U.S. patent application number 13/234092 was filed with the patent office on 2012-01-05 for uzm-35 zeolitic composition, method of preparation and processes.
This patent application is currently assigned to UOP LLC.. Invention is credited to Deng-Yang Jan, Jaime G. Moscoso.
Application Number | 20120003147 13/234092 |
Document ID | / |
Family ID | 44882485 |
Filed Date | 2012-01-05 |
United States Patent
Application |
20120003147 |
Kind Code |
A1 |
Moscoso; Jaime G. ; et
al. |
January 5, 2012 |
UZM-35 ZEOLITIC COMPOSITION, METHOD OF PREPARATION AND
PROCESSES
Abstract
A new family of crystalline aluminosilicate zeolitic
compositions, UZM-35 compositions, has been synthesized. These
zeolitic compositions are represented by the empirical formula.
M.sub.m.sup.n+R.sub.r.sup.+Al.sub.1-xE.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 compositions comprise a MSE zeolite, a MFI
zeolite and an ERI zeolite. The compositions are similar to MCM-68
but are characterized by unique x-ray diffraction patterns and have
catalytic properties for carrying out various hydrocarbon
conversion processes.
Inventors: |
Moscoso; Jaime G.; (Mount
Prospect, IL) ; Jan; Deng-Yang; (Elk Grove Village,
IL) |
Assignee: |
UOP LLC.
Des Plaines
IL
|
Family ID: |
44882485 |
Appl. No.: |
13/234092 |
Filed: |
September 15, 2011 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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13151482 |
Jun 2, 2011 |
8053618 |
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13234092 |
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12820079 |
Jun 21, 2010 |
8022262 |
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13151482 |
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Current U.S.
Class: |
423/703 ;
423/700 |
Current CPC
Class: |
C10G 2300/1088 20130101;
C10G 2400/20 20130101; B01J 29/50 20130101; C10G 29/205 20130101;
C10G 45/64 20130101; B01J 29/40 20130101; C07C 6/126 20130101; C07C
5/02 20130101; C07C 6/123 20130101; C07C 2529/80 20130101; B01J
29/70 20130101; C07C 2/66 20130101; C07C 5/22 20130101; C10G 50/00
20130101; C10G 2400/22 20130101; C07C 5/32 20130101; B01J 29/80
20130101; C07C 2/58 20130101 |
Class at
Publication: |
423/703 ;
423/700 |
International
Class: |
C01B 39/46 20060101
C01B039/46; C01B 39/48 20060101 C01B039/48 |
Claims
1. A UZM-35 composition comprising a MFI zeolite, an ERI zeolite,
and a MSE zeolite, the UZM-35 composition 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.+R.sub.r.sup.+Al.sub.1-xE.sub.xSi.sub.yO.sub.z
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
dimethyldipropylammonium cation, "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
O 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-00011 TABLE A 2.theta. d (.ANG.)
I/Io % 6.48-6.51 13.32-13.58 m 6.78-6.83 12.91-13.02 m-s 7.79-7.96
11.09-11.32 m 8.05-8.07 10.93-10.96 m 8.71-8.75 10.08-10.13 m
9.61-9.65 9.15-9.18 m-s 10.75-10.79 8.18-8.21 w 13.61-13.65
6.47-6.49 w 14.74-14.79 5.98-6 w 15.56-15.59 5.67-5.69 w
15.86-15.86 5.58-5.58 w 19.46-19.5 4.54-4.55 m 19.89-19.92
4.45-4.45 m 20.48-20.51 4.32-4.33 m 20.94-20.96 4.23-4.23 m
21.61-21.64 4.1-4.1 vs 21.79-21.81 4.07-4.07 s 22.39-22.45
3.95-3.96 m 22.93-22.98 3.86-3.87 s-vs 23.29-23.31 3.81-3.81 m
23.5-23.5 3.78-3.78 m 23.78-23.86 3.72-3.73 m 24.39-24.41 3.64-3.64
w 24.82-24.82 3.58-3.58 w 25.76-25.79 3.45-3.45 w-m 26.09-26.12
3.4-3.41 m 26.74-26.81 3.32-3.33 m 27.14-27.14 3.28-3.28 m
27.42-27.46 3.24-3.249 m 27.69-27.69 3.21-3.21 m 28.02-28.06
3.17-3.18 m 29.1-29.15 3.06-3.06 m 29.54-29.61 3.01-3.02 w
29.75-29.86 2.98-2.99 w 30.12-30.14 2.96-2.96 m 30.73-30.79 2.9-2.9
m 31.26-31.27 2.85-2.85 w 31.47-31.47 2.83-2.83 w 33.19-33.25
2.69-2.69 w 34.34-34.48 2.59-2.6 w 34.76-34.76 2.57-2.57 w
35.18-35.2 2.54-2.54 w 35.57-35.59 2.51-2.52 w 36.02-36.04
2.48-2.49 w 41.65-41.71 2.16-2.16 w 44.57-44.61 2.02-2.03 w
47.48-47.58 1.9-1.91 w 49.53-49.59 1.83-1.83 w
wherein the UZM-35 composition is thermally stable up to a
temperature of at least 400.degree. C.
2. The UZM-35 composition of claim 1 wherein "x" is zero.
3. The UZM-35 composition of claim 1 where the composition is
thermally stable up to a temperature of at least 600.degree. C.
4. The UZM-35 composition of claim 1 wherein the amount of MSE
zeolite varies from about 55 wt-% to about 90 wt-% of the
composition.
5. The UZM-35 composition of claim 1 wherein the amount of MFI
zeolite varies from about 10 wt-% to about 35 wt-% of the
composition.
6. The UZM-35 composition of claim 1 wherein the amount of ERI
varies from about 3 wt-% to about 10 wt-% of the composition.
7. A process for preparing a UZM-35 composition comprising a MFI
zeolite, an ERI zeolite, and a MSE zeolite, the composition 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.+R.sub.r.sup.+Al.sub.1-xE.sub.xSi.sub.yO.sub.z
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
dimethyldipropylammonium cation, "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
O 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-00012 TABLE A 2.theta. d (.ANG.)
