U.S. patent application number 13/151780 was filed with the patent office on 2011-12-08 for process for alkylation of aromatic hydrocarbons using uzm-35.
This patent application is currently assigned to UOP LLC. Invention is credited to Deng-Yang Jan, Jaime G. Moscoso, Christopher P. Nicholas.
Application Number | 20110301397 13/151780 |
Document ID | / |
Family ID | 45034390 |
Filed Date | 2011-12-08 |
United States Patent
Application |
20110301397 |
Kind Code |
A1 |
Nicholas; Christopher P. ;
et al. |
December 8, 2011 |
PROCESS FOR ALKYLATION OF AROMATIC HYDROCARBONS USING UZM-35
Abstract
Alkylation processes such as the alkylation of aromatics, are
catalyzed by the UZM-35 family of crystalline aluminosilicate
zeolites represented by the empirical formula:
M.sub.m.sup.n+R.sub.r.sup.+Al.sub.(1-x)E.sub.xSi.sub.yO.sub.z where
M represents a combination of potassium and sodium exchangeable
cations, R is a singly charged organoammonium cation such as the
dimethyldipropylammonium cation and E is a framework element such
as gallium. These UZM-35 zeolites are active and selective in
alkylation processes.
Inventors: |
Nicholas; Christopher P.;
(Evanston, IL) ; Jan; Deng-Yang; (Elk Grove
Village, IL) ; Moscoso; Jaime G.; (Mount Prospect,
IL) |
Assignee: |
UOP LLC
Des Plaines
IL
|
Family ID: |
45034390 |
Appl. No.: |
13/151780 |
Filed: |
June 2, 2011 |
Related U.S. Patent Documents
|
|
|
|
|
|
Application
Number |
Filing Date |
Patent Number |
|
|
12493373 |
Jun 29, 2009 |
7982081 |
|
|
13151780 |
|
|
|
|
Current U.S.
Class: |
585/467 |
Current CPC
Class: |
C01B 39/48 20130101;
B01J 29/70 20130101; C07C 2/66 20130101; C07C 2/66 20130101; C07C
2/66 20130101; Y02P 20/52 20151101; C07C 2529/40 20130101; C07C
15/085 20130101; C07C 15/073 20130101 |
Class at
Publication: |
585/467 |
International
Class: |
C07C 2/68 20060101
C07C002/68 |
Claims
1. A process for alkylating aromatic hydrocarbons comprising
contacting a hydrocarbon feedstock comprising at least alkylatable
aromatics and a stream comprising olefins having from 2 to about 6
carbon atoms with a catalyst at alkylation conditions and producing
an alkylated aromatic product wherein the catalyst comprises a
UZM-35HS microporous crystalline zeolite, wherein the UZM-35HS has
a three-dimensional framework of at least AlO.sub.2 and SiO.sub.2
tetrahedral units and an empirical composition 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' 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 mixtures 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 mixtures 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 4 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 in that it has the
x-ray diffraction pattern having at least the d-spacings and
intensities set forth in Table A: TABLE-US-00008 TABLE A 2.theta. d
(.ANG.) I/Io % 6.45-6.8 13.7-13 m 6.75-7.13 13.1-12.4 m-vs
7.86-8.26 11.25-10.7 m 8.64-9.04 10.23-9.78 m 9.51-10.09 9.3-8.77
m-vs 10.62-11.23 8.33-7.88 w-m 13.4-14.22 6.61-6.23 w-m 14.76-15.55
6-5.7 w 17.63-18.37 5.03-4.83 m 19.17-19.91 4.63-4.46 w-m
19.64-20.56 4.52-4.32 m 20.18-21.05 4.4-4.22 w-m 20.7-21.57
4.29-4.12 w-m 21.36-22.28 4.16-3.99 vs 22.17-23.6 4.01-3.77 m-s
24.12-25.23 3.69-3.53 w 25.6-26.94 3.48-3.31 m 26.37-27.79
3.38-3.21 m 27.02-28.42 3.3-3.14 m 27.53-28.89 3.24-3.09 m
28.7-30.09 3.11-2.97 m 29.18-30.72 3.06-2.91 w-m 30.19-31.73
2.96-2.82 m 30.83-32.2 2.9-2.78 w 32.81-34.22 2.73-2.62 w
35.63-36.99 2.52-2.43 w 41.03-42.86 2.2-2.11 w 44.18-45.83
2.05-1.98 w 44.87-46.57 2.02-1.95 w 46.07-47.35 1.97-1.92 w
48.97-50.42 1.86-1.81 w
and is thermally stable up to a temperature of at least 400.degree.
C.
2. The process of claim 1 where the alkylation conditions include a
temperature of from 50.degree. C. to 500.degree. C., a pressure of
from about 0 to 6895 kPag (about 0 to 1000 psig), an alkylatable
aromatic to olefin mole ratio of from 10 to 0.1 and a contact time
of from about 0.1 seconds to about 1 hour.
3. The process of claim 2 wherein the UZM-35HS zeolite is mixed
with a binder in a proportion of about 5 to 100 mass-% zeolite and
0 to 95 mass-% binder.
4. The process of claim 1 where the alkylatable aromatic of the
feedstock comprises an unsubstituted or monosubstituted
benzene.
5. The process of claim 1 where the olefin containing stream
contains greater than 20 mol % ethylene and the alkylatable
aromatic stream contains greater than 10 mol % benzene or
monosubstituted benzene.
6. The process of claim 5 where the alkylatable aromatic is benzene
and the olefin containing stream is propylene.
7. The process of claim 6 where the alkylation conditions include a
temperature of from 50.degree. C. to 300.degree. C., a pressure of
from about 1378 to 5515 kPag (about 200 to 800 psig), a benzene to
olefin mole ratio of from 10 to 0.3 and a contact time of from
about 0.1 seconds to about 1 hour.
8. The process of claim 1 wherein "x" of the UZM-35HS zeolite is
zero.
9. The process of claim 1 where the selectivity to monoalkylated
products is greater than about 50 mol %.
10. The process of claim 1 wherein the UZM-35HS is in a composition
comprising the USM-35HS, a MFI topology zeolite and an ERI topology
zeolite.
