Molecular sieve compositions

Claim 2

A crystalline molecular sieve having a three-dimensional microporous framework structure of MO 2 n , AlO 2 and PO 2 tetrahedral oxide units having an empirical chemical composition on an anhydrous basis expressed by the formula: mR:(M.sub.x Al.sub.y P.sub.z)O.sub.2 wherein "R" represents at least one organic templating agent present in the intracrystalline pore system; "M" represents: (1) titanium, or a mixture of titanium and iron; and (2) at least one element from the group consisting of cobalt, magnesium, manganese and zinc; "n" is 0, -1 or -2; "m" represents a molar amount of "R" present per mole of (M x Al y P z )O 2 and has a value of zero (0) to about 0.3; and "x", "y" and "z" represent the mole fractions of "M", aluminum and phosphorus, respectively, present as tetrahedral oxides, said mole fractions being such that they are within the pentagonal compositional area defined by points A, B, C, D and E of FIG. 1, said crystalline molecular sieve having a characteristic X-ray powder diffraction pattern which contains at least the d-spacings set forth in one of the following Tables O, Q, R, S and U. TABLE O ______________________________________ (XAPO-37) 2Θ D (Å) Relative Intensity ______________________________________ 6.1-6.3 14.49-14.03 vs 15.5-15.7 5.72-5.64 w-m 18.5-18.8 4.80-4.72 w-m 23.5-23.7 3.79-3.75 w-m 26.9-27.1 3.31-3.29 w-m ______________________________________ TABLE Q ______________________________________ (XAPO-40) 2Θ D (Å) Relative Intensity ______________________________________ 7.5-7.7 11.79-11.48 vw-m 8.0-8.1 11.05-10.94 s-vs 12.4-12.5 7.14-7.08 w-vs 13.6-13.8 6.51-6.42 m-s 14.0-14.1 6.33-6.28 w-m 27.8-28.0 3.209-3.187 w-m ______________________________________ TABLE R ______________________________________ (XAPO-41) 2Θ D (Å) Relative Intensity ______________________________________ 13.6-13.8 6.51-6.42 w-m 20.5-20.6 4.33-4.31 w-m 21.1-21.3 4.21-4.17 vs 22.1-22.3 4.02-3.99 m-s 22.8-23.0 3.90-3.86 m 23.1-23.4 3.82-3.80 w-m 25.5-25.9 3.493-3.440 w-m ______________________________________ TABLE S ______________________________________ (XAPO-42) 2Θ D (Å) Relative Intensity ______________________________________ 7.15-7.4 12.36-11.95 m-vs 12.5-12.7 7.08-6.97 m-s 21.75-21.9 4.09-4.06 m-s 24.1-24.25 3.69-3.67 vs 27.25-27.4 3.273-3.255 s 30.05-30.25 2.974-2.955 m-s ______________________________________ TABLE U ______________________________________ (XAPO-46) 2Θ D (Å) Relative Intensity ______________________________________ 7.2-8.1 12.3-10.9 vs 21.2-21.8 4.19-4.08 w-m 22.5-23.0 3.95-3.87 vw-m 26.6-27.2 3.351-3.278 vw-w 28.5-29.0 3.132-3.079 vw-w ______________________________________

Claim 3

Molecular sieves according to claim 1 wherein the mole fractions of "M", aluminum and phosphorus present as tetrahedral oxides are within the hexagonal compositional area defined by points a, b, c, d, e and f of FIG. 2.