I/Io % 6.48-6.51 13.32-13.58 m 6.78-6.83 12.91-13.02 m-s 7.79-7.96
11.09-11.32 m 8.05-8.07 10.93-10.96 m 8.71-8.75 10.08-10.13 m
9.61-9.65 9.15-9.18 m-s 10.75-10.79 8.18-8.21 w 13.61-13.65
6.47-6.49 w 14.74-14.79 5.98-6 w 15.56-15.59 5.67-5.69 w
15.86-15.86 5.58-5.58 w 19.46-19.5 4.54-4.55 m 19.89-19.92
4.45-4.45 m 20.48-20.51 4.32-4.33 m 20.94-20.96 4.23-4.23 m
21.61-21.64 4.1-4.1 vs 21.79-21.81 4.07-4.07 s 22.39-22.45
3.95-3.96 m 22.93-22.98 3.86-3.87 s-vs 23.29-23.31 3.81-3.81 m
23.5-23.5 3.78-3.78 m 23.78-23.86 3.72-3.73 m 24.39-24.41 3.64-3.64
w 24.82-24.82 3.58-3.58 w 25.76-25.79 3.45-3.45 w-m 26.09-26.12
3.4-3.41 m 26.74-26.81 3.32-3.33 m 27.14-27.14 3.28-3.28 m
27.42-27.46 3.24-3.249 m 27.69-27.69 3.21-3.21 m 28.02-28.06
3.17-3.18 m 29.1-29.15 3.06-3.06 m 29.54-29.61 3.01-3.02 w
29.75-29.86 2.98-2.99 w 30.12-30.14 2.96-2.96 m 30.73-30.79 2.9-2.9
m 31.26-31.27 2.85-2.85 w 31.47-31.47 2.83-2.83 w 33.19-33.25
2.69-2.69 w 34.34-34.48 2.59-2.6 w 34.76-34.76 2.57-2.57 w
35.18-35.2 2.54-2.54 w 35.57-35.59 2.51-2.52 w 36.02-36.04
2.48-2.49 w 41.65-41.71 2.16-2.16 w 44.57-44.61 2.02-2.03 w
47.48-47.58 1.9-1.91 w 49.53-49.59 1.83-1.83 w
wherein the UZM-35 composition is thermally stable up to a
temperature of at least 400.degree. C.; the process comprising
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., for a
time sufficient to form the zeolitic composition, 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.su-
b.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.
8. The process of claim 7 where the source of M is selected from
the group consisting of halide salts, nitrate salts, acetate salts,
hydroxides, sulfate salts and mixtures thereof.
9. The process of claim 7 where the source of E is selected from
the group consisting of alkali borates, boric acid, precipitated
gallium oxyhydroxide, gallium sulfate, ferric sulfate, ferric
chloride and mixtures thereof.
10. The process of claim 7 where the aluminum source is selected
from the group consisting of aluminum isopropoxide, aluminum
sec-butoxide, precipitated alumina, Al(OH).sub.3, aluminum metal
and aluminum salts.
11. The process of claim 7 where the silicon source is selected
from the group consisting of tetraethylorthosilicate, fumed silica,
colloidal silica and precipitated silica.
12. The process of claim 7 where the reaction mixture is reacted at
a temperature of about 150.degree. C. to about 185.degree. C. for a
time of about 1 day to about 3 weeks.
13. The process of claim 7 where the reaction mixture is reacted at
a temperature of about 165.degree. C. to about 175.degree. C. for a
time of about 1 day to about 3 weeks.
14. The process of claim 7 where R is a combination of
dimethyldipropyl ammonium hydroxide and at least one singly charged
organoammonium cation selected from the group consisting of TEA,
TPA, ETMA, DEDMA, trimethylpropylammonium,
dimethyldiisopropylammonium, trimethylbutylammonium, or
dimethyldiethanolammonium, methyltripropylammonium.
15. The process of claim 7 further comprising adding UZM-35 zeolite
seeds to the reaction mixture.
16. A UZM-35HS composition comprising a MFI zeolite, an ERI
zeolite, and a MSE zeolite, the UZM-35HS composition 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 O 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-00013 TABLE A 2.theta. d
(.ANG.) I/Io % 6.48-6.51 13.32-13.58 m 6.78-6.83 12.91-13.02 m-s
7.79-7.96 11.09-11.32 m 8.05-8.07 10.93-10.96 m 8.71-8.75
10.08-10.13 m 9.61-9.65 9.15-9.18 m-s 10.75-10.79 8.18-8.21 w
13.61-13.65 6.47-6.49 w 14.74-14.79 5.98-6 w 15.56-15.59 5.67-5.69
w 15.86-15.86 5.58-5.58 w 19.46-19.5 4.54-4.55 m 19.89-19.92
4.45-4.45 m 20.48-20.51 4.32-4.33 m 20.94-20.96 4.23-4.23 m
21.61-21.64 4.1-4.1 vs 21.79-21.81 4.07-4.07 s 22.39-22.45
3.95-3.96 m 22.93-22.98 3.86-3.87 s-vs 23.29-23.31 3.81-3.81 m
23.5-23.5 3.78-3.78 m 23.78-23.86 3.72-3.73 m 24.39-24.41 3.64-3.64
w 24.82-24.82 3.58-3.58 w 25.76-25.79 3.45-3.45 w-m 26.09-26.12
3.4-3.41 m 26.74-26.81 3.32-3.33 m 27.14-27.14 3.28-3.28 m
27.42-27.46 3.24-3.249 m 27.69-27.69 3.21-3.21 m 28.02-28.06
3.17-3.18 m 29.1-29.15 3.06-3.06 m 29.54-29.61 3.01-3.02 w
29.75-29.86 2.98-2.99 w 30.12-30.14 2.96-2.96 m 30.73-30.79 2.9-2.9
m 31.26-31.27 2.85-2.85 w 31.47-31.47 2.83-2.83 w 33.19-33.25
2.69-2.69 w 34.34-34.48 2.59-2.6 w 34.76-34.76 2.57-2.57 w
35.18-35.2 2.54-2.54 w 35.57-35.59 2.51-2.52 w 36.02-36.04
2.48-2.49 w 41.65-41.71 2.16-2.16 w 44.57-44.61 2.02-2.03 w
47.48-47.58 1.9-1.91 w 49.53-49.59 1.83-1.83 w
wherein the UZM-35HS composition is thermally stable up to a
temperature of at least 400.degree. C.
