CA1246530A - Manganese-aluminum-phosphorous-silicon-oxide molecular sieve compositions - Google Patents

Abstract

MANGANESE-ALUMINUM-PHOSPHORUS-SILICON-OXIDE
MOLECULAR SIEVES
ABSTRACT

Crystalline molecular sieves having three-dimensional microporous framework structures of MnO2, AlO2, SiO2 and PO2 tetrahedral oxide units are disclosed. These molecular sieves have an empirical chemical composition on an anhydrous basis expressed by the formula:
mR : (MnwAlxPySiz)O2 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 (MnwAlxPySiz)O2; 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.

Description

. ~L2~5~

MA_GANESE-ALUMI~NUM-PHOSPHORUS-SILICON-O~IDE MOLECULAR SIE~S
Field of the Invention T~e instant invention relates to a novel class of crystalline microporous mo].ecular sieves, to the method of their preparation and to their use as adsorbents and catalys~s. The invention relates to manganese-aluminum-phosphorus-silicon-oxide molecular sieves having mangane~e, aluminum, phosphorus and si~licon 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 produc~.
Backqround of the Invention Molecular sieve~ of the crystalline aluminosilicate zeolite type are well known in the art and now comprise oYer 150 species o~ both naturally occurring and synthetic compositions. In general the crystalline zeolites are formed from corner-sharing AlO2 and SiO2 tetrahedra and are charac~erized 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 ~he crystal withou~ displacing any atoms which make up the permanent crystal structure.

D-14,221 ~2~i53~

Other crystalline microporous compo6itions which are not zeolitic, i.e. do not contain A102 tetrahedra as essential framework constituents, bu~
which exhibit the ion-exchange and/or adsorption characteristics of the zeolites are also known.
Metal organosilicates which are said to possess ion-exchan~e properties, have uniform pores and are capable of reversibly adsorbing molecules haYing molecular diameters of about 6R or less, are reported in U.S. Patent No. 3,941,871 issued March

2, 1976 to Dwyer et al. A pure silica poly~orph, silicalite, having molecular sieving properties and a neutral framework containing neither cations nor cation sites is disclosed in U.S. Patent No.
4,061,724 issued December 6, 1977 to R.W. Grose et al.
A recently reported class of microporous compositions and the first framework oxide molecular sieves 6ynthesi~ed without silica, are the crystalline aluminophosphate compositions disclosed in U.S. Patent No. 4,310,440 issued January lZ, 1982 to Wilson e~ al. These materials are formed from A102 and P02 tetrahedra and have electrovalently neutral frameworks as in the case of silica polymorphs. Unlike the silica molecular sieve, ~ilicalite, which is hydrophobic due to the absence of extra-structural cations, the aluminophosphate molecular sieves are moderately hydrophilic, apparsntly due to the difference in electronegativity between aluminu~ and phosphorus.
Their in~racrystalline pore volumes and pore diameters are comparable to those known for zeoli~es and silica molecular sieves.

D-14,2~1 i3C~

In commonly assigned Canadian Patent Serial No. 1,202,016, issued on March 18, 1986, there is described a novel class of silicon-substituted aluminophosphates which are both microporous and crystalline. The materials have a t]hree dimensional crystal ramework of PO2, AlO2 and SiO2 tetrahedral oxide units and, exclusive of any alkali metal or calcium which may optionall~y be present, an as-synthesi~ed empirical chemical composition on an anhydrous basis of:
mR : (SiXAlyPz)O2 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 (SiXAlyPz)O2 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.~2. These silicoaluminophosphates exhibit several physical and chemical properties which are characteristic of aluminosi1icate zeolites and aluminophosphates.
In copending and commonly assigned Canadian Application Serial No. 450,658, filed March 28, 1984 there is described a novel class of titanium-D-14,221-C

.~c ~

3~

containing molecular sieves whose chemical composition in the as synthesized and anhydrous form is represented by the unit empirical formula:
mR:(TixAlyPz)02 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 (TiXAlyPz)02 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, respec~ively, present as tetrahedral oxides.
In copending and commonly assigned Canadian Application Serial No. 458,495, filed July 10, 1984, there is described a novel class of crystalline metal aluminophosphates having three-dimensional microporous framework structures of M02, A102 and P02 tetrahedral units and having an empirical chemical composition on an anhydrous basis expressed by the formula:
mR:(MxAlyPz)02 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 (MXAlyPz)02 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 Canadian Application Serial ~o. 458,914, filed July 13, 1984, D-14,221-C

, ~.
f~'. ~',', there is described a novel class of crystallîne ferroaluminophosphates having a three-dimensional microporous framework structure of YeO2, A102 and P02 tetrahedral units and having an empirical chemical composition on an anhydrous ba is expressed by the formula mR:(FexAlyPz)02 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 (FexAlyP~02 and has a value o~
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 compri~ing framework tetrahedral units of MnO22, A102 and P02 and SiO2.

Description of the Fiqures FIG. 1 is a ternary diagram wherein parame~cers relating to the ins~ant compositions are set ~orth as mole fractions.
FIG. ~ is a ~ernary diagram wherein parameters relating to preferred compositions are set forth as mole fractions.
FIG. 3 is a ternary diagram wherein parameters relating to the reaction mixtures employed in the preparation of the compositions of this invention are set forth as mole fractions.
SummarY o~ ~he Invention The instant invention relàtes to a new class of molecular sieves having a three-dimensional D-14,221 3~

microporous crystal framework structures of MnO22, A102, P02 and SiO2 tetrahedral oxide units.
These new manganese-aluminum phosphorus~silicon~
oxide molecular sieves exhibit ion-exchange, adsorption and catalytic properties and, accordingly, find wide use as adsorbents and catalysts. The members of this novel class of compositions have crystal ~ramework structures of MnO22, A102, P02 and S02 tetrahedral oxide units and have an empirical chamical composition on an anhydrous basis expressed by the formula:
mR : (MnwAlxPySiz)O~
wherein "R" represents at lea~t one organic templating agent present in the intracrystalline pore system; "m" represents ~he molar amount oE "R"
present per mole of (MnwAlxPySiz)02 and has a value of zero to about 0.3; and "w", "x", "y"
and "z" repre~ent the mole fractions of manganese, aluminum, phosphorus and silicon, respectively, present as tetrahedral oxides. The instant molecular sieve compositions are characterized in several ways as distinct from heretofore known molecular sieves, including ~he aforementioned ternary compositions. The instant molecular sieves are characterized by the enhanced thermal stability of cer~ain species and by the exisjtence of species heretofore unknown for binary and ternary molecular sieves.
The molecular sieves of the instant invention will be generally referred to by the acronym "MnAPSO" to designate a structure framework 14,221 ~Z~653D

of MnO22, A102, PO~ and SiOz tetra-hedral units. Actual class members will be iaentified as structural species by assigning a number to the species and, accordingly, are identified as "MnAPSO-i" wherein "i" is an integer.
The given species designation is not intended to denote a similarity in structure to any other species denominated by a numbering system.
Detailed DescriPtion of the Invention The instant invention relates to a new class of molecular sieves having a ~hrae-dimensional microporous crystal framework structures of MnO22, A102, P02 and SiO2 tetrahedral oxide units.
These new molecular sieves exhibit ion-exchange, adsorption and catalytic properties and, accordingly, find wide use as adsorbents and catalysts.
The MnAPSO molecular sieves of the instant invention have a framework structure of MnO22, A102, P02, and SiO2 tetrahedral units having an empirical chemical composition on an anhydrous basis expressed by the formula:
mR (Mnw~lxPySiz~02 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 (MnwAlxPySiz)02 and has a value of zero to about 0.3; and ~'w~l, "x", "y"
and "z" represent the mole fractions of element D-14,221 . ~

6~3~

manganese, aluminum, phosphorus and silicon, respectively, present as tet~ahedral oxides. The mole fractions "w", "x", "y" and "z" are generally defined as being within the pentagonal compositional area defined by points A, B, C, D a:nd E of the ternary diagram of FIG. l and more preferably are generally defined as being within the tetragonal compositional area defined by points a, b, c and d of the ternary diagr~m of PIG. 2. Poin~s A, B, C, D
and E of FIG. l have the following values for "w", "x", "y", and "z":
Mole Fraction Point x y tw+z) A 0.60 0.38 0~.02 B 0.33 0.60 0.02 C 0.01 0.60 0.39 D O.01 0.01 0.98 E 0.60 0.01 0.39 Points a, b, c, and d of FIG. 2 have the following values for "w", "x", "y". and "z":
Mole Fraction Point x Y (w+z) a 0.55 0.43 0.02 b 0.43 0.55 0.02 c 0.10 0.55 0.35 d 0.55 0.10 0.35 The MnAPSOs of this invention are useful as adsorbents, catalysts, ion-exchangers, and the like in much the same fashion as aluminosilicates have D-14,221 been employed here~ofore, although ~heir chemical and physical properties are no~ necessarily similar to those obser~ed for aluminosilicates.
~ nAPS0 composi~ions are generally synthesized by hydrothermal crystallization from a reaction mixture containing reac~ive sources of manganese, silicon, aluminum and phosphorus, preferably an organic templating, i.e., structure-directing, agent, preferably a compound of an element or Group VA of the Periodic Table, andtor optionally an al~ali or other metal. The reaction mix~ure is generally placed in a sealed pressure vessel, preferably lined with an inert plastic material such as polytetrafluoroethylene and heated, preferably under autogenous pressure at-a temperature between about 50C and about 250C', and preferably between about 100C and about 200~C until crystals of the MnAPS0 product are obtained, usually a period of from ~everal hours to several weeks.
Typical effective times of from 2 hours ~o about 30 days with generally from about 4 hours to about 20 days have been observed. The product is recovered by any convenient method such as centrifugation or filtration.
In synthesizing the MnAPS0 compositions of the instant invention, it is preferred to employ a reaction mixture composition expressed in terms of the molar ratios as follows:
aR (MnwAlxPySiz)o2 bH2 wherein "R" is an organic templating agent; "a" is the amount of organic templating agent "R" and has a value of from zero to about 6 and is preferably an D-lq,221 ~2~53~

effective amount wi~hin the range of greater than zero (0) to about 6; "b" has a value of from zero ~0) to about 500, preferably between About 2 and about 300; and "w", "x", lly~ and "z" represent the mole frac~ions of manganese, aluminum, phosphoru~
and silicon, respectively, and each has a value of at 10ast o.Ol.
In a preferred embodiment the reaction mixture is selected such that ~he mole fractions "w", "x", "y" and "z" are generally defined as be;ng within the pentagonal compositional area defined by points E, F, G, H and I of the ternary diagram of FIG. 3. Points E, F, G, H and I of FIG. l have the following values for "w", "x", "y" and "z":
. _ _Mole Frac ~on Point x ~ tw~zl F O.S0 0.~8 0.02 G 0.38 0.60 0.02 H 0.01 0.60 0.39 I 0.01 0.01 0.98 J 0.60 ~.01 0~39 For reasons unknown at present, not every reaction mixture gave crystalline MnAPS0 products when reaction products were examined for MnAPS0 products .by X-ray analysis. Those reaction mixtures from which crystalline MnAPS0 products were obtained are reported in the examples hereinafler as numbered ~xamples. Those reaction mixtures from which ~nAPS0 products were not identified by use of 2-ray analysis are also reported.