11. The process of claim 10 wherein the amount of UZM-35HS in the
composition ranges from about 55 wt % to about 75 wt. % of the
composition, the amount of MFI topology zeolite ranges from about
20 wt-% to about 35 wt-% of the composition, and the amount of ERI
topology zeolite in the composition ranges from about 3 wt-% to
about 9 wt-% of the composition.
12. An alkylation process comprising contacting a feedstock
comprising unsubstituted or monosubstituted benzene and an olefin
stream comprising ethylene with a catalyst at alkylation conditions
and producing an alkylated aromatic product wherein the catalyst
comprises a UZM-35HS microporous crystalline zeolite, wherein the
UZM-35HS has a three-dimensional framework of at least AlO.sub.2
and SiO.sub.2 tetrahedral units and an empirical composition 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' 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 mixtures 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 mixtures 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 4 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 in that it has the
x-ray diffraction pattern having at least the d-spacings and
intensities set forth in Table A: TABLE-US-00009 TABLE A Table
A2.theta. d (.ANG.) I/Io % 6.45-6.8 13.7-13 m 6.75-7.13 13.1-12.4
m-vs 7.86-8.26 11.25-10.7 m 8.64-9.04 10.23-9.78 m 9.51-10.09
9.3-8.77 m-vs 10.62-11.23 8.33-7.88 w-m 13.4-14.22 6.61-6.23 w-m
14.76-15.55 6-5.7 w 17.63-18.37 5.03-4.83 w 19.17-19.91 4.63-4.46
w-m 19.64-20.56 4.52-4.32 m 20.18-21.05 4.4-4.22 w-m 20.7-21.570
4.29-4.12 w-m 21.36-22.28 4.16-3.99 vs 22.17-23.6 4.01-3.77 m-s
24.12-25.23 3.69-3.53 w 25.6-26.94 3.48-3.31 m 26.37-27.79
3.38-3.21 m 27.02-28.42 3.3-3.14 m 27.53-28.89 3.24-3.09 m
28.7-30.09 3.11-2.97 m 29.18-30.72 3.06-2.91 w-m 30.19-31.73
2.96-2.82 m 30.83-32.2 2.9-2.78 w 32.81-34.22 2.73-2.62 w
35.63-36.99 2.52-2.43 w 41.03-42.86 2.2-2.11 w 44.18-45.83
2.05-1.98 w 44.87-46.57 2.02-1.95 w 46.07-47.35 1.97-1.92 w
48.97-50.42 1.86-1.81 w
and is thermally stable up to a temperature of at least 400.degree.
C.
13. The process of claim 12 wherein the alkylation conditions
include a temperature of from about 50.degree. C. to about
500.degree. C., a pressure of from about 0 to about 6895 kPag
(about 0 to about 1000 psig), an aromatic to olefin mole ratio of
from about 10 to about 0.3 and a contact time of from about 0.1
seconds to about 1 hour.
14. The process of claim 12 wherein the UZM-35HS zeolite is mixed
with a binder in a proportion of about 10 to 90 mass % zeolite and
about 10 to 90 mass-% binder.
15. The process of claim 12 where the aromatic feedstock is benzene
and the selectivity to ethylbenzene is greater than about 50 mol
%.
16. The process of claim 12 wherein the UZM-35HS is in a
composition comprising the USM-35HS, a MFI topology zeolite and an
ERI topology zeolite.
17. The process of claim 16 wherein the amount of UZM-35HS in the
composition ranges from about 55 wt % to about 75 wt. % of the
composition, the amount of MFI topology zeolite ranges from about
20 wt-% to about 35 wt-% of the composition, and the amount of ERI
topology zeolite in the composition ranges from about 3 wt-% to
about 9 wt-% of the composition.
18. An alkylation process comprising contacting a feedstock
comprising unsubstituted or monosubstituted benzene and an olefin
stream comprising propylene with a catalyst at alkylation
conditions and producing an alkylated aromatic product wherein the
catalyst comprises a UZM-35HS microporous crystalline zeolite,
wherein the UZM-35HS has a three-dimensional framework of at least
AlO.sub.2 and SiO.sub.2 tetrahedral units and an empirical
composition 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' 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 mixtures 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 mixtures 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 4 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 in that it has the
x-ray diffraction pattern having at least the d-spacings and
intensities set forth in Table A: TABLE-US-00010 TABLE A Table
A2.theta. d (.ANG.) I/Io % 6.45-6.8 13.7-13 m 6.75-7.13 13.1-12.4
m-vs 7.86-8.26 11.25-10.7 m 8.64-9.04 10.23-9.78 m 9.51-10.09
9.3-8.77 m-vs 10.62-11.23 8.33-7.88 w-m 13.4-14.22 6.61-6.23 w-m
14.76-15.55 6-5.7 w 17.63-18.37 5.03-4.83 w 19.17-19.91 4.63-4.46
w-m 19.64-20.56 4.52-4.32 m 20.18-21.05 4.4-4.22 w-m 20.7-21.570
4.29-4.12 w-m 21.36-22.28 4.16-3.99 vs 22.17-23.6 4.01-3.77 m-s
24.12-25.23 3.69-3.53 w 25.6-26.94 3.48-3.31 m 26.37-27.79
3.38-3.21 m 27.02-28.42 3.3-3.14 m 27.53-28.89 3.24-3.09 m
28.7-30.09 3.11-2.97 m 29.18-30.72 3.06-2.91 w-m 30.19-31.73
2.96-2.82 m 30.83-32.2 2.9-2.78 w 32.81-34.22 2.73-2.62 w
35.63-36.99 2.52-2.43 w 41.03-42.86 2.2-2.11 w 44.18-45.83
2.05-1.98 w 44.87-46.57 2.02-1.95 w 46.07-47.35 1.97-1.92 w
48.97-50.42 1.86-1.81 w
and is thermally stable up to a temperature of at least 400.degree.
C.
19. The process of claim 18 where the alkylation conditions include
a temperature of from about 50.degree. C. to about 300.degree. C.,
a pressure of from about 1378 to about 5515 kPag (about 200 to
about 800 psig), an aromatic to olefin mole ratio of from about 10
to about 0.3 and a contact time of from about 0.1 seconds to about
1 hour.