17. The UZM-35HS composition of claim 16 wherein "x" is zero.
18. The UZM-35HS composition of claim 16 wherein the amount of MSE
zeolite varies from about 55 wt-% to about 90 wt-% of the
composition, the amount of MFI zeolite varies from about 10 wt-% to
about 35 wt-% of the composition, and the amount of ERI varies from
about 3 wt-% to about 10 wt-% of the composition.
Description
CROSS-REFERENCE TO RELATED APPLICATION
[0001] This application is a Division of co-pending application
Ser. No. 13/151,482 filed Jun. 2, 2011, which is a
Continuation-in-Part of application Ser. No. 12/820,079 filed on
Jun. 21, 2010 now U.S. Pat. No. 8,022,262, the contents of which
are hereby incorporated by reference in its entirety.
FIELD OF THE INVENTION
[0002] This invention relates to a UZM-35 composition comprising a
MSE zeolite, an MFI zeolite, and an ERI zeolite. The UZM-35
composition is represented by the empirical formula of:
M.sub.m.sup.n+R.sup.+.sub.rAl.sub.1-xE.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 dimethyldipropylammonium and E is a framework element such
as gallium.
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
structure 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] 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.
[0005] Applicants have successfully prepared a new family of
material compositions designated UZM-35 composition. The topology
of one of the zeolites in the composition is similar to that
observed for MCM-68. The materials are prepared via the use of a
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 described in U.S. Pat. No. 7,578,993.
The UZM-35 zeolite having the MSE topology may be synthesized as a
UZM-35 composition comprising the MSE topology zeolite as well as a
MFI topology zeolite and an ERI topology zeolite. Topologies of
MSE, MFI, ERI are as defined in Atlas of Zeolite Framework Types,
which is maintained by the International Zeolite Association
Structure Commission at
http://www.iza-structure.org/databases/.
SUMMARY OF THE INVENTION
[0006] As stated, the present invention relates to a new
aluminosilicate zeolite composition designated UZM-35 composition
which comprises an MSE zeolite, a MFI zeolite and an ERI zeolite.
Accordingly, one embodiment of the invention is a microporous
crystalline zeolitic UZM-35 composition 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.+R.sup.+.sub.rAl.sub.1-xE.sub.xSi.sub.yO.sub.z
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.+), dimethyl
diisopropylammonium (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 O to (Al+E) and has a value
determined by the equation:
z=(m+r+3+4y)/2
and is characterized in that the composition 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 % 6.48-6.51
13.32-13.58 m 6.78-6.83 12.91-13.02 m-s 7.79-7.96 11.09-11.32 m
8.05-8.07 10.93-10.96 m 8.71-8.75 10.08-10.13 m 9.61-9.65 9.15-9.18
m-s 10.75-10.79 8.18-8.21 w 13.61-13.65 6.47-6.49 w 14.74-14.79
5.98-6 w 15.56-15.59 5.67-5.69 w 15.86-15.86 5.58-5.58 w 19.46-19.5
4.54-4.55 m 19.89-19.92 4.45-4.45 m 20.48-20.51 4.32-4.33 m
20.94-20.96 4.23-4.23 m 21.61-21.64 4.1-4.1 vs 21.79-21.81
4.07-4.07 s 22.39-22.45 3.95-3.96 m 22.93-22.98 3.86-3.87 s-vs
23.29-23.31 3.81-3.81 m 23.5-23.5 3.78-3.78 m 23.78-23.86 3.72-3.73
m 24.39-24.41 3.64-3.64 w 24.82-24.82 3.58-3.58 w 25.76-25.79
3.45-3.45 w-m 26.09-26.12 3.4-3.41 m 26.74-26.81 3.32-3.33 m
27.14-27.14 3.28-3.28 m 27.42-27.46 3.24-3.249 m 27.69-27.69
3.21-3.21 m 28.02-28.06 3.17-3.18 m 29.1-29.15 3.06-3.06 m
29.54-29.61 3.01-3.02 w 29.75-29.86 2.98-2.99 w 30.12-30.14
2.96-2.96 m 30.73-30.79 2.9-2.9 m 31.26-31.27 2.85-2.85 w
31.47-31.47 2.83-2.83 w 33.19-33.25 2.69-2.69 w 34.34-34.48
2.59-2.6 w 34.76-34.76 2.57-2.57 w 35.18-35.2 2.54-2.54 w
35.57-35.59 2.51-2.52 w 36.02-36.04 2.48-2.49 w 41.65-41.71
2.16-2.16 w 44.57-44.61 2.02-2.03 w 47.48-47.58 1.9-1.91 w
49.53-49.59 1.83-1.83 w
In addition, the composition is thermally stable up to a
temperature of greater than 400.degree. C. in one embodiment and
600.degree. C. in another embodiment. The UZM-35 composition as
synthesized comprises a MSE topology zeolite, a MFI topology
zeolite and an ERI topology zeolite. Typically, the amount of MSE
zeolite 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.
[0007] The crystalline microporous zeolitic UZM-35 composition
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 composition, 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. The MSE type zeolite UZM-35 zeolite is synthesized
along with additional zeolites MFI and ERI to form the UZM-35
composition.
[0008] Yet another embodiment of the invention is a hydrocarbon
conversion process using the UZM-35 composition. The process
comprises contacting the hydrocarbon with the UZM-35 composition at
conversion conditions to give a converted hydrocarbon.
DETAILED DESCRIPTION OF THE INVENTION
[0009] Applicants have prepared an aluminosilicate zeolitic
composition which comprises a MSE zeolite, a MFI zeolite, and an
ERI zeolite. The MSE zeolite has a topological structure that is
related to MSE as described in Atlas of Zeolite Framework Types and
thus will be called an MSE zeolite herein. As will be shown in
detail, the UZM-35 composition is different from MCM-68 in a number
of its characteristics. The microporous crystalline zeolitic UZM-35
composition has an empirical composition in the as-synthesized form
and on an anhydrous basis expressed by the empirical formula:
M.sub.m.sup.+R.sup.+.sub.rAl.sub.1-xE.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 O 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##
[0010] The microporous crystalline zeolitic UZM-35 composition 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
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.
[0011] 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.
