U.S. patent application number 14/102849 was filed with the patent office on 2014-06-12 for conversion of methane to aromatic compounds using a catalytic composite.
This patent application is currently assigned to UOP LLC. The applicant listed for this patent is UOP LLC. Invention is credited to Lisa M. King, Vincent G. Mezera, Mark A. Miller, Christopher P. Nicholas, Timur V. Voskoboynikov.
Application Number | 20140163281 14/102849 |
Document ID | / |
Family ID | 50881669 |
Filed Date | 2014-06-12 |
United States Patent
Application |
20140163281 |
Kind Code |
A1 |
Voskoboynikov; Timur V. ; et
al. |
June 12, 2014 |
CONVERSION OF METHANE TO AROMATIC COMPOUNDS USING A CATALYTIC
COMPOSITE
Abstract
A catalyst for the conversion of at least one low carbon number
aliphatic hydrocarbon in a feedstream to provide at least one
aromatic hydrocarbon, the catalyst comprising a zeolite and a
promoter metal M, the zeolite characterized by the retention of
greater than 40% of the tetrahedral aluminum sites in the zeolite
following calcination of the catalyst in air at 750.degree. C. for
3 hours when compared to the amount of tetrahedral aluminum in the
same catalyst after calcination in air at 500.degree. C. for 3
hours.
Inventors: |
Voskoboynikov; Timur V.;
(Arlington Heights, IL) ; Nicholas; Christopher P.;
(Evanston, IL) ; Miller; Mark A.; (Niles, IL)
; King; Lisa M.; (Westchester, IL) ; Mezera;
Vincent G.; (Brookfield, IL) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
UOP LLC |
Des Plaines |
IL |
US |
|
|
Assignee: |
UOP LLC
Des Plaines
IL
|
Family ID: |
50881669 |
Appl. No.: |
14/102849 |
Filed: |
December 11, 2013 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
61736287 |
Dec 12, 2012 |
|
|
|
Current U.S.
Class: |
585/417 ; 502/60;
502/61 |
Current CPC
Class: |
B01J 2229/186 20130101;
C07C 2529/78 20130101; B01J 35/1019 20130101; C07C 2/76 20130101;
Y02P 20/584 20151101; B01J 29/70 20130101; C07C 2/76 20130101; B01J
35/1038 20130101; B01J 29/90 20130101; B01J 35/002 20130101; B01J
35/108 20130101; B01J 29/78 20130101; B01J 29/7049 20130101; B01J
29/72 20130101; C07C 15/02 20130101; C07C 2529/70 20130101 |
Class at
Publication: |
585/417 ; 502/60;
502/61 |
International
Class: |
B01J 29/78 20060101
B01J029/78; C07C 2/76 20060101 C07C002/76 |
Claims
1. A catalyst for the conversion of at least one low carbon number
aliphatic hydrocarbon in a feedstream to provide at least one
aromatic hydrocarbon, the catalyst comprising a zeolite and a
promoter metal M, the zeolite characterized by the retention of
greater than 40% of the tetrahedral aluminum sites in the zeolite
following calcination of the catalyst in air at 750.degree. C. for
3 hours when compared to the amount of tetrahedral aluminum in the
same catalyst after calcination in air at 500.degree. C. for 3
hours.
2. The catalyst of claim 1 further comprising a refractory
inorganic-oxide binder.
3. The catalyst of claim 1, where M is selected from the group
consisting of iron, cobalt, vanadium, manganese, gallium, zinc,
chromium, tungsten, molybdenum and combinations thereof.
4. The catalyst of claim 1, wherein the zeolite is further
characterized by the retention of greater than 25% of the
tetrahedral aluminum sites in the zeolite following calcination of
the catalyst in air at 750.degree. C. for 3 hours when compared to
the amount of tetrahedral aluminum in the zeolite prior to
incorporation of the promoter metal.
5. The catalyst of claim 1, where M is Mo or W and the zeolite is
further characterized by the formation of less than 3.0 mol %
aluminum metalate, Al.sub.2(MO.sub.4).sub.3, after calcination of
catalyst at 500.degree. C. for 3 hours in air.
6. The catalyst of claim 1, where M is Mo or W and the zeolite is
further characterized by the formation of less than 15 mol %
aluminum metalate, Al.sub.2(MO.sub.4).sub.3, after calcination of
the catalyst at 750.degree. C. for 3 hours in air
7. The catalyst of claim 1, the zeolite further characterized by
the retention of greater than 15% of the Broensted acid sites in
the zeolite following calcination of the catalyst in air at
750.degree. C. for 3 hours when compared to the amount of Broensted
acid sites in the same catalyst after calcination in air at
500.degree. C. for 3 hours.
8. The catalyst of claim 1, the zeolite further characterized by
the retention of greater than 15% of the Broensted acid sites in
the zeolite following calcination of the catalyst in air at
750.degree. C. for 3 hours when compared to the amount of Broensted
acid sites in the same catalyst prior to incorporation of the
promoter metal.
9. The catalyst of claim 1, the zeolite comprising a coherently
grown composite of TUN and IMF zeotypes having a three-dimensional
framework of at least AlO.sub.2 and SiO.sub.2 tetrahedral units and
an empirical composition in the hydrogen form after calcination,
ion-exchange and calcination and on an anhydrous basis expressed by
an empirical formula of
M1.sub.a.sup.N+Al.sub.(1-x)E.sub.xSi.sub.y'O.sub.z'' and where M1
is at least one exchangeable cation selected from the group
consisting of alkali, alkaline earth metals, rare earth metals,
zinc, ammonium ion, hydrogen ion and combinations thereof, "a" is
the mole ratio of M1 to (Al+E) and varies from about 0.05 to about
50, "N" is the weighted average valence of M1 and has a value of
about +1 to about +3, E is an element selected from the group
consisting of gallium, iron, boron, and combinations thereof, "x"
is the mole fraction of E and varies from 0 to 1.0, y' is the mole
ratio of Si to (Al+E) and varies from greater than about 9 to
virtually pure silica and z'' is the mole ratio of O to (Al+E) and
has a value determined by the equation: z''=(aN+3+4y')/2 and is
characterized by a characteristic selected from the group
consisting of a) that it has TUN regions and IMF regions that are
coherently aligned so that the [010]TUN zone axis and the [001]IMF
zone axis are parallel to each other and there is continuity of
crystal planes of type (002)TUN and (060)IMF, where the indexing is
referred to monoclinic C2/m and orthorhombic Cmcm unit cells for
TUN and IMF respectively, b) that it has the x-ray diffraction
pattern having at least the d-spacings and intensities set forth in
Table B1: TABLE-US-00010 TABLE B1 2.theta. d (.ANG.) I/Io %
7.11-7.16 12.42-12.25 vw-m 7.5-8.1* 11.78-10.91 m-s 8.84 10.00 m-s
9.06-9.08 9.75-9.73 w-m 9.24 9.56 vw-m 12.46-12.53 7.10-7.06 w-m
22.56 3.94 vw-m 22.75-23.2 3.90-3.83 vs 23.40 3.80 m-s 24.12-24.23
3.69-3.67 w-m 24.92-25.37 3.57-3.51 m 28.71-29.27 3.11-3.05 w-m
45.32-45.36 2.00 w *composite peak consisting of multiple
overlapping reflections and c) combinations thereof.
10. A catalyst for the conversion of at least one low carbon number
aliphatic hydrocarbon in a feedstream to provide at least one
aromatic hydrocarbon, the catalyst comprising a zeolite and a
promoter metal M, the zeolite characterized by the retention of
greater than 15% of the Broensted acid sites in the zeolite
following calcination of the catalyst in air at 750.degree. C. for
3 hours when compared to the amount of Broensted acid sites in the
same catalyst prior to incorporation of the promoter metal.
11. The catalyst of claim 10, further comprising a refractory
inorganic-oxide binder.
12. The catalyst of claim 10, where M is selected from the group
consisting of iron, cobalt, vanadium, manganese, gallium, zinc,
chromium, tungsten, molybdenum and combinations thereof.
13. The catalyst of claim 10, the zeolite further characterized by
the retention of greater than 25% of the tetrahedral aluminum sites
in the zeolite following calcination of the catalyst in air at
750.degree. C. for 3 hours when compared to the amount of
tetrahedral aluminum in the zeolite prior to incorporation of the
promoter metal.
14. The catalyst of claim 10, where M is Mo or W and the zeolite is
further characterized by the formation of less than 3.0 mol %
aluminum metalate, Al.sub.2(MO.sub.4).sub.3, after calcination of
the metal incorporated zeolite at 500.degree. C. for 3 hours in
air.
15. The catalyst of claim 10, where M is Mo or W and the zeolite is
further characterized by the formation of less than 15 mol %
aluminum metalate, Al.sub.2(MO.sub.4).sub.3, after calcination of
the metal incorporated zeolite at 750.degree. C. for 3 hours in
air.
16. The catalyst of claim 10, the zeolite further characterized by
the retention of greater than 15% of the Broensted acid sites in
the zeolite following calcination of the catalyst in air at
750.degree. C. for 3 hours when compared to the amount of Broensted
acid sites in the same catalyst after calcination in air at
500.degree. C. for 3 hours.
17. The catalyst of claim 10, the zeolite further characterized by
the retention of greater than 40% of the tetrahedral aluminum sites
in the zeolite following calcination of the catalyst in air at
750.degree. C. for 3 hours when compared to the amount of
tetrahedral aluminum in the same catalyst after calcination in air
at 500.degree. C. for 3 hours.
18. The catalyst of claim 10, the zeolite comprising a coherently
grown composite coherently grown composite of TUN and IMF zeotypes
having a three-dimensional framework of at least AlO.sub.2 and
SiO.sub.2 tetrahedral units and an empirical composition in the
hydrogen form after calcination, ion-exchange and calcination and
on an anhydrous basis expressed by an empirical formula of
M1.sub.a.sup.N+Al.sub.(1-x)E.sub.xSi.sub.y'O.sub.z'' and where M1
is at least one exchangeable cation selected from the group
consisting of alkali, alkaline earth metals, rare earth metals,
zinc, ammonium ion, hydrogen ion and combinations thereof, "a" is
the mole ratio of M1 to (Al+E) and varies from about 0.05 to about
50, "N" is the weighted average valence of M1 and has a value of
about +1 to about +3, E is an element selected from the group
consisting of gallium, iron, boron, and combinations thereof, "x"
is the mole fraction of E and varies from 0 to 1.0, y' is the mole
ratio of Si to (Al+E) and varies from greater than about 9 to
virtually pure silica and z'' is the mole ratio of 0 to (Al+E) and
has a value determined by the equation: z''=(aN+3+4y')/2 and is
characterized by a characteristic selected from the group
consisting of a) that it has TUN regions and IMF regions that are
coherently aligned so that the [010]TUN zone axis and the [001]IMF
zone axis are parallel to each other and there is continuity of
crystal planes of type (002)TUN and (060)IMF, where the indexing is
referred to monoclinic C2/m and orthorhombic Cmcm unit cells for
TUN and IMF respectively, b) that it has the x-ray diffraction
pattern having at least the d-spacings and intensities set forth in
Table B1: TABLE-US-00011 TABLE B1 2.theta. d (.ANG.) I/Io %
7.11-7.16 12.42-12.25 vw-m 7.5-8.1* 11.78-10.91 m-s 8.84 10.00 m-s
9.06-9.08 9.75-9.73 w-m 9.24 9.56 vw-m 12.46-12.53 7.10-7.06 w-m
22.56 3.94 vw-m 22.75-23.2 3.90-3.83 vs 23.40 3.80 m-s 24.12-24.23
3.69-3.67 w-m 24.92-25.37 3.57-3.51 m 28.71-29.27 3.11-3.05 w-m
45.32-45.36 2.00 w *composite peak consisting of multiple
overlapping reflections and c) combinations thereof.
19. A catalyst for the conversion of at least one low carbon number
aliphatic hydrocarbon in a feedstream to provide at least one
aromatic hydrocarbon, the catalyst comprising a zeolite and a
promoter metal M selected from the group consisting of molybdenum,
tungsten and combinations thereof, the zeolite characterized by the
formation of less than 15 mol % aluminum metalate,
Al.sub.2(MO.sub.4).sub.3, after calcination of the metal
incorporated zeolite at 750.degree. C. for 3 hours in air.
20. The catalyst of claim 19, the zeolite further characterized by
the retention of greater than 25% of the tetrahedral aluminum sites
in the zeolite following calcination of the catalyst in air at
750.degree. C. for 3 hours when compared to the amount of
tetrahedral aluminum in the zeolite prior to incorporation of the
promoter metal.
21. A process for the conversion of at least one low carbon number
aliphatic hydrocarbon in a feedstream to provide at least one
aromatic hydrocarbon, the process comprising contacting the
feedstream with a catalyst to generate at least one aromatic
compound, the catalyst comprising a zeolite and a promoter metal M,
the zeolite characterized by a characteristic selected from the
group consisting of (a) the retention of greater than 40% of the
tetrahedral aluminum sites in the zeolite following calcination of
the catalyst in air at 750.degree. C. for 3 hours when compared to
the amount of tetrahedral aluminum in the same catalyst after
calcination in air at 500.degree. C. for 3 hours, (b) the retention
of greater than 15% of the Broensted acid sites in the zeolite
following calcination of the catalyst in air at 750.degree. C. for
3 hours when compared to the amount of Broensted acid sites in the
same catalyst prior to incorporation of the promoter metal, and (c)
wherein the promoter metal M is selected from the group consisting
of molybdenum, tungsten and combinations thereof, the zeolite
characterized by the formation of less than 15 mol % aluminum
metalate, Al.sub.2(MO.sub.4).sub.3, after calcination of the metal
incorporated zeolite at 750.degree. C. for 3 hours in air.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application claims priority from Provisional
Application No. 61/736,287 filed on Dec. 12, 2012, the contents of
which are hereby incorporated by reference in its entirety.
FIELD OF THE INVENTION
[0002] This invention relates to a new catalytic composite and
using the new catalytic composite for the conversion of at least
one low carbon number aliphatic hydrocarbon, such as methane, to at
least one aromatic compound, such as benzene. The catalyst
comprises a zeolite and a promoter metal M, the zeolite
characterized by a characteristic selected from the group
consisting of (a) the retention of greater than 40% of the
tetrahedral aluminum sites in the zeolite following calcination of
the catalyst in air at 750.degree. C. for 3 hours when compared to
the amount of tetrahedral aluminum in the same catalyst after
calcination in air at 500.degree. C. for 3 hours, (b) the retention
of greater than 15% of the Broensted acid sites in the zeolite
following calcination of the catalyst in air at 750.degree. C. for
3 hours when compared to the amount of Broensted acid sites in the
same catalyst prior to incorporation of the promoter metal, and (c)
wherein the promoter metal M is selected from the group consisting
of molybdenum, tungsten and combinations thereof, the zeolite
characterized by the formation of less than 15 mol % aluminum
metalate, Al.sub.2(MO.sub.4).sub.3, after calcination of the metal
incorporated zeolite at 750.degree. C. for 3 hours in air.
BACKGROUND OF THE INVENTION
[0003] Zeolites are crystalline aluminosilicate compositions which
are microporous and which are formed from corner sharing AlO.sub.2
and SiO.sub.2 tetrahedra. Numerous zeolites, both naturally
occurring and synthetically prepared, are used in various
industrial processes. Synthetic zeolites are prepared via
hydrothermal synthesis employing suitable sources of Si, Al and
structure directing agents such as alkali metals, alkaline earth
metals, amines, or organoammonium cations. The structure directing
agents reside in the pores of the zeolite and are largely
responsible for the particular structure that is ultimately formed.
These species balance the framework charge associated with aluminum
and can also serve as space fillers. Zeolites are characterized by
having pore openings of uniform dimensions, having a significant
ion exchange capacity, and being capable of reversibly desorbing an
adsorbed phase which is dispersed throughout the internal voids of
the crystal without significantly displacing any atoms which make
up the permanent zeolite crystal structure. Zeolites can be used as
catalysts for hydrocarbon conversion reactions, which can take
place on outside surfaces as well as on internal surfaces within
the pore.
