Germanium-aluminum-phosphorus-silicon-oxide molecular sieve compositions

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

• mR:(Ge.sub.w Al.sub.x P.sub.y Si.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 (Ge.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2 and has a value of zero to about 0.3;
• and "w", "x", "y" and "z" represent the mole fractions of germanium, aluminum, phosphorus and silicon, 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 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 H and J to W:
• TABLE A ______________________________________ (GeAPSO-5) 2.theta. d(.ANG.) Relative Intensity ______________________________________ 7.2-7.7 12.28-11.48 m-vs 19.4-19.9 4.58-4.46 w-m 20.85-21.3 4.26-4.17 w-vs 22.1-22.6 4.02-3.93 m-vs 25.6-26.2 3.480-3.402 vw-m ______________________________________
• TABLE B ______________________________________ (GeAPSO-11) 2.theta. d(.ANG.) Relative Intensity ______________________________________ 7.8-8.2 11.19-10.85 m-s 9.0-9.8 9.83-9.03 vw-vs 19.9-20.5 4.46-4.33 m-s 20.8-21.8 4.27-4.08 m-vs 22.0-22.6 4.04-3.93 m-vs 22.6-23.1 3.93-3.85 vw-vs 23.1-23.5 3.85-3.79 w-vs ______________________________________
• TABLE C ______________________________________ (GeAPSO-14) 2.theta. d(.ANG.) Relative Intensity ______________________________________ 8.6-8.9 10.3-9.93 vs 13.0 6.81 w 21.9-22.2 4.06-4.00 w 25.4 3.51 w 27.5 3.24 w 29.7 3.01 w ______________________________________
• TABLE D ______________________________________ (GeAPSO-16) 2.theta. d(.ANG.) Relative Intensity ______________________________________ 11.3-11.6 7.83-7.63 w-vs 18.55-18.9 4.78-4.70 vw-m 21.85-22.2 4.07-4.00 m-vs 22.8-23.3 3.900-3.818 w-m 26.4-27.3 3.370-3.267 w-m 29.6-29.9 3.018-2.988 w-m ______________________________________
• TABLE E ______________________________________ (GeAPSO-17) 2.theta. d(.ANG.) Relative Intensity ______________________________________ 7.70-7.75 11.5-11.4 vs 13.4 6.61 s-vs 15.5-15.55 5.72-5.70 s 19.65-19.7 4.52-4.51 w-s 20.5-20.6 4.33-4.31 vs 31.8-32.0 2.812-2.797 w-s ______________________________________
• TABLE F ______________________________________ (GeAPSO-18) 2.theta. d(.ANG.) Relative Intensity ______________________________________ 9.6-9.65 9.21-9.16 vs 15.5-15.55 5.72-5.70 m 16.9-17.1 5.25-5.19 m 20.15-20.25 4.41-4.39 m 20.95-21.05 4.24-4.22 m 31.8-32.5 2.814-2.755 m ______________________________________
• TABLE G ______________________________________ (GeAPSO-20) 2.theta. d(.ANG.) Relative Intensity ______________________________________ 13.8-14.2 6.42-6.23 m-vs 19.6-20.15 4.53-4.41 m 24.1-24.8 3.695-3.603 m-vs 27.9-28.6 3.198-3.121 w 31.3-32.05 2.861-2.791 w 34.35-35.0 2.610-2.601 w-m ______________________________________
• TABLE H ______________________________________ (GeAPSO-31) 2.theta. d(.ANG.) Relative Intensity ______________________________________ 8.4-9.5 10.53-9.31 w-s 20.2-20.4 4.40-4.35 m 22.0-22.1 4.040-4.022 m 22.5-22.7 3.952-3.92 vs 31.6-31.8 2.831-2.814 w-m ______________________________________
