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US 5,302,362 AGranted
Crystalline microporous metallo-zinc phosphate compositions
AssigneeUop LLC
InventorRobert L. Bedard
Life of this patent
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Abstract
A new class of microporous compositions are described along with a process for preparing them and processes for using them. These compositions have a three-dimensional microporous framework structure of ZnO.sub.2, PO.sub.2 and M'O.sub.2 tetrahedral units, and an intracrystalline pore system. The M' metal is selected from the group consisting of magnesium, copper, gallium, aluminum, germanium, cobalt, chromium, iron, manganese, titanium and mixtures thereof. These molecular sieves are prepared by hydrothermal crystallization of a reaction mixture containing reactive sources of phosphorus, zinc, one or more M' metal, at least one alkali metal and water. This invention also relates to processes using these molecular sieves.
Claims13
A crystalline molecular sieve having:
- 1) a three-dimensional microporous framework structure of ZnO.sub.2, PO.sub.2 and M'O.sub.2 tetrahedral units;
- 2) an intracrystalline pore system;
- and 3) an empirical formula, on an anhydrous basis, expressed as the ratio of the oxides of:
- rM.sub.2 O:sZnO:tM'O.sub.n/2 :uP.sub.2 O.sub.5
- where M is at least one alkali metal, M' is a metal selected from the group consisting of magnesium, copper, gallium, aluminum, silicon, germanium, cobalt, chromium, iron, manganese, titanium and mixtures thereof, n is the valence of M' and has a value of +2, +3, or +4, r, s, t and u are defined by the following equations:
- 1) when n=+2 and
- ______________________________________ a) t + s = 2.0 then b) 2.0 <
- t + s .ltoreq. 3.0 then t = 0.02 to 1.98 t = 0.02 to 2.98 s = 1.98 to 0.02 s = 2.98 to 0.02 r = 0.80 to 1.20 r = 0.80 to 1.20 u = 0.98 to 1.02 u = 0.98 to 1.02;
- ______________________________________
- 2) when n=+3 and
- ______________________________________ a) t + s = 2.0 and b) t + s = 2.0 and M' is not Al.sup.+3, then M' is Al.sup.+3 then t = 0.02 to 1.98 t = 0.01 to 0.56 s = 1.98 to 0.02 s = 1.99 to 1.44 r = 0.99 to 0.01 r = 0.99 to 0.72 u = 0.98 to 1.02 u = 0.98 to 1.02;
- c 2.0 <
- t + s .ltoreq. 3.0 then t = 0.02 to 1.98 s = 2.98 to 1.02 r = 0.99 to 0.01 u = 0.98 to 1.02;
- ______________________________________
- 3) when n=+4 and
- ______________________________________ a) t/2 + s = 2.0 then b) 2.0 <
- t/2 + s .ltoreq. 3.5 then t = 0.04 to 3.96 t = 0.04 to 3.96 s = 1.98 to 0.02 s = 2.98 to 0.02 r = 0.99 to 0.01 r = 0.99 to 0.01 u = 0.99 to 0.01 u = 0.99 to 0.01. ______________________________________
- the crystalline molecular sieve characterized in that it has the structure of zeolite ABW or has the structure characterized by the x-ray diffraction pattern, d-spacings and intensities, set forth in Table A
- TABLE A ______________________________________ 2.theta. d (.ANG.) Relative Intensity ______________________________________ 11.60-11.72 7.55-7.63 vs 16.46-16.60 5.35-5.39 w 20.20-20.34 4.37-4.40 m 23.39-23.52 3.78-3.80 w 28.76-28.89 3.09-3.10 vs 33.34-33.48 2.68-2.69 w-m 34.91-35.06 2.56-2.57 w 35.43-35.56 2.52-2.53 m 37.42-37.56 2.39-2.40 w-m 39.32-39.47 2.28-2.29 w 41.14-41.30 2.19 w 44.62-44.76 2.02-2.03 w 47.88-48.06 1.89-1.96 w 49.45-49.61 1.84 w 50.98-51.16 1.79 w 53.96-54.15 1.70-1.69 w. ______________________________________
16 more elements
A process for preparing a crystalline molecular sieve having:
- 1) a three-dimensional microporous framework structure of ZnO.sub.2, PO.sub.2 and M'O.sub.2 tetrahedral units;