[0004] One particular zeolite, designated TNU-9, was first
disclosed by Hong et al. in 2004, (J. Am. Chem. Soc. 2004, 126,
5817-26) and then in a Korean Patent granted in 2005, KR 480229.
This report and patent was followed by a full report of the
synthesis in 2007 (J. Am. Chem. Soc. 2007, 129, 10870-85). These
papers describe the synthesis of TNU-9 from the flexible dicationic
structure directing agent, 1,4-bis(N-methylpyrrolidinium)butane
dibromide in the presence of sodium. After the structure of TNU-9
was solved (Nature, 2006, 444, 79-81), the International Zeolite
Association Structure Commission gave the code of TUN to this
zeolite structure type, see Atlas of Zeolite Framework Types, which
is maintained by the International Zeolite Association Structure
Commission at http://www.iza-structure.org/databases/. The TUN
structure type was found to contain 3 mutually orthogonal sets of
channels in which each channel is defined by a 10-membered ring of
tetrahedrally coordinated atoms. In addition, 2 different sizes of
10-membered ring channels exist in the structure.
[0005] Another particular zeolite, IM-5 was first disclosed by
Benazzi, et al. in 1996 (FR96/12873; WO98/17581) who describe the
synthesis of IM-5 from the flexible dicationic structure directing
agent, 1,5-bis(N-methylpyrrolidinium)pentane dibromide or
1,6-bis(N-methylpyrrolidinium)hexane dibromide in the presence of
sodium. After the structure of IM-5 was solved by Baerlocher et al.
(Science, 2007, 315, 113-6), the International Zeolite Structure
Commission gave the code of IMF to this zeolite structure type, see
Atlas of Zeolite Framework Types. The IMF structure type was also
found to contain three mutually orthogonal sets of channels in
which each channel is defined by a 10-membered ring of
tetrahedrally coordinated atoms, however, connectivity in the third
dimension is interrupted every 2.5 nm, therefore diffusion is
somewhat limited. In addition, multiple different sizes of
10-membered ring channels exist in the structure.
[0006] Applicants have successfully identified characteristics of
catalysts successful for the conversion of at least one low carbon
number aliphatic hydrocarbon, such as methane, to at least one
aromatic compound, such as benzene. Applicants have also prepared a
new family of materials designated UZM-39, which contain the
desired characteristics for successful use in the conversion of at
least one low carbon number aliphatic hydrocarbon to at least one
aromatic compound. The topology of the materials is similar to that
observed for TNU-9 and IM-5. The materials are prepared via the use
of a mixture of simple commercially available structure directing
agents, such as 1,4-dibromobutane and 1-methylpyrrolidine, in
concert with Na.sup.+ using the Layered Material Conversion
approach to zeolite synthesis (described below). These materials,
designated UZM-39, may be employed as a catalyst in processes for
the conversion of low carbon number compounds, such as methane, to
at least one aromatic compound, such as benzene.
[0007] Literature has proposed to produce aromatic compounds such
as benzene, toluene and xylenes from petroleum naphtha streams.
Attempts have also been made to produce useful aromatic compounds
from low molecular weight aliphatic compounds by, for example, the
pyrolysis of natural gas, acetylene and other gases. However, this
technique produces benzene and other useful aromatic compounds in
very low yields while producing large amounts of tar, insoluble
carbon residue and high molecular weight aromatic compounds, all of
which are of little commercial use. Specifically, in the pyrolysis
of methane and acetylene, the reaction is carried out at a
temperature of about 1,000.degree. C. or higher with a conversion
rate of only a few percent and a selectivity to naphthalenes of
less than 1%, and thus has little practical application.
[0008] There are reports in the art of processes for converting
natural gas into aromatic compounds. For example, U.S. Pat. No.
5,288,935 discloses a process for producing liquid hydrocarbons
from natural gas, in which natural gas is first separated into a
methane rich fraction and a C.sub.2+ fraction, the methane is then
selectively oxidized with oxygen, the effluent from the selective
oxidation is then mixed with a part of the C.sub.2+ fraction and
the resulting mixture pyrolyzed to obtain an aromatic product. The
final step is carried out at a temperature of about 300.degree. C.
to about 750.degree. C. in the presence of an aromatizing catalyst
consisting essentially of a zeolite, gallium, at least one metal
from the Group VIII metals and rhenium and at least one additional
metal selected from the group consisting of: tin, germanium, lead,
indium, thallium, copper, gold, nickel, iron, chromium, molybdenum
and tungsten; an alkaline metal or alkaline earth metal and an
aluminum matrix.
[0009] It is also known that the non-oxidative conversion of
methane to benzene via dehydroaromatization can be carried out
using Mo/HZSM-5, see L. Wang, L. Tao, M. Xie, G. Xu, J. Huang, and
Y. Yu Catal. Lett. 1993, 21, 35 and that dehydrocondensation of
methane, optionally in the presence of CO or CO.sub.2, to form
benzene and naphthalene can be carried out using a
molybdenum/HZSM-5 or iron/cobalt modified Mo/HZSM-5, see S. Liu, Q.
Dong, R. Ohonishi and M. Ichikawa, Chem. Commun. (1998), p.
1217-1218, and S. Liu, L. Wang, Q. Dong, R. Ohonishi, and M.
Ichikawa, Stud. Surf Sci. Catal., Vol. 119, p. 241-246. These
catalysts are known to deactivate both by coking and by damage from
the repetitive regenerations required in the process. In contrast
to this art, a catalyst which comprises a UZM-39 zeolite and which
optionally can contain a promoter such as iron, cobalt, tungsten,
or molybdenum can be used to successfully catalyze the conversion
of at least one low carbon number aliphatic hydrocarbon to at least
one aromatic compound. In addition, less deactivation under process
conditions may be observed than typical with MFI based
catalysts.
SUMMARY OF THE INVENTION
[0010] This invention relates to using a new catalytic composite
and to using the catalytic composite for the conversion of at least
one low carbon number aliphatic hydrocarbon, such as methane, to at
least one aromatic compound, such as benzene. The catalytic
composite comprises a zeolite and a promoter metal M, wherein the
zeolite is characterized by a characteristic selected from the
group consisting of (a) the retention of greater than 40% of the
tetrahedral aluminum sites in the zeolite following calcination of
the catalyst in air at 750.degree. C. for 3 hours when compared to
the amount of tetrahedral aluminum in the same catalyst after
calcination in air at 500.degree. C. for 3 hours, (b) the retention
of greater than 15% of the Broensted acid sites in the zeolite
following calcination of the catalyst in air at 750.degree. C. for
3 hours when compared to the amount of Broensted acid sites in the
same catalyst prior to incorporation of the promoter metal, and (c)
wherein the promoter metal M is selected from the group consisting
of molybdenum, tungsten and combinations thereof, the zeolite
characterized by the formation of less than 15 mol % aluminum
metalate, Al.sub.2(MO.sub.4).sub.3, after calcination of the metal
incorporated zeolite at 750.degree. C. for 3 hours in air.
[0011] The Layered Material Conversion approach may be used for
preparing the crystalline microporous zeolite described above. The
process comprises forming a reaction mixture containing reactive
sources of Na, R, Q, Al, Si, seeds of a layered material L and
optionally E and/or M and heating the reaction mixture at a
temperature of about 150.degree. C. to about 200.degree. C., about
155.degree. C. to about 190.degree. C., or about 160.degree. C. to
about 180.degree. C., for a time sufficient to form the zeolite. L
does not have the same zeotype as the UZM-39 coherently grown
composite. The reaction mixture has a composition expressed in
terms of mole ratios of the oxides of:
a-bNa.sub.2O:bM.sub.n/2O:cRO:dQ:1-eAl.sub.2O.sub.3:eE.sub.2O.sub.3:fSiO.-
sub.2:gH.sub.2O
where "a" has a value of about 10 to about 30, "b" has a value of 0
to about 30, "c" has a value of about 1 to about 10, "d" has a
value of about 2 to about 30, "e" has a value of 0 to about 1.0,
"f" has a value of about 30 to about 100, "g" has a value of about
100 to about 4000. Additionally, the reaction mixture comprises
from about 1 to about 10 wt.-% of seed zeolite L based on the
amount of SiO.sub.2 in the reaction mixture, e.g., if there is 100
g of SiO.sub.2 in the reaction mixture, from about 1 to about 10 g
of seed zeolite L would be added to the reaction mixture. With this
number of reactive reagent sources, many orders of addition can be
envisioned. Typically, the aluminum reagent is dissolved in the
sodium hydroxide prior to adding the silica reagents. As can be
seen in the examples, reagents R and Q can be added together or
separately in many different orders of addition.
[0012] The invention uses the catalytic composite as the catalyst
or a catalyst component in a process for the conversion of low
carbon number aliphatic hydrocarbons to higher carbon number
hydrocarbons. In one embodiment the catalyst composite may
additionally comprise a promoter metal selected from the group
consisting of iron, cobalt, vanadium, gallium, zinc, chromium,
manganese, molybdenum, tungsten and combinations thereof. The
process involves converting low carbon number aliphatic
hydrocarbons to higher carbon number hydrocarbons by contacting the
low carbon number aliphatic hydrocarbons with the catalyst
composite at conditions to give the higher carbon number
hydrocarbons. One suitable zeolite is UZM-39.
BRIEF DESCRIPTION OF THE DRAWINGS
[0013] FIG. 1 is an XRD pattern of the UZM-39 zeolite formed in
Example 1. This pattern shows the UZM-39 zeolite in the
as-synthesized form.
[0014] FIG. 2 is also an XRD pattern of the UZM-39 zeolite formed
in Example 1. This pattern shows the UZM-39 zeolite after
calcination.
[0015] FIG. 3 is an XRD pattern of the UZM-39 zeolite formed in
Example 16. This pattern shows the UZM-39 zeolite in the
as-synthesized form.
[0016] FIG. 4 is also an XRD pattern of the UZM-39 zeolite formed
in Example 16. This pattern shows the UZM-39 zeolite in the H.sup.+
form.
[0017] FIG. 5 is an XRD pattern of the UZM-39 zeolite formed in
Example 28. This pattern shows the UZM-39 zeolite in the
as-synthesized form.
[0018] FIG. 6 is also an XRD pattern of the UZM-39 zeolite formed
in Example 28. This pattern shows the UZM-39 zeolite in the H.sup.+
form.
[0019] FIG. 7 shows the results of high-resolution scanning
electron microscopy characterization of the UZM-39 product of
Example 1. The electron micrograph shows that UZM-39 forms in
lathes which assemble into rectangular rod particles, often with a
starburst cluster arrangement. The starburst cluster rods of UZM-39
can be seen in the scanning electron microscopy results of FIG.
7.
[0020] FIG. 8 shows the results of high-resolution scanning
electron microscopy characterization of a different UZM-39, that of
the product of Example 18. The electron micrograph also shows
lathes assembled into rectangular rod particles with a number of
starburst cluster arrangements.
[0021] FIG. 9 shows a wireframe representation of the TUN framework
in the AC plane (left). Each vertex is a T-site and in the middle
of each stick is an oxygen atom. A wireframe representation of the
IMF framework in the AB plane is shown to the right. Along these
projections, both the TUN and IMF frameworks contain nearly
identical projections of chains of 5-rings connected by 6-rings and
10-ring channels.
[0022] FIG. 10 shows the results of transmission electron
microscopy characterization of the UZM-39 product of Example 17
using high resolution imaging and computed optical diffractograms.
The results show that UZM-39 is comprised of a coherently grown
composite structure of TUN and IMF zeotypes.
[0023] FIG. 11 is an electron diffraction analysis of the cross
sectioned rod particle of FIG. 10 and shows that from what appears
to be a single-crystalline zeolite particle, areas that index to
[010] zone axis of TUN and to [001] zone axis of IMF are found. The
TUN regions and IMF regions are coherently aligned.
[0024] FIG. 12 is a plot of the low angle region in XRD analysis of
materials showing that small percentages of IMF can be determined
in samples largely consisting of TUN.
[0025] FIG. 13 is a plot of the low angle region in XRD analysis of
materials showing that small percentages of TUN can be determined
in samples largely consisting of IMF.
DETAILED DESCRIPTION OF THE INVENTION
[0026] A new catalytic composite has been developed where the
catalytic composite comprises a zeolite and a promoter metal M,
wherein the zeolite is characterized by a characteristic selected
from the group consisting of (a) the retention of greater than 40%
of the tetrahedral aluminum sites in the zeolite following
calcination of the catalyst in air at 750.degree. C. for 3 hours
when compared to the amount of tetrahedral aluminum in the same
catalyst after calcination in air at 500.degree. C. for 3 hours,
(b) the retention of greater than 15% of the Broensted acid sites
in the zeolite following calcination of the catalyst in air at
750.degree. C. for 3 hours when compared to the amount of Broensted
acid sites in the same catalyst prior to incorporation of the
promoter metal, and (c) wherein the promoter metal M is selected
from the group consisting of molybdenum, tungsten and combinations
thereof, the zeolite characterized by the formation of less than 15
mol % aluminum metalate, Al.sub.2(MO.sub.4).sub.3, after
calcination of the metal incorporated zeolite at 750.degree. C. for
3 hours in air. The new catalytic composite is useful for the
conversion of at least one low carbon number aliphatic hydrocarbon,
such as methane, to at least one aromatic compound, such as
benzene.
[0027] As one embodiment of the new catalytic composite, applicants
have prepared a catalytic component suitable for catalyzing the
conversion of low carbon number aliphatic hydrocarbons to generate
higher carbon number hydrocarbons where the catalytic component
comprises an aluminosilicate zeolite whose topological structure is
related to TUN as described in Atlas of Zeolite Framework Types,
which is maintained by the International Zeolite Association
Structure Commission at http://www.iza-structure.org/databases/,
the member of which has been designated TNU-9. As will be shown in
detail, UZM-39 is different from TNU-9 in a number of its
characteristics including its x-ray diffraction pattern (XRD).
UZM-39 is also related to IMF as described in the Atlas of Zeolite
Framework Types, the member of which has been designated IM-5. As
will be shown in detail, UZM-39 is different from TNU-9 and IM-5 in
a number of its characteristics including its x-ray diffraction
pattern. The instant microporous crystalline zeolite (UZM-39) has
an empirical composition in the as synthesized and anhydrous basis
expressed by an empirical formula of:
Na.sub.nM.sub.m.sup.k+T.sub.tAl.sub.1-xE.sub.xSi.sub.yO.sub.z
where "n" is the mole ratio of Na to (Al+E) and has a value from
approximately 0.05 to 0.5, M represents a metal or metals selected
from the group consisting of zinc, Group 1 (IUPAC 1), Group 2
(IUPAC 2), Group 3 (IUPAC 3), the lanthanide series of the periodic
table, and any combination thereof, "m" is the mole ratio of M to
(Al+E) and has a value from 0 to 0.5, "k" is the average charge of
the metal or metals M, T is the organic structure directing agent
or agents derived from reactants R and Q where R is an
A,.OMEGA.-dihalogen substituted alkane having between 3 and 6
carbon atoms and Q is at least one neutral monoamine having 6 or
fewer carbon atoms, "t" is the mole ratio of N from the organic
structure directing agent or agents to (Al+E) and has a value of
from 0.5 to 1.5, E is an element selected from the group consisting
of gallium, iron, boron and combinations thereof, "x" is the mole
fraction of E and has a value from 0 to about 1.0, "y" is the mole
ratio of Si to (Al+E) and varies from greater than 9 to about 25
and "z" is the mole ratio of 0 to (Al+E) and has a value determined
by the equation:
z=(n+km+3+4y)/2
Where M is only one metal, then the weighted average valence is the
valence of that one metal, i.e. +1 or +2. However, when more than
one M metal is present, the total amount of:
M.sub.m.sup.k+=M.sub.m1.sup.(k1)++M.sub.m2.sup.(k2)++M.sub.m3.sup.(k3)++-
M.sub.m4.sup.(k4)++ . . . .
and the weighted average valence "k" is given by the equation:
k = m 1 k 1 + m 2 k 2 + m 3 k 3 m 1 + m 2 + m 3 ##EQU00001##
[0028] In one embodiment, the microporous crystalline zeolite,
UZM-39, is synthesized by a hydrothermal crystallization of a
reaction mixture prepared by combining reactive sources of sodium,
organic structure directing agent or agents T, aluminum, silicon,
seeds of a layered material L, and optionally E, M, or both. The
sources of aluminum include but are not limited to aluminum
alkoxides, precipitated aluminas, aluminum metal, aluminum
hydroxide, sodium aluminate, aluminum salts and alumina sols.