[0012] 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, and "e" varies from about 25 to about 4000. 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 zeolite seeds
can optionally be added to the reaction mixture in order to
accelerate the formation of the composition.
[0013] A preferred synthetic approach to make UZM-35 composition
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 the
UZM-35 composition, using, for example, a combination of
dimethyldipropylammonium hydroxide and the alkali cations. The use
of commercially available dimethyldipropylammonium hydroxide to
prepare the UZM-35 composition 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:5Rs,6-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.
[0014] The UZM-35 composition, which is obtained from the
above-described process, is characterized by the x-ray diffraction
pattern using the Rietveld refinement method described in J. Appl.
Cryst. (1969) 2, 65-71, and having at least the d-spacings and
relative intensities set forth in Table A below.
TABLE-US-00002 TABLE A 2.theta. d (.ANG.) I/Io % 6.48-6.51
13.32-13.58 m 6.78-6.83 12.91-13.02 m-s 7.79-7.96 11.09-11.32 m
8.05-8.07 10.93-10.96 m 8.71-8.75 10.08-10.13 m 9.61-9.65 9.15-9.18
m-s 10.75-10.79 8.18-8.21 w 13.61-13.65 6.47-6.49 w 14.74-14.79
5.98-6 w 15.56-15.59 5.67-5.69 w 15.86-15.86 5.58-5.58 w 19.46-19.5
4.54-4.55 m 19.89-19.92 4.45-4.45 m 20.48-20.51 4.32-4.33 m
20.94-20.96 4.23-4.23 m 21.61-21.64 4.1-4.1 vs 21.79-21.81
4.07-4.07 s 22.39-22.45 3.95-3.96 m 22.93-22.98 3.86-3.87 s-vs
23.29-23.31 3.81-3.81 m 23.5-23.5 3.78-3.78 m 23.78-23.86 3.72-3.73
m 24.39-24.41 3.64-3.64 w 24.82-24.82 3.58-3.58 w 25.76-25.79
3.45-3.45 w-m 26.09-26.12 3.4-3.41 m 26.74-26.81 3.32-3.33 m
27.14-27.14 3.28-3.28 m 27.42-27.46 3.24-3.249 m 27.69-27.69
3.21-3.21 m 28.02-28.06 3.17-3.18 m 29.1-29.15 3.06-3.06 m
29.54-29.61 3.01-3.02 w 29.75-29.86 2.98-2.99 w 30.12-30.14
2.96-2.96 m 30.73-30.79 2.9-2.9 m 31.26-31.27 2.85-2.85 w
31.47-31.47 2.83-2.83 w 33.19-33.25 2.69-2.69 w 34.34-34.48
2.59-2.6 w 34.76-34.76 2.57-2.57 w 35.18-35.2 2.54-2.54 w
35.57-35.59 2.51-2.52 w 36.02-36.04 2.48-2.49 w 41.65-41.71
2.16-2.16 w 44.57-44.61 2.02-2.03 w 47.48-47.58 1.9-1.91 w
49.53-49.59 1.83-1.83 w
As will be shown in detail in the examples, the UZM-35 composition
is thermally stable up to a temperature of at least 400.degree. C.
and in another embodiment, up to about 600.degree. C.
[0015] As synthesized, the UZM-35 composition 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 composition comprises large
pore zeolite(s), it is also possible to remove some organic cations
directly by ion exchange. The UZM-35 composition 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 mole ratio, acidity, thermal stability, etc.
[0016] 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 O to (Al+E) and has a value
determined by the equation:
z'=(an+3+4y')/2
[0017] 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 know 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.
[0018] 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.
[0019] The crystalline zeolitic UZM-35 composition of this
invention can be used for separating mixtures of molecular species,
removing contaminants through ion exchange and catalyzing various
hydrocarbon conversion processes. Separation of molecular species
can be based either on the molecular size (kinetic diameter) or on
the degree of polarity of the molecular species.
[0020] The UZM-35 composition of this invention can also be used as
a catalyst or catalyst support in various hydrocarbon conversion
processes. Hydrocarbon conversion processes are well known in the
art and include cracking, hydrocracking, alkylation of both
aromatics and isoparaffin, isomerization of paraffin and
poly-alkylbenzenes such as xylene, trans-alkylation of
poly-alkybenzene with benzene or mono-alkybenzenes,
disproportionation of mono-alkybenzenes, polymerization, reforming,
hydrogenation, dehydrogenation, transalkylation, dealkylation,
hydration, dehydration, hydrotreating, hydrodenitrogenation,
hydrodesulfurization, methanation and syngas shift process.
Specific reaction conditions and the types of feeds which can be
used in these processes are set forth in U.S. Pat. No. 4,310,440
and U.S. Pat. No. 4,440,871 which are hereby incorporated by
reference. Preferred hydrocarbon conversion processes are those in
which hydrogen is a component such as hydrotreating or hydrofining,
hydrogenation, hydrocracking, hydrodenitrogenation,
hydrodesulfurization, etc.
[0021] Hydrocracking conditions typically include a temperature in
the range of about 204.degree. C. to about 649.degree. C.
(400.degree. to 1200.degree. F.) or about 316.degree. C. to about
510.degree. C. (600.degree. F. and 950.degree. F.). Reaction
pressures are in the range of atmospheric to about 24,132 kPa g
(3,500 psig), or between about 1379 to about 20,685 kPa g (200 to
3000 psig). Contact times usually correspond to liquid hourly space
velocities (LHSV) in the range of about 0.1 hr.sup.-1 to 15
hr.sup.-1, preferably between about 0.2 and 3 hr.sup.-1. Hydrogen
circulation rates are in the range of 178 to about 8,888 std.
m.sup.3/m.sup.3 (1,000 to 50,000 standard cubic feet (scf) per
barrel of charge), or about 355 to about 5,333 std. m.sup.3/m.sup.3
(about 2,000 to about 30,000 scf per barrel of charge). Suitable
hydrotreating conditions are generally within the broad ranges of
hydrocracking conditions set out above.
[0022] The reaction zone effluent is normally removed from the
catalyst bed, subjected to partial condensation and vapor-liquid
separation and then fractionated to recover the various components
thereof. The hydrogen, and if desired some or all of the
unconverted heavier materials, are recycled to the reactor.
