US2012003147A1PendingUtilityA1
Uzm-35 zeolitic composition, method of preparation and processes
Est. expiryJun 21, 2030(~3.9 yrs left)· nominal 20-yr term from priority
C10G 29/205C07C 5/32B01J 29/40C07C 2/58C07C 2529/80C07C 6/126B01J 29/50B01J 29/80C07C 2/66C10G 2400/22C07C 6/123C10G 50/00B01J 29/70C10G 2300/1088C10G 45/64C10G 2400/20C07C 5/22C07C 5/02
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Claims
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 m n+ R r + Al 1-x E x Si y O 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.
Claims
exact text as granted — not AI-modified1 . 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 2 and SiO 2 tetrahedral units and an empirical composition in the as synthesized and anhydrous basis expressed by an empirical formula of:
M m + R r + Al 1-x E x Si y O 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+4 ·y )/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 A
2θ
d (Å)
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° 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° 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 2 and SiO 2 tetrahedral units and an empirical composition in the as synthesized and anhydrous basis expressed by an empirical formula of:
M m + R r + Al 1-x E x Si y O 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+4 ·y )/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 A
2θ
d (Å)
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° 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° C. to about 200° 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:
a M 2 O: b R 2/p O:1- c Al 2 O 3 :c E 2 O 3 :d SiO 2 :e H 2 O
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) 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° C. to about 185° 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° C. to about 175° 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 2 and SiO 2 tetrahedral units and an empirical composition on an anhydrous basis expressed by an empirical formula of:
M1 a n+ Al (1-x) E x Si y′ O 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 ′=( a·n+ 3+4 ·y ′)/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 A
2θ
d (Å)
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° 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.Join the waitlist — get patent alerts
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