Metallophosphate 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 AlPO-67 has been synthesized. These metallophosphates are represented by the empirical formula R+rMm2+EPxSiyOz where R is an organoammonium cation such as the ETMA+ or DEDMA+, 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-67 compositions exhibit the LEV framework 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 metallophosphate material having a three-dimensional framework of EO2− and 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:
- RrM2+mEPxSiyOz
- where M is at least one framework cation of +2 valence 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 consisting of ethyltrimethylammonium (ETMA+), diethyldimethylammonium (DEDMA+), 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 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 has a value of 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”≧0.02, and “z” is the mole ratio of O to (Al+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 A1:
- TABLE A1
- 2Θ
- d(Å)
- I/I0 %
- 8.86-8.39
- 9.97-10.53
- w-m
- 11.21-10.51
- 7.89-8.41
- m-s
- 13.65-13.16
- 6.48-6.72
- m-vs
- 17.72-16.91
- 5.00-5.24
- m-vs
- 21.29-20.69
- 4.17-4.29
- m-s
- 22.43-21.5
- 3.96-4.13
- s-vs
- 23.84-22.84
- 3.73-3.89
- w-vs
- 27.51-26.51
- 3.24-3.36
- w-m
- 29.06-27.95
- 3.07-3.19
- w-m
- 32.90-31.59
- 2.72-2.83
- m
- 35.02-33.93
- 2.56-2.64
- w-m
- 36.65-35.31
- 2.45-2.54
- w-m
- 52.23-50.67
- 1.75-1.80
- w-m.
A process for preparing a microporous crystalline metallophosphate having a three-dimensional framework of EO2−, PO2+ and at least one of [M2+O2]2− and SiO2 tetrahedral units and a 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 consisting of ethyltrimethylammonium (ETMA+), diethyldimethylammonium (DEDMA+), 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(III), 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”≧0.02, 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 A1:
- TABLE A1
- 2Θ
- d(Å)
- I/I0 %
- 8.86-8.39
- 9.97-10.53
- w-m
- 11.21-10.51
- 7.89-8.41
- m-s
- 13.65-13.16
- 6.48-6.72
- m-vs
- 17.72-16.91
- 5.00-5.24
- m-vs
- 21.29-20.69
- 4.17-4.29
- m-s
- 22.43-21.5
- 3.96-4.13
- s-vs
- 23.84-22.84
- 3.73-3.89
- w-vs
- 27.51-26.51
- 3.24-3.36
- w-m
- 29.06-27.95
- 3.07-3.19
- w-m
- 32.90-31.59
- 2.72-2.83
- m
- 35.02-33.93
- 2.56-2.64
- w-m
- 36.65-35.31
- 2.45-2.54
- w-m
- 52.23-50.67
- 1.75-1.80
- w-m
- the process comprising forming a reaction mixture containing reactive sources of R, E, P, at least one of 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 metallophosphate, 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 0.25 to about 16, “b” has a value of about 0 to about 2.0, “c” has a value of about 0.8 to about 8, “d” has a value of about 0 to about 4, and “e” has a value of about 30 to 800 and wherein the sum of the values of “b” and “d” is greater than 0.01.
Dependencies are inferred from the claim text.