Alternatively, a two-stage flow may be employed with the
unconverted material being passed into a second reactor. Catalysts
of the subject invention may be used in just one stage of such a
process or may be used in both reactor stages.
[0023] Catalytic cracking processes are preferably carried out with
the UZM-35 composition using feedstocks such as gas oils, heavy
naphthas, deasphalted crude oil residua, etc. with gasoline being
the principal desired product. Temperature conditions of about
454.degree. C. to about 593.degree. C. (about 850.degree. F. to
about 1100.degree. F.), LHSV values of 0.5 to 10 and pressure
conditions of from about 0 to about 344 kPa g (about 0 to 50 psig)
are suitable.
[0024] Alkylation of aromatics usually involves reacting an
aromatic (C.sub.2 to C.sub.12), especially benzene, with a
monoolefin to produce a linear alkyl substituted aromatic. The
process is carried out at an aromatic:olefin (e.g., benzene:olefin)
ratio of between 1:1 and 30:1, a olefin LHSV of about 0.3 to about
10 hr.sup.-1, a temperature of about 100.degree. to about
250.degree. C. and pressures of about 1379 kPa g to about 6895 kPa
g (about 200 to about 1000 psig). Further details on apparatus may
be found in U.S. Pat. No. 4,870,222 which is incorporated by
reference.
[0025] Alkylation of isoparaffins with olefins to produce alkylates
suitable as motor fuel components is carried out at temperatures of
-30.degree. to 40.degree. C., pressures from about atmospheric to
about 6,895 kPa (1,000 psig) and a weight hourly space velocity
(WHSV) of 0.1 to about 120. Details on paraffin alkylation may be
found in U.S. Pat. No. 5,157,196 and U.S. Pat. No. 5,157,197, which
are incorporated by reference.
[0026] 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.
[0027] The structure of the UZM-35 composition 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.
[0028] 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
[0029] 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.
[0030] In order to more fully illustrate the invention, the
following examples are set forth. It is to be understood that the
examples are only 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
[0031] An aluminosilicate reaction solution was prepared by first
mixing 16.64 aluminum hydroxide (27.78 mass-% Al) and 526.79 g
dimethyldipropylammonium hydroxide, 18.8 mass-% solution, while
stirring vigorously. After thorough mixing, 252.98 g of Ludox.TM.
AS-40 (40% SiO.sub.2) was added. The reaction mixture was
homogenized for an additional hour with a high speed mechanical
stirrer and placed in an oven at 100.degree. C. overnight. Analysis
showed the resulting aluminosilicate solution contained 6.52 wt. %
Si and 0.64 wt. % Al yielding a Si/Al ratio of 9.78.
[0032] To a 150 g portion of the aluminosilicate solution prepared
in Example 1, a composite aqueous NaOH/KOH solution containing 1.44
g of NaOH (98%) and 2.02 g of KOH dissolved in 20.0 g distilled
water was added with vigorous stirring and the reaction mixture was
homogenized for an additional 30 minutes. A 24 g portion of the
reaction mixture was transferred to a 45 ml Parr stainless steel
autoclave which was heated to 175.degree. C. and maintained at that
temperature for 120 hrs. The solid product was recovered by
centrifugation, washed with de-ionized water, and dried at
100.degree. C.
[0033] The solid products were recovered by centrifugation, washed
with de-ionized water and dried at 95.degree. C. The product was
identified as UZM-35 zeolite 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-00003 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
[0034] Scanning Electron Microscopy (SEM) revealed crystals of
square shaped morphology, approximately 100 by 350 nm in size. This
sample was calcined at 540.degree. C. for 10 hrs under nitrogen and
then air. Representative diffraction lines observed for the
calcined product are shown in Table 2.
TABLE-US-00004 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 2
[0035] An aluminosilicate reaction solution was prepared by first
mixing 37.17 g of aluminum hydroxide (27.78 mass-% Al) and 1053.58
g of dimethyldipropylammonium hydroxide (18.8 mass-% solution),
while stirring vigorously. After thorough mixing, 505.96 g
Ludox.TM. AS-40 (SiO.sub.2, 40%) was added. The reaction mixture
was homogenized for 1 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=8.83).
[0036] A 100.0 g portion of the above aluminosilicate solution was
continuously stirred. A composite aqueous solution containing 2.38
g of KOH and 0.3 g of NaOH dissolve in 15 g H.sub.2O was added,
dropwise, to the aluminosilicate solution. After the addition was
completed, the resulting reaction mixture was homogenized for 1
hour, transferred to (4) 45 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.
[0037] The solid product from each of these samples was recovered
by centrifugation, washed with de-ionized water and dried at
95.degree. C. The products resulting from all four reactions were
identified by xrd to be UZM-35 zeolite. Table 3 shows
representative diffraction lines observed for the sample that was
reacted for 9 days. Elemental analysis gave a product composition
in mole ratios of: Si/Al=7.58, Na/Al=0.033, K/Al=0.63, C/N=6,
N/Al=0.43.
TABLE-US-00005 TABLE 3 2.theta. d (.ANG.) I/I.sub.0 % 6.56 13.46 m
6.84 12.91 s 8.10 10.90 m 8.80 10.03 m 9.69 9.11 m 10.80 8.18 w
13.69 6.45 w 14.17 6.01 w 15.10 5.86 w 15.88 5.57 w 18.01 4.91 w
19.48 4.55 w 19.98 4.44 m 20.52 4.32 w 21.00 4.22 m 21.68 4.09 vs
22.49 3.94 m 23.04 3.85 s 24.31 3.65 m 24.61 3.61 w 25.85 3.44 m
26.14 3.40 m 26.85 3.31 m 27.68 3.22 m 28.15 3.16 m 29.20 3.05 m
29.90 2.98 m 30.82 2.89 m 31.33 2.85 w 32.49 2.75 w 33.28 2.68 w
34.42 2.60 w 34.84 2.57 w 35.32 2.53 w 35.69 2.51 w 36.10 2.48 w
37.59 2.39 w 41.75 2.16 w 44.67 2.02 w 45.11 2.00 w 45.45 1.99 w
46.10 1.96 w 46.50 1.95 w 47.01 1.93 w 47.62 1.90 w 49.7 1.83 w
Example 3
[0038] An aluminosilicate reaction solution was prepared by first
mixing 37.17 g of aluminum hydroxide (27.78% Al) and 1053.58 g of
dimethyldipropylammonium hydroxide (18.8 mass-% solution), while
stirring vigorously. After thorough mixing, 505.96 g Ludox.TM.
