Gallium-aluminum-phosphorus-oxide molecular sieve compositions

Process for preparing crystalline molecular sieves having three-dimensional microporous framework structures of GaO.sub.2, AlO.sub.2 and PO.sub.2 tetrahedral units having an empirical chemical composition on an anhydrous basis expressed by the formula:

• mR:(Ga.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 the molar amount of "R" present per mole of (Ga.sub.x Al.sub.y P.sub.z)O.sub.2 and has a value of zero to about 0.3;
• and "x", "y" and "z" represent the mole fractions of gallium, aluminum and phosphorus, respectively, present as tetrahedral oxides, said mole fractions being such that they are within the hexagonal compositional area defined by points A, B, C, D, E and F of FIG. 1, said crystalline molecular sieves having a characteristic X-ray powder diffraction pattern which contains at least the d-spacings set forth in one of the following Tables A to V:
• TABLE A ______________________________________ (GaAPO-5) 2.THETA. d(.ANG.) Relative Intensity ______________________________________ 7.3-7.65 12.1-11.56 m-vs 19.5-20.0 4.55-4.44 m-s 20.9-21.3 4.25-4.17 m-vs 22.2-22.7 4.00-3.92 w-vs 25.7-26.2 3.47-3.40 w-m ______________________________________
• TABLE B ______________________________________ (GaAPO-11) 2.THETA. d(.ANG.) Relative Intensity ______________________________________ 9.3-9.65 9.51-9.17 m-s 20.2-20.6 4.40-4.31 m-s 20.9-21.3 4.25-4.17 s-vs 22.0-22.5 4.04-3.95 m-s 22.5-22.9 3.95-3.92 m-s 23.0-23.4 3.85-3.80 m-vs ______________________________________
• TABLE C ______________________________________ (GaAPO-14) 2.THETA. d(.ANG.) Relative Intensity ______________________________________ 8.9-9.1 9.89-9.77 vs 12.9-13.3 6.86-6.67 w-m 15.7-15.8 5.66-5.61 w-m 17.7-18.1 5.02-4.91 w-m 22.2-22.8 4.00-3.89 w 27.1-27.2 3.30-3.28 w ______________________________________
• TABLE D ______________________________________ (GaAPO-16) 2.THETA. d(.ANG.) Relative Intensity ______________________________________ 11.3-11.6 7.83-7.63 m-vs 18.7-18.9 4.75-4.70 w-s 21.9-22.3 4.06-3.99 m-vs 26.5-27.0 3.363-3.302 w-m 29.7-30.05 3.008-2.974 w-m ______________________________________
• TABLE E ______________________________________ (GaAPO-17) 2.THETA. d(.ANG.) Relative Intensity ______________________________________ 7.7-7.8 11.5-11.3 vs 13.3-13.5 6.65-6.57 s-vs 15.4-15.6 5.75-5.69 m-vs 19.5-19.7 4.55-4.51 m-vs 20.5-20.6 4.33-4.31 vs 31.7-32.0 2.819-2.797 w-s ______________________________________
• TABLE F ______________________________________ (GaAPO-18) 2.THETA. d(.ANG.) Relative Intensity ______________________________________ 9.5-9.7 9.27-9.14 vs 15.5-15.7 5.73-5.64 w-m 16.9-17.1 5.25-5.19 m 20.15-20.25 4.41-4.39 m 20.95-21.1 4.24-4.22 w-m 31.8-32.5 2.814-2.755 m ______________________________________
• TABLE G ______________________________________ (GaAPO-20) 2.THETA. d(.ANG.) Relative Intensity ______________________________________ 13.7-14.25 6.46-6.22 m-vs 19.55-20.0 4.54-4.44 w-s 24.05-24.6 3.70-3.63 m-vs 28.3-28.5 3.16-3.13 w-m 34.8-35.2 2.58-2.55 w ______________________________________
• TABLE H ______________________________________ (GaAPO-26) 2.THETA. d(.ANG.) Relative Intensity ______________________________________ 8.2-8.3 10.8-10.7 w-vs 9.6-9.9 9.2-9.0 vw-m 10.5-10.6 8.45-8.35 w-vs 21.8-22.1 4.07-4.01 w-vs 22.5-22.7 3.95-3.92 w-s 28.6-28.9 3.12-3.09 vw-m ______________________________________
• TABLE I ______________________________________ (GaAPO-31) 2.THETA. d(.ANG.) Relative Intensity ______________________________________ 8.5-8.6 10.40-10.28 m-s 20.2-20.3 4.40-4.37 m 21.9-22.1 4.06-4.02 w-m 22.6-22.7 3.93-3.92 vs 31.7-31.8 2.823-2.814 w-m ______________________________________