D-14,221 ~L2~i3~

In the foregoing expre~sion of ~he reaction composi~ion, the reactants are normalized with respect to the total of "w", "x", "y" and "z" such that ~w.-x+y+z~ = 1.00 mole, whereas in the examples the reaction mixtures are expressed in terms of molar oxide ratios and may be normalized to the moles of P205.
This latter ~orm is read;ly converted to the former form by routine calculations by d;viding the number of moles o~ each component (including the template and water) by the total number of moles of manganese, aluminum, phosphorus and silicon which results in normalized mole fractions based on total moles of the aforementioned components.
In forming reaction mixtures from which the instant molecular sie~es are formed the orqanic templating agent can be any of those heretofore proposed for use in the synthesis of conventional zeolite aluminosilicates. In general these compounds contain elements of Group VA of the Periodic Table of Elements, particularly nitrogen, phosphorus, arsenic and antimony, preferably nitrogen or phosphorus and most preferably nitrogen, which compounds also contain at leas~ one alkyl or aryl group having from 1 to 8 carbon atoms. Particularly preferred compounds for use as templating agents are the amines quatenary phosphonium and quaternary ammonium compounds, the latter two being represented generally by the formula R4~ wherein "X" is nitrogen or phosphorous and each R is an alkyl or aryl group containing from 1 to 8 carbon atoms. Polymeric quaternary ammonium salts such ~ ( 14H32N2) (OH) 2}x w~erein "x~ has a valu~ of at least 2 are also sui~ably employed. The D-1~,221 mono-, di- and tri-amines are advantageously utilized, either alone or in combination with a quaternary ammonium compound or other templating compound. Mixtures of two or more templating agents can either produce mixtures of the desired MnAPSOs or the more strongly directing templating species may control the course of the reac~ion with the other templa~ing species serving primarily to establi h the pH conditions of the reaction gel.
~epresentative templating agents include:
tetrame~hylam~onium: tetraethylammonium:
tetrapropylammonium; tetrabutylammonium ions;
tetrapentylammonium ions: di-n-propylamine;
tripropylamine; triethylamine; triethanolamine;
piperidine; cyclohexylamine; 2-methylpyridine;
N,N-dimethylbenzylamine; N,N-dimethylethanolamine;
choline; N,N'-dimethylpiperazine; 1,9-diazabicyclo (2,2,2,) octane: N-methyldiethanolamine, N-methylethanolamine; N-methylpiperidine;
3-methylpiperidine; N-methylcyclohexylamine;
3-me~hylpyridine; ~-methylpyridine; quinuclidine;
N,N'-dimethyl-1,4-diazabicyclo (2,Z,2) octane ion:
di-n-butylami~e, neopentylamine; di-n-pentylamine;
isopropylamine; t-butylamine; ethylenediamine;
pyrrolidine; and 2-imidazolidone. Not every templating agent will direc~ the formation of every species of ~nAPSO, i.e., a single templating agent can, wi~h proper manipulation of the reaction conditions, direct ~he ~ormation of several MnAPSO
compositions, and a given MnAPSO composi~ion can be producsd using several different templating agents.
Most any reactive silicon source may be employed such that SiO2 tetrahedral units are D-14,221 53~
1~

formed from a species present in situ. The reac~ive source of silicon may be silica, either as a silica sol or as fumed silica, a reactive solid amorphous precipitated silica, silica gel, alkoxides of silicon, silicic acid or alkali metal silica~e and the like.
The reacti~e phosphorus source is phosphoric acid, but organic phosphates such as triethyl phosphate may be satisfactory, and so also may crystalline or amorphous aluminophosphates such as the AlPO4 composi~ions of U.S.PO 4,310,440.
Organo-phosphorus compounds, such as ~etrabutylphosphonium bromide do not, apparently, serve as ~eactive sources of phosphorus, but ~hsse compounds may function as templating agents.
Conventional phosphorus salts such as sodium metaphosphate, may be used, at least in part, as the phosphorus source, but are not preferred.
The preferred aluminum source is either an aluminum alkoxide, such as aluminum isoproproxide, or pseudoboehmite. The crystalline or amorphous aluminophospha~es which are a suitable source of pho~phorus are, of course, also suitable sources of aluminum. Other sources of aluminum used in zeolite syntheais, such as gibbsite, ~odium aluminate and aluminum trichloride, can be employed but are not preferred.
The source of manganese can be introduced into ~he reaction system in any form which permits the formation in situ of reactive form of manganese, i.e., reactive to form the framework tetrahedral unit of manganese. Compounds of manganese which may D-14,221 ~L2~53~

be employed herein include oxides, alkoxides, acetate~, hydroxides, chlorides briomides, iodide6, sulfates, nitrates, carboxylates and the like. For example, ~anganese acetate, mangane~e bromide, manganese sulfate, and the like are employable herein.
While not essential to the synthesis of MnAPSO compositions, ~tirring or o~her moderate agitation of the reaction mixture and/or seeding the reaction mixture with seed crystals of either the MnAPSO ~pecies to be produced or a topologically similar aluminophosphate, aluminosilica~e or molecular sie~e composition, facilitates the crystallization procedure.
APter crystallization the MnAPSO product may be isolated a~d advantageously washed with water and dri~d in air. The as-synthesized MnAPSO
generally contains within it~ internal pore system at least one form of the templa~ing agent employed in its formation. Most commonly any organic moiety derived from any organic template is present, a~
least in part, as a charge-balancing ca~ion as is generally the case with as-synt~esized aluminosilicate zeolites prepared from organic-containing reaction systems. It is possible, however, that some or all of the organic moiety is an occluded molecular species in a particular MnAPSO species. As a general rule the templating agent, and hence the occluded organic specie6, is too large to move freely through the pore sys~em of the MnAPSO produc~ and must be removed by calcining the MnAPSO at temperatures of D-14,Z21 . . .

~'Z~536~

200C to 700C to thermally degrade the organic species. In a few instances the pores of the MnAPS0 product are sufficiently large to permit transport of the templating agent, particularly if the latter i8 a small molecule, and accordingly complete or partial removal theraof can be accomplished by conventional desorption procedures such as carried out in the case of zeolites. It ~ill be understood thàt the term "as-synthesized" as used herein does not include the condition of tha MnAPS0 phase wherein the organic ~oiety occupying the intracrystalline pore system as a result of the hydrothermal crystallization process has been reduced by post-synthesl6 treatment such that ~he value of "m" in the composition formula mR (MnwAlxpysiz~o2 has a value of le86 than 0.02. The other symbols of the formula are as defined hereinabove. In those preparations in which an alkoxide is employed as the reac~ive source of manganese, aluminum, phosphorus or sillcon, the corresponding alcohol is necessarily presen~ in ~he reaction mixture since it is a hydrolysis product of the alkoxide. It has not been determined whether this alcohol participates in the synthesis process as a templating agent. For the purposes of this application, however, this alcohol is arbitrarily omitted from the class of templating agents, even if it is present in the as-synthesized MnAPS0 material.
Since the present MnAPS0 compositions are formed from MnO2, A102, P02 and SiO2 tetra-hedral units which, respectively, have a ne~ charge D-14,221 ;S3~

of -2, -1, ~1 and O. The matter of cation exchangeability is considerably more complicated than in ~he case of zeolitic molecular sieves in which, ideally, there i6 a s~oichiometric relationship between A102 tetrahedra and charge-balancing cations. In the ins~ant compositions, an A10z tetrahedron can be balanced electrically ei~her by association with a PO2 tetrahedron or a simple cation such as an alkali metal cation, a ca~ion of manganese present in the reaction mixture, or an organic cation deri ed from the templating agent. 5imilarly an MnO2 tetrahedron can be balanced electrically by association with PO2 tetrahedra, a cation of manganese, organic cations derived fro~ the templating agent, a simple cation such as an alkali metal cation, or other divalent or polyvalent metal cations introduced from an extraneous source.
It has also been postulated that non-adjacent A102 and POz tetrahedral pairs can be balanced by Na+ and OH respectively [Flanigen and Grose, Molecular Sieve Zeolites-I, ACS, ~ashington, DC (1971)]
The MnAPSO compositions of the present invention may exhibit cation-exchange capacity when analyzed using ion-exchange technigues heretofore employed ~ith zeolitic aluminosilicates and have pore diameters which are inherent in the lattice structure of each species and which are at least about 3A in diameter. Ion exchange of MnAPSO
compositions is ordinarily possible only after the organic moiety present as a result of synthesis has D-14,221 53~

been removed from the pore system. Dehydration to remove water present in the as-synthesized MnAPSO
composi~ion~ can usually be accomplished, to some degree at least, in the usual manner without removal of the organic moiety, bu~ the absence of the organic species greatly facilitates adsorption and desoretion procedures. The MnAPSO materials will have various d grees of hydrothermal and ther~al s~ability, some being quite remarkable in ~his regard, and will function as molecular sieve adsorbents and hydrocarbon conversion catalysts or catalyst bases.
The MnAPSOs are ~enerally prepared using a stainless steel reaction vessel lined with the inert plastic material. polytetrafluoroethylene, to avoid contamination of the reaction mixture. In general, the final reaction mixture from which each MnAPSO
composition is crystallized is prepared by forming mixtures of less than all of ~he reagents and thereafter incorporating into these mixtures addi~ional reagents either singly or in the form of other intermediate mixtures of two or more reagents. In some instances the reagents admixed retain their identity in the intermediate mixture and in other cases ~ome or all of the reagents are involved in chemical reactions to produce new reagents. The term "mixture" is applied in both cases. Further, unless otherwise specified, each intermediate mixture as well as the final reaction mixture wa~ s~irred until 6ubstantia}1y homogeneous.
X-ray analysis of reaction products are obtained by X-ray analysis using standard X-ray .