AS-40 (SiO.sub.2, 40 mass-%) was added. The reaction mixture was
homogenized for 1 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 mole ratio=8.83).
[0039] 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 dissolve in 150 g H.sub.2O, was added,
dropwise, 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.
[0040] The solid product from each of these samples was recovered
by centrifugation, washed with de-ionized water and dried at
95.degree. C. The products resulting from this reaction were
identified by xrd to be UZM-35 zeolite. Elemental analysis gave a
product composition in mole ratios of: Si/Al=7.57, Na/Al=0.028,
K/Al=0.73, N/Al=0.37. This sample 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 4.
TABLE-US-00006 TABLE 4 2.theta. d (.ANG.) I/I.sub.0 % 6.54 13.5 m
6.85 12.88 m 8.10 10.90 m 8.82 10.01 m 9.67 9.13 m 10.80 8.18 m
11.08 7.97 w 13.67 6.46 m 14.84 5.96 w 15.21 5.81 w 15.61 5.67 w
15.91 5.56 w 17.47 5.07 w 17.87 4.95 w 19.52 4.54 m 19.96 4.44 m
20.54 4.32 m 21.16 4.19 m 21.67 4.09 vs 21.89 4.05 s 22.54 3.94 s
23.08 3.85 vs 24.45 3.63 m 24.65 3.60 w 25.06 3.55 m 25.84 3.44 m
26.14 3.40 m 26.46 3.36 m 26.90 3.31 m 27.48 3.21 m 27.73 3.21 m
28.19 3.16 m 28.66 3.11 w 29.18 3.05 m 29.58 3.01 w 29.88 2.98 m
30.21 2.95 m 30.80 2.90 m 31.38 2.84 w 33.32 2.68 w 34.52 2.59 w
34.79 2.57 w 35.69 2.51 w 36.15 2.48 w 41.70 2.16 w 44.83 2.01 w
45.46 1.99 w 46.52 1.95 w 47.54 1.91 w 47.88 1.89 w 49.56 1.83
w
Example 4
[0041] This example describes the modification of a UZM-35
material. A 10 g portion of a UZM-35 sample (Si/Al mole ratio 7.57)
was calcined in a nitrogen atmosphere, ramping at 3.degree. C./min
to 540.degree. C. and holding there for an additional hour before
changing the atmosphere to air and continuing the calcination for
another 9 hr. A solution was prepared by first diluting 2 g of
HNO.sub.3 (69 mass-%) followed by dissolving 10 g of
NH.sub.4NO.sub.3 in 120 g de-ionized water. This solution was
heated to 75.degree. C. before adding the calcined UZM-35. The
slurry was stirred for 1 hr at 75.degree. C. The product was
isolated by filtration, washed with de-ionized water and dried at
100.degree. C. for 12 hrs.
[0042] The product was identified as UZM-35HS via x-ray powder
diffraction. Elemental analyses confirmed an increase in Si/Al mole
ratio to Si/Al=8.3, Na/Al=0.01, K/Al=0.44.
Example 5
[0043] This example demonstrates the modification of a UZM-35
material. A 20 g portion of a UZM-35 sample (Si/Al mole ratio 7.57)
was calcined under a nitrogen atmosphere by ramping at 3.degree.
C./min to 560.degree. C. and holding there for 1 hr before changing
the atmosphere to air and continuing the calcination for another 9
hr. Separately, a solution was prepared by dissolving 20 g of
NH.sub.4NO.sub.3 in 490 g de-ionized water. The solution was heated
to 75.degree. C. before adding the calcined UZM-35. The slurry was
stirred for 1 hr at 75.degree. C. The product was isolated by
filtration, washed with de-ionized water and dried at 100.degree.
C. for 12 hrs.
[0044] The product was identified as UZM-35HS via x-ray powder
diffraction. Elemental analyses of this sample shows a Si/Al mole
ratio to Si/Al=8.0, Na/Al=0.01, K/Al=0.47.
Example 6
[0045] An aluminosilicate solution was prepared by first mixing
37.17 g aluminum hydroxide (27.78 mass-% Al) and 1053.58 g
dimethyldipropylammonium hydroxide, 18.8 mass-% solution, with
vigorous stirring. After thorough mixing, 505.96 g of 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 and placed in an oven at 100.degree. C. overnight. Analysis
showed the resulting aluminosilicate solution contained 6.16 wt. %
Si and 0.67 wt. % Al yielding a Si/Al mole ratio of 8.83.
[0046] To a 100 g portion of the aluminosilicate solution prepared
in Example 6 above, an aqueous NaOH solution containing 1.98 g of
NaOH (98%) in 10.0 g distilled water was added with vigorous
stirring and the reaction mixture was homogenized for an additional
30 minutes. A 24 g portion of the reaction mixture was transferred
to a 45 ml Parr stainless steel autoclave which was heated to
175.degree. C. and maintained at that temperature for 144 hrs. The
solid product was recovered by centrifugation, washed with
de-ionized water, and dried at 100.degree. C.
[0047] The solid products were recovered by centrifugation, washed
with de-ionized water and dried at 95.degree. C. The product was
identified as MOR zeolite by xrd.
Example 7
[0048] An aluminosilicate solution was prepared by first mixing
37.17 aluminum hydroxide (27.78 mass % Al) and 1053.58 g
dimethyldipropylammonium hydroxide, 18.8 mass-% solution, with
vigorous stirring. After thorough mixing, 505.96 g of 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 and placed in an oven at 100.degree. C. overnight. Analysis
showed the resulting aluminosilicate solution contained 6.16
wt.-%-Si and 0.67 wt.-% Al yielding a Si/Al mole ratio of 8.83.
[0049] To a 150 g portion of the aluminosilicate solution prepared
in Example 6, an aqueous KOH solution containing 3.84 g of KOH
dissolved in 20.0 g distilled water was added with vigorous
stirring and the reaction mixture was homogenized for an additional
30 minutes. A 24 g portion of the reaction mixture was transferred
to a 45 ml Parr stainless steel autoclave which was heated to
175.degree. C. and maintained at that temperature for 264 hrs. The
solid product was recovered by centrifugation, washed with
de-ionized water, and dried at 100.degree. C.