• TABLE J* ______________________________________ (GaAPO-33) 2.THETA. d(.ANG.) Relative Intensity ______________________________________ 9.25-9.55 9.56-9.26 w-m 12.5-12.9 7.08-6.86 vs 16.9-17.3 5.25-5.13 w-m 20.45-20.9 4.34-4.25 w-m 23.85-24.25 3.73-3.67 w-m 26.05-26.35 3.42-3.38 w-m 27.3-27.6 3.27-3.23 vs ______________________________________ *as-synthesized form
• TABLE K* ______________________________________ (GaAPO-33) 2.THETA. d(.ANG.) Relative Intensity ______________________________________ 13.15-13.4 6.73-6.61 vs 18.05-18.35 4.91-4.83 m 18.4-18.6 4.82-4.77 m 26.55-26.7 3.36-3.34 m 32.0-32.1 2.80-2.79 m ______________________________________ *calcined form
• TABLE L ______________________________________ (GaAPO-34) 2.THETA. d(.ANG.) Relative Intensity ______________________________________ 9.4-9.65 9.41-9.17 s-vs 15.9-16.2 5.57-5.47 vw-m 17.85-18.4 4.97-4.82 w-s 20.3-20.9 4.37-4.25 m-vs 24.95-25.4 3.57-3.51 vs-s 30.3-30.8 2.95-2.90 w-s ______________________________________
• TABLE M ______________________________________ (GaAPO-35) 2.THETA. d(.ANG.) Relative Intensity ______________________________________ 10.8-11.1 8.19-7.97 m 17.2-17.4 5.16-5.10 s-vs 21.0-21.25 4.23-4.18 m-s 21.8-22.0 4.08-4.04 vs 31.8-32.2 2.814-2.788 m ______________________________________
• TABLE N ______________________________________ (GaAPO-36) 2.THETA. d(.ANG.) Relative Intensity ______________________________________ 7.7-7.9 11.5-11.2 vs 16.2-16.6 5.47-5.34 w-m 18.9-19.3 4.70-4.60 m-s 27.4-27.7 3.26-3.22 w-m 27.7-28.0 3.22-3.19 w-m ______________________________________
• TABLE O ______________________________________ (GaAPO-37) 2.THETA. d(.ANG.) 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 P ______________________________________ (GaAPO-39) 2.THETA. d(.ANG.) Relative Intensity ______________________________________ 9.4-9.6 9.4l-9.21 w-m 13.3-13.6 6.66-6.51 m-vs 18.0-18.4 4.93-4.82 m 21.2-21.5 4.19-4.13 m-s 22.5-23.0 3.95-3.87 s-vs 30.2-30.5 2.96-2.93 w-m ______________________________________
• TABLE Q ______________________________________ (GaAPO-40) 2.THETA. d(.ANG.) 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 ______________________________________ (GaAPO-41) 2.THETA. d(.ANG.) 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 ______________________________________ (GaAPO-42) 2.THETA. d(.ANG.) 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 T ______________________________________ (GaAPO-44) 2.THETA. d(.ANG.) Relative Intensity ______________________________________ 9.4-9.55 9.41-9.26 vs 13.0-13.1 6.81-6.76 w-m 16.0-16.2 5.54-5.47 w-m 20.6-20.85 4.31-4.26 s-vs 24.3-24.4 3.66-3.65 w-vs 30.7-30.95 2.912-2.889 w-s ______________________________________
• TABLE U ______________________________________ (GaAPO-46) 2.THETA. d(.ANG.) 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 ______________________________________
• TABLE V ______________________________________ (GaAPO-47) 2.THETA. d(.ANG.) Relative Intensity ______________________________________ 9.4 9.41 vs 15.9-16.0 5.57-5.54 w-m 20.5-20.6 4.33-4.31 s 24.5-24.7 3.63-3.60 w 25.8-25.9 3.45-3.44 w 30.4-30.5 2.940-2.931 w ______________________________________
• which process comprises providing a reaction mixture composition at an effective temperature and for an effective time sufficient to produce said molecular sieves, said reaction mixture composition being expressed in terms of molar oxide ratios as follows:
• aR:(Ga.sub.u Al.sub.v P.sub.w)O.sub.2 :bH.sub.2 O
• wherein "R" is an organic templating agent;
• "a" is an effective amount of "R" greater than zero;
• "b" has a value of from zero to about 500;
• and "u", "v" and "w" represent the mole fractions, respectively, of gallium, aluminum and phosphorus in the (Ga.sub.u Al.sub.v P.sub.w)O.sub.2 constituent, and each has a value of at lest 0.01.