Claim 4

A process for preparing a molecular sieve having a crystalline three-dimensional microporous framework structure of MO 2 n , AlO 2 and PO 2 tetrahedral oxide units having an empirical chemical composition on an anhydrous basis expressed by the formula: mR:(M.sub.x Al.sub.y P.sub.z)O.sub.2 wherein "R" represents at least one organic templating agent present in the intracrystalline pore system; "M" represents: (1) titanium, or a mixture of titanium and iron; and (2) at least one element from the group consisting of cobalt, magnesium, manganese and zinc; "n" is 0, -1 or -2; "m" represents a molar amount of "R" present per mole of (M x Al y P z )O 2 and has a value of zero (0) to about 0.3; and "x", "y" and "z" represent the mole fractions of "M", aluminum and phosphorus, respectively, present as tetrahedral oxides, said mole fractions being such that they are within the pentagonal compositional area defined by points A, B, C, D and E of FIG. 1, said crystalline molecular sieve having a characteristic X-ray powder diffraction pattern which contains at least the d-spacings set forth in one of the following Tables O, Q, R, S and U. TABLE O ______________________________________ (XAPO-37) 2Θ D (Å) Relative Intensity ______________________________________ 6.1-6.3 14.49-14.03 vs 15.5-15.7 5.72-5.64 w-m 18.5-18.8 4.80-4.72 w-m 23.5-23.7 3.79-3.75 w-m 26.9-27.1 3.31-3.29 w-m ______________________________________ TABLE Q ______________________________________ (XAPO-40) 2Θ D (Å) Relative Intensity ______________________________________ 7.5-7.7 11.79-11.48 vw-m 8.0-8.1 11.05-10.94 s-vs 12.4-12.5 7.14-7.08 w-vs 13.6-13.8 6.51-6.42 m-s 14.0-14.1 6.33-6.28 w-m 27.8-28.0 3.209-3.187 w-m ______________________________________ TABLE R ______________________________________ (XAPO-41) 2Θ D (Å) Relative Intensity ______________________________________ 13.6-13.8 6.51-6.42 w-m 20.5-20.6 4.33-4.31 w-m 21.1-21.3 4.21-4.17 vs 22.1-22.3 4.02-3.99 m-s 22.8-23.0 3.90-3.86 m 23.1-23.4 3.82-3.80 w-m 25.5-25.9 3.493-3.440 w-m ______________________________________ TABLE S ______________________________________ (XAPO-42) 2Θ D (Å) Relative Intensity ______________________________________ 7.15-7.4 12.36-11.95 m-vs 12.5-12.7 7.08-6.97 m-s 21.75-21.9 4.09-4.06 m-s 24.1-24.25 3.69-3.67 vs 27.25-27.4 3.273-3.255 s 30.05-30.25 2.974-2.955 m-s ______________________________________ TABLE U ______________________________________ (XAPO-46) 2Θ D (Å) Relative Intensity ______________________________________ 7.2-8.1 12.3-10.9 vs 21.2-21.8 4.19-4.08 w-m 22.5-23.0 3.95-3.87 vw-m 26.6-27.2 3.351-3.278 vw-w 28.5-29.0 3.132-3.079 vw-w ______________________________________ which process comprises providing a reaction mixture composition at an effective temperature and for an effective time sufficient to produce said molecular sieve, said reaction mixture composition being expressed in terms of molar oxide ratios as follows: aR:(M.sub.u Al.sub.v P.sub.w)O.sub.2 :bH.sub.2 O where "R" is an organic templating agent; "a" is the amount of "R" and is an effective amount greater than zero to about 6; "M" represents titanium, or a mixture of titanium and iron, and at least one of cobalt, magnesium, manganese and zinc; "b" has a value of between zero and about 500; and "u", "v" and "w" represent the mole fractions, respectively, of "M", aluminum and phosphorus in the (M u Al v P w )O 2 constituent, and each has a value of at least 0.01.