S3~

powder diffraction techniques. The radiation source is a high-intensity, copper target, ~-ray tube operated at 50 Kv and 40 ma. The diffraction pattern from the copper K-alpha radiation and graphite monochromator is suitably recorded by an ~-ray spectrometer scintillation counter, pulse height analyzer and strip chart recorder. Flat compressed powder samples are scanned at 2 (2 theta) per minute, using a two ~econd time constant. Interplanar spacings (d) in Angstrom units are obtained from the position of the diffraction peaks expressed as 2~ where a is the Bragg angle as observed on the strip chart.
Intensities are determined from the heights o diffraction peaks after subtracting background, "Io" beiny the intensity of the s~rongest line or peak, and "I" being the intensity of each of the other peaks. Alternatively, ~he X-ray patterns are obtained from the copper K-alpha radiation by use of computer based techniques using Siemens D-500 ~-ray powder diffractometers, Siemens Type K-805 ~-ray sources, a~ailable from Siemens Corporation, Cherry Hill, New Jersey, with appropriate computer in~erface.
As will be understood by those skilled in the art the determination of the parameter 2 theta is subjec~ to both human and mechanical error, which in combination, can impose an uncertainty of about ~0.4 on each reported value of 2 theta. This uncertainty is, of course, also manifested in the reported values of the d-~pacings, which are calculated from the 2 theta ~alues. This ~-14,221 3~

imprecision is general throughout the art and is no~
sufficient to preclude the differentiation of the present crystalline materials from each other and fro~ the compositions of the prior art. In some of the X-ray patterns reported, the relative intensities of the d-spacings are indicated by the notations vs, s, m, w and vw which represent very strong, strong, medium, weak and very weak respec~ively.
In certain instances the purity of a syn~hesized product may be assessed with reference to its ~-ray powder diffraction pattern. Thus, for example, if a sample is stated to be pure, i~ is intended only that the ~-ray pattern of the sample i8 free of lines attributable to crystalline impurities, not that there are no amorphous materials present.
The molecular sieves of the instant invention may be characterized by their x-ray powder diffraction ~atterns and such may have one of the x-ray patterns set forth in ~he following Tables A
through K, wherein said x-ray pat~erns are ~or both the as-synthesi2ed and calcined ~orms unless o~herwise noted:
TA~LE A (MnAPS0-5~
29 ~ Relative Intensity 7.3 - 7.7 12.11 - 11.48 ~s 1~.7 - 15.1 6.03 - 5.87 ~
19.6 - 19.9 4.53 - 4.46 m 20.8 - 21.3 4.27 - 4.17 m 22.1 - 22.6 4.02 - 3.93 m 29.8 - 30.2 2.998 - 2.959 m D-14,221 53~ .

~Y~e~
29 d(R~ Relative Intensity 9.4 - 9.8 9.41 - 9.03 m 16.1 - 16.2 5.50 - 5.47 vs-m 21.0 - 21.5 4.23 - 4.13 m-vs 22.1 - 22.2 4.02 - 4.00 m 22.4 - 22.5 3.97 - 3.95 m-s 23.1 - 23.5 3.85 - 3.79 m TABLE C (MnAPS0-16) d(A) Relative_IntensitY
11.4 - 11.5 7.76 - 7.69 m-vs 18.6 - 18.7 4.77 - 4.75 m 21.9 ~.06 m-vs 22.9 - 23.0 3.88 - 3.87 w-m 26.5 - 26.6 3.363 - 3.351 m 29.7 - 29.8 3.008 - 2.998 m .

TABLE D (MnAPS0-20) dtA) Relative IntensitY
13.904 - 13.9986.3692 - 6.3263 m-vs 19.723 - 19.8184.5011 - 4.4918 m 24.223 - 24.3293.6742 - 3.6584 v~
28.039 - 28.1633.1822 - 3.1684 w 31.434 - 31.5602.8458 - 2.8348 w 34.527 - 34.6522.5976 - 2.5886 w TABLE E (MnAPS0-31) 2~ d(~ Relative Intensity 8.482 - 9.501 10.4240 ~ 9.3084 m 20.222 - 20.3534.3913 - 4.3632 m 21.879 - 21.9934.0622 - 4.0415 m 22.071 - 22.0884.0272 - 4.0242 m 22.587 - 22.6983.9364 - 3.9174 vs 31.724 - 31.8~62.8546 - 2.8108 m D-14,221 ~2~i3~

TABLE F ~MnAP50-34~
2e d(A) Relative Intensity 9.4 - 9.6 9.41 - 9.21 vs 15.9 - 16.Z 5.57 - 5.47 m 20.4 - 20.8 4.35 - 4.27 m-v~
25.0 - 25.3 3.562 - 3.520 w-m 31.0 - 31.3 2.885 - 2.858 w-m 33.6 - 33.9 2.667 - 2.6~g m TABLE G tMnAPS0-35) 2e ~L~l Relative Interlsi~
10.8 - 11.0 8.19 - 8.04 m-vs 13.4 - 13.7 6.61 - 6.46 m-s 17.2 - 17.5 5.16 - 5.07 m-s 20.8 - 21.0 4.27 - 4.23 m 21.8 - 22.3 4.0a - 3.99 m vs 28.2 - 28.7 3.16~ - 3.110 m TABLE H tMnAPS0-36~
2~ dtA) Relative In~ensity 7.596 ll.q382 m 7.628 - 7.981 11.5899 - 11.0771 v~
8.105 - 8.299 10.9084 - 10.6537 m 16.395 - 16.673 5.4066 - 5.3172 m 19.052 - 19.414 ~.6580 - 4.5721 w 20.744 - 20.871 4.2819 - 4.2560 m T~BLE J (MnAPS0-44) 2 d(A) Relative Intensitv 9.420 ~ 9.~98 9.3883 - 9.3110 vs 16.062 - 16.131 5.5179 5.4944 m 20.715 ~ 20.790 4.2877 - ~.2725 s 24.396 - 24.4Z4 3.64~5 - 3.6444 m 26.143 - 26.184 3.4085 - 3.4032 m 30.833 - 30.853 2.8999 - 2.8981 m D-14,221 .. . . . .

TABLE K (~nAPSO-47) 2ed~AL RelatiYe Intensity 9.434 - 9.6969.3746 - 9.1214 vs 15.946 - lS.276 5.5579 - 5.4~57 vw 20.539 - 20.940 4.3242 - 4.2423 vw-m 2~.643 3.6125 w 30.511 2.9297 w 30.8~0 - 31.096 2.gOll - 2.8759 vw PREPARATIVE REAGENTS
In the following examples the MnAPSO
compositions were prepared using numerous reagents.
The reaqents employed and abbreviations employed erein, if any, for such reagents are as follows:
a) Alipro: aluminum isopropoxide;
b) CATAPAL; Trademark of Condea Corporation for hydrated pseudoboehomite c) LUDOX-LS: LUDOX-LS is the tradename of DuPont for an aqueous solution of 30 weight percent sio2 and 0.1 weight percent Na20:
d) H3P04: 85 weight percent aqueous phosphoric acid;
e) MnAc: Manganese acetate, Mn(C~ 3 2)2 2 f) TEAOH: 40 weigh~ percent aqueous solu~ion of tetraethylammonium hydroxide:
g) TBAOH: 40 weigh~ percent aqueous solution of tetrabutylammonium hydroxide:

D-14,221 ~2~53~

h) Pr2NH: di-n-propylamine, ~ 3 7)2 i) Pr3N: trimpropylamine ( 3 7)3 ;
j) Quin: Quinucl;dine, (C7H13N);
k) MQuin: Methyl Quinuclidine hydroxide. (C7H13NCH30H);
1) C-hex: cyclohexylamine;
m~ TM~OH: tetramethylammonium hydroxide;
n) TPAOH: tetrapropylammonium hydroxide; and o) DE~A: 2-diethylaminoethanol.
PREPARATIVE PROC~DURES
The ~ollowing preparative examples were carried out by forming a starting reaction mixture by adding the H3POg to one half of the guantity o~ water. This mix~ure was mixed and to this mixture the aluminum i~opropoxide or CATAPAL was added. Thi& mixture was then blended until a homogeneous mixture was observed. To this mixture the LUDOX LS was added and the resulting mixture blended ~about 2 minu~es) until a homogeneous mixture was observed. A second mixture was prepared using the manganese acetate and the remainder (about 50~) of the water. The two mixtures were admixed and the resulting mixture blended until a homogeneous mixture was observed. The organic templating agent was the~ added to the resulting mixture and the resulting mixture blended until a homogeneous mixture was observed, i.e., about 2 to 4 minutes. (The pH of the mixture was measured and D-14,221 . .

`` 3L.~4~5~

adjusted for temperature). The mixture was then placed in a lined (polytetrafluoroethylene) stainless s~eel pressure vessel and digested at a temperature (150C or 200C) for a time or placed in lined screw top bo~tles for digestion at 100C. All diqestions were carried out at the autogeneous pressure.
The molar composition for each preparation will be given by the relative moles of the components of the reaction mixture. H3PO~ and MnAc are given respectively in terms of P2O5 and MnO content of the reaction mixture.
The following e~amples are pro~ided to further illustrate the invention and are not intended to be limiting thereof:
Exam~les 1 to 6~
MnAPSO molecular sieves were prepared according to the above identified procedure and the MnAPSO products determined by X-ray analysis. The results of examples 1 to 64 are set forth in Tables I to IV.

