US 8,911,614 B2Granted

Metallophosphate molecular sieves, methods of preparation and use

AssigneeUop LLC

InventorsGregory J. Lewis, Lisa M. Knight, Paulina Jakubczak, Justin E. Stanczyk

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Abstract

A new family of crystalline microporous metallophosphates designated AlPO-59 has been synthesized. These metallophosphates are represented by the empirical formula R+rMm2+EPxSiyOz where R is an organoammonium cation such as the ETMA+, 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-59 compositions are characterized by a new unique ABC-6 net structure and compositions and have catalytic properties for carrying out various hydrocarbon conversion processes, and separation properties for separating at least one component.

Claims20

Dependent claims

A hydrocarbon conversion process comprising contacting a hydrocarbon stream with a catalyst at hydrocarbon conversion conditions to generate at least one converted product, wherein the catalyst is selected from the group consisting of a microporous crystalline AlPO-59 material, a microporous crystalline AlPO-59M material, a microporous crystalline AlPO-59-C material, or mixtures thereof, where AlPO-59 has a three-dimensional framework of EO2−, PO2+ and at least one of [M2+O2]2− and SiO2 tetrahedral units and an empirical composition in the as synthesized and anhydrous basis expressed by an empirical formula of:

RrMm2+EPxSiyOz
where M is at least one framework cation of valence 2+ selected from the group consisting of alkaline earth and transition metals, “m” is the mole ratio of M to E and varies from 0 to about 1.0, R is an organoammonium cation selected from the group of ethyltrimethylammonium (ETMA+), choline, diethyldimethylammonium (DEDMA+), trimethylpropylammonium, tetramethylammonium (TMA+), tetraethylammonium (TEA+), tetrapropylammonium (TPA+) and mixtures thereof, “r” is the mole ratio of R to E and has a value of about 0.1 to about 2.0, E is a trivalent element selected from the group consisting of aluminum, gallium, iron, boron and mixtures thereof, “x” is the mole ratio of P to E and varies from 0.5 to about 2.0, “y” is the mole ratio of Si to E and varies from 0 to about 1.0, “m”+“y”≧0.1, and “z” is the mole ratio of O to E and has a value determined by the equation:
z=(2·m+r+3+5·x+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
2-Θ
d (Å)
I/I0 %
7.69-7.48
11.48-11.81
w
9.15-8.88
9.66-9.95
m-vs
12.55-12.25
7.05-7.22
m
13.30-13.07
6.65-6.77
w-s
14.90-14.51
5.94-6.10
w
16.13-15.87
5.49-5.58
m
16.75-16.37
5.29-5.41
w
18.28-18.02
4.85-4.92
m
19.94-19.41
4.45-4.57
w-m
20.88-20.64
4.25-4.30
m-vs
21.34-20.79
4.16-4.27
m
22.67-22.26
3.92-3.99
m-vs
23.08-22.78
3.85-3.90
w-s
25.28-24.78
3.52-3.59
w
26.11-25.43
3.41-3.50
s-vs
26.67-26.35
3.34-3.38
w-m
28.40-27.86
3.14-3.20
w
29.36-28.78
3.04-3.10
w-m
30.92-30.27
2.89-2.95
w-m
31.36-30.92
2.85-2.89
w-m
32.29-31.70
2.77-2.82
m
35.60-35.02
2.52-2.56
w-m
36.50-35.45
2.46-2.53
w
42.40-41.58
2.13-2.17
w-m
43.69-42.61
2.07-2.12
w
49.21-48.65
1.85-1.87
w
50.98-49.79
1.79-1.83
w-m
55.30-54.23
1.66-1.69
w-m