20. The process of claim 18 wherein the UZM-35 zeolite is mixed
with a binder in a proportion of about 10 to 90 mass % zeolite and
about 10 to 90 mass-% binder.
21. The process of claim 18 wherein the aromatic feedstock is
benzene and the selectivity to cumene is greater than 50 mol %.
22. The process of claim 18 wherein the UZM-35HS is in a
composition comprising the USM-35HS, a MFI topology zeolite and an
ERI topology zeolite.
23. The process of claim 22 wherein the amount of UZM-35HS in the
composition ranges from about 55 wt % to about 75 wt. % of the
composition, the amount of MFI topology zeolite ranges from about
20 wt-% to about 35 wt-% of the composition, and the amount of ERI
topology zeolite in the composition ranges from about 3 wt-% to
about 9 wt-% of the composition.
Description
CROSS-REFERENCE TO RELATED APPLICATION
[0001] This application is a Continuation-In-Part of co-pending
application Ser. No. 12/493,373 filed Jun. 29, 2009, the contents
of which are hereby incorporated by reference in its entirety.
FIELD OF THE INVENTION
[0002] The present invention relates to the use of zeolite UZM-35
in a process for the alkylation of aromatic hydrocarbons, in
particular for the production of ethylbenzene or cumene. In the
alkylation process, the zeolite UZM-35 may be present in the
alkylation catalyst as the sole zeolite component or may be
combined with at least one additional zeolite component. The
zeolite UZM-35 may be present in the catalyst as unmodified zeolite
UZM-35 or as UZM-35 modified zeolite. The UZM-35 containing
catalyst may take one of several forms, including for example, a
spherical oil-dropped catalyst or an extruded catalyst.
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. Topological zeolite
structures are described in Atlas of Zeolite Framework Types, which
is maintained by the International Zeolite Association Structure
Commission at http://www.iza-structure.org/databases/. 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] The alkylation of aromatic hydrocarbons such as benzene with
light olefins such as ethylene and propylene is a very important
process in a petrochemical refinery. The production of ethylbenzene
is used to provide a feedstock for styrene production, while
alkylation of benzene with propylene produces isopropylbenzene
(cumene). Cumene is an important feedstock to make phenol as well
as a good gasoline blending component. These alkylation processes
typically use a catalyst composed of one of or a combination of
12-ring and 10-ring zeolites structure types such as FAU, BEA, MWW,
and MFI to enable high conversion and high selectivity to alkylated
benzenes. In all these alkylation processes, new catalysts are
continuously needed with high overall conversion of the feedstock
and good selectivity to alkylated benzenes.
[0005] Especially advantageous would be a commercially utilizable
catalyst containing 12-membered rings and 10-membered rings in the
same 3-dimensional structure. Commercial utility is typically seen
in aluminosilicate structures which are synthesized in hydroxide
media with readily available structure directing agents. Zeolites
which contain both 12-membered and 10-membered rings in
3-dimensional structures belong to the CON, DFO, IWR, IWW and MSE
structure types. The synthesis of CIT-1, a zeolite of the CON
structure type, is described in U.S. Pat. No. 5,512,267 and in J.
Am. Chem. Soc. 1995, 117, 3766-79 as a borosilicate form. After
synthesis, a subsequent step can be undertaken to allow
substitution of Al for B. The zeolites SSZ-26 and SSZ-33, also of
the CON structure type are described in U.S. Pat. No. 4,910,006 and
U.S. Pat. No. 4,963,337 respectively. SSZ-33 is also described as a
borosilicate. All 3 members of the CON structure type use very
complicated, difficult to synthesize structure directing agents
which make commercial utilization difficult. The known member of
the DFO structure type is DAF-1 which is described as an
aluminophosphate in Chem. Commun. 1993, 633-35 and in Chem. Mater.
1999, 11, 158-63. Zeolites from the IWR and IWW structure types are
synthesized only in hydrofluoric acid containing synthesis routes,
making commercial utilization difficult.
[0006] One particular zeolite of the MSE structure type, designated
MCM-68, was disclosed by Calabro et al. in 1999 (U.S. Pat. No.
6,049,018). This patent describes the synthesis of MCM-68 from
dication directing agents,
N,N,N',N'-tetraalkylbicyclo[2.2.2]oct-7-ene-2R,3S:5R,6S-dipyrrolidinium
dication, and
N,N,N',N'-tetraalkylbicyclo[2.2.2]octane-2R,3S:5R,6S-dipyrrolidinium
dication. MCM-68 was found to have at least one channel system in
which each channel is defined by a 12-membered ring of
tetrahedrally coordinated atoms and at least two further
independent channel systems in which each channel is defined by a
10-membered ring of tetrahedrally coordinated atoms wherein the
number of unique 10-membered ring channels is twice the number of
12-membered ring channels.
[0007] Applicants have successfully prepared a new family of
materials designated UZM-35. The topology of the materials is
similar to that observed for MCM-68. The materials are prepared via
the use of simple, commercially available structure directing
agents, such as dimethyldipropylammonium hydroxide, in concert with
small amounts of K.sup.+ and Na.sup.+ together using the Charge
Density Mismatch Approach to zeolite synthesis (U.S. Pat. No.
7,578,993).
[0008] The alkylation of benzene with ethylene can be performed in
gas phase conditions where all the reactants are in the gaseous
phase while passing over the solid catalyst or in liquid phase
conditions where at least the benzene is present in the liquid
phase while passing over the solid catalyst. The UZM-35 family of
materials is capable of catalyzing the alkylation of benzene with
ethylene in either commercially relevant condition.
[0009] The UZM-35 family of materials is able to provide and
maintain high conversion of propylene and high selectivity to
isopropylbenzene during alkylation of benzene with propylene due to
its particular pore geometry and framework Si/Al ratio. The UZM-35
zeolite contains significant amounts of Al in the tetrahedral
framework, with the mole ratio of Si/Al ranging from about 2 to
about 12.