Molecular sieves prepared by calcining, at a temperature sufficiently high to remove at least some of the organic templating agent present in the intracrystalline pore system, the crystalline molecular sieves having three-dimensional microporous framework structures of GaO.sub.2, AlO.sub.2 and PO.sub.2 tetrahedral units having an empirical chemical composition on an anhydrous basis expressed by the formula:

• mR:(Ga.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 the molar amount of "R" present per mole of (Ga.sub.x Al.sub.y P.sub.z)O.sub.2 and has a value of zero to about 0.3;
• and "x", "y" and "z" represent the mole fractions of gallium, aluminum and phosphorus, respectively, present as tetrahedral oxides, said mole fractions being such that they are within the hexagonal compositional area defined by points A, B, C, D, E and F of FIG. 1, said crystalline molecular sieves having a characteristic X-ray powder diffraction pattern which contains at least the d-spacings set forth in one of the following Tables A to V:
• TABLE A ______________________________________ (GaAPO-5) 2.THETA. d(.ANG.) Relative Intensity ______________________________________ 7.3-7.65 12.1-11.56 m-vs 19.5-20.0 4.55-4.44 m-s 20.9-21.3 4.25-4.17 m-vs 22.2-22.7 4.00-3.92 w-vs 25.7-26.2 3.47-3.40 w-m ______________________________________
• TABLE B ______________________________________ GaAPO-11) 2.THETA. d(.ANG.) Relative Intensity ______________________________________ 9.3-9.65 9.51-9.17 m-s 20.2-20.6 4.40-4.31 m-s 20.9-21.3 4.25-4.17 s-vs 22.0-22.5 4.04-3.95 m-s 22.5-22.9 3.95-3.92 m-s 23.0-23.4 3.85-3.80 m-vs ______________________________________
• TABLE C ______________________________________ (GaAPO-14) 2.THETA. d(.ANG.) Relative Intensity ______________________________________ 8.9-9.1 9.89-9.77 vs 12.9-13.3 6.86-6.67 w-m 15.7-15.8 5.66-5.61 w-m 17.7-18.1 5.02-4.91 w-m 22.2-22.8 4.00-3.89 w 27.1-27.2 3.30-3.28 w ______________________________________
• TABLE D ______________________________________ (GaAPO-16) 2.THETA. d(.ANG.) Relative Intensity ______________________________________ 11.3-11.6 7.83-7.63 m-vs 18.7-18.9 4.75-4.70 w-s 21.9-22.3 4.06-3.99 m-vs 26.5-27.0 3.363-3.302 w-m 29.7-30.05 3.008-2.974 w-m ______________________________________
• TABLE E ______________________________________ (GaAPO-17) 2.THETA. d(.ANG.) Relative Intensity ______________________________________ 7.7-7.8 11.5-11.3 vs 13.3-13.5 6.65-6.57 s-vs 15.4-15.6 5.75-5.69 m-vs 19.5-19.7 4.55-4.51 m-vs 20.5-20.6 4.33-4.31 vs 31.7-32.0 2.819-2.797 w-s ______________________________________
• TABLE F ______________________________________ (GaAPO-18) 2.THETA. d(.ANG.) Relative Intensity ______________________________________ 9.5-9.7 9.27-9.14 vs l5.5-15.7 5.73-5.64 w-m 16.9-17.1 5.25-5.19 m 20.15-20.25 4.41-4.39 m 20.95-21.1 4.24-4.22 w-m 31.8-32.5 2.814-2.755 m ______________________________________
• TABLE G ______________________________________ (GaAPO-20) 2.theta. d(.ANG.) Relative Intensity ______________________________________ 13.7-14.25 6.46-6.22 m-vs 19.55-20.0 4.54-4.44 w-s 24.05-24.6 3.70-3.63 m-vs 28.3-28.5 3.16-3.13 w-m 34.8-35.2 2.58-2.55 w ______________________________________
• TABLE H ______________________________________ (GaAPO-26) 2.theta. d(.ANG.) Relative Intensity ______________________________________ 8.2-8.3 10.8-10.7 w-vs 9.6-9.9 9.2-9.0 vw-m 10.5-10.6 8.45-8.35 w-vs 21.8-22.1 4.07-4.01 w-vs 22.5-22.7 3.95-3.92 w-s 28.6-28.9 3.12-3.09 vw-m ______________________________________