the microporous crystalline AlPO-59M material comprises a three-dimensional framework of EO2−, PO2+ and at least one of [M2+O2]2− and SiO2 tetrahedral units the composition given by the empirical formula:
M′np+Mm2+EPxSiyOz
where M is at least one metal cation of valence +2 selected from the group consisting of Be2+, Mg2+, Zn2+, Co2+, Mn2+, Fe2+, Ni2+, “m” is the mole ratio of M to E and varies from 0 to about 1.0, M′ is selected from the group consisting of NH4+, H+, alkali metals, alkaline earth metals, rare earth metals, and mixtures thereof, “n” is the mole ratio of M′ to E and has a value of about 0.03 to about 2.0, “p” is the weighted average valence of M′, E is a trivalent element selected from the group consisting of aluminum, gallium, iron, boron and mixtures thereof, “x” is mole ratio of P to E and varies from 0.5 to about 2.0, “y” is the mole ratio of Si to E and varies from 0 to about 1.0, “m”+“y”≧0.1, and “z” is the mole ratio of O to E and has a value determined by the equation:
z=(p·n+2·m+3+5·x+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
2-Θ
d (Å)
I/I0 %
7.69-7.48
11.48-11.81
w
9.15-8.88
9.66-9.95
m-vs
12.55-12.25
7.05-7.22
m
13.30-13.07
6.65-6.77
w-s
14.90-14.51
5.94-6.10
w
16.13-15.87
5.49-5.58
m
16.75-16.37
5.29-5.41
w
18.28-18.02
4.85-4.92
m
19.94-19.41
4.45-4.57
w-m
20.88-20.64
4.25-4.30
m-vs
21.34-20.79
4.16-4.27
m
22.67-22.26
3.92-3.99
m-vs
23.08-22.78
3.85-3.90
w-s
25.28-24.78
3.52-3.59
w
26.11-25.43
3.41-3.50
s-vs
26.67-26.35
3.34-3.38
w-m
28.40-27.86
3.14-3.20
w
29.36-28.78
3.04-3.10
w-m
30.92-30.27
2.89-2.95
w-m
31.36-30.92
2.85-2.89
w-m
32.29-31.70
2.77-2.82
m
35.60-35.02
2.52-2.56
w-m
36.50-35.45
2.46-2.53
w
42.40-41.58
2.13-2.17
w-m
43.69-42.61
2.07-2.12
w
49.21-48.65
1.85-1.87
w
50.98-49.79
1.79-1.83
w-m
55.30-54.23
1.66-1.69
w-m
and the microporous crystalline AlPO-59C material comprises a three-dimensional framework of EO2−, PO2+, SiO2 and optionally [M2+O2]2− tetrahedral units characterized by the empirical formula:
HaMm2+EPxSiyOz
where M is at least one metal cation of valence +2 selected from the group consisting of Be2+, Mg2+, Zn2+, Co2+, Mn2+, Fe2+, Ni2+, “m” is the mole ratio of M to E and varies from 0 to about 1.0, H is a proton, “a” is the mole ratio of H to E and has a value of about 0.1 to about 2.0, E is a trivalent element selected from the group consisting of aluminum, gallium, iron, boron and mixtures thereof, “x” is mole ratio of P to E and varies from 0.5 to about 2.0, “y” is the mole ratio of Si to E and varies from 0.05 to about 1.0, “m”+“y”≧0.1, and “z” is the mole ratio of O to E and has a value determined by the equation:
z=(a+2·m+3+5·x+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 B:
TABLE B
2-Θ
d (Å)
I/I0 %
9.42-9.02
9.38-9.80
m-s
12.95-12.49
6.83-7.08
m-s
13.68-13.20
6.47-6.70
vs
15.34-14.90
5.77-5.94
w-m
16.53-15.98
5.36-5.54
w-m
18.71-18.20
4.74-4.87
w-m
21.45-20.88
4.14-4.25
w-s
21.93-21.39
4.05-4.15
w-m
23.14-22.72
3.84-3.91
w-s
25.96-25.35
3.43-3.51
w-m
26.75-26.27
3.33-3.39
m-s
27.25-26.83
3.27-3.32
w-s
29.16-28.68
3.06-3.11
w-m
30.06-29.55
2.97-3.02
w-m
31.82-31.36
2.81-2.85
w-m
33.03-32.53
2.71-2.75
w-m