D-14,221 ~2~i53q~

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6~3~

Example 65 (a) Samples of the MnAPS0 products w~re calcined in air or nitrogen to remove at least par~
of the organic templating agent of ~he product. The example in which a given MnAP50 product was peepared is given in parenthesis. The adsorption capacities of each calcined sample were measured using a standard McBain-Bakr gravimetric adsorption apparatu~. The samples were activated in a vacuum (less than 0.04 torr) at 350C prior to measurement. The McBain-Bakr data for the aforementioned MnAPS0 molecular sieves are set forth hereinafter~.
(a) MnAPS0 5 (Example 31):
Kinetic Pressure Temp W~. %
Adsorbate Diameter, A (Torr) 1~ Adsorbed*
2 3 46 102 -183 8.9 2 3 46 750 -183 10.8 n-butane 4.3 504 23.04.4 cyclohexane 6.0 65 23.45.4 H20 2.65 4.6 23.08.1 H20 2.65 19.5 23.017.1 *MnAPS0-5 was calcined at 600C in air for 4 hours.
The above da~a demonstrate that t~e pore size of the ca}cined MnAPS0-5 product is greater than 6.2A.
(b) MnAPS0-11 (Example 24):
Kinetic Pressure Temp ~t. %
Adsorbate Diameter, A (Torr~ (C2 Adsorbed*
2 3.46 106 -1~3 7.0 2 1,46 744 -183 11.1 neopentane 6.2 741 25.32.5 isobutane 5.0 740 24.23.5 cyclohexane 6.0 82 23.910.7 H20 2.65 4.6 24.95.1 H20 2.65 19 24.814.9 *MnAPS0 was calcined at 600 in air for 2 hours.

D-14,221 53~

The above data demonstrate that the pore size of the calcined MnAPS0-11 product is about 6.0A.
(c) MnAPS0-20 (Example 46):
Kinetic Pressure Temp Wt. %
Adsorba~e Diameter,~ rr) (C) Adsorbed 2 3.46 102 -183 0.7 2 3.46 744 -183 1.2 H20 2.65 4.6 23.39.0 H20 2.65 19 23.213.7 *MnAPS0 calcined at 500C in air for 1 hour.
The above data demonstrate that the pore size of the calcined MnAPS0-20 product is greater than about 2.65R and less than about 3.46R.
(d) MnAPS0-31 [Example 55):
Kinetic Pressure Temp Wt.
Adsorbate Diameter,_~ (Torr) (Cl Adsorbed 2 3.4~ 105 -183 5.6 2 3.g6 741 -183 9.7 Neopentane 6.2 739 23.54.6 H20 2.65 4.6 23.85.8 H20 2.65 20 24.015.5 *MnAPS0-31 calcined at 500C in air for 1.5 hours.
The above data demonstrate that the pore size o~ the calcined MnAPS0-31 product is greater than about 6.2A.
(e) MnAPS0-34 (Example 11):
Kinetic Pressure Temp ~t. ~ -Adsorba~e Diame~er, A ~Torr) (C) Adsorbed*
2 3.46 103 -183 11.4 0~ 3.46 731 -183 15.~
i~obutane 5.0 741 24.50.8 n-hexane ~.3 103 24.44.6 D-14,221 ~653~3 Rinetic Pressure Temp Wt. %
Adzorba~e Diameter,_A (Torr2 (C~ Adsorbed*
H2O 2.65 4.6 24.4 15.2 H2O 2.65 18~5 23.9 24.4 *MnAPSO-34 was calcined at 425C in nitrogen for 2 hours, The above data demon&trate that the pore ~ize of the calcined MnAPSO-34 product is abou~

4.3A.
(f) MnAPSO-35 (Example 21):
Kinetic Pressure Temp Wt. ~
Adsorbat_ Diameter, A (Torr) ~ Adsorbed*
2 3.46 103 -lB3 l.B
2 3.~6 731 -183 2.6 n-hexane 4.3 103 2~.40.8 H20 2.65 4.6 24.49.9 H20 2.6518.5 23.915.9 *MnAPSO-35 was calcined a~ 500C in nitrogen for 2 hours.
The above data demonstrate that the pore ~ize of the calcined MnAPSO-35 product is about g.3A.
(g) MnAPSO-44 (Example 64):
Kine~ic Pressure Temp Wt.
Adsorbate Diameter, A (Torr) (C) Adsorbed 2 3.46 102 -lB3 18.2 2 3.46 744 -183 20.1 n-hexane 4.3 95 23.61.3 isobutane 5.0 746 24.10.5 H2O 2.65 4.6 24.822.7 H2O 2.65 19 29 . B 27.7 *MnAPS0 ~4 was calcined at 500~C in air for 1.0 hour.

D-14,221 ;S3~

The above data demonstra~e tha~ th~ pore ~ize of ~he calcined ~nAPSO-~4 product about ~.3A.
E:xamDle_ 6~
Samples of the as-~ynthesized product~ of certain exa~ples were subjected to chemieal analy6is. The example in which a given MnAPSO was prepared is noted in p~renthesis. The chemical analysis for these ~nAPSOs was as ~ollows:
(a) The chemical analysis for MnAPSO-5 (Example 31) was:
Çom~onentWeiqht Percent A123 31.8 P205 46.4 MnO 9.1 SiO2 3.0 Carbon 5.2 LOI* 14.5 ~LOI = Loss on Ignition The above chemical analysis ~ives an overall product composition in molar oxide ratios (anhydrous basis) of: 0.058 MnO; 0.312 A1203:
0.327 P205: 0.050 SiO2; and a formula (anhydrous basis) of: .
o.o~ R (MnO 04Alo 4~Po.47sio.o~)~2 (b) The chemical analysis of MnAPSO-ll (~xample 2~) wa~:
omponentWeiqht Pereent A12~3 32.5 P205 46.7 MnO 4.~
SiO~ 2.1 Carbon 4.1 LOI~ 14.0 ._~", ,.
*LOI - Loss on Ignition D-14,221 ... ... . . .

~ 6~;i3~

The above chemical analysis gives an overall product composition in molar oxide ra~ios (anhydrous basis) of: 0.061 MnO; 0.3:l9 A1203;
0.329 P205; 0.035 SiO2; and a formula (anhydrous basis) of:
Q.06 X (MnO oqA1o.46PO.475iO~33 2 (c) The chemical analysis ~Eor MnAPSO-20 (~xample 46) was:
Component~eiqh~ Percen~
A123 27.3 P205 ~9.6 ~nO 4.6 SiO2 8.
Carbon 8.4 LOI* 19.4 *LOI = I,oss on Ignition The above chemical analysis gives an overall product composition in molar oxide ratios (anhydrous basis) of: 0.065 MnO: 0.268 A1203:
0.279 P205: 0.133 SiO2; and a formula (anhydrous basis) of:
0.18 R (MnO 05Alo 41Po 43sio lo) 2 ~d) The chemical analysis of MnAPSO-31 was:
ComPonentWeiqht_Percent A123 31.8 P205 43.8 MnO 3.2 SiO2 2.6 Car~on 2.9 LOI~ 16.7 *LOI = Loss on Ignition D-14,221 .

3~
- ~4 -The above chemical analysis gives an overall product composition in molar oxide ratios tanhYdrous basis) of: 0.058 MnO: 0.312 A1203 0.309 P205; 0.043 SiO2; and a formula (anhydrous basis) of:
o.o~ R (MnO 04A10 47PO.46SiO.03) 2 (e) The chemical analysis of MnAPSO-3 (Example 6) was:
Component Weiaht Percent A123 25.0 P205 35.8 MnO 7-9 SiO2 11.6 Carbon 3.3 LOI~ 19.7 *LOI = Loss on Ignition The above chemic~al analysis gi~es an overall product composition in molar oxide ra~ios (anhydrous basis) of: 0.1} MnO; 0.25 A1203; 0.19 P205: 0.19 SiO2;and a formula (anhydrous basis) of:
0,04 R (MnO ogA10.38PO.39SiO.1~)02 ~f) The chemical analysis of MnAPSO-35 (Example 23) was:
ComPonent Weiqht Percent A123 25.2 P205 41.3 MnO 7.1 SiOz 4.2 Carbon 12.8 LOI* 21.3 *LOI = Loss on Ignition D-14,221 6~i3~

The above chemical analysis gives an overall product composition in molar oxide ratios (anhydrous basis) of: 0.100 MnO; 0.247 Al203:
0.291 P205; 0.07 SiO2; and a formula (~nhydrous basi~) of:
0.13 R (MnO 08AlO 40Po.~7sio-o6) 2 (g) The chemical analy~is of MnAPSO-36 (Example 59) was:
ComPOnentWeiaht Psrcent Al23 27.7 P205 37.2 HnO 4.6 SiO2 9.5 Carbon 3.0 LQI~ 19.6 *LOI - Loss on Ignition The above chemical analysis gives an overall product composition in molar oxide ratios anhydrous basis) of: 0.065 MnO; 0.272 Al203;
0.262 P205; 0.158 SiO2: and a formula ~anhydrous ~asis) of:
0.03 R (MnO 05Alo 42PO.4lSio 12) 2 (h~ The chemical analysis of MnAPSO-44 (Example 64) was:
ComPonent~eiqht Percent Al2~3 25.8 P205 36.6 MnO 4.4 SiO2 9.7 Carbon 2.5 LOI* 23.1 *LOI = Loss on Igni~ion D-14,221 S3~

The above chemical analysis gives an overall product composition in molar oxide ratios (anhydrous basis) of: 0.062 MnO; 0.253 A1203:
0.258 P205; 0.161 5iO2:; and a formula (anhydrous ~asis) of:
0.04 R (MnO 05AlO.4lpo.glsio-l3) 2 ~ i ) The chemical analysis of MnAPSO-47 (Example 49) was:
Component Weiqht Percen~
A12~3 27.
P~05 36.Z
MnO 5.
SiO2 5.7 Carbon 9.9 LOI~ 25.1 *LOI = Loss on Ignition The above che~ical analysis gives an overall product composition in molar oxide ratios (anhydrous basis) of: 0.071 MnO; 0.271 A1~03;
0.255 P205: 0.095 SiO2: and a formula (anhydrous basis) of:
0.17 R (MnO 06~1o.44PO. 4~sio . 08)2 ExamPle 67 EDAg ~energy dispersive analysis by x-ray) microprobe analysis in conjunction with SEM
(scanning electron microscope) was carried out on clear cry~tals from the products of certain examples, as identified in parenthesis hereinafter.
Analysis of crystals having a morphology characteris~ic of each MnAPSO product ga~e the following analysis based on relative peak heights:

D-14~221 2~6S~ID

a) MnAPS0-5 LExample 4 L:
Averaqe of Spot Probes Mn 0~5 Al 8.0 P 9.5 Si 0 7 b) MnAPS0-11 (ExamPle 2~:
Averaqe o Spo~ Probes Mn 1.0 Al 8.0 P 9.5 Si 1.5 c) MnAPS0-20 (ExamPle 46):
Averaqe of Spot Probes Mn 0.8 Al B.2 P 9.
Si 1.7 d) MnAPS0-34 (Exam~le 6):
Averaqe of SPot Probes Mn 1.3 Al 7 0 p 9.0 Si 1.5 e) MnAPS0-35 (Exam~e 23)~
Averaqe of Spot Probes Mn 1.0 ~1 7.0 p 10.0 Si 1.2 D-14,221 ~2~

~) MnAPS0-36 (ExamPle 59):
Avera~e of_Spot Probes Mn 0.8 Al g.3 P 9.9 Si 1.6 g) MnAPS0-44 (ExamPle 4~2:
Averaqe of_Spot Probes Mn 0.7 Al 9.0 P 10.
Si 1.7 h) ~nAPS0-44 (Example 64~
Averaqe of SPot Probes Mn 1.1 Al 8.7 P 10.0 Si 5.6 i) MnAPS0--47 (Exam~le ~9):
Averaqe of SPot Probes Mn 1.0 Al 9.0 - P 9.5 Si . 1.9 Example 68 (a) The MnAPS0-5, prepared in Example 31, was subjected to x-ray analysis. The MnAPSO-5 was impure but the major phase was de~ermined to have an x-ray powder diffraction pattern characterized by ~e following data:

D-14,221 6~0 2~ I/Io x 100 6.9* 12.~1 13 7.5 11.79 100 B.0* 11.05 5 9.1* 9.72 4 9.3* 9.51 13.0 6.81 14 13.7* 6.46 3 15.0 5.91 27 16.5* 5.37 3 18.5~ 4.80 7 19.8 4.48 43 21.0 4.23 58 22.3 3.99 75 24.7 3.60 6 25.9 3.~40 42 29.0 3.079 18 30.0 2.979 34 33.6 2.667 34.5 2.600 21 36.9 2.43h 4 37~7 2.3~6 10 ~1.5 2.176 5 4Z.1 2.1~6 5 42.2 2.141 5 ~2.6 2.122 5 43.5 2.080 3 44.9 2.01g 3 47.5 1.914 7 51.4 1.778 5 ~1.9 1.762 3 ~5.~ 1.656 5 * Peak may contain an impurity (b) A portion of ~he as-synthesized ~nAPS0-5 of part a) was calcined in air at 500C for about two (2~ hours. The calcined product was characterized by ~he following x-ray powder diffraction pattern:

D-14,221 3~3 29 d, (A~ I~Io x 100 7.4 11.95 100 *7.~ 11.33 1~.9 6.86 25 1~.0 5.91 21 *1~.5 5.37 ~16.7 5.31 3 *17.5 5.07 5 19.8 4.4~ go 21.2 4.19 40 22.5 3.95 43 6.0 3.427 30 29.1 3.069 11 30.1 2.969 35 33.7 2.66~ 5 34.6 2.592 19 37.1 2.~23 4 37.9 2.374 6 42.5 2.~27 4 43.1 2.099 3 46.0 1.973 3 47.9 1.899 5 55.8 1.647 4 *Peak may con~ain an impurity (c) The species denominated herein as MnAPS0-5 is a molecular sieve having a three dimensional microporous crystalline framswork s~ructure of MnO22, A102, P0+2 and SiO2 tetrahedral oxide units and have an empiracal chemical composi~ion on an anhydrous basis expressed ~y the ~ormula:
mR- ~MnwAlxPySiz)02 wherein l'RII represents at least one organic templating agent present in the intracrystalline pore system: ~Im~l represen~s the molar amount of "R"
present per mole of (MnwAlxPySiz)02 and has a ~alue of zero to about 0.3; and "~". "x", "y"

D-14,221 ~Z~653~
~ . . . .

and "z" represent the mole fractions of manganese~
alu~inum, phosphorus and silicon resE~ectively, present as tetrahedral oxide~ 6aid mole fractions being within the pentagonal compostional area defined by point~ A, B, C, D and E of FIG. 1, more preferably by the tetragonal compostional area defined by points a, b, c and d of FIG. 2, said MnAPS0-5 having a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth in Table ~ as follows:
TABLE V

~ L Relative Intensitv 7.3 - 7.7 12.11 - 11.48 v~
14.7 - 15.1 6.03 - 5.87 m 19.6 - 1~.9 4.53 - 4.46 m 20.3 - 21.3 4.27 - 4.17 m 22.1 - 22.6 4.Q2 - 3.93 m 29.8 - 30.2 2.998 - 2.959 m (d) All of ~he MnAPS0-5 compositions, both as-synthesized and calcined, for which x-ra~
power diffraction data have presently been obtain have patterns which are within the generalized pattern of Table VI below:
TABLE VI
2e d,(A) I/Io x 100 7.3 - 7.7 12.11 - 11.~8 100 1~.7 - 13.0 6.97 - 6.81 14-27 14.7 - 15.1 6.03 - 5.87 20-~
l9.S - 19.9 4.53 - 4.46 3~-51 20.8 - 21.3 4.27 - 4.17 29-58 22.1 - 22.6 4.02 - 3.93 30-75 ~4.5 - 24.7 3.63 - 3.60 4-6 ~5.7 - 26.1 3.4~6 - 3.41~ ~-42 D-14,221 .

~L2~653~1 .

TABLE VI (Continued) 2~ d, CA) I/Io x 100 28.8-29.2 3.100-3.058 10-30 29.8-30.2 2.998-2.959 3~-50 33.4-33.8 2.683-2.652 4-10 34.3-34.7 2.61~-2.585 19-44 36.7-37.2 2.44g-2.417 3-~
37.5~38.0 2.398-2.368 5-20 41.3-41.5 2.186-2.176 3-5 41.9-42.1 2.156-2.146 4-5 42.0-42.~ 2~151-2.141 3-~
42.~-~Z.6 2.132-2.122 3-5 43.1-~3.5 2.099-2.080 3-5 44.7-~9.9 2.027-2.019 3-S
46.0-46.1 1.973-1.969 3-~
47.3-47.6 1.922-1.910 5-7 47.9-4~.0 1.899-1.~95 4-5 51.2-51.4 1.78g~1.778 5-7 51.7-51.9 1.768-1.762 3-5 55.3-55.9 1.661-1.645 2-7 Example 69 (a) MnAPS0-11. as prepared in example 24, was ~ubjec~ed to x-ray analysis. The MnAPS0-11 ~as determined to have an x-ray powder diffraction pattern characterized by the follo~ing data:
2e ~ L I/Io x 100 8.1 10.92 36 9.5 9.31 61 13.1 6.76 19 15.7 5.64 36 16.2 5.47 10 19.1 4.65 13 20.5 4.33 45 21.1 4.21 100 22.2 4.00 55 22~5 3.95 52 22.7 3.92 61 23.2 3.83 71 24.5 3.63 13 24.8 3.59 16 25.0 3.562 13 26.4 3.38 26 D-14,221 i53~

2~ d, (A) I/Io x 100 28.3 3.153 13 2B,6 3.121 23 29.5 3.028 13 31.5 2.84 16 32.3 2.730 23 34.2 2.62~ 16 ~5.4 2.54 10 35.~ 2.508 10 3~.3 2.. 475 10 37.5 2.398 13 37.8 2.370 16 39.4 Z.287 1~
42.9 2.108 10 4~.8 2.023 10 48.8 1.866 3 50.6 l.B04 10 54.6 1.681 10 (b) A portion of the as-synthesized MnAPS0-11 of part a) was calcined in air at 600C
for about two (2) hours. The calcined product was characterized by the following x-ray powder diffraction pattern:
2~ d, ~A~ I/Io x 100 a.l 10.92 33 9.8 9.03 60 11.8 7.50 13 12.8 6.92 2?
13.5 6.56 13 14.8 5.99 sh 16.1 5.51 67 19.5 4.55 27 19.9 4.46 ~0 20.4 4-35 33 21 5 ~.13 73 21 8 4.08 100 22 2 4.00 73 22 4 3.g7 80 23.5 3.7g 73 24.3 3.66 27 25.8 3.453 33 26.7 3.339 27 27.3 3.267 33 D-14,221 ~Z4~53~ .
- 4~ -2~ d, (A~ ~/Io x 100 27.8 3.Z09 33 2~.~ 3.132 27 29.5 3.028 33 29.8 2.998 40 30.~ 2.~40 27 31.~ 2.814 ~0 32.6 2.7A7 33 34.0 2.~37 20 35.5 2.529 27 37.1 2.423 ~0 37.4 2.404 20 ~.2 2.3~6 - 2 38.6 2.332 27 41.~ 2.201 20 ~ c) The species denominated herein as MnAPS0-11 i8 a molecular sieve having a three dimensional microporous crystalline framework structure of MnO22, A10~, P02 and SiO2 tetrahedral oxide units and have an empirical chemical composition on an anhydrous basis expressed by the formula:
mR (MnwAlxPySiz)2 wherein "R" represents a~ least one organic templating agent present in the intracrystalline por~ system; ~'m~' represent~ the molar amount o~ "R"
present per mole of (~nwAlxPySi2)02 and has a value of zero to about 0.3; and "w", "x", "y"
and "z" represent the mole fractions of manganese, aluminum, phosphorus and silicon respectively, presen~ as tetrahedral oxide, said mole fractions being within the pentagonal compostional area defined by poin~s ~, B, C, D and E of FIG. 1, more preferably by ~he tetragonal compostional area defined by point~ a, b, c and d of FIG. 2, said MnAPS0-11 having a characteristic x-ray powder D-14,~21 6~3~

diffraction pa~tern which contains at leas~ the d-~pacings se~ forth in Tabl~ VII as follows:
TABLE VII