• TABLE I ______________________________________ (GaAPO-31) 2.theta. d(.ANG.) Relative Intensity ______________________________________ 8.5-8.6 10.40-10.28 m-s 20.2-20.3 4.40-4.37 m 21.9-22.1 4.06-4.02 w-m 22.6-22.7 3.93-3.92 vs 31.7-31.8 2.823-2.814 w-m ______________________________________
• TABLE J* ______________________________________ (GaAPO-33) 2.theta. d(.ANG.) Relative Intensity ______________________________________ 9.25-9.55 9.56-9.26 w-m 12.5-12.9 7.08-6.86 vs 16.9-17.3 5.25-5.13 w-m 20.45-20.9 4.34-4.25 w-m 23.85-24.25 3.73-3.67 w-m 26.05-26.35 3.42-3.38 w-m 27.3-27.6 3.27-3.23 vs ______________________________________ *as-synthesized form
• TABLE K* ______________________________________ (GaAPO-33) 2.theta. d(.ANG.) Relative Intensity ______________________________________ 13.15-13.4 6.73-6.61 vs 18.05-18.35 4.91-4.83 m 18.4-18.6 4.82-4.77 m 26.55-26.7 3.36-3.34 m 32.0-32.1 2.80-2.79 m ______________________________________ *calcined form
• TABLE L ______________________________________ (GaAPO-34) 2.theta. d(.ANG.) Relative Intensity ______________________________________ 9.4-9.65 9.41-9.17 s-vs 15.9-16.2 5.57-5.47 vw-m 17.85-18.4 4.97-4.82 w-s 20.3-20.9 4.37-4.25 m-vs 24.95-25.4 3.57-3.51 vw-s 30.3-30.8 2.95-2.90 w-s ______________________________________
• TABLE M ______________________________________ (GaAPO-35) 2.theta. d(.ANG.) Relative Intensity ______________________________________ 10.8-11.1 8.19-7.97 m 17.2-17.4 5.16-5.10 s-vs 21.0-21.25 4.23-4.18 m-s 21.8-22.0 4.08-4.04 vs 31.8-32.2 2.814-2.788 m ______________________________________
• TABLE N ______________________________________ (GaAPO-36) 2.theta. d(.ANG.) Relative Intensity ______________________________________ 7.7-7.9 11.5-11.2 vs 16.2-16.6 5.47-5.34 w-m 18.9-19.3 4.70-4.60 m-s 27.4-27.7 3.26-3.22 w-m 27.7-28.0 3.22-3.19 w-m ______________________________________
• TABLE O ______________________________________ (GaAPO-37) 2.theta. d(.ANG.) 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 P ______________________________________ (GaAPO-39) 2.theta. d(.ANG.) Relative Intensity ______________________________________ 9.4-9.6 9.41-9.21 w-m 13.3-13.6 6.66-6.51 m-vs 18.0-18.4 4.93-4.82 m 21.2-21.5 4.19-4.13 m-s 22.5-23.0 3.95-3.87 s-vs 30.2-30.5 2.96-2.93 w-m ______________________________________
• TABLE Q ______________________________________ (GaAPO-40) 2.theta. d(.ANG.) 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 ______________________________________ (GaAPO-41) 2.theta. d(.ANG.) 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 ______________________________________ (GaAPO-42) 2.theta. d(.ANG.) 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 T ______________________________________ (GaAPO-44) 2.theta. d(.ANG.) Relative Intensity ______________________________________ 9.4-9.55 9.41-9.26 vs 13.0-13.1 6.81-6.76 w-m 16.0-16.2 5.54-5.47 w-m 20.6-20.85 4.31-4.26 s-vs 24.3-24.4 3.66-3.65 w-vs 30.7-30.95 2.912-2.889 w-s ______________________________________
• TABLE U ______________________________________ (GaAPO-46) 2.theta. d(.ANG.) 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 ______________________________________
• TABLE V ______________________________________ (GaAPO-47) 2.theta. d(.ANG.) Relative Intensity ______________________________________ 9.4 9.41 vs 15.9-16.0 5.57-5.54 w-m 20.5-20.6 4.33-4.31 s 24.5-24.7 3.63-3.60 w 25.8-25.9 3.45-3.44 w 30.4-30.5 2.940-2.931 w. ______________________________________