239 more elements

A separation process comprising contacting at least two components with a material to generate at least one separated component, wherein the material is selected from the group consisting of a microporous crystalline AlPO-59 material, a microporous crystalline AlPO-59M material, a microporous crystalline AlPO-59-C material, or mixtures thereof, where AlPO-59 has a three-dimensional framework of EO2−, PO2+ and at least one of [M2+O2]2− and SiO2 tetrahedral units and an empirical composition in the as synthesized and anhydrous basis expressed by an empirical formula of:

RrMm2+EPxSiyOz
where M is at least one framework cation of valence 2+ selected from the group consisting of alkaline earth and transition metals, “m” is the mole ratio of M to E and varies from 0 to about 1.0, R is an organoammonium cation selected from the group of ethyltrimethylammonium (ETMA+), choline, diethyldimethylammonium (DEDMA+), trimethylpropylammonium, tetramethylammonium (TMA+), tetraethylammonium (TEA+), tetrapropylammonium (TPA+) and mixtures thereof, “r” is the mole ratio of R to E and has a value of about 0.1 to about 2.0, E is a trivalent element selected from the group consisting of aluminum, gallium, iron, boron and mixtures thereof, “x” is the mole ratio of P to E and varies from 0.5 to about 2.0, “y” is the mole ratio of Si to E and varies from 0 to about 1.0, “m”+“y”≧0.1, and “z” is the mole ratio of O to E and has a value determined by the equation:
z=(2·m+r+3+5·x+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
2-Θ
d (Å)
I/I0 %
7.69-7.48
11.48-11.81
w
9.15-8.88
9.66-9.95
m-vs
12.55-12.25
7.05-7.22
m
13.30-13.07
6.65-6.77
w-s
14.90-14.51
5.94-6.10
w
16.13-15.87
5.49-5.58
m
16.75-16.37
5.29-5.41
w
18.28-18.02
4.85-4.92
m
19.94-19.41
4.45-4.57
w-m
20.88-20.64
4.25-4.30
m-vs
21.34-20.79
4.16-4.27
m
22.67-22.26
3.92-3.99
m-vs
23.08-22.78
3.85-3.90
w-s
25.28-24.78
3.52-3.59
w
26.11-25.43
3.41-3.50
s-vs
26.67-26.35
3.34-3.38
w-m
28.40-27.86
3.14-3.20
w
29.36-28.78
3.04-3.10
w-m
30.92-30.27
2.89-2.95
w-m
31.36-30.92
2.85-2.89
w-m
32.29-31.70
2.77-2.82
m
35.60-35.02
2.52-2.56
w-m
36.50-35.45
2.46-2.53
w
42.40-41.58
2.13-2.17
w-m
43.69-42.61
2.07-2.12
w
49.21-48.65
1.85-1.87
w
50.98-49.79
1.79-1.83
w-m
55.30-54.23
1.66-1.69
w-m
the microporous crystalline AlPO-59M material comprises a three-dimensional framework of EO2−, PO2+ and at least one of [M2+O2]2− and SiO2 tetrahedral units the composition given by the empirical formula:
M′np+Mm2+EPxSiyOz
where M is at least one metal cation of valence +2 selected from the group consisting of Be2+, Mg2+, Zn2+, Co2+, Mn2+, Fe2+, Ni2+, “m” is the mole ratio of M to E and varies from 0 to about 1.0, M′ is selected from the group consisting of NH4+, H+, alkali metals, alkaline earth metals, rare earth metals and mixtures thereof, “n” is the mole ratio of M′ to E and has a value of about 0.03 to about 2.0, “p” is the weighted average valence of M′, E is a trivalent element selected from the group consisting of aluminum, gallium, iron, boron and mixtures thereof, “x” is mole ratio of P to E and varies from 0.5 to about 2.0, “y” is the mole ratio of Si to E and varies from 0 to about 1.0, “m”+“y”≧0.1, and “z” is the mole ratio of O to E and has a value determined by the equation:
z=(p·n+2·m+3+5·x+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
2-Θ
d (Å)
I/I0 %
7.69-7.48
11.48-11.81
w
9.15-8.88
9.66-9.95
m-vs
12.55-12.25
7.05-7.22
m
13.30-13.07
6.65-6.77
w-s
14.90-14.51
5.94-6.10
w
16.13-15.87
5.49-5.58
m
16.75-16.37
5.29-5.41
w
18.28-18.02
4.85-4.92
m
19.94-19.41
4.45-4.57
w-m
20.88-20.64
4.25-4.30
m-vs
21.34-20.79
4.16-4.27
m
22.67-22.26
3.92-3.99
m-vs
23.08-22.78
3.85-3.90
w-s
25.28-24.78
3.52-3.59
w
26.11-25.43
3.41-3.50
s-vs
26.67-26.35
3.34-3.38
w-m
28.40-27.86
3.14-3.20
w
29.36-28.78
3.04-3.10
w-m
30.92-30.27
2.89-2.95
w-m
31.36-30.92
2.85-2.89
w-m
32.29-31.70
2.77-2.82
m
35.60-35.02
2.52-2.56
w-m
36.50-35.45
2.46-2.53
w
42.40-41.58
2.13-2.17
w-m
43.69-42.61
2.07-2.12
w
49.21-48.65
1.85-1.87
w
50.98-49.79
1.79-1.83
w-m
55.30-54.23
1.66-1.69
w-m
and the microporous crystalline AlPO-59C material comprises a three-dimensional framework of EO2−, PO2+ and at least one of [M2+O2]2− and SiO2 tetrahedral units characterized by the empirical formula:
HaMm2+EPxSiyOz
where M is at least one metal cation of valence +2 selected from the group consisting of Be2+, Mg2+, Zn2+, Co2+, Mn2+, Fe2+, Ni2+, “m” is the mole ratio of M to E and varies from 0 to about 1.0, H is a proton, “a” is the mole ratio of H to E and has a value of about 0.1 to about 2.0, E is a trivalent element selected from the group consisting of aluminum, gallium, iron, boron and mixtures thereof, “x” is mole ratio of P to E and varies from 0.5 to about 2.0, “y” is the mole ratio of Si to E and varies from 0.05 to about 1.0, “m”+“y”≧0.1, and “z” is the mole ratio of O to E and has a value determined by the equation:
z=(a+2·m+3+5·x+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 B:
TABLE B
2-Θ
d (Å)
I/I0 %
9.42-9.02
9.38-9.80
m-s
12.95-12.49
6.83-7.08
m-s
13.68-13.20
6.47-6.70
vs
15.34-14.90
5.77-5.94
w-m
16.53-15.98
5.36-5.54
w-m
18.71-18.20
4.74-4.87
w-m
21.45-20.88
4.14-4.25
w-s
21.93-21.39
4.05-4.15
w-m
23.14-22.72
3.84-3.91
w-s
25.96-25.35
3.43-3.51
w-m
26.75-26.27
3.33-3.39
m-s
27.25-26.83
3.27-3.32
w-s
29.16-28.68
3.06-3.11
w-m
30.06-29.55
2.97-3.02
w-m
31.82-31.36
2.81-2.85
w-m
33.03-32.53
2.71-2.75
w-m.