Specific examples of aluminum alkoxides include, but are not
limited to aluminum sec-butoxide and aluminum ortho isopropoxide.
Sources of silica include but are not limited to
tetraethylorthosilicate, colloidal silica, precipitated silica and
alkali silicates. Sources of sodium include but are not limited to
sodium hydroxide, sodium aluminate, sodium bromide, and sodium
silicate.
[0029] T is the organic structure directing agent or agents derived
from reactants R and Q where R is an A,.OMEGA.2-dihalogen
substituted alkane having between 3 and 6 carbon atoms and Q
comprises at least one neutral monoamine having 6 or fewer carbon
atoms. R may be an A,.OMEGA.2-dihalogen substituted alkane having
between 3 and 6 carbon atoms selected from the group consisting of
1,3-dichloropropane, 1,4-dichlorobutane, 1,5-dichloropentane,
1,6-dichlorohexane, 1,3-dibromopropane, 1,4-dibromobutane,
1,5-dibromopentane, 1,6-dibromohexane, 1,3-diiodopropane,
1,4-diiodobutane, 1,5-diiodopentane, 1,6-diiodohexane and
combinations thereof. Q comprises at least one neutral monoamine
having 6 or fewer carbon atoms such as 1-ethylpyrrolidine,
1-methylpyrrolidine, 1-ethylazetidine, 1-methylazetidine,
triethylamine, diethylmethylamine, dimethylethylamine,
trimethylamine, dimethylbutylamine, dimethylpropylamine,
dimethylisopropylamine, methylethylpropylamine,
methylethylisopropylamine, dipropylamine, diisopropylamine,
cyclopentylamine, methylcyclopentylamine, hexamethyleneimine. Q may
comprise combinations of multiple neutral monoamines having 6 or
fewer carbon atoms.
[0030] L comprises at least one seed of a layered zeolite. Suitable
seed zeolites are layered materials that are microporous zeolites
with crystal thickness in at least one dimension of less than about
30 to about 50 nm. The microporous materials have pore diameters of
less than about 2 nm. The seed layered zeolite is of a different
zeotype than the UZM-39 coherently grown composite being
synthesized. Examples of suitable layered materials include but are
not limited to UZM-4M (U.S. Pat. No. 6,776,975), UZM-5 (U.S. Pat.
No. 6,613,302), UZM-8 (U.S. Pat. No. 6,756,030), UZM-8HS (U.S. Pat.
No. 7,713,513), UZM-26 (US-2010-0152023-A1), UZM-27 (U.S. Pat. No.
7,575,737), BPH, FAU/EMT materials, *BEA or zeolite Beta, members
of the MWW family such as MCM-22P and MCM-22, MCM-36, MCM-49,
MCM-56, ITQ-1, ITQ-2, ITQ-30, ERB-1, EMM-10P and EMM-10, SSZ-25,
and SSZ-70 as well as smaller microporous materials such as PREFER
(pre ferrierite), NU-6 and the like.
[0031] M represents at least one exchangeable cation of a metal or
metals from Group 1 (IUPAC 1), Group 2 (IUPAC 2), Group 3 (IUPAC
3), or the lanthanide series of the periodic table and or zinc.
Specific examples of M include but are not limited to lithium,
potassium, rubidium, cesium, magnesium, calcium, strontium, barium,
zinc, yttrium, lanthanum, gadolinium, and combinations thereof.
Reactive sources of M include, but are not limited to, the group
consisting of halide, nitrate, sulfate, hydroxide, or acetate
salts. E is an element selected from the group consisting of
gallium, iron, boron and combinations thereof, and suitable
reactive sources include, but are not limited to, boric acid,
gallium oxyhydroxide, gallium sulfate, gallium nitrate, ferric
sulfate, ferric nitrate, ferric chloride and combinations
thereof.
[0032] The reaction mixture containing reactive sources of the
desired components can be described in terms of molar ratios of the
oxides by the formula:
a-bNa.sub.2O:bM.sub.n/2O:cRO:dQ:1-eAl.sub.2O.sub.3:eE.sub.2O.sub.3:fSiO.-
sub.2:gH.sub.2O
where "a" has a value of about 10 to about 30, "b" has a value of 0
to about 30, "c" has a value of about 1 to about 10, "d" has a
value of about 2 to about 30, "e" has a value of 0 to about 1.0,
"f" has a value of about 30 to about 100, "g" has a value of about
100 to about 4000. Additionally in the reaction mixture is from
about 1 to about 10 wt.-% of seed zeolite L based on the amount of
SiO.sub.2 in the reaction, e.g., if there is 100 g of SiO.sub.2 in
the reaction mixture, from about 1 to about 10 g of seed zeolite L
would be added. The examples demonstrate a number of specific
orders of addition for the reaction mixture which lead to UZM-39.
However, as there are at least 6 starting materials, many orders of
addition are possible. For example, the seed crystals L can be
added as the last ingredient to the reaction mixture, to the
reactive Si source, or at other suitable points. Also, if alkoxides
are used, a distillation or evaporative step may be included to
remove the alcohol hydrolysis products. While the organic structure
directing agents R and Q can be added separately or together to the
reaction mixture at a number of points in the process, it is
preferred to mix R and Q together at room temperature and add the
combined mixture to a cooled mixture of reactive Si, Al and Na
sources maintained at 0-10.degree. C. Alternatively, the mixture of
R and Q, after mixing at room temperature, could be cooled and the
reactive sources of Si, Al and Na added to the organic structure
directing agent mixture while maintaining a temperature of
0-10.degree. C. In an alternative embodiment, the reagents R and Q
could be added, separately or together, to the reaction mixture at
room temperature.
[0033] The reaction mixture is then reacted at a temperature of
about 150.degree. C. to about 200.degree. C., about 155.degree. C.
to about 190.degree. C., or about 160.degree. C. to about
180.degree. C., for a period of about 1 day to about 3 weeks, and
in another embodiment for a time of about 3 days to about 12 days,
in a stirred, sealed reaction vessel under autogenous pressure.
After crystallization is complete, the solid product is isolated
from the heterogeneous mixture by means such as filtration or
centrifugation, and then washed with deionized water and dried in
air at ambient temperature up to about 100.degree. C.
[0034] The as-synthesized coherently grown composite of TUN and IMF
zeotypes, UZM-39, is characterized by the x-ray diffraction
pattern, having at least the d-spacings and relative intensities
set forth in Tables A1-A3 below. Diffraction patterns herein were
obtained using a typical laboratory powder diffractometer,
utilizing the K.sub..alpha. line of copper; Cu K alpha. From the
position of the diffraction peaks represented by the angle 2theta,
the characteristic interplanar distances d.sub.hkl of the sample
can be calculated using the Bragg equation. The intensity is
calculated on the basis of a relative intensity scale attributing a
value of 100 to the line representing the strongest peak on the
X-ray diffraction pattern, and then: very weak (vw) means less than
5; weak (w) means less than 15; medium (m) means in the range 15 to
50; strong (s) means in the range 50 to 80; very strong (vs) means
more than 80. Intensities may also be shown as inclusive ranges of
the above. The X-ray diffraction patterns from which the data (d
spacing and intensity) are obtained are characterized by a large
number of reflections some of which are broad peaks or peaks which
form shoulders on peaks of higher intensity. Some or all of the
shoulders may not be resolved. This may be the case for samples of
low crystallinity, of particular coherently grown composite
structures or for samples with crystals which are small enough to
cause significant broadening of the X-rays. This can also be the
case when the equipment or operating conditions used to produce the
diffraction pattern differ significantly from those used in the
present case.
[0035] The X-ray diffraction pattern for UZM-39 contains many
peaks. Examples of the x-ray diffraction patterns for various
as-synthesized UZM-39 products are shown in FIGS. 1, 3, and 5.
Those peaks characteristic of UZM-39 are shown in Tables A1-A3 for
various coherently grown composite structures. Additional peaks,
particularly those of very weak intensity, may also be present. All
peaks of medium or higher intensity present in the UZM-39 family of
coherently grown composite structures are represented in at least
Table A3.
[0036] Table A1 contains selected d-spacings and relative
intensities of the UZM-39 X-ray diffraction pattern. The relative
intensities are shown as a range covering UZM-39 materials with
varying relative amounts of TUN and IMF zeotypes.
TABLE-US-00001 TABLE A1 2.theta. d (.ANG.) I/Io % 7.17-7.21
12.25-12.31 vw-m 7.5-8.1* 11.78-10.91 w-m 8.88 9.95 m 9.17 9.63 w-m
12.47-12.62 7.09-7.00 w-m 17.7 5.01 vw-m 22.8-23.2 3.90-3.83 vs
23.39-23.49 3.80-3.78 m-s 25.01-25.31 3.56-3.52 m 28.74-29.25
3.10-3.05 w-m 45.08-45.29 2.01-2.00 w *composite peak consisting of
multiple overlapping reflections
[0037] The zeolite may be further characterized by the x-ray
diffraction pattern having at least the d-spacings and intensities
set forth in Table A2 where the d-spacings and intensities are
provided at different relative concentrations of the components of
the coherently grown composite structure.
TABLE-US-00002 TABLE A2 I II III high TUN, low IMF med TUN, med IMF
low TUN, high IMF 2-Theta d( ) I/Io % 2-Theta d( ) I/Io % 2-Theta
d( ) I/Io % 7.21 12.25 w-m 7.17 12.31 w-m 7.21 12.25 vw 7.5-8.1*
11.78-10.91 w-m 7.5-8.1* 11.78-10.91 w-m 7.5-8.1* 11.78-10.91 w-m
8.88 9.95 m 8.88 9.95 s 8.88 9.95 m 9.17 9.63 m 9.16 9.65 m 9.17**
9.63 w-m 9.34** 9.46 vw-w 9.30 9.50 m 9.33 9.47 m 12.62 7.00 w
12.50 7.08 w-m 12.47 7.09 w-m 17.70 5.01 vw-w 17.72 5.00 w-m 17.70
5.01 vw-w 19.20 4.62 w-m 22.8-23.2* 3.90-3.83 vs 18.71 4.74 w-m
22.89 3.88 vs 23.43 3.79 s 22.55 3.94 m 23.49 3.78 m 25.12 3.54 m
23.03 3.86 vs 25.31 3.52 m 28.74-29.25* 3.10-3.05 w-m 23.39 3.80 s
29.10 3.07 w 45.29 2.00 w 25.01 3.56 m 45.08 2.01 w 28.76 3.10 w-m
45.08 2.01 w *composite peak consisting of multiple overlapping
reflections **typically a shoulder
[0038] The zeolite may be yet further characterized by the x-ray
diffraction pattern having at least the d-spacings and intensities
set forth in Table A3 where the d-spacings and intensities are
provided at different relative concentrations of the components of
the coherently grown composite structure.
TABLE-US-00003 TABLE A3 I II III high TUN, low IMF med TUN, med IMF
low TUN, high IMF 2-Theta d( ) I/Io % 2-Theta d( ) I/Io % 2-Theta
d( ) I/Io % 7.21 12.25 w-m 7.17 12.31 w-m 7.21 12.22 vw 7.5-8.1*
11.78-10.91 w-m 7.5-8.1* 11.78-10.91 w-m 7.5-8.1* 11.78-10.91 w-m
8.88 9.95 m 8.88 9.95 m-s 8.88 9.95 m 9.17 9.63 m 9.16 9.65 m
9.17** 9.63 w-m 9.34** 9.46 vw-w 9.30 9.50 m 9.33 9.47 m 9.98 8.85
vw 12.50 7.08 w-m 12.47 7.09 w-m 11.68 7.57 vw 15.27 5.80 vw-w
12.85 6.88 vw 12.62 7.00 w 15.58 5.68 w 14.62 6.05 vw-w 13.69 6.46
vw-w 17.70 5.01 vw-w 15.27 5.80 w 15.33 5.77 vw-w 18.72 4.74 vw-m
15.57 5.68 w 16.48 5.37 vw-w 19.28 4.60 w 16.60 5.34 w 17.01 5.20
vw 22.61** 3.93 w-m 17.70 5.01 vw-w 17.70 5.01 vw-w 22.8-23.2*
3.90-3.83 vs 18.71 4.74 w-m 19.20 4.62 w-m 23.43 3.79 s 19.30 4.59
w 21.59 4.11 vw-w 24.20 3.68 m 22.55 3.94 m 22.61** 3.93 w-m 25.12
3.54 m 22.86** 3.89 m-s 22.89 3.88 vs 26.34 3.38 w-m 23.03 3.86 vs
23.49 3.78 m 26.75 3.33 w-m 23.39 3.80 s 23.93 3.72 vw-w
28.74-29.25* 3.10-3.05 w-m 24.17 3.68 m 24.13 3.68 m 35.72 2.51
vw-w 25.01 3.56 m 24.64 3.61 w 45.29 2.00 w 26.19 3.40 vw-w 24.93
3.57 w 45.62-47.19* 1.99-1.92 vw-w 26.68 3.34 w-m 25.31 3.52 m
28.76 3.10 w-m 26.62 3.35 w 35.72 2.51 vw-w 29.10 3.07 w 45.08 2.01
w 35.72 2.51 vw-w 45.62-47.19* 1.99-1.92 vw-w 45.08 2.01 w
45.62-47.19* 1.99-1.92 vw-w *composite peak consisting of multiple
overlapping reflections **Typically a shoulder
[0039] In Tables A2 and A3, the term "high" refers to about 60 to
about 95 mass-% of the specified component, the term "med" refers
to about 25 to about 70 mass-% of the specified component, and the
term "low" refers to about 5 to about 40 mass-% of the specified
component. Some peaks may be shoulders on more intense peaks, and
some peaks may be a composite peak consisting of multiple
overlapping reflections.
[0040] As will be shown in detail in the examples, the UZM-39
material is thermally stable up to a temperature of at least
600.degree. C. and in another embodiment, up to at least
800.degree. C. Also as shown in the examples, the UZM-39 material
may have a micropore volume as a percentage of total pore volume of
greater than 60%.
[0041] Characterization of the UZM-39 product by high-resolution
scanning electron microscopy shows that the UZM-39 forms in lathes
which assemble into rectangular rod particles, often with a
starburst cluster arrangement. The starburst cluster rods of UZM-39
can be seen in the scanning electron microscopy results for two
particular UZM-39 products in FIG. 7 and in FIG. 8.
[0042] UZM-39 is a coherently grown composite structure of TUN and
IMF zeotypes. By coherently grown composite structure is meant that
both structures are present in a major portion of the crystals in a
given sample. This coherently grown composite structure is possible
when the two zeotypic structures have nearly identical spacial
arrangements of atoms along at least a planar projection of their
crystal structure and possess similar pore topologies. FIG. 9 shows
a wireframe representation of the TUN framework in the AC plane
(left). Each vertex is a tetrahedral site (or T-site) and in the
middle of each stick is a corner-shared oxygen atom. A wireframe
representation of the IMF framework in the AB plane is shown on the
right of FIG. 9. Along these projections, both the TUN and IMF
zeotypes contain nearly identical projections of chains of 5-rings
connected by 6-rings and 10-rings which form channels running
perpendicular to the plane.
[0043] As both the TUN and IMF zeotypes are 3-dimensional 10-ring
zeolites and have nearly identical projections in one plane, the
two structures can thereby coherently grow off crystals of the
other structure with interfaces at the compatible planes to form a
coherently grown composite structure.
[0044] A coherently grown composite structure is not a physical
mixture of the two molecular sieves. Electron diffraction,
transmission electron microscopy and x-ray diffraction analysis are
employed to show that a material is a coherently grown composite
structure instead of a physical mixture. Usually the combination of
electron diffraction and TEM imaging is most definitive in
determining whether one has produced a coherently grown composite
structure because it provides direct evidence of the existence of
both structures within one crystal.