• TABLE J* ______________________________________ (GeAPSO-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* ______________________________________ (GeAPSO-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 ______________________________________ (GeAPSO-34) 2.theta. d(.ANG.) Relative Intensity ______________________________________ 9.3-9.8 9.51-9.03 m-vs 12.6-13.2 7.03-6.71 w-m 15.8-16.3 5.61-5.44 vw-m 20.25-21.2 4.39-4.19 w-vs 24.8-25.4 3.59-3.507 vw-m 30.0-30.9 2.979-2.894 vw-m ______________________________________
• TABLE M ______________________________________ (GeAPSO-35) 2.theta. d(.ANG.) Relative Intensity ______________________________________ 10.6-11.1 8.35-7.97 vw-vs 13.1-13.7 6.76-6.46 vw-vs 17.0-17.6 5.22-5.04 w-s 20.6-21.25 4.31-4.18 vw-m 21.6-22.3 4.11-3.99 m-vs 28.1-28.8 3.175-3.100 vw-m ______________________________________
• TABLE N ______________________________________ (GeAPSO-36) 2.theta. d(.ANG.) Relative Intensity ______________________________________ 7.45-8.0 11.14-11.05 vs 8.1-8.3 10.91-10.65 w-m 16.3-16.6 5.44-5.34 w-m 18.9-19.4 4.70-4.57 w-m 20.7-21.0 4.29-4.23 w-m ______________________________________
• TABLE O ______________________________________ (GeAPSO-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 ______________________________________ (GeAPSO-39) 2.theta. d(.ANG.) Relative Intensity ______________________________________ 9.2-9.6 9.61-9.21 m 13.1-13.5 6.76-6.56 m 17.8-18.4 4.98-4.82 w-m 20.8-21.3 4.27-4.17 m-vs 22.2-22.85 4.00-3.892 m-vs 26.4-27.05 3.376-3.296 w-m ______________________________________
• TABLE Q ______________________________________ (GeAPSO-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 ______________________________________ (GeAPSO-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 3.493-3.44 w-m ______________________________________
• TABLE S ______________________________________ (GeAPSO-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 ______________________________________ (GeAPSO-43) 2.theta. d(.ANG.) Relative Intensity ______________________________________ 12.3-12.95 7.20-6.83 m-vs 16.8-17.45 5.28-5.09 vw-w 21.45-21.85 4.145-4.071 m-vs 27.0-27.85 3.297-3.232 w-vs 32.4-33.2 2.763-2.699 vw-m ______________________________________
• TABLE U ______________________________________ (GeAPSO-44) 2.theta. d(.ANG.) Relative Intensity ______________________________________ 9.2-9.6 9.61-9.21 m-vs 15.9-16.3 5.57-5.44 vw-m 20.5-21.0 4.33-4.23 m-vs 24.3-25.1 3.66-3.548 w-m 30.5-31.1 2.931-2.876 vw-m ______________________________________
• TABLE V ______________________________________ (GeAPSO-46) 2.theta. d(.ANG.) Relative Intensity ______________________________________ 7.2-8.1 12.28-10.92 vs 12.9-13.6 6.86-6.51 vw 21.2-22.2 4.19-4.501 vw-m 22.5-23.45 3.95-3.793 vw-m 26.6-27.9 3.351-3.198 vw-m ______________________________________
• the process comprising 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:(Ge.sub.r Al.sub.s P.sub.t Si.sub.u)O.sub.2 :bH.sub.2 O
• wherein "R" is an organic templating agent;
• "a" is the amount of "R" and is an effective amount greater than zero to about 6;
• "b" has a value of from zero to about 500;
• and "r", "s", "t" and "u" represent the mole fractions, respectively, of germanium, aluminum, phosphorus and silicon in the (Ge.sub.r Al.sub.s P.sub.t Si.sub.u)O.sub.2 constituent, and each has a value of at least 0.01.

