Back to results
US 2014/0005452 A1Published application
Metallophosphate molecular sieves, methods of preparation and use
AssigneeUop LLC
InventorsGregory J. Lewis, Lisa M. Knight, Paulina Jakubczak, Justin E. Stanczyk
Life of this patent
Estimating the term…
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
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
The process of claim 20 wherein the separation is based on molecular size of the components, degree of polarity of the components, or ion exchange of the components with the material.
Dependencies are inferred from the claim text.