SUMMARY OF THE INVENTION
[0010] The present invention relates to a process of aromatic
alkylation using a catalyst of the aluminosilicate zeolite
designation UZM-35. The process comprises contacting olefinic and
alkylatable aromatic hydrocarbons with the UZM-35 zeolite at
alkylation conditions to give an alkylated aromatic product.
[0011] The UZM-35 is a microporous crystalline zeolite having a
three-dimensional framework of at least AlO.sub.2 and SiO.sub.2
tetrahedral units and an empirical composition in the as
synthesized and anhydrous basis expressed by an empirical formula
of:
M.sub.m.sup.n+R.sub.r.sup.+Al.sub.(1-x)E.sub.xSi.sub.yO.sub.z
[0012] where M represents a combination of potassium and sodium
exchangeable cations, "m" is the mole ratio of M to (Al+E) and
varies from about 0.05 to about 3, R is a singly charged
organoammonium cation selected from the group consisting of
dimethyldipropylammonium (DMDPA.sup.+), dimethyldiisopropylammonium
(DMDIP.sup.+), choline, ethyltrimethylammonium (ETMA.sup.+),
diethyldimethylammonium (DEDMA.sup.+), trimethylpropylammonium,
trimethylbutylammonium, dimethyldiethanolammonium,
tetraethylammonium (TEA.sup.+), tetrapropylammonium (TPA.sup.+),
methyltripropylammonium, and mixtures thereof, "r" is the mole
ratio of R to (Al+E) and has a value of about 0.25 to about 2.0, E
is an element selected from the group consisting of gallium, iron,
boron and mixtures 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 2 to about 12 and "z" is the mole
ratio of 0 to (Al+E) and has a value determined by the
equation:
z=(m+r+3+4y)/2
and is characterized in that it has the x-ray diffraction pattern
having at least the d-spacings and intensities set forth in Table
A
TABLE-US-00001 TABLE A 2.theta. d (.ANG.) I/Io % 6.45-6.8 13.7-13 m
6.75-7.13 13.1-12.4 m-vs 7.86-8.26 11.25-10.7 m 8.64-9.04
10.23-9.78 m 9.51-10.09 9.3-8.77 m-vs 10.62-11.23 8.33-7.88 w-m
13.4-14.22 6.61-6.23 w-m 14.76-15.55 6-5.7 w 17.63-18.37 5.03-4.83
w 19.17-19.91 4.63-4.46 w-m 19.64-20.56 4.52-4.32 m 20.18-21.05
4.4-4.22 w-m 20.7-21.57 4.29-4.12 w-m 21.36-22.28 4.16-3.99 vs
22.17-23.6 4.01-3.77 m-s 24.12-25.23 3.69-3.53 w 25.6-26.94
3.48-3.31 m 26.37-27.79 3.38-3.21 m 27.02-28.42 3.3-3.14 m
27.53-28.89 3.24-3.09 m 28.7-30.09 3.11-2.97 m 29.18-30.72
3.06-2.91 w-m 30.19-31.73 2.96-2.82 m 30.83-32.2 2.9-2.78 w
32.81-34.22 2.73-2.62 w 35.63-36.99 2.52-2.43 w 41.03-42.86
2.2-2.11 w 44.18-45.83 2.05-1.98 w 44.87-46.57 2.02-1.95 w
46.07-47.35 1.97-1.92 w 48.97-50.42 1.86-1.81 w
and is thermally stable up to a temperature of greater than
400.degree. C. in one embodiment and 600.degree. C. in another
embodiment.
[0013] The crystalline microporous zeolite described above may be
synthesized by forming a reaction mixture containing reactive
sources of M, R, Al, Si and optionally E and heating the reaction
mixture at a temperature of about 150.degree. C. to about
200.degree. C., or about 165.degree. C. to about 185.degree. C.,
for a time sufficient to form the zeolite, the reaction mixture
having a composition expressed in terms of mole ratios of the
oxides of:
aM.sub.2O:bR.sub.2/pO:1-cAl.sub.2O.sub.3:cE.sub.2O.sub.3:dSiO.sub.2:eH.s-
ub.2O
where "a" has a value of about 0.05 to about 1.25, "b" has a value
of about 1.5 to about 40, "p" is the weighted average valance of R
and varies from 1 to about 2, "c" has a value of 0 to about 1.0,
"d" has a value of about 4 to about 40, "e" has a value of about 25
to about 4000.
[0014] Yet another embodiment of the invention is a catalytic
process for alkylation of aromatic hydrocarbons using the
above-described zeolite. The process comprises contacting the light
olefin and the aromatic hydrocarbon with the zeolite at conversion
conditions to give an alkylated aromatic hydrocarbon.
[0015] In another embodiment, the invention relates to a process of
aromatic alkylation using a catalyst of the aluminosilicate zeolite
designation UZM-35HS. The process comprises contacting the
hydrocarbon with the UZM-35HS zeolite at aromatic alkylation
conditions to give an alkylated aromatic product. The UZM-35HS is a
microporous crystalline zeolite having a three-dimensional
framework of at least AlO.sub.2 and SiO.sub.2 tetrahedral units and
an empirical composition 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'
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 mixtures 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 mixtures 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 4 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 in that it has the x-ray diffraction pattern
having at least the d-spacings and intensities set forth in Table
A:
TABLE-US-00002 TABLE A 2.theta. d (.ANG.) I/Io % 6.45-6.8 13.7-13 m
6.75-7.13 13.1-12.4 m-vs 7.86-8.26 11.25-10.7 m 8.64-9.04
10.23-9.78 m 9.51-10.09 9.3-8.77 m-vs 10.62-11.23 8.33-7.88 w-m
13.4-14.22 6.61-6.23 w-m 14.76-15.55 6-5.7 w 17.63-18.37 5.03-4.83
m 19.17-19.91 4.63-4.46 w-m 19.64-20.56 4.52-4.32 m 20.18-21.05
4.4-4.22 w-m 20.7-21.57 4.29-4.12 w-m 21.36-22.28 4.16-3.99 vs
22.17-23.6 4.01-3.77 m-s 24.12-25.23 3.69-3.53 w 25.6-26.94
3.48-3.31 m 26.37-27.79 3.38-3.21 m 27.02-28.42 3.3-3.14 m
27.53-28.89 3.24-3.09 m 28.7-30.09 3.11-2.97 m 29.18-30.72
3.06-2.91 w-m 30.19-31.73 2.96-2.82 m 30.83-32.2 2.9-2.78 w
32.81-34.22 2.73-2.62 w 35.63-36.99 2.52-2.43 w 41.03-42.86
2.2-2.11 w 44.18-45.83 2.05-1.98 w 44.87-46.57 2.02-1.95 w
46.07-47.35 1.97-1.92 w 48.97-50.42 1.86-1.81 w
and is thermally stable up to a temperature of at least 400.degree.