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

• mR:(Ge.sub.w Al.sub.x P.sub.y Si.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 (Ge.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2 and has a value of zero to about 0.3;
• and "w", "x", "y" and "z" represent the mole fractions of germanium, aluminum, phosphorus and silicon, 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 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 H and J to W:
• TABLE A ______________________________________ (GeAPSO-5) 2.theta. d(.ANG.) Relative Intensity ______________________________________ 7.2-7.7 12.28-11.48 m-vs 19.4-19.9 4.58-4.46 w-m 20.85-21.3 4.26-4.17 w-vs 22.1-22.6 4.02-3.93 m-vs 25.6-26.2 3.480-3.402 vw-m ______________________________________
• TABLE B ______________________________________ (GeAPSO-11) 2.theta. d(.ANG.) Relative Intensity ______________________________________ 7.8-8.2 11.19-10.85 m-s 9.0-9.8 9.83-9.03 vw-vs 19.9-20.5 4.46-4.33 m-s 20.8-21.8 4.27-4.08 m-vs 22.0-22.6 4.04-3.93 m-vs 22.6-23.1 3.93-3.85 vw-vs 23.1-23.5 3.85-3.79 w-vs ______________________________________
• TABLE C ______________________________________ (GeAPSO-14) 2.theta. d(.ANG.) Relative Intensity ______________________________________ 8.6-8.9 10.3-9.93 vs 13.0 6.81 w 21.9-22.2 4.06-4.00 w 25.4 3.51 w 27.5 3.24 w 29.7 3.01 w ______________________________________
• TABLE D ______________________________________ (GeAPSO-16) 2.theta. d(.ANG.) Relative Intensity ______________________________________ 11.3-11.6 7.83-7.63 w-vs 18.55-18.9 4.78-4.70 vw-m 21.85-22.2 4.07-4.00 m-vs 22.8-23.3 3.900-3.818 w-m 26.4-27.3 3.370-3.267 w-m 29.6-29.9 3.018-2.988 w-m ______________________________________
• TABLE E ______________________________________ (GeAPSO-17) 2.theta. d(.ANG.) Relative Intensity ______________________________________ 7.70-7.75 11.5-11.4 vs 13.4 6.61 s-vs 15.5-15.55 5.72-5.70 s 19.65-19.7 4.52-4.51 w-s 20.5-20.6 4.33-4.31 vs 31.8-32.0 2.812-2.797 w-s ______________________________________
• TABLE F ______________________________________ (GeAPSO-18) 2.theta. d(.ANG.) Relative Intensity ______________________________________ 9.6-9.65 9.21-9.16 vs 15.5-15.55 5.72-5.70 m 16.9-17.1 5.25-5.19 m 20.15-20.25 4.41-4.39 m 20.95-21.05 4.24-4.22 m 31.8-32.5 2.814-2.755 m ______________________________________
• TABLE G ______________________________________ (GeAPSO-20) 2.theta. d(.ANG.) Relative Intensity ______________________________________ 13.8-14.2 6.42-6.23 m-vs 19.6-20.15 4.53-4.41 m 24.1-24.8 3.695-3.603 m-vs 27.9-28.6 3.198-3.121 w 31.3-32.05 2.861-2.791 w 34.35-35.0 2.610-2.601 w-m ______________________________________
• TABLE H ______________________________________ (GeAPSO-31) 2.theta. d(.ANG.) Relative Intensity ______________________________________ 8.4-9.5 10.53-9.31 w-s 20.2-20.4 4.40-4.35 m 22.0-22.1 4.040-4.022 m 22.5-22.7 3.952-3.92 vs 31.6-31.8 2.831-2.814 w-m ______________________________________
• TABLE J* ______________________________________ (GeAPSO-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* ______________________________________ (GeAPSO-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 ______________________________________ (GeAPSO-34) 2.theta. d(.ANG.) Relative Intensity ______________________________________ 9.3-9.8 9.51-9.03 m-vs 12.6-13.2 7.03-6.71 w-m 15.8-16.3 5.61-5.44 vw-m 20.25-21.2 4.39-4.19 w-vs 24.8-25.4 3.59-3.507 vw-m 30.0-30.9 2.979-2.894 vw-m ______________________________________
• TABLE M ______________________________________ (GeAPSO-35) 2.theta. d(.ANG.) Relative Intensity ______________________________________ 10.6-11.1 8.35-7.97 vw-vs 13.1-13.7 6.76-6.46 vw-vs 17.0-17.6 5.22-5.04 w-s 20.6-21.25 4.31-4.18 vw-m 21.6-22.3 4.11-3.99 m-vs 28.1-28.8 3.175-3.100 vw-m ______________________________________
• TABLE N ______________________________________ (GeAPSO-36) 2.theta. d(.ANG.) Relative Intensity ______________________________________ 7.45-8.0 11.14-11.05 vs 8.1-8.3 10.91-10.65 w-m 16.3-16.6 5.44-5.34 w-m 18.9-19.4 4.70-4.57 w-m 20.7-21.0 4.29-4.23 w-m ______________________________________
• TABLE O ______________________________________ (GeAPSO-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 ______________________________________ (GeAPSO-39) 2.theta. d(.ANG.) Relative Intensity ______________________________________ 9.2-9.6 9.61-9.21 m 13.1-13.5 6.76-6.56 m 17.8-18.4 4.98-4.82 w-m 20.8-21.3 4.27-4.17 m-vs 22.2-22.85 4.00-3.892 m-vs 26.4-27.05 3.376-3.296 w-m ______________________________________
• TABLE Q ______________________________________ (GeAPSO-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 ______________________________________ (GeAPSO-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 3.493-3.44 w-m ______________________________________
• TABLE S ______________________________________ (GeAPSO-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 ______________________________________ (GeAPSO-43) 2.theta. d(.ANG.) Relative Intensity ______________________________________ 12.3-12.95 7.20-6.83 m-vs 16.8-17.45 5.28-5.09 vw-w 21.45-21.85 4.145-4.071 m-vs 27.0-27.85 3.297-3.232 w-vs 32.4-33.2 2.763-2.699 vw-m ______________________________________
• TABLE U ______________________________________ (GeAPSO-44) 2.theta. d(.ANG.) Relative Intensity ______________________________________ 9.2-9.6 9.61-9.21 m-vs 15.9-16.3 5.57-5.44 vw-m 20.5-21.0 4.33-4.23 m-vs 24.3-25.1 3.66-3.548 w-m 30.5-31.1 2.931-2.876 vw-m ______________________________________
• TABLE V ______________________________________ (GeAPSO-46) 2.theta. d(.ANG.) Relative Intensity ______________________________________ 7.2-8.1 12.28-10.92 vs 12.9-13.6 6.86-6.51 vw 21.2-22.2 4.19-4.501 vw-m 22.5-23.45 3.95-3.793 vw-m 26.6-27.9 3.351-3.198 vw-m ______________________________________
• TABLE W ______________________________________ (GeAPSO-47) 2.theta. d(.ANG.) Relative Intensity ______________________________________ 9.4-9.6 9.41-9.21 vs 12.8-13.1 6.92-6.76 vw-m 16.0-16.3 5.54-5.44 vw-m 20.5-21.0 4.31-4.23 m-vs 24.6-25.3 3.613-3.526 vw-m 30.6-31.1 2.921-2.876 vw-m. ______________________________________