239 more elements

Dependencies are inferred from the claim text.

Facts

Application: 13/537,448Filed 29 Jun 2012
Published: US 2014/0005452 A12 Jan 2014
Granted: 16 Dec 2014
Term ends: Not estimatedThe source records don’t support an estimate.

Classification24 codes

B01J 23/06
Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00: of zinc, cadmium or mercury
B01J 23/02
Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00: of the alkali- or alkaline earth metals or beryllium
B01J 23/75
Iron group metals: cobalt
B01J 29/83
Phosphates: aluminophosphates [APO compounds]

Family

US 2014/0005452 A1Pre-grant publication · published 2 Jan 2014
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Abstract

RrMm2+EPxSiyOz
where M is at least one framework cation of valence 2+ selected from the group consisting of alkaline earth and transition metals, “m” is the mole ratio of M to E and varies from 0 to about 1.0, R is an organoammonium cation selected from the group of ethyltrimethylammonium (ETMA+), choline, diethyldimethylammonium (DEDMA+), trimethylpropylammonium, tetramethylammonium (TMA+), tetraethylammonium (TEA+), tetrapropylammonium (TPA+) and mixtures thereof, “r” is the mole ratio of R to E and has a value of about 0.1 to about 2.0, E is a trivalent element selected from the group consisting of aluminum, gallium, iron, boron and mixtures thereof, “x” is the mole ratio of P to E and varies from 0.5 to about 2.0, “y” is the mole ratio of Si to E and varies from 0 to about 1.0, “m”+“y”≧0.1, and “z” is the mole ratio of O to E and has a value determined by the equation:
z=(2·m+r+3+5·x+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
2-Θ
d (Å)
I/I0 %
7.69-7.48
11.48-11.81
w
9.15-8.88
9.66-9.95
m-vs
12.55-12.25
7.05-7.22
m
13.30-13.07
6.65-6.77
w-s
14.90-14.51
5.94-6.10
w
16.13-15.87
5.49-5.58
m
16.75-16.37
5.29-5.41
w
18.28-18.02
4.85-4.92
m
19.94-19.41
4.45-4.57
w-m
20.88-20.64
4.25-4.30
m-vs
21.34-20.79
4.16-4.27
m
22.67-22.26
3.92-3.99
m-vs
23.08-22.78
3.85-3.90
w-s
25.28-24.78
3.52-3.59
w
26.11-25.43
3.41-3.50
s-vs
26.67-26.35
3.34-3.38
w-m
28.40-27.86
3.14-3.20
w
29.36-28.78
3.04-3.10
w-m
30.92-30.27
2.89-2.95
w-m
31.36-30.92
2.85-2.89
w-m
32.29-31.70
2.77-2.82
m
35.60-35.02
2.52-2.56
w-m
36.50-35.45
2.46-2.53
w
42.40-41.58
2.13-2.17
w-m
43.69-42.61
2.07-2.12
w
49.21-48.65
1.85-1.87
w
50.98-49.79
1.79-1.83
w-m
55.30-54.23
1.66-1.69
w-m
the microporous crystalline AlPO-59M material comprises a three-dimensional framework of EO2−, PO2+ and at least one of [M2+O2]2− and SiO2 tetrahedral units the composition given by the empirical formula:
M′np+Mm2+EPxSiyOz
where M is at least one metal cation of valence +2 selected from the group consisting of Be2+, Mg2+, Zn2+, Co2+, Mn2+, Fe2+, Ni2+, “m” is the mole ratio of M to E and varies from 0 to about 1.0, M′ is selected from the group consisting of NH4+, H+, alkali metals, alkaline earth metals, rare earth metals, and mixtures thereof, “n” is the mole ratio of M′ to E and has a value of about 0.03 to about 2.0, “p” is the weighted average valence of M′, E is a trivalent element selected from the group consisting of aluminum, gallium, iron, boron and mixtures thereof, “x” is mole ratio of P to E and varies from 0.5 to about 2.0, “y” is the mole ratio of Si to E and varies from 0 to about 1.0, “m”+“y”≧0.1, and “z” is the mole ratio of O to E and has a value determined by the equation:
z=(p·n+2·m+3+5·x+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
2-Θ
d (Å)
I/I0 %
7.69-7.48
11.48-11.81
w
9.15-8.88
9.66-9.95
m-vs
12.55-12.25
7.05-7.22
m
13.30-13.07
6.65-6.77
w-s
14.90-14.51
5.94-6.10
w
16.13-15.87
5.49-5.58
m
16.75-16.37
5.29-5.41
w
18.28-18.02
4.85-4.92
m
19.94-19.41
4.45-4.57
w-m
20.88-20.64
4.25-4.30
m-vs
21.34-20.79
4.16-4.27
m
22.67-22.26
3.92-3.99
m-vs
23.08-22.78
3.85-3.90
w-s
25.28-24.78
3.52-3.59
w
26.11-25.43
3.41-3.50
s-vs
26.67-26.35
3.34-3.38
w-m
28.40-27.86
3.14-3.20
w
29.36-28.78
3.04-3.10
w-m
30.92-30.27
2.89-2.95
w-m
31.36-30.92
2.85-2.89
w-m
32.29-31.70
2.77-2.82
m
35.60-35.02
2.52-2.56
w-m
36.50-35.45
2.46-2.53
w
42.40-41.58
2.13-2.17
w-m
43.69-42.61
2.07-2.12
w
49.21-48.65
1.85-1.87
w
50.98-49.79
1.79-1.83
w-m
55.30-54.23
1.66-1.69
w-m
and the microporous crystalline AlPO-59C material comprises a three-dimensional framework of EO2−, PO2+, SiO2 and optionally [M2+O2]2− tetrahedral units characterized by the empirical formula:
HaMm2+EPxSiyOz
where M is at least one metal cation of valence +2 selected from the group consisting of Be2+, Mg2+, Zn2+, Co2+, Mn2+, Fe2+, Ni2+, “m” is the mole ratio of M to E and varies from 0 to about 1.0, H is a proton, “a” is the mole ratio of H to E and has a value of about 0.1 to about 2.0, E is a trivalent element selected from the group consisting of aluminum, gallium, iron, boron and mixtures thereof, “x” is mole ratio of P to E and varies from 0.5 to about 2.0, “y” is the mole ratio of Si to E and varies from 0.05 to about 1.0, “m”+“y”≧0.1, and “z” is the mole ratio of O to E and has a value determined by the equation:
z=(a+2·m+3+5·x+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 B:
TABLE B
2-Θ
d (Å)
I/I0 %
9.42-9.02
9.38-9.80
m-s
12.95-12.49
6.83-7.08
m-s
13.68-13.20
6.47-6.70
vs
15.34-14.90
5.77-5.94
w-m
16.53-15.98
5.36-5.54
w-m
18.71-18.20
4.74-4.87
w-m
21.45-20.88
4.14-4.25
w-s
21.93-21.39
4.05-4.15
w-m
23.14-22.72
3.84-3.91
w-s
25.96-25.35
3.43-3.51
w-m
26.75-26.27
3.33-3.39
m-s
27.25-26.83
3.27-3.32
w-s
29.16-28.68
3.06-3.11
w-m
30.06-29.55
2.97-3.02
w-m
31.82-31.36
2.81-2.85
w-m
33.03-32.53
2.71-2.75
w-m

239 more elements

Facts

Application

13/537,448Filed 29 Jun 2012

Published

US 2014/0005452 A12 Jan 2014

Granted

16 Dec 2014

Term ends

Not estimatedThe source records don’t support an estimate.

Classification24 codes

B01J 23/06
Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00: of zinc, cadmium or mercury
B01J 23/02
Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00: of the alkali- or alkaline earth metals or beryllium
B01J 23/75
Iron group metals: cobalt
B01J 29/83
Phosphates: aluminophosphates [APO compounds]