[0045] Since the coherently grown composite structure zeolites of
this invention can have varying amounts of the two structure types,
it is to be understood that the relative intensity and line width
of some of the diffraction lines will vary depending on the amount
of each structure present in the coherently grown composite
structure. Although the degree of variation in the x-ray powder
diffraction patterns is theoretically predictable for specific
structures, the more likely mode of a coherently grown composite
structure is random in nature and therefore difficult to predict
without the use of large hypothetical models as bases for
calculation.
[0046] Unlike a physical mixture of TNU-9 and IM-5, transmission
electron microscopy (TEM) analysis using high resolution imaging
and computed optical diffractograms shows that UZM-39 is comprised
of a coherently grown composite structure of TUN and IMF
zeotypes.
[0047] In FIG. 10, TEM analysis of a cross sectioned rod particle
from the product of Example 17 shows that areas with TUN and IMF
structure occur as coherent sub-regions within an effectively
single-crystalline zeolite particle. On the left side of FIG. 11,
electron diffraction analysis of the left side of the particle
shown in FIG. 10 shows an electron diffraction pattern which can be
indexed to the 002 plane of TUN. On the right side of FIG. 11, the
electron diffraction pattern from the right side of the particle
shown in FIG. 10 is shown. This pattern can be indexed to the 060
plane of IMF. The TUN regions and IMF regions are coherently
aligned such that the [010].sub.TUN zone axis and the [001].sub.IMF
zone axis are parallel to each other and there is continuity of
crystal planes of type (002).sub.TUN and (060).sub.IMF, where the
indexing is referred to monoclinic C.sub.2/m and orthorhombic
C.sub.mcm unit cells for TUN and IMF respectively (details of
structures found on IZA website). In spite of the presence of the
two zeotypes in different portions of the particle, the image does
not show any distinct boundary delineating separate crystals of TUN
and IMF, indicating that the particle is a coherently grown
composite.
[0048] Additionally, UZM-39 zeolite can be characterized by
Rietveld analysis of the XRD pattern. Rietveld analysis is a
least-squares approach developed by Rietveld (Journal of Applied
Crystallography 1969, 2: 65-71) to refine a theoretical line XRD
profile until it matches the measured XRD pattern as closely as
possible and is the preferred method of deriving structural
information from samples such as UZM-39 which contain strongly
overlapping reflections. It is often used to quantify the amounts
of two different phases in a XRD diffractogram. The accuracy of the
Rietveld method is determined by parameters such as crystallite
size (peak broadening), peak shape function, lattice unit cell
constants and background fits. For the samples shown in the
examples, applicants have determined the error in the reported
value to be .+-.5% under the conditions used. Applicants have also
determined that the Rietveld model used was unable to quantify the
amounts of minority composite structure phase components at values
less than 10%, but visually, amounts of the minority components can
be seen at levels greater than 5% by comparing against the model
patterns. Table 1 shows Rietveld refinement results on various
UZM-39 samples from the examples and shows that UZM-39 contains
greater than 0 and less than 100 wt. % IMF zeotype and less than
100 wt. % and greater than 0 wt. % TUN zeotype. In another
embodiment, UZM-39 contains greater than 5 and less than 95 wt. %
IMF zeotype and less than 95 wt. % and greater than 5 wt. % TUN
zeotype, and in yet another embodiment, UZM-39 contains greater
than 10 and less than 90 wt. % IMF zeotype and less than 90 wt. %
and greater than 10 wt. % TUN zeotype. As can be seen in Table 1
and examples, a wide range of coherently grown composite structures
are possible by modifying the synthesis conditions.
[0049] As synthesized, the UZM-39 material will contain some
exchangeable or charge balancing cations in its pores. These
exchangeable cations can be exchanged for other cations, or in the
case of organic cations, they can be removed by heating under
controlled conditions. It is also possible to remove some organic
cations from the UZM-39 zeolite directly by ion exchange. The
UZM-39 zeolite may be modified in many ways to tailor it for use in
a particular application. Modifications include calcination,
ion-exchange, steaming, various acid extractions, ammonium
hexafluorosilicate treatment, or any combination thereof, as
outlined for the case of UZM-4M in U.S. Pat. No. 6,776,975 B1 which
is incorporated by reference in its entirety. Conditions may be
more severe than shown in U.S. Pat. No. 6,776,975. Properties that
are modified include porosity, adsorption, Si/Al ratio, acidity,
thermal stability, and the like.
[0050] After calcination, ion-exchange and calcination and on an
anhydrous basis, the microporous crystalline zeolite UZM-39 has a
three-dimensional framework of at least AlO.sub.2 and SiO.sub.2
tetrahedral units and an empirical composition in the hydrogen form
expressed by an empirical formula of
M1.sub.a.sup.N+Al.sub.(1-x)E.sub.xSi.sub.y'O.sub.z''
where M1 is at least one exchangeable cation selected from the
group consisting of alkali, alkaline earth metals, rare earth
metals, ammonium ion, hydrogen ion and combinations thereof, "a" is
the mole ratio of M1 to (Al+E) and varies from about 0.05 to about
50, "N" is the weighted average valence of M1 and has a value of
about +1 to about +3, E is an element selected from the group
consisting of gallium, iron, boron, and combinations thereof, x is
the mole fraction of E and varies from 0 to 1.0, y' is the mole
ratio of Si to (Al+E) and varies from greater than about 9 to
virtually pure silica and z'' is the mole ratio of 0 to (Al+E) and
has a value determined by the equation:
z''=(aN+3+4y')/2
[0051] In the hydrogen form, after calcination, ion-exchange and
calcination to remove NH.sub.3, UZM-39 displays the XRD pattern
shown in Table B1-B3. Those peaks characteristic of UZM-39 are
shown in Tables B1-B3 for various coherently grown composite
structures. Additional peaks, particularly those of very weak
intensity, may also be present. All peaks of medium or higher
intensity present in the UZM-39 family of coherently grown
composite structures are represented in at least Tables B3.
[0052] Table B1 contains selected d-spacings and relative
intensities of the hydrogen form of UZM-39 X-ray diffraction
pattern. The relative intensities are shown as a range covering
UZM-39 materials with varying relative amounts of TUN and IMF
zeotypes.
TABLE-US-00004 TABLE B1 2.theta. d (.ANG.) I/Io % 7.11-7.16
12.42-12.25 vw-m 7.5-8.1* 11.78-10.91 m-s 8.84 10.00 m-s 9.06-9.08
9.75-9.73 w-m 9.24 9.56 vw-m 12.46-12.53 7.10-7.06 w-m 22.56 3.94
vw-m 22.75-23.2 3.90-3.83 vs 23.40 3.80 m-s 24.12-24.23 3.69-3.67
w-m 24.92-25.37 3.57-3.51 m 28.71-29.27 3.11-3.05 w-m 45.32-45.36
2.00 w *composite peak consisting of multiple overlapping
reflections
[0053] The zeolite may be further characterized by the x-ray
diffraction pattern having at least the d-spacings and intensities
set forth in Table B2 where the d-spacings and intensities are
provided at different relative concentrations of the components of
the coherently grown composite structure.
TABLE-US-00005 TABLE B2 A B C high TUN, low IMF med TUN, med IMF
low TUN, high IMF 2-Theta d( ) I/Io % 2-Theta d( ) I/Io % 2-Theta
d( ) I/Io % 7.12 12.40 w-m 7.11 12.42 w-m 7.16 12.25 vw-w 7.5-8.1*
11.78-10.91 m 7.5-8.1* 11.78-10.91 m-s 7.5-8.1* 11.78-10.91 m-s
8.84 10.00 m-s 8.84 10.00 m-s 8.84 10.00 m-s 9.06 9.75 m 9.08 9.73
m 9.06** 9.75 w 9.24** 9.56 vw-w 9.24 9.56 m 9.24 9.56 m 12.53 7.06
w 12.48 7.09 m 12.46 7.10 m 22.89 3.88 vs 22.56** 3.94 w-m 22.56
3.94 w-m 23.40 3.80 m 22.75-23.2* 3.90-3.83 vs 23.06 3.85 vs 24.23
3.67 w-m 23.40 3.80 s 23.40 3.80 s 25.22 3.53 m 24.17 3.68 m 24.12
3.69 m 29.08 3.07 w-m 24.92-25.37* 3.57-3.51 m 25.06 3.55 m 45.36
2.00 w 28.71-29.27* 3.11-3.05 w-m 28.82 3.10 w-m 45.34 2.00 w 45.32
2.00 w *composite peak consisting of multiple overlapping
reflections **Typically a shoulder
[0054] The zeolite may be yet further characterized by the x-ray
diffraction pattern having at least the d-spacings and intensities
set forth in Table B3 where the d-spacings and intensities are
provided at different relative concentrations of the components of
the coherently grown composite structure.
TABLE-US-00006 TABLE B3 I II III high TUN, low IMF med TUN, med IMF
low TUN, high IMF 2-Theta d( ) I/Io % 2-Theta d( ) I/Io % 2-Theta
d( ) I/Io % 7.12 12.40 w-m 7.11 12.42 w-m 7.16 12.25 vw-w 7.5-8.1*
11.78-10.91 m 7.5-8.1* 11.78-10.91 m-s 7.5-8.1* 11.78-10.91 m-s
8.84 10.00 m-s 8.84 10.00 m-s 8.84 10.00 m-s 9.06 9.75 m 9.08 9.73
m 9.06** 9.75 w 9.24** 9.56 vw-w 9.24 9.56 m 9.24 9.56 m 12.53 7.06
w 11.76 7.52 vw-w 11.76 7.52 vw-w 14.38 6.15 w 12.48 7.09 m 12.46
7.10 m 14.64 6.05 vw 14.38 6.15 vw-w 14.38 6.15 vw 15.26 5.80 vw-w
14.64 6.05 vw-w 14.64 6.05 w 15.52 5.70 vw 15.26 5.80 w 15.26 5.80
w 16.46 5.38 vw 15.52 5.70 w-m 15.52 5.70 w-m 17.72 5.00 w 16.50
5.37 vw-w 16.58 5.34 w 22.56** 3.94 vw-w 17.72 5.00 w-m 17.72 5.00
w-m 22.89 3.88 vs 18.64 4.76 vw-w 18.64 4.76 w 23.06** 3.85 w-m
22.56** 3.94 w-m 22.56 3.94 w-m 23.40 3.80 m 22.75-23.2* 3.90-3.83
vs 23.06 3.85 vs 23.82 3.73 w-m 23.40 3.80 s 23.40 3.80 s 24.23
3.67 w-m 24.17 3.68 m 24.12 3.69 m 24.70 3.60 w-m 24.70 3.60 w-m
25.06 3.55 m 25.22 3.53 m 24.92-25.37* 3.57-3.51 m 26.16 3.40 vw-w
26.51 3.36 w-m 26.32 3.38 w 26.74 3.33 w-m 29.08 3.07 w-m 26.76
3.33 w-m 28.82 3.10 w-m 35.86 2.50 vw-w 28.71-29.27* 3.11-3.05 w-m
30.12 2.96 w 45.36 2.00 w 30.13 2.96 vw-w 35.86 2.50 vw-w
45.66-47.37* 1.98-1.91 vw-w 35.86 2.50 vw-w 45.32 2.00 w 45.34 2.00
w 45.66-47.37* 1.98-1.91 vw-w 45.66-47.37* 1.98-1.91 vw-w
*composite peak consisting of multiple overlapping reflections
**Typically a shoulder
[0055] In Tables B2 and B3, the term "high" refers to about 60 to
about 95 mass-% of the specified component, the term "med" refers
to about 25 to about 70 mass-% of the specified component, and the
term "low" refers to about 5 to about 40 mass-% of the specified
component. Some peaks may be shoulders on more intense peaks, and
some peaks may be a composite peak consisting of multiple
overlapping reflections.
[0056] After acid treating, such as exposure to HNO.sub.3 or
H.sub.2SiF.sub.6, and on an anhydrous basis, the microporous
crystalline zeolite UZM-39 has a three-dimensional framework of at
least AlO.sub.2 and SiO.sub.2 tetrahedral units and an empirical
composition in the acid treated form expressed by an empirical
formula of
M1.sub.a.sup.N+Al.sub.(1-x)E.sub.xSi.sub.y'O.sub.z''
where M1 is at least one exchangeable cation selected from the
group consisting of alkali, alkaline earth metals, rare earth
metals, ammonium ion, hydrogen ion and combinations thereof, "a" is
the mole ratio of M1 to (Al+E) and varies from about 0.05 to about
50, "N" is the weighted average valence of M1 and has a value of
about +1 to about +3, E is an element selected from the group
consisting of gallium, iron, boron, and combinations thereof, x is
the mole fraction of E and varies from 0 to 1.0, y' is the mole
ratio of Si to (Al+E) and varies from greater than about 9 to
virtually pure silica and z'' is the mole ratio of 0 to (Al+E) and
has a value determined by the equation:
z''=(aN+3+4y')/2
[0057] Similar to the as-synthesized material, the modified UZM-39
materials are thermally stable up to a temperature of at least
600.degree. C. and in another embodiment, up to at least
800.degree. C. and may have a micropore volume as a percentage of
total pore volume of greater than 60%.
[0058] By virtually pure silica is meant that virtually all the
aluminum and/or the E metals have been removed from the framework.
It is well known that it is virtually impossible to remove all the
aluminum and/or E metal. Numerically, a zeolite is virtually pure
silica when y' has a value of at least 3,000, preferably 10,000 and
most preferably 20,000. Thus, ranges for y' are from 9 to 3,000;
from greater than 20 to about 3,000; from 9 to 10,000; from greater
than 20 to about 10,000; from 9 to 20,000; and from greater than 20
to about 20,000. In specifying the proportions of the zeolite
starting material or adsorption properties of the zeolite product
and the like herein, the "anhydrous state" of the zeolite will be
intended unless otherwise stated. The term "anhydrous state" is
employed herein to refer to a zeolite substantially devoid of both
physically adsorbed and chemically adsorbed water.
[0059] The UZM-39 zeolite is used as a catalyst or catalyst support
in various reactions. The catalyst composite comprising UZM-39
zeolite and modifications thereof can be used as a catalyst or
catalyst support in processes for the conversion of low carbon
number aliphatic hydrocarbons to generate higher carbon number
hydrocarbons. The catalytic composite may further comprise a
promoter selected from the group consisting of iron, cobalt,
vanadium, manganese, gallium, zinc, chromium, tungsten, molybdenum
and combinations thereof. The promoter metal can be dispersed on
the porous support by means well known in the art such as
impregnation, spray-drying, ion-exchange, vapor deposition, etc.
Impregnation of the support with the promoter metal can be carried
out using decomposable compounds of the promoter metals. By
"decomposable compound" is meant that upon heating the compound
decomposes to give the corresponding metal or metal oxides.
Examples of the compounds of iron, cobalt, vanadium, manganese, or
molybdenum tungsten which can be used include the halides,
nitrates, sulfates, phosphates, carbonates, acetates and oxalates.
Other examples of molybdenum compounds which can be used include
molybdates such as ammonium hexamolybdate, 12-phosphomolybdic acid,
12-silicomolybdic acid and 12-phosphomolybdic vanadic acid,
MoS.sub.3, Mo(CO).sub.6,
[Mo.sub.3(CH.sub.3C)(O)(CH.sub.3COO).sub.9]X (X=Cl, Br and I) and
(Mo.sub.2(CH.sub.3COO).sub.6 and combinations thereof. Any soluable
tungsten containing compound may be used. A particular tungsten
compound which can be used is ammonium metatungstate. It should be
pointed out that both deposition and ion-exchange of the metals can
occur. Therefore, in the present context, impregnation will
encompass ion-exchange as well as conventional impregnation. The
impregnation is carried out with a solution containing at least one
metal compound followed by calcination at a temperature of about
50.degree. C. to about 800.degree. C. for a time of about 5 minutes
to about 10 hr. Next, the calcined catalyst may be activated by
treating the catalyst with a hydrogen/ and/or methane treatment gas
at a temperature of about 100.degree. C. to about 800.degree. C.
for a time of about 5 minutes to about 10 hr. The amount of
promoter metal which is dispersed in the final catalyst can vary
considerably, but usually the promoter metal varies from about
0.001 wt. % to about 25 wt. % of the catalytic composite.