C.
DETAILED DESCRIPTION OF THE INVENTION
[0016] Applicants have prepared an aluminosilicate zeolite which
has been designated UZM-35 whose topological structure is related
to MSE 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/. As is shown
in U.S. AN 12/241,302 in detail, UZM-35 is different from MCM-68 in
a number of its characteristics. The instant microporous
crystalline zeolite, UZM-35, has an empirical composition in the
as-synthesized form and on an anhydrous basis expressed by the
empirical formula:
M.sub.m.sup.n+R.sub.r.sup.+Al.sub.(1-x)E.sub.xSi.sub.yO.sub.z
where M represents a combination of potassium and sodium
exchangeable cations. R is a singly charged organoammonium cation,
examples of which include but are not limited to the
dimethyldipropylammonium cation (DMDPA.sup.+),
dimethyldiisopropylammonium (DMDIP.sup.+), choline
[(CH.sub.3).sub.3N(CH.sub.2).sub.2OH].sup.+, ETMA.sup.+,
DEDMA.sup.+, trimethylpropylammonium, trimethylbutylammonium,
dimethyldiethanolammonium, methyltripropylammonium, TEA.sup.+,
TPA.sup.+ and mixtures thereof and "r" is the mole ratio of R to
(Al+E) and varies from about 0.25 to about 2.0 while "m" is the
mole ratio of M to (Al+E) and varies from about 0.05 to about 3.
The mole ratio of silicon to (Al+E) is represented by "y" which
varies from about 2 to about 30. E is an element which is
tetrahedrally coordinated, is present in the framework and is
selected from the group consisting of gallium, iron and boron. The
mole fraction of E is represented by "x" and has a value from 0 to
about 1.0, while "z" is the mole ratio of 0 to (Al+E) and is given
by the equation:
z=(mn+r+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.n+=M.sub.m1.sup.(n1)++M.sub.m2.sup.(n2)++M.sub.m3.sup.(n3)++
. . .
and the weighted average valence "n" is given by the equation:
n = m 1 n 1 + m 2 n 2 + m 3 n 3 + m 1 + m 2 + m 3 +
##EQU00001##
[0017] The microporous crystalline zeolite, UZM-35, is prepared by
a hydrothermal crystallization of a reaction mixture prepared by
combining reactive sources of M, R, aluminum, silicon and
optionally E. The sources of aluminum include but are not limited
to aluminum alkoxides, precipitated aluminas, aluminum metal,
aluminum salts and alumina sols. Specific examples of aluminum
alkoxides include, but are not limited to aluminum ortho
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 the E
elements include but are not limited to alkali borates, boric acid,
precipitated gallium oxyhydroxide, gallium sulfate, ferric sulfate,
and ferric chloride. Sources of the M metals, potassium and sodium,
include the halide salts, nitrate salts, acetate salts, and
hydroxides of the respective alkali metals. R is an organoammonium
cation selected from the group consisting of
dimethyldiisopropylammonium, dimethyldipropylammonium, choline,
ETMA, DEDMA, TEA, TPA, trimethylpropylammonium,
trimethylbutylammonium, dimethyldiethanolammonium and mixtures
thereof, and the sources include the hydroxide, chloride, bromide,
iodide and fluoride compounds. Specific examples include without
limitation dimethyldipropylammonium hydroxide,
dimethyldipropylammonium chloride, dimethyldipropylammonium
bromide, dimethyldiisopropylammonium hydroxide,
dimethyldiisopropylammonium chloride, dimethyldiisopropylammonium
bromide, ethyltrimethylammonium hydroxide, diethyldimethylammonium
hydroxide, tetraethylammonium hydroxide, tetrapropylammonium
hydroxide, and tetrapropylammonium chloride.
[0018] Note that during synthesis, the metal M is +1 valance,
specifically potassium and sodium. However, in an alternative
embodiment, the composition may undergo additional ion exchange
steps, post synthesis, to provide a material with one or more
metals, M, having a+2 valance.
[0019] The reaction mixture containing reactive sources of the
desired components can be described in terms of molar ratios of the
oxides by the formula:
aM.sub.2O:bR.sub.2/pO:1-cAl.sub.2O.sub.3:cE.sub.2O.sub.3:dSiO.sub.2:eH.s-
ub.2O
where "a" varies from about 0.05 to about 1.25, "b" varies from
about 1.5 to about 40, "c" varies from 0 to 1.0, "d" varies from
about 4 to about 40, "e" varies from about 25 to about 4000, and
"p" is the weighted average valence of R and varies from 1 to about
2. If alkoxides are used, it is preferred to include a distillation
or evaporative step to remove the alcohol hydrolysis products. The
reaction mixture is now reacted at a temperature of about
150.degree. C. to about 200.degree. C., about 165.degree. C. to
about 185.degree. C., or about 170.degree. C. to about 180.degree.
C., for a period of about 1 day to about 3 weeks and preferably for
a time of about 5 days to about 12 days in a 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. It should be pointed out that UZM-35 seeds can
optionally be added to the reaction mixture in order to accelerate
the formation of the zeolite.
[0020] A preferred synthetic approach to make UZM-35 utilizes the
charge density mismatch concept, which is disclosed in U.S. Pat.
No. 7,578,993 and Studies in Surface Science and Catalysis, (2004),
Vol. 154A, 364-372. The method disclosed in U.S. Pat. No. 7,578,993
employs quaternary ammonium hydroxides to solubilize
aluminosilicate species, while crystallization inducing agents such
as alkali and alkaline earth metals and more highly charged
organoammonium cations are often introduced in a separate step.
