZ-47B
product (identified by X-ray diffraction) forms after nine days.
Example 2
[0150] The reaction of Example 1 is repeated, except the alumina
content is reduced to 0.066 gram. The SAR of the reaction mixture
is 40. The reaction produces SSZ-47B (identified by X-ray diffraction).
Example 3
[0151] The reaction of Example 1 is repeated, except the alumina
content is reduced to 0.044 gram. The SAR of the reaction mixture
is 64. The reaction produces SSZ-47B with a little quartz impurity
(identified by X-ray diffraction).
Example 4
[0152] The reaction of Example 1 is repeated, except the N-cyclopentyl
DABCO hydroxide content is reduced to 0.5 millimole. The reaction
produces SSZ-47B (identified by X-ray diffraction).
Example 5
[0153] The reaction of Example 4 is repeated, except that the reaction
mixture is seeded with 2 wt. % (based on the weight of silica) SSZ-47B
crystals from the product of Example 1. The reaction produces SSZ-47B
(identified by X-ray diffraction).
Example 6
Calcination of SSZ-47B
[0154] SSZ-47B as synthesized in Example 3 is calcined to remove
the structure directing agent (SDA) and amine. A thin bed of SSZ-47B
in a calcination dish is heated in a muffle furnace from room temperature
to 120.degree. C. at a rate of 1.degree. C./minute and held for
2 hours. Then, the temperature is ramped up to 540.degree. C. at
a rate of 1.degree. C./minute and held for 5 hours. The temperature
is ramped up again at 1.degree. C./minute to 595.degree. C. and
held there for 5 hours. A 50/50 mixture of air and nitrogen passes
through the muffle furnace at a rate of 20 standard cubic feet (0.57
standard cubic meters) per minute during the calcination process.
Example 7
Ammonium-Ion Exchange of SSZ-47B
[0155] The Na.sup.+ form of SSZ-47B (prepared as in Example 3 or
as in Example 5 and calcined as in Example 6) is converted to NH.sub.4.sup.+-SSZ-47B
form by heating the material in an aqueous solution of NH.sub.4NO.sub.3
(typically 1 gm NH.sub.4NO.sub.3/1 gm SSZ-47B in 20 ml H.sub.2O)
at 90.degree. C. for 2-3 hours. The mixture is then filtered and
the obtained NH.sub.4-exchanged-product is washed with de-ionized
water and dried. The ion exchange procedure is repeated again. The
NH.sub.4.sup.+ form of SSZ-47B can be converted to the H.sup.+ form
by calcination (as described in Example 6) to 540.degree. C.
Example 8
Nitrogen Adsorption Analysis
[0156] The hydrogen form of the products of Example 3 (after a
treatment as in Examples 6 and 7 is subjected to a micropore volume
analysis using nitrogen as adsorbate and via the BET method. The
micropore volume is 0.153 cc/g, thus exhibiting considerable void
volume.
Example 9
Constraint Index
[0157] The hydrogen form of SSZ-47B of Example 3 (after treatment
according to Examples6 and 7) is pelletized at 3 KPSI, crushed and
granulated to 20-40 mesh. A 0.6 gram sample of the granulated material
is calcined in air at 540.degree. C. for 4 hours and cooled in a
desiccator to ensure dryness. Then, 0.5 gram is packed into a 3/8
inch stainless steel tube with alundum on both sides of the molecular
sieve bed. A Lindburg furnace is used to heat the reactor tube.
Helium is introduced into the reactor tube at 10 cc/min. and at
atmospheric pressure. The reactor is heated to about 315.degree.
C., and a 50/50 feed of n-hexane and 3-methylpentane is introduced
into the reactor at a rate of 8 .mu.l/min. The feed is delivered
by a Brownlee pump. Direct sampling into a GC begins after 10 minutes
of feed introduction. The Constraint Index (CI) value is calculated
from the GC data using methods known in the art. SSZ-47B has a CI
of 1.5 and a conversion at 600.degree. F. (315.degree. C.) of 80.6%
after 20 minutes on stream. The data suggests a large pore molecular
sieve.
Example 10
Hydrocracking of n-Hexadecane
[0158] A 1 gm sample of SSZ-47B (prepared as in Example 3 and treated
as in Examples 6 and 7) is suspended in 10 gm de-ionized water.
To this suspension, a solution of Pd(NH.sub.3).sub.4(NO.sub.3).sub.2
at a concentration which would provide 0.5 wt. % Pd with respect
to the dry weight of the molecular sieve sample is added. The pH
of the solution is adjusted to pH of .about.9 by a drop-wise addition
of dilute ammonium hydroxide solution. The mixture is then stirred
at room temperature for 48 hours. The mixture is then filtered through
a glass frit, washed with de-ionized water, and air-dried. The collected
Pd-SSZ-47B sample is slowly calcined up to 482.degree. C. in air
and held there for three hours.
[0159] The calcined Pd/SSZ-47B catalyst is pelletized in a Carver
Press and granulated to yield particles with a 20/40 mesh size.
Sized catalyst (0.5 g) is packed into a 1/4 inch OD tubing reactor
in a micro unit for n-hexadecane hydroconversion. The table below
gives the run conditions and the products data for the hydrocracking
test on n-hexadecane.
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