Claim 5

A process for preparing a molecular sieve having a crystalline three-dimensional microporous framework structure of MO 2 n , AlO 2 and PO 2 tetrahedral oxide units having an empirical chemical composition on an anhydrous basis expressed by the formula: mR:(M.sub.x Al.sub.y P.sub.z)O.sub.2 wherein "R" represents at least one organic templating agent present in the intracrystalline pore system; "M" represents: (1) titanium, or a mixture of titanium and iron; and (2) at least one element from the group consisting of cobalt, magnesium, manganese and zinc; "n" is 0, -1 or -2; "m" represents a molar amount of "R" present per mole of (M x Al y P z )O 2 and has a value of zero (0) to about 0.3; and "x", "y" and "z" represent the mole fractions of "M", aluminum and phosphorus, respectively, present as tetrahedral oxides, said mole fractions being such that they are within the pentagonal compositional area defined by points A, B, C, D and E of FIG. 1, said crystalline molecular sieve having a characteristic X-ray powder diffraction pattern which contains at least the d-spacings set forth in one of the following Tables O, Q, R, S and U. TABLE O ______________________________________ (XAPO-37) 2Θ D (Å) Relative Intensity ______________________________________ 6.1-6.3 14.49-14.03 vs 15.5-15.7 5.72-5.64 w-m 18.5-18.8 4.80-4.72 w-m 23.5-23.7 3.79-3.75 w-m 26.9-27.1 3.31-3.29 w-m ______________________________________ TABLE Q ______________________________________ (XAPO-40) 2Θ D (Å) Relative Intensity ______________________________________ 7.5-7.7 11.79-11.48 vw-m 8.0-8.1 11.05-10.94 s-vs 12.4-12.5 7.14-7.08 w-vs 13.6-13.8 6.51-6.42 m-s 14.0-14.1 6.33-6.28 w-m 27.8-28.0 3.209-3.187 w-m ______________________________________ TABLE R ______________________________________ (XAPO-41) 2Θ D (Å) Relative Intensity ______________________________________ 13.6-13.8 6.51-6.42 w-m 20.5-20.6 4.33-4.31 w-m 21.1-21.3 4.21-4.17 vs 22.1-22.3 4.02-3.99 m-s 22.8-23.0 3.90-3.86 m 23.1-23.4 3.82-3.80 w-m 25.5-25.9 3.493-3.440 w-m ______________________________________ TABLE S ______________________________________ (XAPO-42) 2Θ D (Å) Relative Intensity ______________________________________ 7.15-7.4 12.36-11.95 m-vs 12.5-12.7 7.08-6.97 m-s 21.75-21.9 4.09-4.06 m-s 24.1-24.25 3.69-3.67 vs 27.25-27.4 3.273-3.255 s 30.05-30.25 2.974-2.955 m-s ______________________________________ TABLE U ______________________________________ (XAPO-46) 2Θ D (Å) Relative Intensity ______________________________________ 7.2-8.1 12.3-10.9 vs 21.2-21.8 4.19-4.08 w-m 22.5-23.0 3.95-3.87 vw-m 26.6-27.2 3.351-3.278 vw-w 28.5-29.0 3.132-3.079 vw-w ______________________________________ which process comprises providing a reaction mixture composition at an effective temperature and for an effective time sufficient to produce said molecular sieve, said reaction mixture composition being expressed in terms of molar oxide ratios as follows: aR:(M.sub.u Al.sub.v P.sub.w)O.sub.2 :bH.sub.2 O where "R" is an organic templating agent; "a" is the amount of "R" and is an effective amount greater than zero to about 6; "M" represents titanium, or a mixture of titanium and iron, and at least one of cobalt, magnesium, manganese and zinc; "b" has a value of between zero and about 500; and "u", "v" and "w" represent the mole fractions, respectively, of "M", aluminum and phosphorus in the (M u Al v P w )O 2 constituent, and each has a value of at least 0.01.

Claim 6

The process of claim 3 wherein "u", "v" and "w" are within the pentagonal compositional area defined by points F, G, H, I and J of FIG. 3.

Claim 7

Process according to claim 3 wherein the source of phosphorus in the reaction mixture is orthophosphoric acid.

Claim 8

Process according to claim 3 wherein the source of phosphorus in the reaction mixture is orthophosphoric acid and the source of aluminum is at least one compound selected from the group consisting of pseudo-boehmite and aluminum alkoxide.

Claim 9

Process according to claim 6 wherein the aluminum alkoxide is aluminum isopropoxide.

Claim 10

Process according to claim 3 wherein the sources of titanium, iron, cobalt, magnesium, manganese and zinc are selected from the group consisting of chlorides, bromides, iodides, oxides, hydroxides, alkoxides, nitrates, sulfates, acetates and mixtures thereof.

