Crystalline molecular sieves having three-dimensional microporous framework structures of MnO.sub.2, AlO.sub.2, SiO.sub.2 and PO.sub.2 tetrahedral oxide units are disclosed. These molecular sieves have an empirical chemical composition on an anhydrous basis expressed by the formula: EQU mR:(Mn.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 (Mn.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2 ; and "w", "x", "y" and "z" represent the mole fractions of manganese, aluminum, phosphorus and silicon, respectively, present as tetrahedral oxides. Their use as adsorbents, catalysts, etc. is also disclosed.

FIELD OF THE INVENTION 
The instant invention relates to a novel class of crystalline microporous 
molecular sieves, and to the method of their preparation. The invention 
relates to manganese-aluminum-phosphorus-silicon-oxide molecular sieves 
having manganese, aluminum, phosphorus and silicon in the form of 
framework tetrahedral oxides. These compositions may be prepared 
hydrothermally from gels containing reactive compounds of manganese, 
aluminum, phosphorus and silicon capable of forming framework tetrahedral 
oxides, and preferably at least one organic templating agent which 
functions in part to determine the course of the crystallization mechanism 
and the structure of the crystalline product. 
BACKGROUND OF THE INVENTION 
Molecular sieves of the crystalline aluminosilicate zeolite type are well 
known in the art and now comprise over 150 species of both naturally 
occurring and synthetic compositions. In general the crystalline zeolites 
are formed from corner-sharing AlO.sub.2 and SiO.sub.2 tetrahedra and are 
characterized by having pore openings of uniform dimensions, having a 
significant ion-exchange capacity and being capable of reversibly 
desorbing an adsorbed phase which is dispersed throughout the internal 
voids of the crystal without displacing any atoms which make up the 
permanent crystal structure. 
Other crystalline microporous compositions which are not zeolitic, i.e. do 
not contain AlO.sub.2 tetrahedra as essential framework constituents, but 
which exhibit the ion-exchange and/or adsorption characteristics of the 
zeolites are also known. Metal organosilicates which are said to possess 
ion-exchange properties, have uniform pores and are capable of reversibly 
adsorbing molecules having molecular diameters of about 6 .ANG. or less, 
are reported in U.S. Pat. No. 3,941,871 issued Mar. 2, 1976 to Dwyer et 
al. A pure silica polymorph, silicalite, having molecular sieving 
properties and a neutral framework containing neither cations nor cation 
sites is disclosed in U.S. Pat. No. 4,061,724 issued Dec. 6, 1977 to R. W. 
Grose et al. 
A recently reported class of microporous compositions and the first 
framework oxide molecular sieves synthesized without silica, are the 
crystalline aluminophosphate compositions disclosed in U.S. Pat. No. 
4,310,440 issued Jan. 12, 1982 to Wilson et al. These materials are formed 
from AlO.sub.2 and PO.sub.2 tetrahedra and have electrovalently neutral 
frameworks as in the case of silica polymorphs. Unlike the silica 
molecular sieve, silicalite, which is hydrophobic due to the absence of 
extra-structural cations, the aluminophosphate molecular sieves are 
moderately hydrophilic, apparently due to the difference in 
electronegativity between aluminum and phosphorus. Their intracrystalline 
pore volumes and pore diameters are comparable to those known for zeolites 
and silica molecular sieves. 
In copending and commonly assigned application Ser. No. 400,438, filed July 
26, 1982, now U.S. Pat. No. 4,440,871, there is described a novel class of 
silicon-substituted aluminophosphates which are both microporous and 
crystalline. The materials have a three dimensional crystal framework of 
PO.sub.2.sup.+, AlO.sub.2.sup.- and SiO.sub.2 tetrahedral oxide units 
and, exclusive of any alkali metal or calcium which may optionally be 
present, an as-synthesized empirical chemical composition on an anhydrous 
basis of: 
EQU 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.sub.x Al.sub.y P.sub.z)O.sub.2 and has a value of from zero to 
0.3, the maximum value in each case depending upon the molecular 
dimensions of the templating agent and the available void volume of the 
pore system of the particular silicoaluminophosphate species involved; and 
"x", "y", and "z" represent the mole fractions of silicon, aluminum and 
phosphorus, respectively, present as tetrahedral oxides. The minimum value 
for each of "x", "y", and "z" is 0.01 and preferably 0.02. The maximum 
value for "x" is 0.98; for "y" is 0.60; and for "z" is 0.52. These 
silicoaluminophosphates exhibit several physical and chemical properties 
which are characteristic of aluminosilicate zeolites and 
aluminophosphates. 
In copending and commonly assigned application Ser. No. 480,738, filed Mar. 
31, 1983, now U.S. Pat. No. 4,500,651, there is described a novel class of 
titanium-containing molecular sieves whose chemical composition in the 
as-synthesized and anhydrous form is represented by the unit empirical 
formula: 
EQU mR:(Ti.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 (Ti.sub.x Al.sub.y P.sub.z)O.sub.2 and has a value of between zero 
and about 5.0; and "x", "y" and "z" represent the mole fractions of 
titanium, aluminum and phosphorus, respectively, present as tetrahedral 
oxides. 
In copending and commonly assigned application Ser. No. 514,334, filed July 
15, 1983 now U.S. Pat. No. 4,567,029, there is described a novel class of 
crystalline metal aluminophosphates having three-dimensional microporous 
framework structures of MO.sub.2, AlO.sub.2 and PO.sub.2 tetrahedral units 
and having an empirical chemical composition on an anhydrous basis 
expressed by the formula: 
EQU 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 the moles of "R" present per 
mole of (M.sub.x Al.sub.y P.sub.z)O.sub.2 and has a value of from zero to 
0.3; "M" represents at least one metal of the group magnesium, manganese, 
zinc and cobalt; "x", "y" and "z" represent the mole fraction of the metal 
"M", aluminum and phosphorus, respectively, present as tetrahedral oxides. 
In copending and commonly assigned application Ser. No. 514,335, filed July 
15, 1983 now U.S. Pat. No. 4,554,143, there is described a novel class of 
crystalline ferroaluminophosphates having a three-dimensional microporous 
framework structure of FeO.sub.2, AlO.sub.2 and PO.sub.2 tetrahedral units 
and having an empirical chemical composition on an anhydrous basis 
expressed by the formula 
EQU mR:(Fe.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 (Fe.sub.x Al.sub.y P.sub.z)O.sub.2 and has a value of from zero to 
0.3; and "x", "y" and "z" represent the mole fraction of the iron, 
aluminum and phosphorus, respectively, present as tetrahedral oxides. 
The instant invention relates to new molecular sieves comprising framework 
tetrahedral units of MnO.sub.2.sup.-2, AlO.sub.2.sup.- and PO.sub.2.sup.+ 
and SiO.sub.2.