2e d,~ Rel,ati~e Intensitx 9.4 - 9.89.41 - 9.03 m 16.1 - 16.25.50 - 5.47 vw-m 21.0 - 21.54.23 - 4.13 m-vs 22.1 - 22.24.02 - 4.00 m 22.4 - 22.53.97 - 3.95 m-s 23.1 - 23.53.85 - 3.79 m (d) All of the MnAPS0-11 composition~, both as--synthesized and calcined, for which x-ray power difPrac~lon data have presently been obtain have patterns which are within the generalized pattern of Table VIII below:
TABLE VITI
2e d,~A) I/Io x 100 8.0 - 8.111.05 ~ 10.92 31-36 9.4 - 9.8 9.41 - 9.03 56-61 11.8 7.50 13 12.8 - 13.1 6.92 - 6.76 17-27 13.5 6.56 13 14.8 5.99 sh 15.6 - 15.7 5.68 - 5.64. 33-36 16.1 - ].6.2 5.50 5.47 8-67 19.0 - 19.5 9.68 - 9.55 8-27 19.9 4.46 40 20 4 - 20.5 ~.35 - 4.33 33-~5 21 0 - Zl.5 4.23 - 4.13 73-100 21.8 4.08 100 22.1 - 22.2 4.02 - 4.00 55-73 22.4 - 22.5 3.97 - 3.95 52-80 ~.6 - 22.7 3.93 - 3.92 61 23.1 - 23.5 3.85 - 3.79 69-73 D-14,221 ~2~53~
- ~6 -TABLE VIII (Continued~
2~ d, (A~ I/Io x 100 24.3-24.5 3.66-3.63 11-27 24.7-24.8 3.60-3.59 14-16 24.9-25.0 3.58-3.562 sh-13 25.B 3.453 33 26.3-26.7 3.389-3.339 25-Z7 27.3 3.267 33 Z7.8 3.209 33 28.2-28.3 3.1~4-3.153 11-~3 28.5-28.6 3.132-3.121 22-27 29.~-29.5 3.038-3.02~ 33 29.8 2.998 40 30.~ 2.940 27 31.4-31.8 2.849-2.814 14-20 3Z.6-32.8 2.747-2.730 19-33 34.0-34.2 2.637-2.622 14-20 35.3-35.5 2.543-2.529 sh-27 35.7-35.8 2.515-2.508 ~-10 36.2-26.3 2.481-2.475 8-10 37.1 2.423 20 37.~-37.5 2.404-2.398 11-20 37.7-37.8 2.386-2.380 16-17 38.2 2.356 20 38.6 2.332 27 39.3-39.4 2.292~2.287 8-10 ~1.0 2.201 20 42.8-~2.9 2.113-2.108 8-10 4g.7-~4.8 2.027-2.023 ~-10 48.7-48.8 1.870-1.866 3-5 50.5-50.6 1.807-1.80q 8-10 54.5-54.6 1.684-1.681 8-10 Example 70 (a) MnAPS0-16, as prepared in example 14 wa~ subjected to x-ray analysis. The MnAPS0-16 ~as determined to have an x-ray powder diffraction pattern characterized by the following data:
2e d, (A~ I~Io x 100 8.6* lO.~a 8 11.0* 3.04 23 ll.q 7.76 4~
13.3* 6.66 11 D-14,221 3~

2~ d,_L~LItIo x 100_ ~ * 5.57 5 17.3* 5.1-~ 24 17.7* 5.01 8 18.7 4,75 4 21.1* 4.21 19 21.g** 4.06 1~0 2~.0 3.87 13 23.2* 3.83 10 23.7* 3.75 5 25.1 3.548 5 26.6** 3.351 2~
26.7* 3.339 (~h) 27.8 3.209 5 28. a* 3.100 15 29.0 3.079 15 2g.8 2.998 2~
3~.0* 2.797 16 32.6 2.747 7 34.7** 2.585 10 35.7* 2.515 5 37.~ 2.38Q 11 39,7 ~.270 5 42.0~ 2.151 5 44.2 2.049 5 48.S** 1.~77 10 49.4* 1.845 5 52.4 1.746 5 54.7 1.678 5 * Impurity Peak ** Peak may contain impurity (b) A portion of the as-synthesized MnAPS0-16 of part a? was calcined in nitrogen at 600C for about 2 ~ours. The calcined product was characterized by the following x-ray powder diffrac~ion pattern:
2e d, tA) X~Io x 100 11.5 7.69 100 13.3* 6.66 9 D-14,221 6~ii3~

2e d, ~A) I/Io x 10 18.6 4.77 25 2~.3* 4.37 44 2~5* ~.33 41 21.5* 4.13 66 21.9** 4.06 72 22.~ 3.88 ~1 2~.5* 3.79 13 26.5~* 3.363 31 27.9 3.198 13 29.0 3.079 19 zg.7 3.008 3 32.6 2.747 13 3~.7~* 2.585 13 35.6~ 2.522 16 37.8 2.380 13 ~8.2*~ 88 9 * Impurity Peak ** Peak may contain impurity tc) The species denominated herein as ~nAPS0-16 is a molecular sieve having a three dimensional microporous crystalline framework structure of MnO22, A102, P02 and SiO2 tetrahedral oxide units and have an empirical chemical composition on an anhydrous basis expressed by the formula:
mR: (~nwAl2PySiz)O~
wherein l'R'I represents at least one organic templating agent present in the intracrystalline pore system; llm" represent~ the molar amount of 'IR"
present per mole of (MnwAlxPySiz)02 and has a value of zero to about 0.3; and "w", "x", "y"
and ~'z" cepresent the mole fractions of manganese, aluminum, phosphorus and silicon respectively, pressnt as tetrahedral oxide, said mole fractions D-14,221 being within ~he pentagonal compostional area defined by points A, B, C, D and E of FIG. 1, more preferably by the tetragonal compostional area defined by points a, b, c and d of FIG. 2, said MnAPS0-16 having a characteri~tic x-ray powder diffrac~ion pattern which contain6 at least the d-spacings set forth in Table IX as follows:
TABLE I~

2~ L Relative Intensity 11.~-11.5 7.76-7.69 m-vs 18.6-18.7 4.77-4.75 m 21.9 4.06 m-vs 22.9-23.0 3.88-3.87 w-m 26.5-26.6 3.363-3.351 m 29.7-29. a 3.008-2.998 m (d) All of the MnAPS0-16 compo~itions, both as-synthe~ized and calcined, for which x-ray power diffra~tion data have presently been obtain have pattern~ which are ~ithin the generalized pattern of Tahle X below:

23 d, (A) I/Io x 100 11.4~ 5 7.76-7.69 48-100 18.6-18.7 4.77-4.75 25-~0 21.9* 4.06 72-ao 22.9-23.0 3.8~-3.87 13-31 26.5-26.6~ 3.363-3.351 26-31 27.8-27.9 3.20~-2.198 5-13 29.0 3.079 15-19 29.7-29.8 3.008-2.998 2~-34 32.6 2.747 7-14 34.7* 2.585 9-14 37.8 2.380 11-15 39.7 2.270 5-6 D-14,221 TABLE ~ (Continuedl 2~ I/Io x 100 ~4.2 2.049 5-6 48.2-48.5* 1.888-1.877 9-lZ
4g.4 1.845 ~-s

5~.4 1.746 4_5 54.7 1.678 4-5 * Peak might contain an impurity ExamPle 71 (a) MnAPS0-20, as prepared in example 46 was subjected to x-ray analysis. The ~nAPS0-20 was determined to have an x-ray powder diffraction pattern characterized by the following data:
2~ d, (A) I~Io x 100 14.0 6.35 ~9 19.8 ~.49 ~3 22.1 4,0~ 3 23.7* 3.75 24.3 3.67 100 2~.1 3.177 13 31.5 2.842 11 34.6 2.595 16 37.5 2.400 2 40.1 2.2~7 4 42.7 2.118 4 47.4 1.917 51.8 1.764 7 _ * Peak may contain an impurity (b) A portion of the as-synthesized ~nAPS0-20 of part a) was calcined in air at 500C
for about 1 hour. The calcined product was characteriz~d by ~he following x-ray powder diffraction pattern:

D-14,221 3~

2~ Relative Intensity 7.1 12.51 2 14.0 6.33 100 19.a 4.48 ~o Z2.2 4.00 24.3 3.~6 99 28.2 3.168 1~
31.6 2.835 15 34.7 2.589 17 40.2 2.2~3 3 42.7 2.116 4 ~7.5 1.913 (c) The species denominated herein as MnAPS0-20 is a molecular slev~ having a three dimensional microporous crystalline framework structure of MnO22, A102, P02 and SiO2 tetrahedral oxide units and have an empirical chemical composition on an anhydrous basis expressed by the formula:
mR (MnwAlxPysiz~2 wherein "R" represents at least one organic templating agent pr2sent in the intracrystalline pore system; "m" represents the molar amount of "R
present per mole of (MnwAlxPySiz)02 and has a value of zero to about 0,3; and "w", "x", "y' and "z~' represent the mole fractions of manganese, aluminum, phosphorus and silicon respecti~ely, present as tetrahedral oxide, said mole fractions being within the pentagonal compostional area D-14,221 ~z~530 defined by poin~s A, B, C, D and E of FIG. 1, more preferably by the tetragonal com~ostional area defined by points a, b, c and d of ~IG. 2, said MnAPS0-20 having a characteri6tic x-ray powder diffraction pattern which contains at least the ~-spacing~ set forth in Table ~I as follo~s:
TABLE ~I

2~ d,(A) Relative Intensity 13.904-13.998 6.3692 -6.3263 m-vs 19.72~-19.818 4.5011-4.4918 m 24.223-24.329 3.6742-3.65&4 vs 28.039-28.163 3.1822-3.1684 w 31.434-31.56~ 2.~45~-2.8348 w 34.527-34.652 2.597~-2.5866 w td) All of the MnAPS0-20 compositions, both as-synthe~ized and calcined for which x-ray power diffra~tion data have pres~ntly been obtain have patterns which are within the generalized pattern of Table ~II below:
TABLE ~II
2e d,(A) I/Io x 100 13.904-13.9g8 6.3692-6.3263 49-100 19.723-19.818 4.5011-4.491B 40-43 22.091-22.200 9.0236-4.0041 3-~
24.223-24.329 3.6742-3.6584 9g-100 2~.039-2~.163 3.1822-3.1684 13-17 31.43~-31.S60 2.8~58-2.8348 11-15 34.527-34.652 Z.5976-2.58~6 15-17 34.413-27.46~ 2.2501-2.4004 2 ~0.071-gO.207 2.2501-2.2428 3-4 42.627-42.730 2.1209-2.1160 ~-~
47.383-47.519 1.91~5-1.9134 3-4 51.790 51.840 1.765~-1.7636 7 ,221 i3 [9 ~ 53 -Example 72 (a) MnAPS0-31, as prepared in example 5 was subjected ~o ~-ray analysis. MnAPS0-31 was determined to have an x-ray powder diffraction pattern characterized by the followiang data:

