Silicometallophosphate molecular sieves, method 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 MAPSO-64 has been synthesized. These metallophosphates are represented by the empirical formula R+rMmn+EPxSiyOz where R is an organoammonium cation such as ETMA+ or DEDMA−, M is a divalent metal such as an alkaline earth or transition metal, and E is a framework element such as aluminum or gallium. The microporous MAPSO-64 compositions BPH topology and have catalytic properties for carrying out various hydrocarbon conversion processes and separation properties for separating at least one component.
Claims22
A microporous crystalline silicometallophosphate material having a three-dimensional framework of EO2−, PO2+, [M2+O2]2− and SiO2 tetrahedral units and an empirical composition in the as synthesized and anhydrous basis expressed by an empirical formula of:
- RrM2+mEPxSiyOz
- where M is at least one divalent cation selected from the group consisting of alkaline earth and transition metals, “m” is the mole ratio of M to E and varies from 0.01 to about 1.5, R is an organoammonium cation selected from the group of choline, tetrametylammonium (TMA+), ethyltrimethylammonium (ETMA+), diethyldimethylammonium (DEDMA+), methyltriethylammonium (MTEA+), propyltrimethylammonium (PTMA+), dimethyldiethanolammonium, tetraethylammonium (TEA+), dipropyldimethylammonium (DPDMA+), 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, E is an 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 has a value of 0.5 to about 2.5, “y” is the mole ratio of Si to E and varies from 0.01 to about 1.0 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
- 2Θ
- d(Å)
- I/I0
- 6.81-6.61
- 12.98-13.34
- m-vs
- 7.75-7.55
- 11.40-11.70
- m-vs
- 13.36-13.14
- 6.62-6.73
- w-m
- 13.51-13.32
- 6.55-6.64
- w-m
- 14.98-14.68
- 5.91-6.03
- w
- 15.51-15.34
- 5.71-5.77
- w-m
- 18.99-18.79
- 4.67-4.72
- w-m
- 20.26-20.07
- 4.38-4.42
- w-m
- 21.50-21.24
- 4.13-4.18
- w-s
- 24.10-23.84
- 3.69-3.73
- w-m
- 24.30-24.03
- 3.66-3.70
- w-m
- 24.57-24.23
- 3.62-3.67
- w-m
- 26.83-26.51
- 3.32-3.36
- w-m
- 27.59-27.42
- 3.23-3.25
- w-m
- 27.86-27.59
- 3.20-3.23
- w
- 28.68-28.49
- 3.11-3.13
- w
- 28.87-28.59
- 3.09-3.12
- w
- 30.06-29.76
- 2.97-3.00
- w-m
- 30.27-29.96
- 2.95-2.98
- w-m
- 31.03-30.70
- 2.88-2.91
- w-m
- 33.80-33.54
- 2.65-2.67
- w-m
- 34.06-33.80
- 2.63-2.65
- w
- 35.60-35.31
- 2.52-2.54
- w-m
- 36.65-36.34
- 2.45-2.47
- w
- 38.44-38.10
- 2.34-2.36
- w
A process for preparing a microporous crystalline silicometallophosphate material having a three-dimensional framework of at least EO2−, PO2+, [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 divalent cation selected from the group consisting of alkaline earth and transition metals, “m” is the mole ratio of M to E and varies from 0.01 to about 1.5, R is an organoammonium cation selected from the group consisting of choline, tetramethylammonium (TMA+), ethyltrimethylammonium (ETMA+), diethyldimethylammonium (DEDMA+), methyltriethylammonium (MTEA+), propyltrimethylammonium (PTMA+), dimethyldiethanolammonium, tetraethylammonium (TEA+), dipropyldimethylammoniun (DPDMA+), tetrapropylammonium (TPA+) cations 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 2.5, “y” is the mole ratio of Si to E and varies from 0.01 to about 1.0 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
- 2Θ
- d(Å)
- I/I0
- 6.81-6.61
- 12.98-13.34
- m-vs
- 7.75-7.55
- 11.40-11.70
- m-vs
- 13.36-13.14
- 6.62-6.73
- w-m
- 13.51-13.32
- 6.55-6.64
- w-m
- 14.98-14.68
- 5.91-6.03
- w
- 15.51-15.34
- 5.71-5.77
- w-m
- 18.99-18.79
- 4.67-4.72
- w-m
- 20.26-20.07
- 4.38-4.42
- w-m
- 21.50-21.24
- 4.13-4.18
- w-s
- 24.10-23.84
- 3.69-3.73
- w-m
- 24.30-24.03
- 3.66-3.70
- w-m
- 24.57-24.23
- 3.62-3.67
- w-m
- 26.83-26.51
- 3.32-3.36
- w-m
- 27.59-27.42
- 3.23-3.25
- w-m
- 27.86-27.59
- 3.20-3.23
- w
- 28.68-28.49
- 3.11-3.13
- w
- 28.87-28.59
- 3.09-3.12
- w
- 30.06-29.76
- 2.97-3.00
- w-m
- 30.27-29.96
- 2.95-2.98
- w-m
- 31.03-30.70
- 2.88-2.91
- w-m
- 33.80-33.54
- 2.65-2.67
- w-m
- 34.06-33.80
- 2.63-2.65
- w
- 35.60-35.31
- 2.52-2.54
- w-m
- 36.65-36.34
- 2.45-2.47
- w
- 38.44-38.10
- 2.34-2.36
- w
- the process comprising forming a reaction mixture containing reactive sources of R, E, P, M and Si and heating the reaction mixture at a temperature of about 60° C. to about 200° C., for a time sufficient to form the silicometallophosphate material, the reaction mixture having a composition expressed in terms of mole ratios of the oxides of:
- aR2O:bMO:E2O3:cP2O5:dSiO2:eH2O
- where “a” has a value of about 0.75 to about 16, “b” has a value of about 0.01 to about 3.0, “c” has a value of about 0.8 to about 8, “d” has a value of about 0.01 to about 4, and “e” has a value of about 20 to 800.
Dependencies are inferred from the claim text.