Crystalline silicoaluminophosphates

Claim 2

Microporous crystalline silicoaluminophosphates the pores of which are uniform and have nominal diameters of greater than about 3 Angstroms and whose essential empirical chemical composition in the as-synthesized and anhydrous form is mR:(Si.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" has a value of from 0.02 to 0.3; "m" represents the moles of "R" present per mole of (Si x Al y P z )O 2 ; "x", "y" and "z" represent the mole fractions of silicon, aluminum and phosphorus respectively, present as tetrahedral oxides, said mole fractions being such that they are within the pentagonal compositional area defined by points ABCD and E of the ternary diagram which is FIG. 1 of the drawings.

Claim 3

Microporous crystalline silicoaluminophosphates according to claim 1 wherein the mole fractions of silicon, aluminum and phosphorus are within the pentagonal compositional area defined by points a, b, c, d and e of the ternary diagram which is FIG. 2 of the drawings.

Claim 4

Crystalline silicoaluminophosphate according to claim 1 or claim 2 having a characteristic X-ray powder diffraction pattern which contains at least the d-spacings set forth in Table I.

Claim 5

Crystalline silicoaluminophosphate according to claim 1 or claim 2 having a characteristic X-ray powder diffraction pattern which contains at least the d-spacings set forth in Table III.

Claim 6

Crystalline silicoaluminophosphate according to claim 1 or claim 2 having a characteristic X-ray powder diffraction pattern which contains at least the d-spacings set forth in Table V.

Claim 7

Crystalline silicoaluminophosphate according to claim 1 or claim 2 having a characteristic X-ray powder diffraction pattern which contains at least the d-spacings set forth in Table VII.

Claim 8

Crystalline silicoaluminophosphate according to claim 1 or claim 2 having a characteristic X-ray powder diffraction pattern which contains at least the d-spacings set forth in Table IX.

Claim 9

Crystalline silicoaluminophosphate according to claim 1 or claim 2 having a characteristic X-ray powder diffraction pattern which contains at least the d-spacings set forth in Table XI.

Claim 10

Crystalline silicoaluminophosphate according to claim 1 or claim 2 having a characteristic X-ray powder diffraction pattern which contains at least the d-spacings set forth in Table XIII.

Claim 11

Crystalline silicoaluminophosphate according to claim 1 or claim 2 having a characteristic X-ray powder diffraction pattern which contains at least the d-spacings set forth in Table XV.

Claim 12

Crystalline silicoaluminophosphate according to claim 1 or claim 2 having a characteristic X-ray powder diffraction pattern which contains at least the d-spacings set forth in Table XVII.

Claim 13

Crystalline silicoaluminophosphate according to claim 1 or claim 2 having a characteristic X-ray powder diffraction pattern which contains at least the d-spacings set forth in Table XIX.

Claim 14

Crystalline silicoaluminophosphate according to claim 1 or claim 2 having a characteristic X-ray powder diffraction pattern which contains at least the d-spacings set forth in Table XXI.

Claim 15

Crystalline silicoaluminophosphate according to claim 1 or claim 2 having a characteristic X-ray powder diffraction pattern which contains at least the d-spacings set forth in Table XXIII.

Claim 16

Crystalline silicoaluminophosphate according to claim 1 or claim 2 having a characteristic X-ray powder diffraction pattern which contains at least the d-spacings set forth in Table XXV.

Claim 17

Crystalline silicoaluminophosphate prepared by calcining the compositions of claim 1 or claim 2 or claim 3 or claim 4 or claim 5 or claim 6 or claim 7 or claim 8 or claim 9 or claim 10 or claim 11 or claim 12 or claim 13 or claim 14 or claim 15 at a temperature sufficiently high to remove at least some of the organic templating agent present in the intracrystalline pore system.

Claim 18

Silicoaluminophosphate material having a three-dimensional microporous framework structure of PO 2 + , AlO 2 - and SiO 2 tetrahedral units, and whose essential empirical chemical composition on an anhydrous basis is: mR:(Si.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 moles of "R" present per mole of (Si x Al y P z )O 2 and has a value of from zero to 0.3; "x", "y" and "z" represent respectively, the mole fractions of silicon, aluminum and phosphorus present in the oxide moiety, said mole fractions being within the compositional area bounded by points A, B, C, D and E on the ternary diagram which is FIG. 1, said silicoaluminophosphate having a characteristic X-ray powder diffraction pattern which contains at least the d-spacings set forth below in any one of Tables I, III, V, VII, IX, XIII, XVII, XXI, XXIII or XXV.

Claim 19

Silicoaluminophosphate material having a three-dimensional microporous framework structure of PO 2 + , AlO 2 - and SiO 2 tetrahedral units, and whose essential empirical chemical composition on an anhydrous basis is: mR:(Si.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 moles of "R" present per mole of (Si x Al y P z )O 2 and has a value of from zero to 0.3; "x", "y" and "z" represent respectively, the mole fractions of silicon, aluminum and phosphorus present in the oxide moiety, said mole fractions being within the compositional area bounded by points A, B, C, D and E on the ternary diagram which is FIG. 1, said silicoaluminophosphate having a characteristic X-ray powder diffraction pattern which contains at least the d-spacings set forth below in any one of Tables I, III, V, VII, IX, XIII, XVII, XXI, XXIII or XXV.