2~ d, (RlI~Io x 100 7.9 11.22 4 8.6 10.27 61 17.2 5.17 5 18.5 ~.81 4 20.4 4.36 49 21.2 4.19 4 22.0 4.04 30 22.1 4,02 32 22.7 3.g2 100 25.3 3.526 5 25.8 3.459 3 28.1 3.181 12 29.~ 2.9g5 6 31.8 2.812 22 35.2 2.54~ 9 36.2 2.482 3 37 3 2.411 3 37 8 2.382 3 38.3 2.353 3 38.~ 2.346 3 39.4 2.285 3 3g.8 2.266 3 40.3 2.241 3 46.8 1.942 3 ~8.8 1.866 2 51.~ 1.766 5 5S.6 1.654 2 lb) A portion of the as-synthesized MnAPS0-31 of part a) was calcined in air at 500C
for about 1.5 hours. The calcined product was ~haracterized by ~he following x-ray powder diffrac~ion pattern:

D-14,221 53~

2~ d~ (A) I/Io x lOG
B.~ 10.31 5a 14.8 5.98 4 17.1 5.18 9 18.5 4.81 4 20.4 4.36 52 22.1 4.03 4~
22.7 3.92 100 25.3 ~.526 7 25.8 3.460 8 28.1 3.181 15 29.8 2.998 11 31.1 2.879 3 31.8 2.811 33 35.~ 2.546 11 36.3 2.~77 6 37.3 2.~09 3 37.8 2.383 3 38.3 2.348 3 39.4 2.289 4 40.3 2.2~6 3 45.4 2.000 3 46.~ 1.942 5 47.6 1.909 48.9 1.~64 3 51.7 1.767 . 6 (c) T~e species denominated herein as MnAPS0-31 is a molecular ~ieve having a three dimensional microporous crystalline framework structure of MnO22, A102, P02 and SiO2 tetrahedral oxide uni~s and have an e~pirical chemical composition on an anhydrous basis expressed y the formula:
mR: (MnwAlxPySiz)02 wherein "R" represents at least one organic templa~ing agent present in the intracrystalline pore system; "m" represents the molar amount of "R"
present per mole of (MnwAl~PySiz)02 and has a ~alue of zero to about 0.3; and "w", "x", "y"

D-14,221 ~LZ~5i3~

and "z" represent the mole fractions of manganese, aluminum, phosphorus and æilicon respectively, present as tetrahedral oxide, said mole fractions being within the pentagonal compostional area defined by points A, B, C, D and E of FIGA 1, more preferably by the tetragonal compostional area defined by points a, b, c and d of FIG. 2, said MnAPS0-31 ha~ing a characteristic x-ray powder diffraction pattern which contains at least the d-6pacings set forth in Table ~III as follows:
TABLE ~III

2~ d,~Rl Relative Intensi~v 8.482 - 9.501 10.4240 - 9.3084 m 20.222 - 20.35~ 4.3913 ~ 4,3632 m 21.879 - 21,993 4.0622 - g.0415 m 22.071 - 22.088 4.0272 -~4.0242 m 22.S87 - 22.698 3.9364 - 3.9174 vs 31.724 - 31.836 2.a546 - 2.8108 m ~ d) All of the MnAPS0-31 compositions, both as-synthesized and calcined for which x-ray power diffraction data have presently been obtain have patterns which are within the generalized pat~ern of Table ~IV below:
TABLE ~IV
d,(A) I~Io x 100 7.694 - 7.~83 11.4904 - 11.21~52-4 8.4B2 - 9.50110.4240 - 9.3084 58-66 ~4.756 - 14.822 6.0034 -5.9767 2-~
17.016 - 17.1~8 5.2105 -5.1679 ~-9 18.310 - 18.466 4.8451 -4.804~ 3-~
20.222 - 20.353 4.3913 -4.3632 45-52 D-14,221

6~3~
- ~6 -TABLE XIV (Continued~
2_ d. ~ I/Io x 100 21.032-21.221 ~.223a-4.1867 4-5 21.87~-21.9~3 4.0622-~.041S 30-51 2~.071-22.088 4.0272-~.0242 32-4 22.5~7-22.698 3.9364-3.917~ 100 2~.164-Z3.190 3.8398-3.8355 2-3 ~5.115-~5-260 3.5457-3.5256 ~-7 25.663-25.757 3.4712-3.~588 3-8 27.922-28.0~0 3.1953-~.1809 12-1 29.701-29.831 3.0078-2.9950 6 11 31.068-31.315 2.87~5-2.8564 2-3 31.7~-31.836 2.8564-2.8108 21-33 35.117-35.2~1 2.5553~2.5460 9-11 35.~71 2.5033 36.070-36.2S1 2.49~0-2.4730 2-6 37.123-37.325 2.4217-2.4091 2-3 37.628-27.763 2.3904-2.3822 2-3 38.163-38.254 2.3581-2.3527 ~-3 38.334-38.367 2.3480-2.3461 3 39.2~5-39.~42 2.2933-2.2845 3-4 39.654-39.772 2.2728-2.2663 2-4 40.111-~0.337 2.2480-2.2359 2-3 45.179-45.354 2.0069-1.9996 , 2-3 46.617-46.786 1.9483-1.9416 3-5 47.454-47.631 1.9158-1.9091 2-4 48.610-48.846 1.8729-1.8644 2-3 50.679-50.750 1.8012-1.79~9 2 51.~88-51.766 1.7716-1.7659 4-6 55.glO-55.557 1.65~1-1.6541 2 Exam~le ?3 (a) MnAPS0-3~, as prepared in example 11 was subjected to x-ray analysis. MnAPS0-39 was determined to have an x-ray powder diffraction pattern charac~erized by the following data:
2~ d, (A) I/Io x 100 9.6 9.21 100 12.9 6.86 17 14.2 6.24 15 16.1 5.51 33 18.1 4.90 23 20.6 ~.31 69 D-14,221 ~2~536~
- 57 _ 2a d, (A) I/Io ~ 100 22.3 3.99 10 23.1 3.e5 8 25.2 3.534 25 25.~ 3.453 19 27.5 3.2~3 10 28.4 3.143 10 29.5 3.028 10 30.5 2.931 27 31.2 2.867 23 33.8 2.652 8 34.3 2.614 12 36.3 2.475 43.0 2.103 43.5 2.080 . 6 47.5 1.914 6 48.9 1.863 8 50.9 1.794 6 53.0 1.728 6 55.7 1.650 6 (b) A portion of the as-synthesized MnAPS0-3~ of part a) was calcined in nitrogen at 425C for about 2 hours. The calcined product was characterized by the following x-ray powder diffraction pat~ern:
2e d,_~A) I/Io x 100 9.6 9.21 100 13.0 6.86 25 14.1 6.28 5 16.2 5.47 15 17.9 4.96 15 19.1 ~.65 5 20.~ 4.27 37 22.2 4.00 5 22.4 3.97 5 23.2 3.83 7 25.2 3.534 15 26.0 3.427 12 27.7 3.220 28.3 3.153 5 29.7 3.0Q8 30.7 2.912 17 D-14,221 ~2~i53~

2~ dL (A) I/Io ~ lOo .. . . . _ 31.3 2.8~9 11 3204 ~.763 3 34.6 2.592 36.~ 2.481 38.8 2.321 39~8 2.265 3 43.1 ~.099 3 ~3.6 2.07S 3 47.8 1.903 ~9.0 1.859 3 51.0 1.791 3 53.3 1.719 54.6 1.681 3 (c) The species denominated herein as MnAPS0-3~ is a molecular sieve having a three dimensional microporous crystalline framework structure of MnO22, A102, P0z and SiO2 tetrahedral oxide units and have an empitical chemical composition on an anhydrous basis expreæsed by the formula:
mR: ~MnwAlxPySiz)02 wherein "R" repre~ents a~ least one organic templating agent present in the intracrystalline pore system; "m" repre~ents the molar amount of "R"
present per mole of ~MnwAlxPySiz)02 and ~as a ~alue of zero to about 0.3; and "w", "x", "y"
and "z" represent the mole fractions of manganese, aluminum, phosphorus and silicon respectively, prssent as tetrahedral oxide, ~aid mole fractions being within the pentagonal compostional area defined by poin~s A, B, C, D and E of FIG. 1, more preferably by the tetragonal compostional area defined by points a, b, c and d of FIG. 2, said ~nAPS0-~4 having a characteristic x-ray powder D~14,221 ~2~6~ii3~

diffrac~ion p~tern which contains at least the d-spacings ~t forth in Table XV as follows:
TABLE ~V

2~ d.(A~ Rela~ive Tntensity 9.~ - 9.6 9.41 - 9.21 vs 15.9 - 16.2 5.57 - 5.47 m 20.g - 20.8 4.35 - 4.27 m-vs 25.0 - 25.3 3.562 - 3.520 w-m 31.0 - 3103 2.8~5 - 2.858 w-~
33.6 - 33.9 2.667 - 2.644 m (d) All of the MnAPS0-34 compositions, both as-synthesized and calcined for which x-ray power diffraction data have presently been obtain have patternfi which are within the generalized pattern of Table ~IV below:
TABLE ~IV
2~ d,(A~ ILIo x 100 9.4 - 9.6 9.41 - 9.21 100 12.7 - 13.0 6.97 - 6.86 17-25 14.0 - 14.2 6.33 - 6.24 5-17 15.9 - 16.2 5.~7 - 5.47 15-44 17.9 - 18.1 4.96 - 4.90 15-3 19.1 4.65 5 20.4 - 20.8 4.35 - 4.27 37-92 22.1 - 22.3 4.02 - 3.99 5-16 22.4 3.97 S
22.9 - 23.2 3.88 - 3.83 7-16 25 0 - 25.3 3.562 - 3.520 15-3~
25 ~ - 26.0 3.~53 - 3.427 12-19 ~7.3 - 27.7 3.267 - 3.220 4-28 2~.2 - 28.~ 3.164 - 3.132 5-16 29.3 - 29.7 3.048 - 3.008 4-16 30.3 - 30.7 2.950 - 2.912 10-17 31.0 - 31.3 2.885 - 2.849 11-40 32.4 2.763 3 D 14,221 ~2~ i3~