- 2) an intracrystalline pore system;
- and 3) an empirical formula, on an anhydrous basis, expressed as the ratio of the oxides of:
- rM.sub.2 O:sZnO:sM'O.sub.n/2 :P.sub.2 O.sub.5
- where M is at least one alkali metal, M' is a metal selected from the group consisting of magnesium, copper, gallium, silicon, germanium, cobalt, chromium, iron, manganese, titanium and mixtures thereof, n is the valence of M' and has a value of +2, +3, or +4, r, s, t and u are defined by the following equations:
- 1) when n=+2 and
- ______________________________________ a) t + s = 2.0 then b) 2.0 <
- t + s .ltoreq. 3.0 then t = 0.02 to 1.98 t = 0.02 to 2.98 s = 1.98 to 0.02 s = 2.98 to 0.02 r = 0.80 to 1.20 r = 0.80 to 1.20 u = 0.98 to 1.02 u = 0.98 to 1.02;
- ______________________________________
- 2) when n=+3 and
- ______________________________________ a) t + s = 2.0 [and [b) 2.0 <
- t + s .ltoreq. 3.0 and ] M' is not Al.sup.+3,] then [M' is Al.sup.+3 then] t = 0.02 to 1.98 [t = 0.01 to 0.56] s = 1.98 to 0.02 [s = 1.99 to 1.44] r = 0.99 to 0.01 [r = 0.99 to 0.72] u = 0.98 to 1.02 [u = 0.98 to 1.02;] [c)] -b) 2.0 <
- t + s .ltoreq. 3.0 then t = 0.02 to 1.98 s = 2.98 to 1.02 r = 0.99 to 0.01 u = 0.98 to 1.02 ______________________________________
- 3) when n=+4 and
- ______________________________________ a) t/2 + s = 2.0 then b) 2.0 <
- t/2 + s .ltoreq. 3.5 then t = 0.04 to 3.96 t = 0.04 to 3.96 s = 1.98 to 0.02 s = 2.98 to 0.02 r = 0.99 to 0.01 r = 0.99 to 0.01 u = 0.99 to 0.01 u = 0.99 to 0.01 ______________________________________
- the process comprising reacting a mixture containing reactive sources of zinc, phosphorus, M and M' at a temperature and time sufficient to form the crystalline molecular sieve, the mixture having a composition expressed in terms of mole ratios of oxides of
- xM.sub.2 O:yZnO:zM'O.sub.n/2 :P.sub.2 O.sub.5 :aH.sub.2 O
- where x ranges from greater than 1 to about 5.5, y ranges from about 0.02 to about 3.0, z ranges from about 0.02 to about 5.00 and a ranges from about 20 to about 500.
16 more elements
A crystalline molecular sieve having:
- 1) a three-dimensional microporous framework structure of ZnO.sub.2, PO.sub.2 and M'O.sub.2 tetrahedral units;
- 2) an intracrystalline pore system;
- and 3) an empirical formula, on an anhydrous basis, expressed as the ratio of the oxides of:
- rM.sub.2 O:sZnO:tM'O.sub.n/2 :uP.sub.2 O.sub.5
- where M is at least one alkali metal, M' is a metal selected from the group consisting of magnesium, copper, gallium, silicon, germanium, cobalt, chromium, iron, manganese, titanium and mixtures thereof, n is the valence of M' and has a value of +2, +3, or +4, r, s, t and u are defined by the following equations:
- 1) when n=+2 and
- ______________________________________ a) t + s = 2.0 then b) 2.0 <
- t + s .ltoreq. 3.0 then t = 0.02 to 1.98 t = 0.02 to 2.98 s = 1.98 to 0.02 s = 2.98 to 0.02 r = 0.80 to 1.20 r = 0.80 to 1.20 u = 0.98 to 1.02 u = 0.98 to 1.02;
- ______________________________________
- 2) when n=+3 and
- ______________________________________ a) t + s = 2.0 then b) 2.0 <
- t + s .ltoreq. 3.0 then t = 0.02 to 1.98 t = 0.02 to 1.98 s = 1.98 to 0.02 s = 2.98 to 1.02 r = 0.99 to 0.01 r = 0.99 to 0.01 u = 0.98 to 1.02 u = 0.98 to 1.02;
- ______________________________________
- 3) when n=+4 and
- ______________________________________ a) t/2 + s = 2.0 then b) 2.0 <
- t/2 + s .ltoreq. 3.5 then t = 0.04 to 3.96 t = 0.04 to 3.96 s = 1.98 to 0.02 s = 2.98 to 0.02 r = 0.99 to 0.01 r = 0.99 to 0.01 u = 0.99 to 0.01 u = 0.99 to 0.01. ______________________________________
13 more elements
Dependencies are inferred from the claim text.