[0060] The UZM-39 catalyst composite may further comprise a
refractory inorganic-oxide binder. The UZM-39 may be mixed with a
binder for convenient formation of catalyst particles in a
proportion of about 5 to 100 mass % UZM-39 zeolite and 0 to 95 mass
% binder, with the UZM-39 zeolite typically comprising from about
10 to 90 mass % of the composite. In one embodiment, the binder is
porous, has a surface area of about 5 to about 800 m.sup.2/g, and
is relatively refractory to the conditions utilized in the
hydrocarbon conversion process. Non-limiting examples of binders
are silica, aluminas, titania, zirconia, zinc oxide, magnesia,
boria, thoria, chromia, stannicoxide, as well as combinations and
composites thereof, for example, silica-alumina, silica-magnesia,
silica-zirconia, chromia-alumina, alumina-boria, alumina-titainia,
aluminophosphates, silica-zirconia, silica gel, and clays. In one
embodiment the binder is one or more of amorphous silica and
alumina, including gamma-, eta-, and theta-alumina. In another
embodiment the binder is gamma- and or eta-alumina. Alumina may be
employed as the refractory inorganic oxide for use herein, and the
alumina may be any of the various hydrous aluminum oxides or
alumina gels such as alpha-alumina monohydrate of the boehmite
structure, alpha-alumina trihydrate of the gibbsite structure,
beta-alumina trihydrate of the bayerite structure, and the
like.
[0061] The binder and zeolite may be combined in any conventional
or otherwise convenient manner to form spheres, pills, pellets,
granules, extrudates, or other suitable particle shape. For
example, finely divided zeolite and metal salt particles can be
dispersed in an alumina sol, and the mixture in turn dispersed as
droplets in a hot oil bath whereby gelation occurs with the
formation of spheroidal gel particles. The method is described in
greater detail in U.S. Pat. No. 2,620,314. One method comprises
commingling a finely divided form of the selected zeolite,
refractory inorganic oxide and a metal salt with a binder and/or
lubricant and compressing the mixture into pills or pellets of
uniform size and shape. Alternatively, and still more preferably,
the zeolite, refractory inorganic oxide and metal salt are combined
and admixed with a peptizing agent in a mix-muller, a dilute nitric
acid being one example of the suitable peptizing agent. The
resulting dough can be pressured through a die or orifice of
predetermined size to form extrudate particles which can be dried
and calcined and utilized as such. A multitude of different
extrudate shapes are possible, including, but not limited to,
cylinders, cloverleaf, dumbbell and symmetrical and asymmetrical
polylobates, with a trilobe form being favored. The extrudates also
may be formed into spheres by means of a spinning disc or drum and
then dried and calcined.
[0062] In one embodiment the shapes are extrudates and or spheres.
Extrudates are prepared by conventional means which involves mixing
of the composition either before or after adding metallic
components, with the binder and a suitable peptizing agent to form
a homogeneous dough or thick paste having the correct moisture
content to allow for the formation of extrudates with acceptable
integrity to withstand direct calcination. The dough then is
extruded through a die to give the shaped extrudate. A multitude of
different extrudate shapes are possible, including, but not limited
to, cylinders, cloverleaf, dumbbell and symmetrical and
asymmetrical polylobates. It is also within the scope of this
invention that the extrudates may be further shaped to any desired
form, such as spheres, by any means known to the art.
[0063] Spheres can be prepared by the well known oil-drop method
which is described in U.S. Pat. No. 2,620,314 which is incorporated
by reference. The method involves dropping a mixture of zeolite,
and for example, alumina sol, and gelling agent into an oil bath
maintained at elevated temperatures. The droplets of the mixture
remain in the oil bath until they set and form hydrogel spheres.
The spheres are then continuously withdrawn from the oil bath and
typically subjected to specific aging treatments in oil and an
ammoniacal solution to further improve their physical
characteristics. The resulting aged and gelled particles are then
washed and dried at a relatively low temperature of about 50 to
about 200.degree. C. and subjected to a calcination procedure at a
temperature of about 450 to about 700.degree. C. for a period of
about 1 to about 20 hours. This treatment effects conversion of the
hydrogel to the corresponding alumina matrix.
[0064] The catalyst of the invention optionally may comprise an
additional zeolitic component, The additional zeolite component
preferably is selected from one or more of MFI, MEL, EUO, FER, MFS,
MOR, MTT, MTW, MWW, MAZ, TON, TUN, IMF, SVR, SZR, and FAU (Atlas
Structure Commission of International Zeolite Association) and
UZM-8 (see WO 2005/113439). Suitable total zeolite amounts in the
catalyst range from about 1 to about 100 wt-%, preferably from
about 10 to about 95 wt-%, and more preferably between about 60 and
about 90 wt-%.
[0065] The catalytic composite is employed in a process for
converting low carbon number aliphatic hydrocarbons to higher
carbon number hydrocarbons. More specifically, the process is a
dehydroaromatization process in which low carbon number aliphatic
compounds such as methane are converted to aromatic compounds such
as benzene and naphthalene plus ethylene. Since dehydrogenation is
part of the reaction, hydrogen is produced during the process. By
low carbon number aliphatic hydrocarbons is meant any aliphatic
hydrocarbon having from 1 to about 4 carbon atoms. The feedstream
which can be used in the process of the invention can be any
feedstream which contains at least 5 mass-% of an aliphatic
hydrocarbon having from 1 to about 4 carbon atoms. In another
embodiment the feedstream contains at least 20 mass-% of an
aliphatic hydrocarbon having from 1 to about 4 carbon atoms. In
another embodiment, the feedstream contains at least 50 mass-% of
aliphatic hydrocarbons having from 1 to about 4 carbon atoms. In
one embodiment the low carbon number aliphatic hydrocarbon is
methane. In one embodiment, in addition to at least 5 mass-%
methane, the feedstream may also contain C.sub.2-C.sub.4 saturated
hydrocarbons such as ethane, propane, n-butane, isobutane, etc. In
one embodiment. In one embodiment, in addition to at least 5 mass-%
methane, the feedstream may also contain C.sub.2-C.sub.4
unsaturated hydrocarbons such as ethylene, acetylene, propylene,
butene, isobutene, etc. The feed stream may further comprise
diluents such as hydrogen, nitrogen, or argon. The feed stream may
comprise from greater than zero to 100 wt % methane. The feed
stream may comprise from about 50 wt % to 100 wt % methane. The
feed stream may comprise from about 80 wt % to about 90 wt %
methane. The feed stream may comprise from about 80 wt % to greater
than 99 wt % methane.
[0066] The feedstream is contacted with the catalyst comprising
UZM-39 at conversion conditions either in a batch mode or a
continuous flow mode. In the continuous flow mode, the catalyst can
be present as a fixed bed, moving bed, or fluidized bed. The
process is carried out by contacting the feedstream in the absence
of oxygen at a temperature of about 300.degree. C. to about
1000.degree. C. and in another embodiment, from about 450.degree.
C. to about 900.degree. C., a pressure of about 10 kPa to about
1000 kPa and in another embodiment from about 100 to about 1000 kPa
and a gas hourly space velocity in the range of about 100 to about
200,000 hr.sup.-1. The reaction zone may further contain CO,
CO.sub.2 or mixtures thereof, in order to improve catalyst
performance. The CO, CO.sub.2 or mixtures thereof to aliphatic
hydrocarbon mole ratio varies from about 0.001 to about 0.5 and in
another embodiment from about 0.01 to about 0.3.
[0067] A particular benefit of the invention is the stability of
the catalyst comprising UZM-39 at temperatures above about
550.degree. C., above, 600.degree. C., above 650.degree. C., above
700.degree. C. or above 750.degree. C. in an oxygen-containing
environment. The effluent from the reaction zone can be separated
by conventional means and the unreacted feedstream components
recycled to the reaction zone.
[0068] During regeneration operations at high temperatures, such as
greater than 500.degree. C., in an oxygen containing atmosphere
designed to burn coke, the promoter metal, such as molybdenum, may
interact with the zeolites which results in deactivation of the
zeolite. One technique possible to minimize deactivation of the
zeolite during regeneration is performing the regeneration at low
temperatures, such as less than 500.degree. C. However,
operationally is it difficult and costly to operate a commercial
process with temperature swing between the process of
dehydroaromatization, which may require temperatures greater than
700.degree. C., and catalyst regeneration if it is performed at
less than 500.degree. C. A benefit of the process herein is
improved stability of the catalyst, which allows for regeneration
of the catalyst either at the same temperature as
dehydroaromatization, or with a minimal temperature swing such as
less than 50.degree. C. By providing a more temperature tolerant
catalyst, the process solves the problem of zeolite deactivation
during regeneration while at the same time provides the benefit of
desirable and less costly operations with regeneration temperatures
that are closer to the conversion temperatures.
[0069] Catalysts suitable for the conversion of at least one low
carbon number hydrocarbon in a feedstream to provide at least one
aromatic hydrocarbon may comprise a zeolite which is temperature
tolerant. Following incorporation of the promoter metal, such as
molybdenum or tungsten, temperature tolerant zeolites may be those
characterized by the retention, as evidenced by quantitative solid
state .sup.27Al NMR, of greater than 40% of the tetrahedral
aluminum sites in the zeolite following calcination of the catalyst
in air at 750.degree. C. for 3 hours when compared to the amount of
tetrahedral aluminum in the same catalyst after calcination in air
at 500.degree. C. for 3 hours. A zeolite may by characterized by 81
mol % tetrahedral aluminum by .sup.27Al solid state NMR after
incorporation of a promoter metal such as molybdenum and
calcination of the resulting catalyst at 500.degree. C. for 3 hours
in air. The same promoter incorporated zeolite may instead by
calcined at 750.degree. C. for 3 hours in air and be characterized
by 61 mol % tetrahedral aluminum. This zeolite thus demonstrates
75.3% retention of the tetrahedral aluminum sites in the zeolite.
In an embodiment, the retention of tetrahedral aluminum sites in
the zeolite may be greater than 50% or greater than 65% or greater
than 70% or greater than 75% or greater than 80% following
calcination of the catalyst in air at 750.degree. C. for 3 hours
when compared to the amount of tetrahedral aluminum in the same
catalyst after calcination in air at 500.degree. C. for 3 hours.
The retention of tetrahedral aluminum sites in the zeolite may be
greater than 25% following calcination of the catalyst in air at
750.degree. C. for 3 hours when compared to the amount of
tetrahedral aluminum in the zeolite prior to incorporation of the
promoter metal. In an embodiment, the retention of tetrahedral
aluminum sites in the zeolite may be greater than 35% or greater
than 50% or greater than 65% or greater than 70% or greater than
80% following calcination of the catalyst in air at 750.degree. C.
for 3 hours when compared to the amount of tetrahedral aluminum in
the zeolite prior to incorporation of the promoter metal. The
zeolite may be characterized by formation of less than 3.0 mol % or
less than 2.0 mol % or less than 1.0 mol % aluminum metalate
Al.sub.2(MO.sub.4).sub.3, after calcination of the metal
incorporated zeolite at 500.degree. C. for 3 hours in air, where M
is Mo or W, as evidenced by quantitative solid state .sup.27Al NMR.
The zeolite may be characterized by the formation of essentially no
aluminum metalate, i.e., an undetectable quantity of aluminum
metalate. The zeolite may be characterized by formation of less
than 15 mol % or less than 10 mol % or less than 5 mol % or less
than 1 mol % aluminum metalate Al.sub.2(MO.sub.4).sub.3, after
calcination of the metal incorporated zeolite at 750.degree. C. for
3 hours in air, where M is Mo or W, as evidenced by quantitative
solid state .sup.27Al NMR. The zeolite may be characterized by the
formation of essentially no aluminum metalate, i.e., an
undetectable quantity of aluminum metalate. Following incorporation
of the promoter metal, such as molybdenum or tungsten, suitable
zeolites may be those characterized by the retention, as evidenced
by pyridine IR, of greater than 15% of the Broensted acid sites in
the zeolite following calcination of the catalyst in air at
750.degree. C. for 3 hours when compared to the amount of Broensted
acid sites in the same catalyst after calcination in air at
500.degree. C. for 3 hours. The retention of Broensted acid sites
in the zeolite may be greater than 15% following calcination of the
catalyst in air at 750.degree. C. for 3 hours when compared to the
amount of Broensted acid sites in the same catalyst prior to
incorporation of the promoter metal. In an embodiment, the
retention of Broensted acid sites may be greater than 25% or
greater than 30% or greater than 35% or greater than 40%. Pyridine
IR is generally carried out via the methods described by Parry in
J. Catal. 1963, 2, 371-9 using a 150.degree. C. desorption
temperature and integrating the peak at 1540 cm.sup.-1 to quantify
the Broensted acidity. In an embodiment, the zeolite may be
characterized by any combination of or all of the characteristics
set forth in the preceding paragraph.
[0070] The following examples are presented in illustration of this
invention and are not intended as undue limitations on the
generally broad scope of the invention as set out in the appended
claims. The structure of the UZM-39 zeolite of this invention was
determined by x-ray analysis. The x-ray patterns presented in the
following examples were obtained using standard x-ray powder
diffraction techniques. The radiation source was a high-intensity,
x-ray tube operated at 45 kV and 35 ma. The diffraction pattern
from the copper K-alpha radiation was obtained by appropriate
computer based techniques. Flat compressed powder samples were
continuously scanned at 2.degree. to 56.degree. (2.theta.).
Interplanar spacings (d) in Angstrom units were obtained from the
position of the diffraction peaks expressed as .theta. where
.theta. is the Bragg angle as observed from digitized data.
Intensities were determined from the integrated area of diffraction
peaks after subtracting background, "I.sub.o" being the intensity
of the strongest line or peak, and "I" being the intensity of each
of the other peaks.
[0071] As will be understood by those skilled in the art the
determination of the parameter 2.theta. is subject to both human
and mechanical error, which in combination can impose an
uncertainty of about .+-.0.4.degree. on each reported value of
2.theta.. This uncertainty is, of course, also manifested in the
reported values of the d-spacings, which are calculated from the
2.theta. values. This imprecision is general throughout the art and
is not sufficient to preclude the differentiation of the present
crystalline materials from each other and from the compositions of
the prior art. In some of the x-ray patterns reported, the relative
intensities of the d-spacings are indicated by the notations vs, s,
m, and w which represent very strong, strong, medium, and weak,
respectively. In terms of 100.times.I/I.sub.o, the above
designations are defined as: [0072] vw=<5; w=6-15; m=16-50:
s=51-80; and vs=80-100
[0073] In certain instances the purity of a synthesized product may
be assessed with reference to its x-ray powder diffraction pattern.
Thus, for example, if a sample is stated to be pure, it is intended
only that the x-ray pattern of the sample is free of lines
attributable to crystalline impurities, not that there are no
amorphous materials present.
[0074] In order to more fully illustrate the invention, the
following examples are set forth. It is to be understood that the
examples are only by way of illustration and are not intended as an
undue limitation on the broad scope of the invention as set forth
in the appended claims.
Example 1
[0075] A sample of UZM-39 was prepared as follows. 6.02 g of NaOH,
(97%) was dissolved in 125.49 g water. 0.62 g Al(OH).sub.3, (29.32
wt.-% Al) was added to the NaOH solution to form a first solution.
Separately, 0.24 g of the layered material UZM-8 was stirred into
30.0 g Ludox AS-40 to form a second solution. The second solution
was added to the first solution. The mixture was cooled to
0.degree. C.-4.degree. C. Separately, 6.54 g 1,4-dibromobutane, (99
wt.-%) was mixed with 7.65 g 1-methylpyrrolidine, (97 wt.-%) to
form a third solution. The third solution was added to the cooled
mixture of the first and second solutions to form the final
reaction mixture. The final reaction mixture was transferred to a
300 cc stirred autoclave and digested at 160.degree. C. for 144
hours with stirring at 100 rpm. The product was isolated by
filtration. The product was identified as UZM-39 by XRD as shown in
FIG. 1. Analytical results show this material has the following
molar rations: Si/Al of 12.64, Na/Al of 0.116, N/Al of 0.92, C/N of
7.23.