Claim 11

Process according to claim 3 wherein the organic templating agent is a quaternary ammonium or quaternary phosphonium compound having the formula: R.sub.4 X.sup.+ wherein X is nitrogen or phosphorus and each R is an alkyl or aryl group containing from 1 to 8 carbon atoms.

Claim 12

Process according to claim 3 wherein the organic templating agent is an amine.

Claim 13

Process according to claim 3 wherein the templating agent is selected from the group consisting of tetrapropylammonium ion; tetraethylammonium ion; tripropylamine; triethylamine; triethanolamine; piperidine; cyclohexylamine; 2-methyl pyridine; N,N-dimethylbenzylamine; N,N-dimethylethanolamine; choline; N,N-dimethylpiperazine; 1,4-diaziabicyclo-(2,2,2) octane; N-methyldiethanolamine; N-methylethanolamine; N-methylpiperidine; 3-methylpiperidine; N-methylcyclohexylamine; 3-methylpyridine; 4-methylpyridine; quinuclidine; N,N'-dimethyl-1,4-diazabicyclo (2,2,2) octane ion; tetramethylammonium ion; tetrabutylammonium ion; tetrapentylammonium ion; di-n-butylamine; neopentylamine; di-n-pentylamine; isopropylamine; t-butylamine; ethylenediamine; pyrrolidine; 2-imidazolidone; di-n-propylamine; and a polymeric quaternary ammonium salt [(C 14 H 32 N 2 ) (OH) 2 ] x wherein x has a value of at least 2.

Claim 14

A molecular sieve prepared by calcining, at a temperature sufficiently high to remove at least some of the organic templating agent present in the intracrystalline pore system, a crystalline molecular sieve having a three-dimensional microporous framework structure of MO 2 n , AlO 2 and PO 2 tetrahedral oxide units having an empirical chemical composition on an anhydrous basis expressed by the formula: mR:(M.sub.x Al.sub.y P.sub.z)O.sub.2 wherein "R" represents at least one organic templating agent present in the intracrystalline pore system; "M" represents: (1) titanium, or a mixture of titanium and iron; and (2) at least one element from the group consisting of cobalt, magnesium, manganese and zinc; "n" is 0, -1 or -2; "m" represents a molar amount of "R" present per mole of (M x Al y P z )O 2 and has a value of zero (0) to about 0.3; and "x", "y" and "z" represent the mole fractions of "M", aluminum and phosphorus, respectively, present as tetrahedral oxides, said mole fractions being such that they are within the pentagonal compositional area defined by points A, B, C, D and E of FIG. 1, said crystalline molecular sieve having a characteristic X-ray powder diffraction pattern which contains at least the d-spacings set forth in one of the following Tables O, Q, R, S and U. TABLE O ______________________________________ (XAPO-37) 2Θ D (Å) Relative Intensity ______________________________________ 6.1-6.3 14.49-14.03 vs 15.5-15.7 5.72-5.64 w-m 18.5-18.8 4.80-4.72 w-m 23.5-23.7 3.79-3.75 w-m 26.9-27.1 3.31-3.29 w-m ______________________________________ TABLE Q ______________________________________ (XAPO-40) 2Θ D (Å) Relative Intensity ______________________________________ 7.5-7.7 11.79-11.48 vw-m 8.0-8.1 11.05-10.94 s-vs 12.4-12.5 7.14-7.08 w-vs 13.6-13.8 6.51-6.42 m-s 14.0-14.1 6.33-6.28 w-m 27.8-28.0 3.209-3.187 w-m ______________________________________ TABLE R ______________________________________ (XAPO-41) 2Θ D (Å) Relative Intensity ______________________________________ 13.6-13.8 6.51-6.42 w-m 20.5-20.6 4.33-4.31 w-m 21.1-21.3 4.21-4.17 vs 22.1-22.3 4.02-3.99 m-s 22.8-23.0 3.90-3.86 m 23.1-23.4 3.82-3.80 w-m 25.5-25.9 3.493-3.440 w-m ______________________________________ TABLE S ______________________________________ (XAPO-42) 2Θ D (Å) Relative Intensity ______________________________________ 7.15-7.4 12.36-11.95 m-vs 12.5-12.7 7.08-6.97 m-s 21.75-21.9 4.09-4.06 m-s 24.1-24.25 3.69-3.67 vs 27.25-27.4 3.273-3.255 s 30.05-30.25 2.974-2.955 m-s ______________________________________ TABLE U ______________________________________ (XAPO-46) 2Θ D (Å) Relative Intensity ______________________________________ 7.2-8.1 12.3-10.9 vs 21.2-21.8 4.19-4.08 w-m 22.5-23.0 3.95-3.87 vw-m 26.6-27.2 3.351-3.278 vw-w 28.5-29.0 3.132-3.079 vw-w ______________________________________