[0050] The solid products were recovered by centrifugation, washed
with de-ionized water and dried at 95.degree. C. The product was
identified as ZSM-5 zeolite by xrd.
Example 8
[0051] An aluminosilicate reaction solution was prepared by first
mixing 86.33 g of aluminum hydroxide (26.97 mass-% Al) and 1437.67
g of dimethyldipropylammonium hydroxide (40.66 mass-% solution),
while stirring vigorously. After thorough mixing, 1366.88 g
Ludox.TM. AS-40 (SiO.sub.2, mass-40%) was added. The reaction
mixture was homogenized for 20 minutes with a high-speed mechanical
stirrer, the aluminosilicate colloidal solution was continuously
stirred and an aqueous solution containing 83.04 g of KOH and 17.38
g of NaOH dissolved in 808.7 g H.sub.2O, was added, drop wise, to
the aluminosilicate solution. After the addition was completed, the
resulting reaction mixture was homogenized for 1/2 hour,
transferred to (3) 2000 ml Parr stainless steel autoclave which
were heated to 175.degree. C. and maintained at that temperature
for 9 days. The solid products were recovered by filtration, washed
with de-ionized water, and dried at 100.degree. C.
[0052] The product resulting from this reaction was identified by
x-ray diffraction (Rietveld refinement method described in J. Appl.
Cryst. (1969) 2, 65-71) to be a UZM-35 composition of 72.1 wt-% MSE
type zeolite with a lattice parameter of 18.372 angstroms for a and
20.285 angstroms for c; 24.1 wt-% MFI zeolite with a lattice
parameter of 20.101 angstroms for a, 19.862 angstroms for b and
13.402 for c, and 3.7 wt-% ERI zeolite with a lattice parameter of
13.222 angstroms for a and 14.900 angstroms for c. Chemical
analysis gave a product composition of mole ratio Si/Al=8.9. BET
Surface area was determined to be 408 m2/g and micropore volume was
0.197 cc/g. Representative diffraction lines observed for the
product are shown in Table 5.
TABLE-US-00007 TABLE 5 2.theta. d (.ANG.) I/Io % 6.5 13.58 m 6.8
12.99 s 7.79 11.32 m 8.07 10.93 m 8.719 10.13 m 9.63 9.17 s 10.75
8.21 w 13.63 6.49 w 14.74 6.00 w 15.56 5.69 w 15.86 5.58 w 19.46
4.55 m 19.899 4.45 m 20.518 4.32 m 20.94 4.23 w 21.618 4.1 vs
21.799 4.07 s 22.399 3.96 m 22.93 3.87 s 23.299 3.81 m 23.78 3.73 m
24.82 3.58 w 25.76 3.45 w 26.09 3.41 m 26.74 3.33 m 27.42 3.24 m
28.04 3.17 w 29.10 3.06 w 29.54 3.02 w 29.75 2.99 w 30.13 2.96 m
30.73 2.9 m 31.47 2.83 w 33.19 2.69 w 34.46 2.6 w 35.18 2.54 w
35.59 2.51 w 36.04 2.49 w 41.65 2.16 w 44.57 2.03 w 47.48 1.91 w
49.53 1.83 w
[0053] This sample was calcined at 600.degree. C. for 5 hrs under
nitrogen and then air. The product resulting from the calcination
was identified by x-ray diffraction (Rietveld refinement method
described in J. Appl. Cryst. (1969) 2, 65-71) to be a mixture of
64.4 wt % UZM-35 with a lattice parameter of 18.371 angstroms for a
and 20.235 angstroms for c; 30.7 wt % MFI with a lattice parameter
of 20.048 angstroms for a, 19.880 angstroms for b and 13.403
angstroms for c, and 4.8 wt % ERI with a lattice parameter of
13.071 angstroms for a and 15.238 angstroms for c. A 160 g portion
of the calcined UZM-35 sample (Si/Al mole ratio of 8.9) was NH4
exchanged. A solution was prepared by dissolving 160 g of
NH.sub.4NO.sub.3 in 1800 g de-ionized water. The solution was
heated to 75.degree. C. before adding the calcined UZM-35. The
slurry was stirred for 1 hr at 75.degree. C. The product was
isolated by filtration, washed with de-ionized water. This NH4
exchange procedure was repeated 3 times then it was dried at
100.degree. C. for 12 hrs.
[0054] Elemental analyses of this sample shows a Si/Al mole ratio
to Si/Al=9.07, Na/Al=0.01, K/Al=0.11.
[0055] Representative diffraction lines observed for the product
are shown in Table 6.
TABLE-US-00008 TABLE 6 2.theta. d (.ANG.) I/Io % 6.67 13.22 m 6.97
12.65 m-s 7.94 11.12 m 8.14 10.85 m 8.93 9.88 m 9.79 9.01 m-s 10.92
8.09 m 13.78 6.42 w 14.1 6.27 w 14.97 5.91 w 15.7 5.63 w 16.05 5.51
w 17.57 5.04 w 19.64 4.51 m 20.05 4.42 m 20.65 4.29 m 21.13 4.19 w
21.77 4.07 vs 21.98 4.04 s-vs 22.62 3.92 s 23.14 3.84 vs 23.46 3.78
m 23.94 3.71 m 24.58 3.61 w 24.83 3.58 w 25.2 3.53 m 25.92 3.43 w
26.24 3.39 m 26.52 3.35 m 26.96 3.3 m 27.6 3.22 m-s 28.25 3.15 m
28.79 3.09 m 29.3 3.04 m 29.68 3 w 29.96 2.98 m 30.35 2.94 m 30.89
2.89 m 31.46 2.84 m 31.81 2.81 m 33.4 2.68 m 36.22 2.47 w 41.83
2.15 w 44.86 2.01 w 47.64 1.9 w 49.69 1.83 w
Example 9
[0056] An aluminosilicate reaction solution was prepared by first
mixing 29.01 g of aluminum hydroxide (26.97 wt. % Al) and 483.08 g
of dimethyldipropylammonium hydroxide (40.66% solution), while
stirring vigorously. After thorough mixing, 461.58 g Ludox.TM.