[0076] Scanning Electron Microscopy (SEM) revealed crystals of
intergrown, square rod morphology in starbursts, approximately 250
to 700 nm along a face of the square with an aspect ratio of from
2:1 to 5:1. The micrograph is shown in FIG. 7. The product was
calcined at 550.degree. C. for 3 hrs under air. The XRD pattern of
the calcined material is shown in FIG. 2.
Comparative Example 2
[0077] The preparation of Example 1 was followed, except that the
layered material UZM-8 was not added to the second solution. After
144 hours of stirring at 100 rpm at 160.degree. C., the product was
isolated by filtration. The product was identified as analcime by
XRD.
Comparative Example 3
[0078] 6.68 g of NaOH, (97%) was dissolved in 145.44 g water. 2.86
g Al(NO.sub.3).sub.3.9H.sub.2O (97%) was added to the sodium
hydroxide solution. 13.33 g Aerosil 200 was stirred into the
mixture. 13.1 g H.sub.2O was added. 7.26 g 1,4-dibromobutane, (99%)
and 5.84 g 1-methylpyrrolidine, (97%) were added and the mixture
was stirred vigorously for a day. The mixture was divided equally
and loaded into eight 45 cc Parr vessels and placed into a
rotisserie oven at 160.degree.. The mixture in one of the Parr
vessels produced a material at 256 hours identified by XRD as
having the TUN structure. Analytical results showed this material
to have the following molar ratios, Si/Al of 15.51, Na/Al of 0.12,
N/Al of 1.29, and C/N of 6.89. SEM analysis revealed a squat rod
cluster morphology, about 300-800 nm in length and with an aspect
ratio of about 1.
[0079] The product generated by this synthesis was calcined under
flowing air at 600.degree. for 6 hours. It was then ion exchanged
four times with 1 M ammonium nitrate solution at 75.degree.
followed by a calcination at 500.degree. under air for 2 hours to
convert NH.sub.4.sup.+ into H.sup.+. Analysis for the calcined,
ion-exchanged sample showed 39.2 wt. % Si, 2.34 wt. % Al, <0.005
wt. % Na with a BET surface area of 378 m.sup.2/g, pore volume of
0.220 cm.sup.3/g, and micropore volume of 0.190 cm.sup.3/g.
[0080] Analysis of the H+-form of this material by Rietveld XRD
refinement showed that the material consisted entirely of TUN
structure type. TEM analysis confirmed that no coherent growth of
IMF crystals occurred.
Example 4
[0081] 6.40 g of NaOH, (97%) was dissolved in 111.88 g water. 1.16
g Al(OH).sub.3, (29.32 wt.-% Al), was added to the sodium hydroxide
solution to create a first solution. Separately, 0.30 g of the
layered material (UZM-8) was stirred into 37.5 g Ludox AS-40 to
form a second solution. The second solution was added to the first
solution and vigorously stirred for 1-2 hours. The mixture was
cooled to 0.degree. C.-4.degree. C. Separately, 8.18 g
1,4-dibromobutane, (99 wt.-%) was mixed with 9.56 g
1-methylpyrrolidine, (97 wt.-%) to form a third solution. The third
solution was added to the cooled mixture to create the final
reaction mixture. The final reaction mixture was vigorously stirred
and transferred to a 300 cc stirred autoclave. The final reaction
mixture was digested at 160.degree. C. for 144 hours with stirring
at 100 rpm. The product was isolated by filtration. The product was
identified as UZM-39 by XRD. Analytical results showed this
material to have the following molar ratios, Si/Al of 12.07, Na/Al
of 0.124, N/Al of 0.90, C/N of 6.85.
Example 5
[0082] 7.19 g of NaOH, (99 wt.-%%) was dissolved in 90.1 g water.
1.56 g Al(OH).sub.3, (29.32 wt.-% Al), was added to the sodium
hydroxide solution to create a first solution. Separately, 0.405 g
of the layered material (UZM-8) was stirred into 50.62 g Ludox
AS-40 to form a second solution. The second solution was added to
the first solution and vigorously stirred for 1-2 hours. The
mixture was cooled to 0.degree. C.-4.degree. C. Separately, 11.04 g
1,4-dibromobutane, (99 wt.-%), was mixed with 12.90 g
1-methylpyrrolidine, (97 wt.-%) to form a third solution. The third
solution was added to the cooled mixture to create the final
reaction mixture. The final reaction mixture was vigorously stirred
for 5 minutes and transferred to a 300 cc stirred autoclave. The
final reaction mixture was digested at 160.degree. C. for 144 hours
with stirring at 100 rpm. 16.5 g of the product was isolated by
filtration. The product was identified by XRD to be UZM-39 with a
very slight MOR impurity. Analytical results showed this material
to have the following molar ratios, Si/Al of 14.14, Na/Al of 0.16,
N/Al of 1.02, C/N of 7.33.
Example 6
[0083] 37.62 g of NaOH, (97 wt.-%) was dissolved in 600 g water to
create a sodium hydroxide solution. 6.96 g Al(OH).sub.3 (29.32 mass
% Al) was added to the sodium hydroxide solution to create a first
solution. Separately, 1.80 g of the layered material (UZM-8) was
stirred into 225 g Ludox AS-40 to form a second solution. The
second solution was added to the first solution and vigorously
stirred for 1-2 hours. The mixture was cooled to 0.degree.
C.-4.degree. C. Separately, 49.08 g 1,4-dibromobutane (99 wt.-%)
was mixed with 57.36 g 1-methylpyrrolidine (97 wt.-%) for 1-5
minutes to form a third solution. The third solution was added to
the cooled mixture to create the final reaction mixture. The final
reaction mixture was vigorously stirred for 5 minutes and
transferred to a 2 liter stirred autoclave. The final reaction
mixture was digested at 160.degree. C. for 144 hours with stirring
at 250 rpm. The product was isolated by filtration. The product was
identified by XRD as UZM-39. Analytical results showed this
material to have the following molar ratios, Si/Al of 11.62, Na/Al
of 0.12, N/Al of 0.88, C/N of 7.36.
[0084] The product generated by this synthesis was calcined under
flowing air at 600.degree. for 6 hours. It was then ion exchanged
four times with 1 M ammonium nitrate solution at 75.degree.followed
by a calcination at 500.degree. C. under air for 2 hours to convert
NH.sub.4.sup.+ into H.sup.+. Analysis of the H.sup.+ form of this
material by Rietveld XRD refinement gave the results shown in Table
1.
Example 7
[0085] 505.68 g of NaOH, (99 wt.-%) was dissolved in 10542 g water.
52.08 g Al(OH).sub.3, (29.3 wt.-% Al), was added to the sodium
hydroxide solution to create a first solution. Separately, 20.16 g
of the layered material (UZM-8) was stirred into 2520 g Ludox AS-40
to form a second solution. The second solution was added to the
first solution and vigorously stirred for 1-2 hours. The mixture
was cooled to 0.degree. C.-4.degree. C. Separately, 549.36 g
1,4-dibromobutane (99 wt.-%) was mixed with 642.6 g
1-methylpyrrolidine, (97 wt.-%), for 3-5 minutes to form a third
solution. The third solution was added to the cooled mixture to
create the final reaction mixture. The final reaction mixture was
vigorously stirred for 5 minutes and pumped into a 5 gallon stirred
autoclave. The final reaction mixture was digested at 160.degree.
C. for 150 hours with stirring at 100 rpm. The product was isolated
by filtration. The product was identified by XRD as UZM-39.
Analytical results showed this material to have the following molar
ratios, Si/Al=13.35, Na/Al=0.087, N/Al=0.96, C/N=7.12.
Example 8
[0086] The preparation of Example 4 was followed except that UZM-8
was replaced with 0.30 g UZM-26. The product was identified by XRD
as UZM-39. Analytical results showed this material to have the
following molar ratios: Si/Al=12.88, Na/Al=0.25, N/Al=0.88,
C/N=7.31.
Example 9
[0087] 6.27 g of NaOH, (99%), was dissolved in 111.88 g water to
create a sodium hydroxide solution. 1.16 g Al(OH).sub.3 (29.32 mass
% Al) was added to the sodium hydroxide solution to create a first
solution. 37.5 g Ludox AS-40 and then 0.22 g of the layered
material UZM-5 were added to the first solution. The first solution
was vigorously stirred for 1-2 hours. The first solution was cooled
to 0.degree. C.-4.degree. C. Separately, 8.18 g 1,4-dibromobutane
(99%) was mixed with 9.56 g 1-methylpyrrolidine (97%) for 1-5
minutes to form a second solution. The second solution was added to
the cooled first solution to create the final reaction mixture. The
final reaction mixture was vigorously stirred for approximately 5
minutes and transferred to a 300 cc stirred autoclave. The final
reaction mixture was digested at 160.degree. C. for 144 hours with
stirring at 100 rpm. The product was isolated by filtration. The
product was identified by XRD as UZM-39 with a very small EUO or
NES contaminant.
Comparative Example 10
[0088] This example is identical to example 4 except that UZM-8 was
replaced with 0.30 g UZM-39. The product was identified as a
composition comprising MTW, UZM-39, ANA and MOR.
Example 11
[0089] 6.27 g of NaOH, (97 wt.-%) was dissolved in 111.88 g water.
1.16 g Al(OH).sub.3, (29.32 wt. % Al), was added to the sodium
hydroxide solution to create a first solution. Separately, 0.30 g
of the layered material (UZM-8) was stirred into 37.5 g Ludox AS-40
to form a second solution. The second solution was added to the
first solution and vigorously stirred for 1-2 hours. The mixture
was cooled to 0.degree. C.-4.degree. C. Separately, 12.27 g
1,4-dibromobutane (99 wt.-%) was mixed with 14.34 g
1-methylpyrrolidine (97 wt.-%) to form a third solution. The third
solution was added to the cooled mixture to create the final
reaction mixture. The final reaction mixture was vigorously stirred
and transferred to a 300 cc stirred autoclave. The final reaction
mixture was digested at 160.degree. C. for 144 hours with stirring
at 100 rpm. The product was isolated by filtration. The product was
identified as UZM-39 with an ESV impurity by XRD. Analytical
results showed this material to have the following molar ratios,
Si/Al=13.17, Na/Al=0.126, N/Al=1.03, C/N=7.22.
Example 12
[0090] The procedure of Example 4 was followed except 9.56 g
1-methylpyrrolidine, (97 wt.-%), was replaced with 8.05 g
dimethylethylamine, (97 wt.-%). The product was identified as a
composition comprising mordenite and UZM-39.
Example 13
[0091] 6.27 g of NaOH (99 wt.-%) was dissolved in 111.88 g water.
1.16 g Al(OH).sub.3 (29.32 wt.-% Al) was added to the sodium
hydroxide solution to create a first solution. 0.30 g of the
layered material UZM-8 and 37.5 g Ludox AS-40 were added to the
first solution. The first solution was vigorously stirred for 1-2
hours. The first solution was cooled to 0.degree. C.-4.degree. C.
Separately, 4.02 g dimethylethylamine (97 wt.-%) was mixed with
4.78 g 1-methylpyrrolidine (97 wt.-%) for 1-2 minutes to form an
amine solution. 8.18 g 1,4-dibromobutane (99 wt.-%) was added to
the amine solution and then mixed for 1-2 minutes to form a second
solution. The second solution was added to the cooled first
solution to create the final reaction mixture. The final reaction
mixture was vigorously stirred for approximately 5 minutes and
transferred to a 300 cc stirred autoclave. The final reaction
mixture was digested at 160.degree. C. for 192 hours with stirring
at 100 rpm. The product was isolated by filtration. The product was
identified as UZM-39 by XRD. Analytical results showed this
material to have the following molar ratios, Si/Al=12.42,
Na/Al=0.175, N/Al=0.91, C/N=6.92.
[0092] The product generated by this synthesis was calcined under
flowing air at 600.degree. for 6 hours. It was then ion exchanged
four times with 1 M ammonium nitrate solution at 75.degree.
followed by a calcination at 500.degree. C. under air for 2 hours
to convert NH.sub.4.sup.+ into H.sup.+. Analysis for the calcined,
ion-exchanged sample shows 38.7% Si, 2.97% Al, 0.0089% Na with a
BET surface area of 375 m.sup.2/g, pore volume of 0.238 cm.sup.3/g,
and micropore volume of 0.184 cm.sup.3/g. Analysis of the H.sup.+
form of this material by Rietveld XRD refinement gave the results
shown in Table 1.
Example 14
[0093] 6.21 g of NaOH, (99%), was dissolved in 111.88 g water to
create a sodium hydroxide solution. 1.16 g Al(OH).sub.3 (29.32
wt.-% Al) was added to the sodium hydroxide solution to create a
first solution. 0.30 g of the layered material (UZM-8) and 37.5 g
Ludox AS-40 were added to the first solution. The first solution
was vigorously stirred for 1-2 hours. The first solution was cooled
to 0.degree. C.-4.degree. C. Separately, 8.18 g 1,4-dibromobutane
(99 wt.-%) was mixed with 9.56 g 1-methylpyrrolidine (97 wt.-%) for
1-5 minutes to form a second solution. The second solution was
added to the cooled first solution to create the final reaction
mixture. The final reaction mixture was vigorously stirred for
approximately 5 minutes and transferred to a 300 cc stirred
autoclave. The final reaction mixture was digested at 170.degree.
C. for 96 hours with stirring at 100 rpm. The product was isolated
by filtration. The product was identified as UZM-39 by XRD.
Analytical results showed this material to have the following molar
ratios, Si/Al of 12.76, Na/Al of 0.116, N/Al of 0.94, C/N of
6.98.
Example 15
[0094] 6.21 g of NaOH, (99%), was dissolved in 111.88 g water to
create a sodium hydroxide solution. 1.16 g Al(OH).sub.3 (29.32
wt.-% Al) was added to the sodium hydroxide solution to create a
first solution. 0.30 g of the layered material (UZM-8) and 37.5 g
Ludox AS-40 were added to the first solution. The first solution
was vigorously stirred for 1-2 hours. The first solution was cooled
to 0.degree. C.-4.degree. C. Separately, 8.18 g 1,4-dibromobutane
(99 wt.-%) was mixed with 9.56 g 1-methylpyrrolidine (97 wt.-%) for
1-5 minutes to form a second solution. The second solution was
added to the cooled first solution to create the final reaction
mixture. The final reaction mixture was vigorously stirred for
approximately 5 minutes and transferred to a 300 cc stirred
autoclave. The final reaction mixture was digested at 175.degree.
C. for 44 hours with stirring at 100 rpm. The product was isolated
by filtration. The product was identified as UZM-39 by XRD.
Analytical results showed this material to have the following molar
ratios, Si/Al of 12.97, Na/Al of 0.20, N/Al of 0.95, C/N of
6.98.
Example 16
[0095] 5.96 g of NaOH, (97%) and 0.25 g KOH, (86%) were dissolved
in 111.88 g water. 1.22 g Al(OH).sub.3, (27.9 wt.-% Al), was added
to the sodium hydroxide solution. 37.5 g Ludox AS-40 and then 0.30
g of the layered material UZM-8 were added to the first solution
and stirred vigorously for 1-2 hours. The mixture was cooled to
0.degree. C.-4.degree. C. Separately, 8.18 g 1,4-dibromobutane,
(99%) was mixed with 9.56 g 1-methylpyrrolidine, (97%) to form a
third mixture. The third mixture was added to the cooled mixture to
create the final reaction mixture. The final reaction mixture was
vigorously stirred and transferred to a 300 cc stirred autoclave.
The final reaction mixture was digested at 160.degree. C. for 144
hours with stirring at 100 rpm. The product was isolated by
filtration. The product was identified as UZM-39 by XRD. The x-ray
diffraction pattern is shown in FIG. 3. Analytical results showed
this material to have the following molar ratios, Si/Al of 11.69,
Na/Al of 0.137, K/Al of 0.024, N/Al of 0.848, C/N of 7.16.