Claim 15

A molecular sieve prepared by calcining, at a temperature sufficiently high to remove at least some of the organic templating agent present in the intracrystalline pore system, a crystalline molecular sieve having a three-dimensional microporous framework structure of MO 2 n , AlO 2 and PO 2 tetrahedral oxide units having an empirical chemical composition on an anhydrous basis expressed by the formula: mR:(M.sub.x Al.sub.y P.sub.z)O.sub.2 wherein "R" represents at least one organic templating agent present in the intracrystalline pore system; "M" represents: (1) titanium, or a mixture of titanium and iron; and (2) at least one element from the group consisting of cobalt, magnesium, manganese and zinc; "n" is 0, -1 or -2; "m" represents a molar amount of "R" present per mole of (M x Al y P z )O 2 and has a value of zero (0) to about 0.3; and "x", "y" and "z" represent the mole fractions of "M", aluminum and phosphorus, respectively, present as tetrahedral oxides, said mole fractions being such that they are within the pentagonal compositional area defined by points A, B, C, D and E of FIG. 1, said crystalline molecular sieve having a characteristic X-ray powder diffraction pattern which contains at least the d-spacings set forth in one of the following Tables O, Q, R, S and U. TABLE O ______________________________________ (XAPO-37) 2Θ D (Å) Relative Intensity ______________________________________ 6.1-6.3 14.49-14.03 vs 15.5-15.7 5.72-5.64 w-m 18.5-18.8 4.80-4.72 w-m 23.5-23.7 3.79-3.75 w-m 26.9-27.1 3.31-3.29 w-m ______________________________________ TABLE Q ______________________________________ (XAPO-40) 2Θ D (Å) Relative Intensity ______________________________________ 7.5-7.7 11.79-11.48 vw-m 8.0-8.1 11.05-10.94 s-vs 12.4-12.5 7.14-7.08 w-vs 13.6-13.8 6.51-6.42 m-s 14.0-14.1 6.33-6.28 w-m 27.8-28.0 3.209-3.187 w-m ______________________________________ TABLE R ______________________________________ (XAPO-41) 2Θ D (Å) Relative Intensity ______________________________________ 13.6-13.8 6.51-6.42 w-m 20.5-20.6 4.33-4.31 w-m 21.1-21.3 4.21-4.17 vs 22.1-22.3 4.02-3.99 m-s 22.8-23.0 3.90-3.86 m 23.1-23.4 3.82-3.80 w-m 25.5-25.9 3.493-3.440 w-m ______________________________________ TABLE S ______________________________________ (XAPO-42) 2Θ D (Å) Relative Intensity ______________________________________ 7.15-7.4 12.36-11.95 m-vs 12.5-12.7 7.08-6.97 m-s 21.75-21.9 4.09-4.06 m-s 24.1-24.25 3.69-3.67 vs 27.25-27.4 3.273-3.255 s 30.05-30.25 2.974-2.955 m-s ______________________________________ TABLE U ______________________________________ (XAPO-46) 2Θ D (Å) Relative Intensity ______________________________________ 7.2-8.1 12.3-10.9 vs 21.2-21.8 4.19-4.08 w-m 22.5-23.0 3.95-3.87 vw-m 26.6-27.2 3.351-3.278 vw-w 28.5-29.0 3.132-3.079 vw-w ______________________________________