AS-40 (SiO.sub.2, 40 wt. %) was added. The reaction mixture was
homogenized for 20 minutes with a high-speed mechanical stirrer,
the aluminosilicate colloidal solution was continuously stirred and
an aqueous solution containing 27.90 g of KOH and 3.46 g of NaOH
dissolved in 269.98 g H.sub.2O, was added, drop wise, to the
aluminosilicate solution. After the addition was completed, the
resulting reaction mixture was homogenized for 1/2 hour,
transferred to a 2000 ml Parr stainless steel autoclave, which was
heated to 175.degree. C. and maintained at that temperature for 10
days. The solid products were recovered by filtration, washed with
de-ionized water, and dried at 100.degree. C.
[0057] The product resulting from this reaction was identified by
x-ray diffraction (Rietveld refinement method described in J. Appl.
Cryst. (1969) 2, 65-71) to be a UZM-35 composition of 66.3 wt % MSE
type zeolite with a lattice parameter of 18.369 angstroms for a and
20.284 angstroms for c; 25.5 wt % MFI with a lattice parameter of
20.136 angstroms for a, 19.976 angstroms for b and 13.443 angstroms
for c, and 8.2 wt % ERI with a lattice parameter of 13.152
angstroms for a and 15.107 angstroms for c. Chemical analysis gave
a product composition (mole ratio) of Si/Al=7.65, N/Al=0.38,
K/Al=0.68, Na/Al=0.03. BET surface area was determined to be 404
m2/g and a micropore volume was 0.188 cc/g. Representative
diffraction lines observed for the product are shown in Table
7.
TABLE-US-00009 TABLE 7 2.theta. d (.ANG.) I/Io % 6.48 13.32 31.9
6.78 13.02 58.5 8.05 10.96 25.7 8.71 10.13 33.6 9.61 9.18 53.6
10.75 8.21 11.2 13.61 6.49 12.9 14.74 6 7.3 15.86 5.58 7.2 19.48
4.55 41.5 19.9 4.45 21.1 20.5 4.32 13.4 20.96 4.23 25.6 21.61 4.1
100 21.81 4.07 63.8 22.42 3.96 45.7 22.94 3.87 85.5 23.3 3.81 38.5
23.5 3.78 31.3 23.86 3.72 17.8 24.41 3.64 6.8 25.78 3.45 20.2 26.09
3.41 19.8 26.81 3.32 39.8 27.14 3.28 20.9 27.44 3.24 42.9 27.69
3.21 33 28.06 3.17 14.7 29.15 3.06 16.2 29.55 3.01 13.5 29.86 2.98
20.8 30.14 2.96 18.7 30.75 2.9 24.1 31.26 2.85 8.9 33.21 2.69 11.1
34.34 2.6 8.8 34.76 2.57 10.5 35.2 2.54 6.8 35.57 2.52 8.6 36.02
2.49 8 41.71 2.16 9.8 44.61 2.02 8.2 47.48 1.91 8 49.56 1.83
10.1
[0058] This sample was calcined at 600.degree. C. for 5 hrs under
nitrogen and then air. The product resulting from the calcination
was identified by x-ray diffraction (Rietveld refinement method
described in J. Appl. Cryst. (1969) 2, 65-71) to be a UZM-35
composition of 61.9 wt-% MSE zeolite with a lattice parameter of
18.401 angstroms for a and 20.280 angstroms for c; 30.8 wt-% MFI
zeolite with a lattice parameter of 20.114 angstroms for a, 19.919
angstroms for b and 13.432 angstroms for c, and 7.3-wt % ERI
zeolite with a lattice parameter of 13.189 angstroms for a and
15.174 angstroms for c. This sample was calcined at 600.degree. C.
for 5 hrs under nitrogen and then air. The product resulting from
the calcination was identified by x-ray diffraction (Rietveld
refinement method described in J. Appl. Cryst. (1969) 2, 65-71) to
be a UZM-35 composition of 61.9 wt-% MSE zeolite with a lattice
parameter of 18.401 angstroms for a and 20.280 angstroms for c;
30.8 wt-% MFI zeolite with a lattice parameter of 20.114 angstroms
for a, 19.919 angstroms for b and 13.432 angstroms for c, and
7.3-wt % ERI zeolite with a lattice parameter of 13.189 angstroms
for a and 15.174 angstroms for c. A 100 g portion of the calcined
UZM-35 sample (Si/Al mole ratio=7.65) was NH4 exchanged. A solution
was prepared by dissolving 160 g of NH.sub.4NO.sub.3 in 1800 g
de-ionized water. The solution was heated to 75.degree. C. before
adding the calcined UZM-35. The slurry was stirred for 1 hr at
75.degree. C. The product was isolated by filtration, washed with
de-ionized water. This NH4 exchange procedure was repeated 3 times
then it was dried at 100.degree. C. for 12 hrs.
[0059] Elemental analyses of this sample shows a Si/Al mole ratio
to Si/Al=9.20, Na/Al=0.01, K/Al=0.10.
[0060] Representative diffraction lines observed for the product
are shown in Table 8.
TABLE-US-00010 TABLE 8 2.theta. d (.ANG.) I/Io % 6.5 13.58 m 6.81
12.95 m 7.98 11.07 m 8.76 10.08 m 9.63 9.16 m 10.77 8.2 m 13.63
6.48 m 14.8 5.98 w 15.84 5.58 w 19.51 4.54 m 19.91 4.45 m 20.49
4.32 m 21.01 4.22 m 21.62 4.1 vs 22.49 3.94 s 23.02 3.86 vs 23.3
3.81 m-s 23.64 3.76 m 23.91 3.71 m 24.41 3.64 m 24.62 3.61 w 25.11
3.54 w 25.81 3.44 m 26.09 3.41 m 26.41 3.37 m 26.86 3.31 m-s 27.45
3.24 m-s 27.65 3.22 m 28.13 3.16 m 28.82 3.09 w 29.14 3.06 m 29.57
3.01 w 29.84 2.99 m 30.21 2.95 m 30.76 2.9 m 31.31 2.85 w 33.27
2.69 w 36.12 2.48 w 41.68 2.16 w 44.74 2.02 w 47.56 1.91 w 49.57
1.83 w
* * * * *
References