[0096] The product generated by this synthesis was calcined under
flowing air at 600.degree. for 6 hours. It was then ion exchanged
four times with 1 M ammonium nitrate solution at 75.degree.
followed by a calcination at 500.degree. C. under air for 2 hours
to convert NH.sub.4.sup.+ into H.sup.+. Analysis for the calcined,
ion-exchanged sample shows 39.4% Si, 3.23% Al, 0.011% Na, 0.005% K
with a BET surface area of 362 m.sup.2/g, pore volume of 0.231
cm.sup.3/g, and micropore volume of 0.176 cm.sup.3/g. The x-ray
diffraction pattern in shown in FIG. 4.
Example 17
[0097] 5.96 g of NaOH, (99%) and 0.50 g KOH, (86%) were dissolved
in 111.88 g water. 1.16 g Al(OH).sub.3, (29.32 wt.-% Al), was added
to the sodium hydroxide solution. 37.5 g Ludox AS-40 and then 0.30
g of the layered material UZM-8 were added to the first solution
and stirred vigorously for 1-2 hours. The mixture was cooled to
0.degree. C.-4.degree. C. Separately, 4.09 g 1,4-dibromobutane,
(99%) was mixed with 11.15 g 1-methylpyrrolidine, (97%) to form a
third mixture. The third mixture was added to the cooled mixture to
create the final reaction mixture. The final reaction mixture was
vigorously stirred and transferred to a 300 cc stirred autoclave.
The final reaction mixture was digested at 160.degree. C. for 144
hours with stirring at 100 rpm. The product was isolated by
filtration. The product was identified as UZM-39 by XRD. Analytical
results showed this material to have the following molar ratios,
Si/Al of 11.98, Na/Al of 0.114, K/Al of 0.0375 N/Al of 0.84, C/N of
7.50.
[0098] The product generated by this synthesis was calcined under
flowing air at 600.degree. for 6 hours. It was then ion exchanged
four times with 1 M ammonium nitrate solution at 75.degree.
followed by a calcination at 500.degree. C. under air for 2 hours
to convert NH.sub.4.sup.+ into H.sup.+. Analysis for the calcined,
ion-exchanged sample shows 37.7% Si, 3.01% Al, 0.012% Na, 0.006% K.
Analysis of the H.sup.+ form of this material by Rietveld XRD
refinement gave the results shown in Table 1. TEM analysis showed
that UZM-39 is a coherently grown composite structure of TUN and
IMF zeotypes, the results of which analysis are shown in FIGS. 10
and 11.
Example 18
[0099] 5.64 g of NaOH, (97%) and 1.00 g KOH, (86%) were dissolved
in 111.88 g water. 1.22 g Al(OH).sub.3, (27.9 wt.-% Al), was added
to the sodium hydroxide solution. 37.5 g Ludox AS-40 and then 0.30
g of the layered material UZM-8 were added to the first solution
and stirred vigorously for 1-2 hours. The mixture was cooled to
0.degree. C.-4.degree. C. Separately, 8.18 g 1,4-dibromobutane,
(99%) was mixed with 9.56 g 1-methylpyrrolidine, (97%) to form a
third mixture. The third mixture was added to the cooled mixture to
create the final reaction mixture. The final reaction mixture was
vigorously stirred and transferred to a 300 cc stirred autoclave.
The final reaction mixture was digested at 160.degree. C. for 144
hours with stirring at 100 rpm. The product was isolated by
filtration. The product was identified as UZM-39 by XRD. Analytical
results showed this material to have the following molar ratios,
Si/Al of 11.29, Na/Al of 0.078, K/Al of 0.053 N/Al of 0.88, C/N of
6.92. The SEM image of the product is shown in FIG. 8.
[0100] The product generated by this synthesis was calcined under
flowing air at 600.degree. for 6 hours. It was then ion exchanged
four times with 1 M ammonium nitrate solution at 75.degree.
followed by a calcination at 500.degree. C. under air for 2 hours
to convert NH.sub.4.sup.+ into H.sup.+. Analysis for the calcined,
ion-exchanged sample shows 42.6% Si, 3.65% Al, 0.0018% Na, 0.02% K
with a BET surface area of 351 m.sup.2/g, pore volume of 0.218
cm.sup.3/g, and micropore volume of 0.170 cm.sup.3/g. Analysis of
the H.sup.+ form of this material by Rietveld XRD refinement gave
the results shown in Table 1.
Example 19
[0101] 5.02 g of NaOH, (97%) and 2.00 g KOH, (86%) were dissolved
in 111.88 g water. 1.22 g Al(OH).sub.3, (27.9 wt.-% Al), was added
to the sodium hydroxide solution. 37.5 g Ludox AS-40 and then 0.30
g of the layered material UZM-8 were added to the first solution
and stirred vigorously for 1-2 hours. The mixture was cooled to
0.degree. C.-4.degree. C. Separately, 8.18 g 1,4-dibromobutane,
(99%) was mixed with 9.56 g 1-methylpyrrolidine, (97%) to form a
third mixture. The third mixture was added to the cooled mixture to
create the final reaction mixture. The final reaction mixture was
vigorously stirred and transferred to a 300 cc stirred autoclave.
The final reaction mixture was digested at 160.degree. C. for 136
hours with stirring at 100 rpm. The product was isolated by
filtration. The product was identified as UZM-39 by XRD with a
likely small amount of NES contaminant Analytical results showed
this material to have the following molar ratios, Si/Al of 10.99,
Na/Al of 0.088, K/Al of 0.11 N/Al of 0.84, C/N of 7.36.
Example 20
[0102] 5.96 g of NaOH, (99%) was dissolved in 111.88 g water. 1.22
g Al(OH).sub.3, (27.9 wt.-% Al), was added to the sodium hydroxide
solution. Then 0.24 g Mg(OH).sub.2 (95%), 37.5 g Ludox AS-40, and
0.30 g of the layered material UZM-8 were added in the order listed
to the first solution and stirred vigorously for 1-2 hours. The
mixture was cooled to 0.degree. C.-4.degree. C. Separately, 8.18 g
1,4-dibromobutane, (99%) was mixed with 9.56 g 1-methylpyrrolidine,
(97%) and added to the cooled mixture to create the final reaction
mixture. The final reaction mixture was vigorously stirred and
transferred to a 300 cc stirred autoclave. The final reaction
mixture was digested at 160.degree. C. for 144 hours with stirring
at 100 rpm. The product was isolated by filtration. The product was
identified as UZM-39 by XRD. Analytical results showed this
material to have the following molar ratios, Si/Al of 12.12, Na/Al
of 0.148, Mg/Al of 0.38 N/Al of 0.91, C/N of 6.96.
[0103] The product generated by this synthesis was calcined under
flowing air at 600.degree. for 6 hours. It was then ion exchanged
four times with 1 M ammonium nitrate solution at 75.degree.
followed by a calcination at 500.degree. C. under air for 2 hours
to convert NH.sub.4.sup.+ into H.sup.+. Analysis for the calcined,
ion-exchanged sample shows 39.6% Si, 2.99% Al, 83 ppm Na, 0.14% Mg
with a BET surface area of 351 m.sup.2/g, pore volume of 0.218
cm.sup.3/g, and micropore volume of 0.170 cm.sup.3/g.
Example 21
[0104] 5.96 g of NaOH, (99%) and 0.51 g La(OH).sub.3, (99.9%) were
dissolved in 111.88 g water. 1.16 g Al(OH).sub.3, (29.32 wt.-% Al),
was added to the sodium hydroxide solution. 37.5 g Ludox AS-40 and
then 0.30 g of the layered material UZM-8 were added to the first
solution and stirred vigorously for 1-2 hours. The mixture was
cooled to 0.degree. C.-4.degree. C. Separately, 8.18 g
1,4-dibromobutane, (99%) was mixed with 9.56 g 1-methylpyrrolidine,
(97%) and added to the cooled mixture to create the final reaction
mixture. The final reaction mixture was vigorously stirred and
transferred to a 300 cc stirred autoclave. The final reaction
mixture was digested at 160.degree. C. for 168 hours with stirring
at 100 rpm. The product was isolated by filtration. The product was
identified as UZM-39 by XRD. Analytical results showed this
material to have the following molar ratios, Si/Al of 12.22, Na/Al
of 0.20, La/Al of 0.18, N/Al of 0.89, C/N of 7.13.
[0105] The product generated by this synthesis was calcined under
flowing air at 600.degree. for 6 hours. It was then ion exchanged
four times with 1 M ammonium nitrate solution at 75.degree.
followed by a calcination at 500.degree. C. under air for 2 hours
to convert NH.sub.4.sup.+ into H.sup.+. Analysis for the calcined,
ion-exchanged sample shows 39.1% Si, 3.06% Al, 60 ppm Na, 0.25% La
with a BET surface area of 335 m.sup.2/g, pore volume of 0.226
cm.sup.3/g, and micropore volume of 0.163 cm.sup.3/g.
Example 22
[0106] 3.14 g of NaOH, (97%) was dissolved in 106.41 g water. 1.16
g Al(OH).sub.3, (29.32 wt.-% Al), was added to the sodium hydroxide
solution. 37.5 g Ludox AS-40 and then 0.30 g of the layered
material UZM-8 were added to the first solution. Next 26.7 g Na
silicate solution (13.2 wt. % Si; 6.76 wt. % Na) is added to the
above and stirred vigorously for 1-2 hours. The mixture was cooled
to 0.degree. C.-4.degree. C. Separately, 8.18 g 1,4-dibromobutane,
(99%) was mixed with 9.56 g 1-methylpyrrolidine, (97%) to form a
third mixture. The third mixture was added to the cooled mixture to
create the final reaction mixture. The final reaction mixture was
vigorously stirred and transferred to a 300 cc stirred autoclave.
The final reaction mixture was digested at 160.degree. C. for 224
hours with stirring at 100 rpm. The product was isolated by
filtration. The product was identified as UZM-39 by XRD. Analytical
results showed this material to have the following molar ratios,
Si/Al of 11.75, Na/Al of 0.11, N/Al of 0.90, C/N of 6.99.
[0107] The product generated by this synthesis was calcined under
flowing air at 600.degree. for 6 hours. It was then ion exchanged
three times with 1 M ammonium nitrate solution at 75.degree.
followed by a calcination at 500.degree. C. under air for 2 hours
to convert NH.sub.4.sup.+ into H.sup.+. Analysis for the calcined,
ion-exchanged sample shows 38.8% Si, 3.05% Al, 0.011% Na, with a
BET surface area of 364 m.sup.2/g, pore volume of 0.273 cm.sup.3/g,
and micropore volume of 0.174 cm.sup.3/g. Analysis of the H.sup.+
form of this material by Rietveld XRD refinement gave the results
shown in Table 1.
Example 23
[0108] 5.33 g of NaOH, (99%) was dissolved in 111.88 g water. 1.16
g Al(OH).sub.3, (29.32 wt.-% Al), was added to the sodium hydroxide
solution. Separately, 0.30 g of Beta zeolite was stirred into 37.5
g Ludox AS-40 to make a second mixture. This second mixture was
added to the first solution and stirred vigorously for 1-2 hours.
The mixture was cooled to 0.degree. C.-4.degree. C. Separately,
8.89 g 1,5-dibromopentane, (97%) was mixed with 9.56 g
1-methylpyrrolidine, (97%) to form a third mixture. The third
mixture was added to the cooled mixture to create the final
reaction mixture. The final reaction mixture was vigorously stirred
and transferred to a 300 cc stirred autoclave. The final reaction
mixture was digested at 160.degree. C. for 256 hours with stirring
at 100 rpm. The product was isolated by filtration. The product was
identified as UZM-39 by XRD. Analytical results showed this
material to have the following molar ratios, Si/Al of 13.24, Na/Al
of 0.13, N/Al of 0.91, C/N of 7.21.
[0109] The product generated by this synthesis was calcined under
flowing air at 600.degree. for 6 hours. It was then ion exchanged
three times with 1 M ammonium nitrate solution at 75.degree.
followed by a calcination at 500.degree. C. under air for 2 hours
to convert NH.sub.4.sup.+ into H.sup.+. Analysis of the H.sup.+
form of this material by Rietveld XRD refinement gave the results
shown in Table 1.
Comparative Example 24
[0110] 10.8 g of Aerosil 200 was added, while stirring, to a
solution of 12.24 g 1,5-bis(N-methylpyrrolidinium)pentane dibromide
in 114 g H.sub.2O. A very thick gel was formed. Separately, a
solution was made from 60 g H.sub.2O, 3.69 g NaOH (99%), 0.95 g
sodium aluminate (26.1% Al by analysis), and 1.86 g NaBr (99%).
This second solution was added to the above mixture which thins out
a bit. The final mixture was divided equally between 7 45 cc Parr
vessels. One vessel, which was digested for 12 days at 170.degree.
C. in a rotisserie oven at 15 rpm, yielded a product which was
determined by XRD as having the IMF structure. The product was
isolated by filtration. The product generated by this synthesis was
calcined under flowing air at 600.degree. for 6 hours. It was then
ion exchanged four times with 1 M ammonium nitrate solution at
75.degree. followed by a calcination at 500.degree. under air for 2
hours to convert NH.sub.4.sup.+ into H.sup.+. Analysis of the
H+-form of this material by Rietveld XRD refinement showed that the
material consisted entirely of IMF structure type. TEM analysis
confirmed that no coherent growth of TUN crystals occurred.
Example 25
[0111] 31.98 g of NaOH, (99%) was dissolved in 671.3 g water. 6.96
g Al(OH).sub.3, (29.32 wt.-% Al), was added to the sodium hydroxide
solution. Separately, 1.80 g of the layered material UZM-8 was
stirred into 225.0 g Ludox AS-40 to make a second mixture. This
second mixture was added to the first solution and stirred
vigorously for 1-2 hours. The mixture was cooled to 0.degree.
C.-4.degree. C. Separately, 53.34 g 1,5-dibromopentane, (97%) was
mixed with 57.36 g 1-methylpyrrolidine, (97%) to form a third
mixture. The third mixture was added to the cooled mixture to
create the final reaction mixture. The final reaction mixture was
vigorously stirred and transferred to a 2 L stirred autoclave. The
final reaction mixture was digested at 160.degree. C. for 256 hours
with stirring at 250 rpm. The product was isolated by filtration.
The product was identified as UZM-39 by XRD. Analytical results
showed this material to have the following molar ratios, Si/Al of
12.30, Na/Al of 0.13, N/Al of 0.92, C/N of 7.51.
[0112] The product generated by this synthesis was calcined under
flowing air at 600.degree. for 6 hours. It was then ion exchanged
three times with 1 M ammonium nitrate solution at 75.degree.
followed by a calcination at 500.degree. under air for 2 hours to
convert NH.sub.4.sup.+ into H.sup.+. Analysis for the calcined,
ion-exchanged sample shows 39.0% Si, 2.93% Al, 0.008% Na. Analysis
of the H+-form of this material by Rietveld XRD refinement gave the
results shown in Table 1.
Example 26
[0113] 5.76 g of NaOH, (97%) was dissolved in 111.88 g water. 1.22
g Al(OH).sub.3, (27.9 wt.-% Al), was added to the sodium hydroxide
solution. When this became a solution, 37.5 g Ludox AS-40 was
added. Next 0.30 g of the layered material UZM-8 was added. The
mixture was stirred vigorously for 1-2 hours. The mixture was
cooled to 0.degree. C.-4.degree. C. Separately, 0.89 g
1,5-dibromopentane, (97%) was mixed with 7.36 g 1,4-dibromobutane,
(99%), then 9.56 g 1-methylpyrrolidine, (97%) was added to form a
second mixture. The second mixture was added to the cooled mixture
to create the final reaction mixture. The final reaction mixture
was vigorously stirred and transferred to a 300 cc stirred
autoclave. The final reaction mixture was digested at 160.degree.
C. for 176 hours with stirring at 100 rpm. The product was isolated
by filtration. The product was identified as UZM-39 by XRD.
Analytical results showed this material to have the following molar
ratios, Si/Al of 12.15, Na/Al of 0.15, N/Al of 0.90, C/N of
7.59.