Claim 20

Composition according to claim 17 wherein the mole fractions of silicon, aluminum and phosphorus are within the pentagonal compositional area defined by points a, b, c, d and e of the ternary diagram which is FIG. 2 of the drawings.

Claim 21

Composition according to claim 17 or claim 16 which has the characteristic X-ray powder diffraction pattern containing at least the d-spacings of Table I.

Claim 22

Composition according to claim 17 or claim 18 which has the characteristic X-ray powder diffraction pattern containing at least the d-spacings of Table III.

Claim 23

Composition according to claim 17 or claim 18 which has the characteristic X-ray powder diffraction pattern containing at least the d-spacings of Table V.

Claim 24

Composition according to claim 17 or claim 18 which has the characteristic X-ray powder diffraction pattern containing at least the d-spacings of Table VII.

Claim 25

Composition according to claim 17 or claim 18 which has the characteristic X-ray powder diffraction powder containing at least the d-spacings of Table IX.

Claim 26

Composition according to claim 17 or claim 18 which has the characteristic X-ray powder diffraction pattern containing at least the d-spacings of Table XIII.

Claim 27

Composition according to claim 17 or claim 18 which has the characteristic X-ray powder diffraction pattern containing at least the d-spacings of Table XVII.

Claim 28

Composition according to claim 17 or claim 18 which has the characteristic X-ray powder diffraction pattern containing at least the d-spacings of Table XXI.

Claim 29

Composition according to claim 17 or claim 18 which has the characteristic X-ray powder diffraction pattern containing at least the d-spacings of Table XXIII.

Claim 30

Composition according to claim 17 or claim 18 which has the characteristic X-ray powder diffraction pattern containing at least the d-spacings of Table XXV.

Claim 31

Composition according to claim 17 or claim 18 wherein in the formula mR:(Si.sub.x Al.sub.y P.sub.z)O.sub.2 "m" has a value of zero, said composition having an X-ray powder diffraction pattern essentially as set forth in any one of Tables D, J, N, U, BB, EE, FF, and JJ.

Claim 32

Process for preparing a crystalline silicoaluminophosphate of claim 1 which comprises forming a reaction mixture containing reactive sources of SiO 2 , Al 2 O 3 , and P 2 O 5 and an organic templating agent, said reaction mixture having a composition expressed in terms of molar oxide ratios of: aR.sub.2 O:(Si.sub.x Al.sub.y P.sub.z)O.sub.2 :bH.sub.2 O wherein "R" is an organic templating agent; "a" has a value large enough to constitute an effective amount of "R" and is within the range of greater than 0 to 3; "b" has a value of from zero to 500; "x", "y" and "z" represent the mole fractions, respectively, of silicon, aluminum and phosphorus in the (Si x Al y P z )O 2 constituent and each has a value of at least 0.01 and crystallizing the reaction mixture thus formed at a temperature of at least 100° C. until crystals of the silicoaluminophosphate are formed.

Claim 33

Process according to claim 30 wherein "b" has a value of from 2 to 30.

Claim 34

Process according to claim 30 or claim 1 wherein the source of phosphorus in the reaction mixture is orthophosphoric acid.

Claim 35

Process according to claim 30 or claim 1 wherein the source of aluminum in the reaction mixture is at least one compound selected from the group consisting of pseudo-boehmite and aluminum alkoxide, and the source of phosphorus is orthophosphoric acid.

Claim 36

Process according to claim 33 wherein the aluminum alkoxide is aluminum isopropoxide.

Claim 37

Process according to claim 30 or claim 1 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 38

Process according to claim 35 wherein the organic templating agent is an amine.

Claim 39

Process according to claim 35 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-diethylethanolamine; dicyclohexylamine; N,N-dimethylethanolamine; choline; N,N-dimethylpiperazine; 1,4-diazabicyclo-(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 and 2-imidazolidone; di-n-propylamine; and a polymeric quaternary ammonium salt [(C 14 H 32 N 2 )] x + wherein x is a value of at least 2.

Claim 40

Process for preparing a crystalline silicoaluminophosphate of claim 1 which comprises forming a reaction mixture having a composition expressed in terms of molar oxide rations of: aR.sub.2 O:bM.sub.2 O:(Si.sub.x Al.sub.y P.sub.z)O.sub.2 :cH.sub.2 O wherein "R" is an organic templating agent; "a" has a value great enough to constitute an effective concentration of "R" and is within the range >0 to 3; "M" is an alkali metal; "b" has a value of zero to 2.5; "c" has a value of from zero to 500; "x", "y" and "z" represent the mole fractions, respectively, of silicon, aluminum and phosphorus in the (Si x Al y P z )O 2 constituent, and each have a value of at least 0.01 and being within the quadrilateral compositional area defined by points f, g, h and i which is FIG. 3 of the drawings, the said points f, g, h and i representing the following values for "x", "y" and "z": ______________________________________ Mole Fraction Point x y z ______________________________________ f 0.01 0.98 0.01 g 0.01 0.01 0.98 h 0.32 0.24 0.44 i 0.98 0.01 0.01; ______________________________________ said reaction mixture having been formed by combining at least a portion of each of the aluminum and phosphorus sources in the substantial absence of the silicon source and thereafter combining the resulting mixture with the remaining constituents to form the complete reaction mixture, and thereafter crystallizing said complete reaction mixture at a temperature of from 100° C. to about 250° C. in a sealed reactor until crystals of the silicoaluminophosphate are formed.