Crystalline molecular sieves comprising three-dimensional microporous framework structures of GeO.sub.2, AlO.sub.2, PO.sub.2 and SiO.sub.2 tetrahedral units having an empirical chemical composition on an anhydrous basis expressed by the formula:

• mR:(Ge.sub.w Al.sub.x P.sub.y Si.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 (Ge.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2 and has a value of zero to about 0.3;
• and "w", "x", "y" and "z" represent the mole fractions of germanium, aluminum, phosphorus and silicon, 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.

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

• mR:(Ge.sub.w Al.sub.x P.sub.y Si.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 (Ge.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2 and has a value of zero to about 0.3;
• and "w", "x", "y" and "z" represent the mole fractions of germanium, aluminum, phosphorus and silicon 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, wherein the 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:(Ge.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2 :bH.sub.2 O
• wherein "R" is an organic templating agent;
• "a" is the amount of "R" and is an effective amount greater than zero to about 6;
• "b" has a value of from zero to about 500;
• and "w", "x", "y" and "z" represent the mole fractions, respectively, of germanium, aluminum, phosphorus and silicon in the (Ge.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2 constituent, and each has a value of at least 0.01.

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

• mR:(Ge.sub.r Al.sub.s P.sub.t Si.sub.u)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 (Ge.sub.r Al.sub.s P.sub.t Si.sub.u)O.sub.2 and has a value of zero to about 0.3;
• and "r", "s", "t" and "u" represent the mole fractions of germanium, aluminum, phosphorus and silicon, 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.