[0114] The product generated by this synthesis was calcined under
flowing air at 600.degree. C. for 6 hours. It was then ion
exchanged four times with 1 M ammonium nitrate solution at
75.degree. C. followed by a calcination at 500.degree. C. under air
for 2 hours to convert NH.sub.4.sup.+ into H.sup.+. Analysis for
the calcined, ion-exchanged sample shows 38.6% Si, 2.85% Al,
<0.01% Na. Analysis of the H.sup.+ form of this material by
Rietveld XRD refinement gave the results shown in Table 1.
Example 27
[0115] 5.76 g of NaOH, (97%) was dissolved in 111.88 g water. 1.22
g Al(OH).sub.3, (27.9 wt.-% Al), was added to the sodium hydroxide
solution. When this became a solution, 37.5 g Ludox AS-40 was
added. Next, 0.30 g of the layered material UZM-8 was added and the
mixture was stirred vigorously for 1-2 hours. The mixture was
cooled to 0.degree. C.-4.degree. C. Separately, 1.78 g
1,5-dibromopentane, (97%) was mixed with 6.54 g 1,4-dibromobutane,
(99%), then 9.56 g 1-methylpyrrolidine, (97%) was added to form a
second mixture. The second mixture was added to the cooled mixture
to create the final reaction mixture. The final reaction mixture
was vigorously stirred and transferred to a 300 cc stirred
autoclave. The final reaction mixture was digested at 160.degree.
C. for 176 hours with stirring at 100 rpm. The product was isolated
by filtration. The product was identified as UZM-39 by XRD.
Analytical results showed this material to have the following molar
ratios, Si/Al of 12.24, Na/Al of 0.107, N/Al of 0.93, C/N of
6.91.
[0116] The product generated by this synthesis was calcined under
flowing air at 600.degree. for 6 hours. It was then ion exchanged
four times with 1 M ammonium nitrate solution at 75.degree. C.
followed by a calcination at 500.degree. C. under air for 2 hours
to convert NH.sub.4.sup.+ into H.sup.+. Analysis for the calcined,
ion-exchanged sample shows 38.7% Si, 2.98% Al, 158 ppm Na with a
BET surface area of 333 m.sup.2/g, pore volume of 0.201 cm.sup.3/g,
and micropore volume of 0.164 cm.sup.3/g. Analysis of the H.sup.+
form of this material by Rietveld XRD refinement gave the results
shown in Table 1.
Example 28
[0117] 5.76 g of NaOH, (97%) was dissolved in 111.88 g water. 1.22
g Al(OH).sub.3, (27.9 wt.-% Al), was added to the sodium hydroxide
solution. When this became a solution, 37.5 g Ludox AS-40 was
added. Next, 0.30 g of the layered material UZM-8 was added and the
mixture was stirred vigorously for 1-2 hours. The mixture was
cooled to 0.degree. C.-4.degree. C. Separately, 2.67 g
1,5-dibromopentane, (97%) was mixed with 5.73 g 1,4-dibromobutane,
(99%), then 9.56 g 1-methylpyrrolidine, (97%) was added to form a
second mixture. The second mixture was added to the cooled mixture
to create the final reaction mixture. The final reaction mixture
was vigorously stirred and transferred to a 300 cc stirred
autoclave. The final reaction mixture was digested at 160.degree.
C. for 176 hours with stirring at 100 rpm. The product was isolated
by filtration. The product was identified as UZM-39 by XRD. The
x-ray diffraction pattern is shown in FIG. 5. Analytical results
showed this material to have the following molar ratios, Si/Al of
12.15, Na/Al of 0.108, N/Al of 0.86, C/N of 7.68.
[0118] The product generated by this synthesis was calcined under
flowing air at 600.degree. C. for 6 hours. It was then ion
exchanged four times with 1 M ammonium nitrate solution at
75.degree. C. followed by a calcination at 500.degree. under air
for 2 hours to convert NH.sub.4.sup.+ into H.sup.+. Analysis for
the calcined, ion-exchanged sample shows 38.7% Si, 2.98% Al, 79 ppm
Na. The x-ray diffraction pattern is shown in FIG. 6. Analysis of
the H.sup.+ form of this material by Rietveld XRD refinement gave
the results shown in Table 1.
Example 29
[0119] 5.80 g of NaOH, (97%) was dissolved in 111.88 g water. 1.16
g Al(OH).sub.3, (29.32 wt.-% Al), was added to the sodium hydroxide
solution. When this became a solution, 37.5 g Ludox AS-40 was
added. Next, 0.30 g of the layered material UZM-8 was added and the
mixture was stirred vigorously for 1-2 hours. The mixture was
cooled to 0.degree. C.-4.degree. C. Separately, 4.45 g
1,5-dibromopentane, (97%) was mixed with 4.09 g 1,4-dibromobutane,
(99%), then 9.56 g 1-methylpyrrolidine, (97%) was added to form a
second mixture. The second mixture was added to the cooled mixture
to create the final reaction mixture. The final reaction mixture
was vigorously stirred and transferred to a 300 cc stirred
autoclave. The final reaction mixture was digested at 160.degree.
C. for 224 hours with stirring at 100 rpm. The product was isolated
by filtration. The product was identified as UZM-39 by XRD.
Analytical results showed this material to have the following molar
ratios, Si/Al of 11.75, Na/Al of 0.13, N/Al of 0.86, C/N of
7.59.
[0120] The product generated by this synthesis was calcined under
flowing air at 600.degree. for 6 hours. It was then ion exchanged
four times with 1 M ammonium nitrate solution at 75.degree. C.
followed by a calcination at 500.degree. C. under air for 2 hours
to convert NH.sub.4.sup.+ into H.sup.+. Analysis for the calcined,
ion-exchanged sample shows 40.1% Si, 3.32% Al, 90 ppm Na with a BET
surface area of 305 m.sup.2/g, pore volume of 0.224 cm.sup.3/g, and
micropore volume of 0.146 cm.sup.3/g. Analysis of the H.sup.+ form
of this material by Rietveld XRD refinement gave the results shown
in Table 1.
TABLE-US-00007 TABLE 1 Example # % TUN % IMF 3 100 0 6 95 5 13 83
17 17 46 54 18 36.5 63.5 23 24 76 24 0 100 25 19 81 26 58 42 27 30
70 28 13 87 29 8 92
Example 30
[0121] To determine the quantities of TUN or IMF structure able to
be detected in a UZM-39 coherently grown composite structure
material, a detection limit study was performed. A series of
simulated diffraction patterns were electronically created from the
observed diffraction patterns of the H.sup.+ forms of Example 3 and
Example 24 products using JADE XRD analysis software (available
from Materials Data Incorporated). Mixture levels ranged from 1% to
99% TUN and were created by scaling the smaller percentage
constituent to the required level, adding the patterns and saving
the composite pattern.
[0122] Rietveld analysis was able to quantify the level of IMF in
the UZM-39 coherently grown composite structure at the 10% or
greater level, however visually, small percentages of IMF can be
determined in samples (FIG. 12) largely consisting of TUN at the 5%
or greater level from intensity of peak at d-spacing of .about.9.46
A, while at higher levels, other peaks can be followed such as the
increase in peak at d-spacing of .about.11.4 A amongst others. In
FIG. 12, spectrum 1 is 1% IMF, 99% TUN; spectrum 2 is -3% IMF, 97%
TUN; spectrum 3 is -5% IMF, 95% TUN; and spectrum 4 is -10% IMF,
90% TUN.
[0123] Rietveld analysis was able to quantify the level of TUN in
the UZM-39 coherently grown composite structure at the 10% or
greater level, however FIG. 13 shows that, visually, small
percentages of TUN can be seen in samples largely consisting of IMF
at the 5% or greater level from intensity of peak at d-spacing
.about.12.25 A, while at higher levels, other peaks can be followed
such as the increase in peak at d-spacing of .about.9.63 A amongst
others. In FIG. 13, spectrum 1 is -1% TUN, 99% IMF; spectrum 2 is
-3% TUN, 97% IMF; spectrum 3 is -5% TUN, 95% IMF; and spectrum 4 is
-10% TUN, 90% IMF.
Example 31
[0124] 44.9 g of NaOH, (97%) was dissolved in 1122.3 g water. To
this solution was added 10.8 g liquid sodium aluminate (22.9%
Al.sub.2O.sub.3, 20.2% Na.sub.2O) followed by 105.9 g Ultrasil VN3
(90% SiO.sub.2, available from Evonik) to form a first mixture.
Separately, 53.5 g 1,4-dibromobutane, (99%), was combined with 62.6
g 1-methylpyrrolidine, (97%) to form a second mixture. The second
mixture was added to the first mixture to create the final reaction
mixture. Last, 1 g of the layered material UZM-8 was added and the
mixture was stirred vigorously for 1-2 hours before transferring to
a 2 L stirred autoclave. The final reaction mixture was digested at
160.degree. C. for 7 days while stirring at 200 rpm. The product
was isolated by filtration and identified as UZM-39 by XRD.
Analytical results showed this material to have the following molar
ratios, Si/Al of 12.40, Na/Al of 0.21, N/Al of 1.10, C/N of
7.06.
Example 32
[0125] NaOH, Al(OH).sub.3, Ga(NO3)3.9H.sub.2O, Ludox AS-40,
1,4-dibromobutane, 1-methylpyrrolidine, water and layered material
UZM-8 were combined to form a mixture of composition
0.5Al.sub.2O.sub.3:0.5Ga.sub.2O.sub.3:65.4SiO.sub.2:24.6Na.sub.2O:9.9C.su-
b.4Br.sub.2:29.4 1-MP:2636H.sub.2O and stirred vigorously for 1-2
hours before transferring to a 2 L stirred autoclave. The final
reaction mixture was digested at 160.degree. C. for 150 hours while
stirring at 250 rpm. The product was isolated by filtration and
identified as UZM-39 by XRD. Analytical results showed this
material to have the following molar ratios, Si/Al of 21.61, Si/Ga
of 31.35, Si/(Al+Ga) of 12.79, Na/(Al+Ga) of 0.10, N/(Al+Ga) of
0.91, C/N of 7.39.
Example 33
[0126] A UZM-39 containing a high quantity of TUN and low quantity
of IMF in the H+ form was loaded into a vertical steamer. The
UZM-39 was exposed to 100% steam at 725.degree. C. for 12 hours or
24 hours. The starting UZM-39 had a BET surface area of 385
m.sup.2/g, pore volume of 0.248 cm.sup.3/g, and micropore volume of
0.180 cm.sup.3/g. After 12 hours of steaming, the UZM-39 was still
identified as UZM-39 by XRD though the intensity of the first 5
peaks had increased to strong, strong, very strong, strong and
medium respectively. All other peaks were at positions and
intensities described in Table B. The material had a BET surface
area of 331 m.sup.2/g, pore volume of 0.243 cm.sup.3/g, and
micropore volume of 0.151 cm.sup.3/g. After 24 hours of steaming,
the UZM-39 was still identified as UZM-39 by XRD though the
intensity of the first 5 peaks had increased to medium-strong,
strong, strong, medium-strong and medium respectively. All other
peaks were at positions and intensities described in Table B. The
material had a BET surface area of 327 m.sup.2/g, pore volume of
0.241 cm.sup.3/g, and micropore volume of 0.150 cm.sup.3/g.
Example 34
[0127] A UZM-39 containing a high quantity of TUN and low quantity
of IMF in the H+ form was put into a round bottom flask containing
6N HNO.sub.3 and outfitted with a condenser and stirrer. The
mixture containing UZM-39 and HNO.sub.3 was boiled at reflux for 8
or 16 h. The resulting material was filtered, washed and dried. XRD
analysis showed the material to be UZM-39 consistent with Table
B.
Example 35
[0128] The H+ form of UZM-39 with a high TUN content was
impregnated with about 4 wt.-% of molybdenum and then calcined in
air at 500.degree. C. for about 3 hours, and labeled Catalyst
UZM-39H-Mo. To simulate high temperature deactivation, the catalyst
was then subjected to calcination in air at 750.degree. C. for 60
hours. The activity of 1 gram of catalyst UZM-39H-Mo with and
without the high temperature deactivation was tested by contacting
a feedstream containing 90% wt-% methane, 5 wt.-% hydrogen, and 5
wt.-% argon at 750.degree. C. and 1600 hr.sup.-1 GHSV on methane
and 2 psig for a run time of 3.5 hours and then measuring the
aromatics yield. As a comparison, the experiment was repeated for a
3.5 hour run time using the H+ form of an MFI catalyst impregnated
with 4 wt.-% molybdenum (labeled Catalyst MFI-H-Mo), both with and
without the simulated high temperature deactivation of calcination
in air at 750.degree. C. for about 60 hours. Table 2 shows the
total aromatics yield in wt.-% of each catalyst averaged over a 3.5
hour run time, both with and without the simulated deactivation.
The results show that after the simulated deactivation catalyst
UZM-39H-Mo demonstrated higher yield for total aromatics than that
achieved using catalyst MFI-H-Mo. Thus the catalyst of the
invention deactivated to a lesser extent.
[0129] The above comparison was repeated using tungsten as the
impregnated promoter instead of molybdenum. The H+ form of UZM-39
was impregnated to result in about 8 wt.-% of tungsten and then
calcined in air at 500.degree. C. for about 3 hours, and labeled
Catalyst UZM-39H-W. To simulate high temperature deactivation, the
catalyst was then subjected to calcination in air at 750.degree. C.
for 60 hours. The activity of 1 gram of catalyst UZM-39H-W with and
without the high temperature deactivation was tested by contacting
a feedstream containing 90% wt-% methane, 5 wt.-% hydrogen, and 5
wt.-% argon at 750.degree. C. and 1600 hr.sup.-1 GHSV and 2 psig on
methane for a run time of 3.5 hours and then measuring the
aromatics yield. As a comparison, the experiment was repeated for a
3.5 hour run time using 1 gram of the H+ form of an MFI catalyst
impregnated with 8 wt.-% tungsten (labeled Catalyst MFI-H-W), both
with and without the simulated high temperature deactivation of
calcination in air at 750.degree. C. for about 60 hours. Table 2
shown the total aromatics yield in wt.-% of each catalyst averaged
over a 3.5 hour run time, both with and without the simulated
deactivation. The results show that after the simulated
deactivation catalyst UZM-39H-W demonstrated higher yield for total
aromatics than that achieved using catalyst MFI-H-W or MFI-H-Mo. In
addition, the UZM-39 catalyst composites had higher amounts of
Bronsted acid sites and lower ratios of
Al.sub.2(MoO.sub.4).sub.3/Al(4) and Al(6)/Al(4) after the simulated
deactivation than did MFI catalyst composites, see Table 3. Thus
the catalyst of the invention deactivated to a lesser extent. The
results shown in Table 2 were generated using a first set of
starting materials for the zeolites tested and the results shown in
Table 3 were generated using a second set of starting materials for
the zeolites. In addition, the catalysts of Table 3 were calcined
for only about 3 hours at the temperature indicated.
TABLE-US-00008 TABLE 2 Average Total Aromatics Yield, wt-% Without
Simulated After Simulated Catalyst Deactivation Deactivation
UZM-39H-Mo 3.3 2.5 MFI-H-Mo 3.3 0.4 UZM-39H-W 1.8 1.5 MFI-H-W 2.0
0.6
TABLE-US-00009 TABLE 3 # of Av total Al27 NMR Broensted aromatics
yield Total acid sites 4 hrs test @ integr. by Py- 750 C., 1600
Catalyst Al2(MoO4)3 Al(4) Al(6) intensity FTIR GHSV parent H-MFI 0
93.5 6.5 n/a 0.418 4% Mo/MFI, 3.5 45.8 4.7 54 0.297 5.16 calc. 500
C. above, calc. 17.7 16.5 8.8 43 0.037 2.72 750 C. 3 h 1.5% Mo/MFI,
3.88 calc. 500 C. above, calc. 2.92 750 C. 3 h H-UZM-39 0 83 17 100
0.401 4% Mo/UZM-39, 0 81 19 100 0.324 4.52 calc. 500 C. above,
calc. weak 61 39 92 0.134 3.54 750 C. 3 h H-UZM-39 0 85 15 100
0.389 1.5% Mo/UZM-39, 0 82 18 96 0.383 2.23 calc. 500 C. above,
calc. weak 69 31 76 0.159 3.20 750 C. 3 h
* * * * *
References