High charge density metalloaluminophosphosilicate molecular sieves

A method for preparing a microporous crystalline metalloalumino(gallo)phosphosilicate material having a three-dimensional framework of [M2+O4/2]2−, [EO4/2]−, [PO4/2]+ and SiO4/2 tetrahedral units and an empirical composition in the as synthesized form and on an anhydrous basis expressed by an empirical formula of:

• Rp+rA+mM2+wExPSiyOz
• where R is at least one of any quaternary ammonium cation, diquaternary ammonium cation triquaternary ammonium cation, quatroquaternary ammonium cation and mixtures thereof, “r” is the mole ratio of R to P and has a value of about 0.04 to about 4.0, “p” is the weighted average valence of R and varies from 1 to 4, A is an alkali metal selected from the group consisting of Li+, Na+, K+, Rb+ and Cs+ and mixtures thereof, “m” is the mole ratio of A to P and varies from 0.04 to 4.0, M is a divalent metal selected from the group Zn, Co, Mg, Mn and mixtures thereof, “w” is the mole ratio of M to P and varies from 0.00268 to 1.35, E is a trivalent element selected from the group consisting of aluminum and gallium and mixtures thereof, “x” is the mole ratio of E to P and varies from 0.1 to 4.0, “y” is the mole ratio of Si to P and varies from 0.008 to about 4.5, and “z” is the mole ratio of O to P and has a value determined by the equation:
• z=(m+p·r+2·w+3·x+5+4·y)/2
• where the T-atom compositions for M(“w”), E(“x”), Si(“y”) and P(1) are further constrained when expressed as the mole fraction composition M2+w′Alx′Siy′Pz′, where w′=w/(w+x+y+1), x′=x/(w+x+y+1), y′=y/(w+x+y+1), z′=1/(w+x+y+1) and w′+x′+y′+z′=1, such that the plot of the allowed values of w′, x′, y′ and z′ in a quaternary phase diagram
• conforms to a composition bound by the 8-vertex, 10-sided polyhedron shown in FIG. 1 consisting of the eight vertices whose coordinates are given in Table A:
• TABLE A
• Vertex Coordinates of MeAPSO Polyhedron
• Vertex
• x′ (Al)
• w′ (Me2+)
• z′ (P)
• 1
• 0.18499
• 0.00105
• 0.14799
• 2
• 0.42061
• 0.00105
• 0.10515
• 3
• 0.49637
• 0.00105
• 0.12409
• 4
• 0.48968
• 0.00105
• 0.39174
• 5
• 0.39841
• 0.09960
• 0.49800
• 6
• 0.47801
• 0.11952
• 0.39841
• 7
• 0.04980
• 0.44821
• 0.49801
• 8
• 0.05976
• 0.53785
• 0.39841
• and defined by the plane equation/inequalities given in Table B:
• TABLE B
• MeAPSO Compositions - Criteria for x′, w′ and z′
• Plane Vertices
• Plane Equation/Inequalities
• 1, 2, 3, 4
• w′ ≥ 0.001502
• 5, 6, 7, 8
• x′ + w′ + z′ ≤ 0.996016
• 4, 5, 6
• 1.239 * x′ + 0.065 * w′ + 1.004 * z′ ≤ 1
• 1, 4, 5
• x′ + 2.274 * w′ − 1.25 * z′ ≥ 0
• 1, 5, 7
• 18.471 * x′ + 18.471 * w′ − 16.463 * z′ ≥ 1
• 1, 7, 8
• 4.599 * x′ + 0.6046 * w′ + 1.004 * z′ ≥ 1
• 1, 2, 8
• 1.004 * x′ − 2.341 * w′ + 5.519 * z′ ≥ 1
• 2, 3, 8
• x′ + 2.86 * w′ − 4.00 * z′ ≤ 0
• 3, 4, 6
• 10.009 * x′ + 0.9653 * w′ + 0.2502 * z′ ≤ 5
• 3, 6, 8
• 2.212 * x′ + 2.212 * w′ − 0.808 * z′ ≤ 1
• and the crystalline microporous metalloalumino(gallo)phosphosilicate molecular sieve is characterized by a specific x-ray diffraction pattern, the process comprising forming a reaction mixture containing reactive sources of R, A, E, P, M and Si, and heating the reaction mixture at a temperature of about 60° C. to about 200° C. for a time sufficient to form the metalloalumino(gallo)phosphosilicate molecular sieve, the reaction mixture having a composition expressed in terms of mole ratios of the oxides of:
• aR2/pO:bM2O:cMO:E2O3:dP2O5:eSiO2:fH2O
• where “a” has a value of about 2.1 to about 120, “b” has a value of about 0.1 to about 8, “c” has a value of about 0.01 to about 8, “d” has a value of about 1.69 to about 30, “e” has a value from 0.01 to about 16 and “f” has a value from 50 to about 5000.