Once some UZM-35 seeds have been generated using this approach, the
seeds can be used in a single step synthesis of UZM-35, using, for
example, a combination of dimethyldiisopropylammonium,
dimethyldipropylammonium hydroxide and the alkali cations. The use
of commercially available dimethyldipropylammonium hydroxide to
prepare UZM-35 offers a great economic advantage over the structure
directing agents previously employed
(N,N,N',N'-tetraalkylbicyclo[2.2.2]oct-7-ene-2R,3S:5R,6S-dipyrrolidinium
dication, and
N,N,N',N'-tetraalkylbicyclo[2.2.2]octane-2R,3S:5R,6S-dipyrrolidinium
dication) to prepare aluminosilicates with the MSE topology.
Additionally, dimethyldipropyl ammonium hydroxide can be employed
as the hydroxide or the chloride in concert with other inexpensive
organoammonium hydroxides using the charge density mismatch concept
to reduce costs even further.
[0021] The UZM-35 aluminosilicate zeolite, which is obtained from
the above-described process, is characterized by the x-ray
diffraction pattern, having at least the d-spacings and relative
intensities set forth in Table A below.
TABLE-US-00003 TABLE A 2.theta. d (.ANG.) I/Io % 6.45-6.8 13.7-13 m
6.75-7.13 13.1-12.4 m-vs 7.86-8.26 11.25-10.7 m 8.64-9.04
10.23-9.78 m 9.51-10.09 9.3-8.77 m-vs 10.62-11.23 8.33-7.88 w-m
13.4-14.22 6.61-6.23 w-m 14.76-15.55 6-5.7 w 17.63-18.37 5.03-4.83
w 19.17-19.91 4.63-4.46 w-m 19.64-20.56 4.52-4.32 m 20.18-21.05
4.4-4.22 w-m 20.7-21.57 4.29-4.12 w-m 21.36-22.28 4.16-3.99 vs
22.17-23.6 4.01-3.77 m-s 24.12-25.23 3.69-3.53 w 25.6-26.94
3.48-3.31 m 26.37-27.79 3.38-3.21 m 27.02-28.42 3.3-3.14 m
27.53-28.89 3.24-3.09 m 28.7-30.09 3.11-2.97 m 29.18-30.72
3.06-2.91 w-m 30.19-31.73 2.96-2.82 m 30.83-32.2 2.9-2.78 w
32.81-34.22 2.73-2.62 w 35.63-36.99 2.52-2.43 w 41.03-42.86
2.2-2.11 w 44.18-45.83 2.05-1.98 w 44.87-46.57 2.02-1.95 w
46.07-47.35 1.97-1.92 w 48.97-50.42 1.86-1.81 w
As will be shown in detail in the examples, the UZM-35 material is
thermally and catalytically stable up to a temperature of at least
400.degree. C. and in another embodiment, up to about 600.degree.
C.
[0022] As synthesized, the UZM-35 material will contain some of the
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. Because UZM-35 is a large pore zeolite, it
is also possible to remove some organic cations directly by ion
exchange. The UZM-35 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. Properties that
are modified include porosity, adsorption, Si/Al ratio, acidity,
thermal stability, and the like.
[0023] The UZM-35 compositions which are modified by one or more
techniques described in the '975 patent (herein UZM-35HS) are
described by the empirical formula on an anhydrous basis 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 mixtures 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 mixtures 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 4 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
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 4 to 3,000
preferably greater than 10 to about 3,000; 4 to 10,000 preferably
greater than 10 to about 10,000 and 4 to 20,000 preferably greater
than 10 to about 20,000.
[0024] The UZM-35 as synthesized or as modified may be in a
composition comprising the USM-35 as synthesized or as modified, a
MFI topology zeolite and an ERI topology zeolite. Typically, the
amount of UZM-35 as synthesized or as modified in the composition
will vary from about 55 wt % to about 75 wt. % or from about 55
wt-% to about 90 wt.-%. The amount of MFI zeolite varies from about
20 wt-% to about 35 wt-% of the composition or from about 10 wt-%
to about 35 wt.-%, and the amount of ERI zeolite varies from about
3 wt-% to about 9 wt-% of the composition or from about 3 wt-% to
about 10 wt.-%. Of course, the sum of the amount of the three
zeolites, absent any other impurities, adds up to 100 wt % of the
composition.
[0025] The UZM-35 zeolite as outlined above or a modification
thereof, is used as a catalyst or catalyst support in various
alkylation reactions of aromatic hydrocarbons. The zeolite
preferably is mixed with a binder for convenient formation of
catalyst particles in a proportion of about 5 to 100 mass % zeolite
and 0 to 95 mass-% binder, with the zeolite preferably comprising
from about 10 to 90 mass-% of the composite. The binder should
preferably be porous, have a surface area of about 5 to about 800
m.sup.2/g, and be relatively refractory to the conditions utilized
in the hydrocarbon conversion process. Non-limiting examples of
binders are alumina, titania, zirconia, zinc oxide, magnesia,
boria, silica-alumina, silica-magnesia, chromia-alumina,
alumina-boria, aluminophosphates, silica-zirconia, silica, silica
gel, and clays. Preferred binders are amorphous silica and alumina,
including gamma-, eta-, and theta-alumina, with gamma- and
eta-alumina being especially preferred.
[0026] The zeolite with or without a binder can be formed into
various shapes such as pills, pellets, extrudates, spheres, etc.
Preferred shapes are extrudates and spheres. Extrudates are
prepared by conventional means which involves mixing of zeolite
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.
[0027] 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.
