US 10,493,424 B2Granted

Crystalline metallophosphates, their method of preparation, and use

OwnerBenjamin D. Yuhas, Mark A. Miller +3inventors

InventorsBenjamin D. Yuhas, Mark A. Miller, Melissa M. Galey, John P. S. Mowat, Wharton Sinkler

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Abstract

A new family of crystalline microporous metallophosphates designated AlPO-78 has been synthesized. These metallophosphates are represented by the empirical formula R+rMm2+EPxSiyOz where R is an organoammonium cation, M is a framework metal alkaline earth or transition metal of valence +2, and E is a trivalent framework element such as aluminum or gallium. The AlPO-78 compositions are characterized by a new unique ABC-6 net structure, and have catalytic properties suitable for carrying out various hydrocarbon conversion processes, as well as characteristics suitable for the efficient adsorption of water vapor in a variety of applications, such as adsorption heat pumps.

Claims18

Dependent claims

A microporous crystalline material, AlPO-78 that has an empirical composition in an as-synthesized form and on an anhydrous basis expressed by an empirical formula:

R+rMm2+EPxSiyOz
where M is at least one framework divalent cation and is selected from the group consisting of alkaline earth and transition metals, wherein M is a cation selected from the group consisting of beryllium, magnesium, cobalt (II), manganese, zinc, iron (II), nickel and mixtures thereof, R is an organoammonium cation, “r” is the mole ratio of R to E and varies from about 0.1 to about 2.0, “m” is the mole ratio of M to E and varies from 0 to about 1.0, “x” is a mole ratio of P to E and varies from 0.5 to about 2.0, a ratio of silicon to E is represented by “y” which varies from about 0 to about 1.0, E is a trivalent element which is tetrahedrally coordinated, is present in the framework, and is selected from the group consisting of aluminum, gallium, iron (III) and boron and “z” is a mole ratio of O to E and is given by an equation:
z=(2·m+r+3+5·x+4·y)/2
and is characterized by a following x-ray diffraction pattern, having at least the d-spacings and relative intensities set forth in Table 1:
TABLE 1
2-Theta
d(Å)
Intensity
7.88-7.98
11.21-11.07
m-s
8.15-8.50
10.84-10.39
m-s
8.82-9.05
10.01-9.76
s
9.67-9.96
9.14-8.87
s-vs
10.58-10.81
8.35-8.17
m
10.92-11.71
8.09-7.55
m-s
13.21-13.67
6.69-6.47
s
14.10-14.54
6.27-6.08
s-vs
15.48-16.02
5.72-5.53
m
16.05-16.24
5.52-5.45
s
16.44-16.81
5.39-5.28
m
16.87-17.01
5.25-5.21
m-s
17.19-17.43
5.15-5.08
s
17.78-18.46
4.98-4.80
s-vs
18.73-19.22
4.73-4.61
vw-w
19.48-19.86
4.55-4.47
w-m
20.47-20.96
4.33-4.23
s
21.00-21.45
4.23-4.14
m-s
21.52-21.73
4.12-4.08
m-s
21.88-22.10
4.06-4.02
s
22.15-22.42
4.01-3.96
m-s
22.52-22.95
3.94-3.87
w-m
23.14-23.52
3.84-3.78
w-m
23.58-23.71
3.77-3.75
s
23.75-24.01
3.74-3.70
w-m
24.75-24.93
3.59-3.57
w-m
25.01-25.47
3.56-3.49
vs
26.15-26.31
3.40-3.38
w-m
26.37-26.54
3.38-3.35
m
26.78-27.02
3.33-3.30
w-m
27.11-27.40
3.29-3.25
m
28.39-28.86
3.14-3.09
w-m
29.22-29.65
3.05-3.01
m
30.60-30.95
2.92-2.89
w-m
31.62-31.93
2.83-2.80
w-m
31.97-32.28
2.80-2.77
w-s
32.44-32.89
2.76-2.72
w-m
33.19-33.40
2.70-2.68
vw-w
33.51-33.82
2.67-2.65
w-m
34.72-35.08
2.58-2.55
vw-w.

125 more elements

A method of making a AlPO-78 microporous crystalline material comprising preparing a reaction mixture containing reactive sources described in terms of molar ratios of the oxides by a formula:

aR2O:bMO:E2O3:cP2O5:dSiO2:eH2O
where “a” varies from about 0.75 to about 16, “b” varies from about 0 to about 2, “c” varies from about 0.8 to about 8, “d” varies from about 0 to about 4, and “e” varies from 30 to 800 wherein reactive sources of R, E, phosphorus and one or both M and silicon;
reacting the reaction mixture at a temperature from about 60° C. to about 200° C. for a period of about 1 day to about 21 days;
and isolating a solid product from a heterogeneous mixture wherein the AlPO-78 microporous material, is characterized by the x-ray following diffraction pattern, having at least the d-spacings and relative intensities set forth in Table 1:
TABLE 1
2-Theta
d(Å)
Intensity
7.88-7.98
11.21-11.07
m-s
8.15-8.50
10.84-10.39
m-s
8.82-9.05
10.01-9.76
s
9.67-9.96
9.14-8.87
s-vs
10.58-10.81
8.35-8.17
m
10.92-11.71
8.09-7.55
m-s
13.21-13.67
6.69-6.47
s
14.10-14.54
6.27-6.08
s-vs
15.48-16.02
5.72-5.53
m
16.05-16.24
5.52-5.45
s
16.44-16.81
5.39-5.28
m
16.87-17.01
5.25-5.21
m-s
17.19-17.43
5.15-5.08
s
17.78-18.46
4.98-4.80
s-vs
18.73-19.22
4.73-4.61
vw-w
19.48-19.86
4.55-4.47
w-m
20.47-20.96
4.33-4.23
s
21.00-21.45
4.23-4.14
m-s
21.52-21.73
4.12-4.08
m-s
21.88-22.10
4.06-4.02
s
22.15-22.42
4.01-3.96
m-s
22.52-22.95
3.94-3.87
w-m
23.14-23.52
3.84-3.78
w-m
23.58-23.71
3.77-3.75
s
23.75-24.01
3.74-3.70
w-m
24.75-24.93
3.59-3.57
w-m
25.01-25.47
3.56-3.49
vs
26.15-26.31
3.40-3.38
w-m
26.37-26.54
3.38-3.35
m
26.78-27.02
3.33-3.30
w-m
27.11-27.40
3.29-3.25
m
28.39-28.86
3.14-3.09
w-m
29.22-29.65
3.05-3.01
m
30.60-30.95
2.92-2.89
w-m
31.62-31.93
2.83-2.80
w-m
31.97-32.28
2.80-2.77
w-s
32.44-32.89
2.76-2.72
w-m
33.19-33.40
2.70-2.68
vw-w
33.51-33.82
2.67-2.65
w-m
34.72-35.08
2.58-2.55
vw-w.

125 more elements

A process of separating mixtures of molecular species, removing contaminants or catalyzing hydrocarbon conversion processes comprising contacting a feed stream with a microporous crystalline material, AlPO-78 that has an empirical composition in a calcined form and on an anhydrous basis expressed by an empirical formula:

R+rMm2+EPxSiyOz
where M is at least one framework divalent cation and is selected from the group consisting of alkaline earth and transition metals, wherein M is a cation selected from the group consisting of beryllium, magnesium, cobalt (II), manganese, zinc, iron (II), nickel and mixtures thereof, R is an organoammonium cation, “r” is the mole ratio of R to E and varies from about 0.1 to about 2.0, “m” is the mole ratio of M to E and varies from 0 to about 1.0, “x” is a mole ratio of P to E and varies from 0.5 to about 2.0, a ratio of silicon to E is represented by “y” which varies from about 0 to about 1.0, E is a trivalent element which is tetrahedrally coordinated, is present in the framework, and is selected from the group consisting of aluminum, gallium, iron (III) and boron and “z” is a mole ratio of O to E and is given by an equation:
z=(2·m+r+3+5·x+4·y)/2
and is characterized by an x-ray following diffraction pattern, having at least the d-spacings and relative intensities set forth in Table 2:
TABLE 2
2-Theta
d(Å)
Intensity
8.02-8.12
11.01-10.88
w
8.40-8.51
10.51-10.38
m
8.63-8.73
10.23-10.12
w-m
9.78-9.89
9.03-8.93
m-s
10.70-10.81
8.26-8.17
m-s
12.83-12.95
6.89-6.82
vw
13.71-13.86
6.45-6.38
vs
14.00-14.13
6.32-6.26
m-s
16.16-16.64
5.48-5.32
vw-w
16.92-17.05
5.23-5.19
vw-w
17.44-17.56
5.08-5.04
m
17.79-17.93
4.98-4.94
m-s
19.68-19.89
4.51-4.46
w
20.43-20.61
4.34-4.30
w-m
21.17-21.35
4.19-4.16
w-m
21.81-21.99
4.07-4.04
m-s
22.15-22.53
4.01-3.94
m-s
22.55-22.74
3.94-3.91
w-m
23.95-24.25
3.71-3.67
m-s
24.57-24.79
3.62-3.59
m-s
25.87-26.31
3.44-3.38
w-m
26.49-26.71
3.36-3.33
m
27.40-27.88
3.25-3.20
m-s
28.32-28.52
3.15-3.13
m-s
28.85-29.02
3.09-3.07
vw-w
29.40-29.63
3.03-3.01
w-m
29.71-29.93
3.00-2.98
vw
30.28-30.44
2.95-2.93
vw-w
31.21-31.38
2.86-2.85
vw-w
32.18-32.50
2.79-2.75
w-m
32.65-32.92
2.74-2.72
w-m
33.00-33.15
2.71-2.70
w-m
34.25-34.41
2.61-2.60
vw-w
35.16-35.35
2.55-2.54
w-m.

107 more elements

Dependencies are inferred from the claim text.

Facts

Application: 16/036,709Filed 16 Jul 2018 · us provisional application
Priority: 28 Jul 2017
Published: US 2019/0030511 A131 Jan 2019
Granted: 3 Dec 2019
Term ends: Not estimatedThe source records don’t support an estimate.

Classification20 codes

B01J 20/0292
Characterised by the type of anion: phosphates of compounds other than those provided for in B01J20/048
B01J 20/18
Alumino-silicates: synthetic zeolitic molecular sieves
B01J 29/85
Aluminophosphates containing other elements, e.g. metals, boron: silicoaluminophosphates [SAPO compounds]
B01J 35/70
Catalysts, in general, characterised by their form or physical properties: characterised by their crystalline properties, e.g. semi-crystalline