[0028] The interaction of the feed molecules with the catalyst is
of great importance in catalysis. This interaction may be
characterized by the contact time. Contact time is calculated by
dividing the catalyst volume by the feed flow rate. Lower contact
times indicate less interaction of the feed with the catalyst,
while higher contact times indicate high interaction of the feed
with the catalyst. Selectivity to specific products may be altered
by altering the contact time. For reactions such as alkylation of
aromatic hydrocarbons, where a feedstock containing an alkylatable
hydrocarbon and a stream comprising at least one olefin are both
passed over the catalyst, the contact time is calculated using the
combined feed rate. The alkylation and preferably the
monoalkylation of aromatic compounds involves reacting an
alkylatable aromatic compound with an olefin using the above
described zeolitic catalyst. The olefins which can be used in the
instant process are any of those which contain from 2 up to about 6
carbon atoms. These olefins may be branched or linear olefins and
either terminal or internal olefins. Preferred olefins are
ethylene, propylene, butenes and amylenes.
[0029] The alkylatable aromatic compounds may be selected from the
group consisting of benzene, naphthalene, anthracene, phenanthrene,
and substituted derivatives thereof, with benzene and its
derivatives being the most preferred aromatic compound. By
alkylatable is meant that the aromatic compound can be alkylated by
an olefinic compound. The alkylatable aromatic compounds may have
one or more of the substituents selected from the group consisting
of alkyl groups (having from 1 to about 20 carbon atoms), hydroxyl
groups, and alkoxy groups whose alkyl group also contains from 1 up
to 20 carbon atoms. Where the substituent is an alkyl or alkoxy
group, a phenyl group can also be substituted on the alkyl chain.
Although unsubstituted and monosubstituted benzenes, naphthalenes,
anthracenes, and phenanthrenes are most often used in the practice
of this invention, polysubstituted aromatics also may be employed.
Examples of suitable alkylatable aromatic compounds in addition to
those cited above include biphenyl, toluene, xylene, ethylbenzene,
propylbenzene, butylbenzene, pentylbenzene, hexylbenzene,
heptylbenzene, octylbenzene, phenol, cresol, anisole, ethoxy-,
propoxy-, butoxy-, pentoxy-, hexoxybenzene, etc.
[0030] Reactions involving the alkylation of aromatic hydrocarbons
are processes well known in the art and include the production of
ethylbenzene and cumene. Specific reaction conditions and the types
of feeds which can be used in these processes are set forth in
(U.S. Pat. No. 7,498,472, U.S. Pat. No. 7,525,003, U.S. Pat. No.
7,525,004, U.S. Pat. No. 7,420,098, U.S. Pat. No. 7,525,005, U.S.
Pat. No. 7,525,006) which are all hereby incorporated by reference
in their entirety. 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.
[0031] Reactions involving the alkylation of aromatic hydrocarbons
are processes well known in the art and include the production of
ethylbenzene and cumene. Specific reaction conditions and the types
of feeds which can be used in these processes are set forth in:
U.S. Pat. No. 7,498,472, U.S. Pat. No. 7,525,003, U.S. Pat. No.
7,525,004, U.S. Pat. No. 7,420,098, U.S. Pat. No. 7,525,005, U.S.
Pat. No. 7,525,006 which are all hereby incorporated by reference
in their entirety. 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 claims
[0032] The structure of the UZM-35 family of zeolites 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.
[0033] 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:
w=0-15; m=15-60:s=60-80 and vs=80-100
[0034] 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.
[0035] 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
[0036] An aluminosilicate reaction solution was prepared by first
mixing 27.17 g of aluminum hydroxide (27.78 mass-% Al) and 1053.58
g dimethyldipropylammonium hydroxide (18.8 mass-% solution), while
stirring vigorously. After thorough mixing, 505.96 g Ludox.TM.
AS-40 (40 mass-% SiO.sub.2) was added. The reaction mixture was
homogenized for an additional hour with a high speed mechanical
stirrer, sealed in a Teflon bottle, and placed in an oven overnight
at 100.degree. C. Analysis showed the aluminosilicate solution
contained 6.16 wt. % Si and 0.67 wt. % Al (Si/Al molar ratio of
8.83).
[0037] A 1200 g portion of the above aluminosilicate solution was
continuously stirred. A composite aqueous solution containing 28.56
g of KOH and 3.6 g of NaOH dissolved in 150 g distilled water, was
added, drop-wise, to the aluminosilicate solution. After the
addition was completed, the resulting reaction mixture was
homogenized for 1 hour, transferred to a 2000 ml Parr stainless
steel autoclave which was heated to 175.degree. C. and maintained
at that temperature for 216 hrs. The solid product was recovered by
centrifugation, washed with de-ionized water, and dried at
100.degree. C.
[0038] The solid product was recovered by centrifugation, washed
with de-ionized water and dried at 95.degree. C. The product was
identified as UZM-35 by xrd. Representative diffraction lines
observed for the product are shown in Table 1. The product
composition was determined by elemental analysis to consist of the
following mole ratios: Si/Al=7.92, Na/Al=0.1, K/Al=0.48.
TABLE-US-00004 TABLE 1 2.theta. d (.ANG.) I/I.sub.0 % 6.65 13.26 m
6.95 12.69 m 8.10 10.90 m 8.87 9.95 m 9.76 9.05 m 10.83 8.13 w
13.76 6.43 w 15.22 5.81 w 18.00 4.92 w 19.46 4.55 m 19.62 4.52 m
20.06 4.42 m 20.63 4.3 m 21.1 4.20 m 21.76 4.08 vs 21.92 4.05 m
22.07 4.03 m 22.55 3.93 m 22.73 3.90 m 23.08 3.85 s 23.42 3.79 m
23.51 3.77 m 24.04 3.69 m 24.53 3.62 w 25.9 3.43 m 25.99 3.42 w
26.27 3.38 m 26.92 3.3 m 27.57 3.23 m 27.76 3.21 m 28.17 3.16 m
28.86 3.09 w 29.27 3.04 m 29.72 3.00 w 30.26 2.95 w 30.91 2.88 m
31.38 2.84 w 33.61 2.68 w 34.65 2.58 w 35.43 2.53 w 36.18 2.48 w
41.77 2.16 w 44.7 2.02 w 45.32 1.99 w 45.63 1.98 w 46.55 1.94 w
47.62 1.90 w 47.94 1.89 w 49.70 1.83 w 51.06 1.78 w
Example 2
[0039] The UZM-35 of example 1 was calcined at 540.degree. C. for
10 hrs under nitrogen and then air. Representative diffraction
lines observed for the product are shown in Table 2.
TABLE-US-00005 TABLE 2 2.theta. d (.ANG.) I/I.sub.0 % 6.72 13.13 m
7.02 12.57 vs 8.0 11.04 m 8.2 10.77 m 8.3 10.64 m 8.98 9.83 m 9.87
8.94 vs 11.00 8.03 m 11.29 7.82 w 13.85 6.38 m 14.17 6.24 w 14.95
5.91 w 15.04 5.88 w 17.72 4.99 w 17.90 4.95 w 19.56 4.53 m 19.64
4.51 m 19.70 4.50 m 20.16 4.40 m 20.64 4.29 w 21.15 4.19 w 21.86
4.06 vs 21.98 4.04 s 22.07 4.02 m 22.62 3.92 m 22.72 3.91 s 23.27
3.91 vs 24.08 3.69 m 24.69 3.60 w 25.29 3.51 w 26.28 3.38 m 27.12
3.28 m 27.66 3.22 m 28.28 3.15 m 28.98 3.07 w 29.36 3.03 m 29.99
2.97 w 30.38 2.93 m 31.02 2.88 m 31.54 2.83 w 33.46 2.67 w 34.68
2.58 w 35.07 2.55 w 35.84 2.50 w 36.29 2.47 w 39.37 2.28 w 41.92
2.15 w 44.96 2.01 w 45.72 1.98 w 46.74 1.94 w 47.82 1.9 w 48.13
1.88 w 49.75 1.83 W
Example 3
[0040] The UZM-35 of example 2 then was ammonium ion-exchanged to
exchange Na or K cations for NH.sub.4.
Comparative Example 4
[0041] A sample of H-MFI zeolite, bound 66/34 with AlPO.sub.4 was
obtained. The catalyst consists of 1/16'' diameter spheres. The
SiO.sub.2/Al.sub.2O.sub.3 ratio of the MFI is 38.
Example 5
[0042] The UZM-35 of Example 3 was pressed and meshed to 20-40 mesh
prior to testing. For alkylation of benzene with propylene to form
cumene, 15 mL of meshed catalyst is mixed with 10 mL of gamma
alumina of 20-40 mesh and loaded into the reactor. The reactor was
pressurized to 500 psig with N.sub.2 and benzene flow was then
started. Once the reactor attained the target temperature, the
propylene was introduced. Results of the cumene synthesis tests are
shown in Table 3.
TABLE-US-00006 TABLE 3 n-Pr Temperature LHSV LHSV B/O Conversion
Cumene benzene DIPB Heavy Catalyst (.degree. C.) (olefin)
(C.sub.6H.sub.6) ratio (mol %) Selectivity Selectivity Selectivity
Selectivity Example 5 148 0.7 5.4 7 ~100 84.8% 600 ppm 7.2% 8%
UZM-35 Example 5 148 1.1 4.9 4 ~100 76.3% 800 ppm 11.3% 12.4%
UZM-35 Example 5 148 0.9 6.6 7 ~100 86.0% 600 ppm 7.2% 6.8% UZM-35
Example 5 148 2.0 5.4 2.5 ~100 68.8% 1550 ppm 14.0% 17.2%
UZM-35
[0043] Not only does the UZM-35 catalyst exhibit good selectivity
to cumene under these conditions, it is remarkably stable. In 16
hours of reaction at the first condition, no evidence of
deactivation was observed. Indeed, over the 60 total hours of
reaction time, no deactivation in conversion or change in
selectivity due to deactivation was noted.
Comparative Example 6
[0044] The MFI catalyst of Example 4, 10.3 mL was loaded into the
reactor. The reactor was pressurized to 500 psig with N.sub.2 and
benzene flow was started. Once the reactor attained the target
temperature, the ethylene containing gas was introduced. The gas
feed consisted of 77% CH.sub.4 and 23% C.sub.2H.sub.4. Results of
the ethylbenzene synthesis tests are shown in Table 4.
Example 7
[0045] The UZM-35 of Example 3 then pressed and meshed to 20-40
mesh prior to testing. For alkylation of benzene with ethylene, 15
mL of meshed catalyst was loaded into the reactor. The reactor was
pressurized to 500 psig with N.sub.2. Benzene flow was started and
once the reactor was up to temperature, the ethylene containing gas
was introduced. The gas feed consisted of 77% CH.sub.4 and 23%
C.sub.2H.sub.4. Results of the ethylbenzene synthesis tests are
shown in Table 4.
TABLE-US-00007 TABLE 4 Ethylbenzene Synthesis Temperature WHSV WHSV
B/O Conversion Ethylbenzene DIEB TIEB Other Catalyst (.degree. C.)
(olefin) (C.sub.6H.sub.6) ratio (wt %) Selectivity Selectivity
Selectivity Selectivity Example 6 250 1.0 8.34 3 3% 80% 0.25% ~0%
19.8% MFI Example 6 279 1.0 8.34 3 8.8 86% 1.25% ~0% 12.8% MFI
Example 6 305 1.0 8.34 3 18.5 79% 3.9% ~0% 17.1% MFI Example 7 190
1.0 8.36 3 6.6 89% 5.6% 0.5% 4.9% UZM-35 Example 7 219 1.0 19.5 7
19 88% 4.7% 0.2% 7.1% UZM-35
[0046] As can be seen from the results in Table 4, the UZM-35
family of catalysts is active at much lower temperatures than
typical MFI catalysts, which is used in commercial EB synthesis,
for ethylbenzene synthesis. In addition, the selectivity of UZM-35
catalysts toward ethylbenzene is better than that of MFI. For the
MFI catalyst, other selectivity is composed largely of ethylene
oligomers, 2-butylbenzene, and cumene and light alkanes with trace
amounts of tert-butylbenzene and xylenes and, in the 305.degree. C.
temperature data, toluene, ethyltoluenes and trimethylbenzenes. For
the UZM-35 catalyst, the other selectivity is composed of largely
of 2-butylbenzene and ethylene oligomers, with trace amounts of
cumene and tert-butylbenzene
* * * * *
References