TABLE ~IV (Continued) 2 d, (A)I~Io x 100 3~.~-33~9 2.667-2.64~Z3-32 34.3-34.~ 2.~1~-2.59~5-12 36.2-36.4 2.~l-2~6a ~-16 38.8 Z.321 3 39.8 2.265 3 ~3.0-~3.1 2.103-2.~99 3-1 ~3.5-43.6 2.080-2.0763-12 47.4-47.8 1.918-1.9031-12 48.8-49.0 ~.866-1.8593-12 50.8-51.0 1.797-1.7913-12 52.g-53.3 1.731-1.7194-12 54.6 1.~81 3 55.6-~5.8 1.653-1.647~-12 ~=E~
(a) MnAPS0-35, as prepared in example 22 ~as subjected to x-ray analysis. MnAPS0-35 was determined to have an x-ray powder diffraction pattern characterized by the following data:
2~ d, (A)I/Io x 100 8.6 10.28 14 10.9 8.12 95 13.4 6.61 23 15.9 5.57 11 17.4 5.10 80 17.8 4.9~ 16 20.9 4.25 57 21.9 4.06 100 23.2 3.83 3~
24.8 3.59 9 25.7 3.966 7 26.9 3.314 21 28.3 3.153 50 29.1 3.069 11 31.~ 2.849 9 32.1 2.788 41 34.3 2.614 14 34.9 2.571 7 35.3 2.543 5 35.8 2.508 7 37.7 2.386 5 ~z~

2~ d, (A) T/Io x 100 39.5 2.281 s 41.9 2,156 7 42.7 2.118 7 49.6 2.032 5 ~70~ 1.910 7 48.3 1.884 7 49.5 1.8~1 7 51.0 1.791 9 55.0 1.670 5 55.~ 1.658 7 (b) A portion of the a6-synthesi~ed MnAPS0-35 of part a) wa~ calcined in ni~rogen at 500C for about 2 hours. The cal~ined product was cbaracterized by the follo~ing x-ray powder diffraction pattern:
2~ d. (A) I/Io x 100 8.6 10.28 27 10.9 8.12 96 11.4 7.76 14 13.4 6.61 41 15.8 5.61 14 17.3 5.13 68 17.7 5.01 8h 20.8 4.27 6~
2109 4.06 1~0 23.3 3.82 32 2g.a 3.59 23 25.7 3.466 18 26.9 3.314 27 28.3 3.153 59 29.1 3.069 23 31.4 2.849 la 32.2 2.780 46 34.2 2.622 18 3~.~ 2.578 14 35.8 2.50~ 9 41.9 2.156 9 4Z.5 2.127 9 44.6 2.032 9 ~7.4 1.918 9 48.2 1.888 9 D-14,221 2~ I/Io x 100 49.g 1.845 9 51~0 1.7~1 14 55.2 1.669 9 5~.7 1.650 9 (c) The æpecies denominated herein as MnAPS0-35 is a ~olecular æieve havillg a three dimensional microporous crystalline framework structure of MnO22, A102, P02 and SiO2 tetrahedral oxide units and have an empirical chemical composition on an anhydrous basis expressed by the formula:
~ R: (M~wAlxpysi )2 wberein "R" represents at least one organic templating agent present in the intracrystalline pore sys~em; "m" represents the molar amount o:f "R"
present per mole of (MnwAl~PySiz)02 and has a value of zero to about 0.3; and "w"~ "x", "y"
and "z" represent the mole fractions of manganese, aluminu~, phosphorus and silicon respectively, present as tetrahedral oxide, said mole fractions being within the psntagonal compostional area defined by points A, B, C, D and E of FIG. 1, more preferably by the tetragona~ compos~ional area defined by points a, b, c and d of FIG. 2, said MnAPS0-35 having a characteristic x ray powder diffraction pattern which contains at least the d~spacings æet forth in Table ~VII as follows:

D-14,221 ~o~

TABLE ~VII

2~ d,LAI Relative IntensitY
10.8 - 11.0 8.19 - B.04 m-vs 13.~ - 13.7 S.61 - 6.~6 m-s 17.2 - 17.5 5.16 - 5.07 m-s 20.8 - 21.0 4.27 - 4.23 m 21.8 - 22.3 4.08 - ~.99 m-vs 28.2 - 28.7 3.164 - 3.110 m (d) All o~ the MnAPSO-35 compositions, both as-~ynthesized and calcined, for which x-rdy power diffraction data have pr~sently been obtain have patterns which are within the generalized pattern of Table ~VIII below:
TABLE XVIII
29 d,~A2 I/Io x 100 8.5 - 8.7 10.40 - 10.16 13-31 10.8 - 11.0 8.19 - 8.04 44-lO0 11.4 11.5 7.76 - 7.69 8-14 13.3 - 13.4 6.66 - 6.61 22-41 13.4 - 13.7 6.61 - 6.46 31-81 15.8 - 15.9 5.61 - 5.57 10-1~
17.2 - 17.5 5.16 - 5.07 38-82 17.7 - 18.0 5.01 - 4~93 (8h)-18 20.8 - 21.0 ~.27 - ~.23 44-46 ~1.8 - 22.3 4.08 - 3.99 56-100 23.1 - 23.6 3.8~ - 3.77 31-3~
24.7 - 25.2 3.60 - 3.53~ 13-31 25.6 - 25.~ 3.480 - 3.453 4-25 26.8 - 27.4 3.3~6 - 3.255 19-44 2~.2 - 2~.7 3.164 - 3.110 50-59 29.0 - 29.6 3.079 - 3.01a 10-31 31.3 - 31.4 2.~58 - 2.8~9 9-18 32.0 - 32.8 2.797 - 2.730 31-46 34.2 - 3~.3 2.622 - 2.614 11~18 34.~ - 34.9 2.57~ - 2.571 4-14 35.2 - 35.3 2.550 - 2.~43 5-7 35.7 - 35.8 2.515 - 2.50~ 4-9 37.6 - 37.7 2.392 - 2.3a6 4-5 D-14,221 3L2~

TABLE ~III tContinued) 2~ T~Io x 100 3g.4-39.5 2.287-2.2~1 ~-7 91.8-42.0 2.16~-2.151 6-9 92.5-42.8 2.127-2.113 5-9 44.5-4~.7 2.036-2.027 5-9 ~7.4-47.7 1.91~-1.907 6-9 ~8~2-48.4 1.888-1.881 6-9 49.~-49.6 1.8~5-1.838 6-g 50.9-51.1 1.794-1.787 5-14 54.9-55.2 1.672-1.66g 5-9 5S.3-55.7 1.661-1.650 6-9 Example 75 (a) MnAPS0-36, as prepared in example 59 was subjected to x-ray analysis. The MnAPS0-36 was determined to have an x-ray powder diffraction pattern characterized by the following data:
Z~ d, (A) I/Io x 100

7.4 11.88 15 7.g 11.22 100

8.2 lO.Q2 33 13.5 6.55 5 15.8 5.61 10 16.4 5.41 31 19.1 4.66 14 20.7 ~.28 34 21.2 4.19 4 21.7 ~.10 16 22.0 4.04 1~
22.5 3.96 15 23.0 3.87 5 23.9 3.73 6 27.2 3.276 15 27.9 3.193 3 2~.3 3.153 29.0 3,079 7 3~.2 2.958 4 30.3 2.951 4 32.0 2.798 8 34.8 ~.579 7 D-14,2Zl i3~

(b~ A portion of the as-synthesized MnAPS0-36 of par~ a) was calcined in air at 530C
or about 1 hour. The calcined product was characterized by the following X-rdy powder diffraction pattern:
2~ d, ~A~ ;r/Io x 100 7.1 12.39 s 7.6 11.64 21 ~ . 0 11 . 11 100 8.3 10.65 37 13.6 6.53 17 16.6 5.35 31 19.4 4.~7 17 20.8 4.27 19 21.9 ~.06 8 22.4 3.97 15 22.7 3.92 11 23.g ~.80 5 23.9 ~.73 7 27.3 3.271 16 2a.3 3.15g 6 2~.4 3.141 6 29.1 3.074 7 29.4 3.0~3 5 32.0 2.798 6 (c) The species denominated herein as MnAPS0-36 is a molecular sieve having a three dimensional microporous crystalline framework structure of MnO22, A102, P02 and SiO2 tetrahedral oxide units and have an empirical chemical co~position on an anhydrous basis expressed by the formula:
mR: (Mn~AlxPySiz)02 wherein "R" represen~s at least one organic templating agent present in ~he intracrys~alline pore system: "~" represents the molar amount of "R"
present per mole of (MnwAlxPySiz)02 and D-14,221 53~

has a value of zero to about 0.3: and "w", "x", "y"
and "~" represent the mole fractions of manganese, aluminum, phosphorus and silicon respeceively, present as tetrahedral oxide, said mole fr~ctions being within the pentagonal compo~tional area defined by point~ A, B, C, D and ~ oiE FIG. 1, more preferably by the tetragonal compostional area defined by points a, b, c and d of FIG. 2, said MnAPS0-36 having a charasteristic x-ray powder diffraction pattern which contains at least the d-spacing~ set forth in Table ~I~ a6 follo~s:
TABLE ~I~

2~ d,(A2 elative Intensity 7.596 11.6382 m 7.628 ~ 7.9al 11.5899 - 11.0771 vs 8.105 - 8.299 10.908q - 10.6537 m 16.395 - 16.673 5.4066 - 5.317Z m 19.052 - 19.~14 4.6580 - 4.5721 w 20.744 - 20.871 4.Z819 - 4.2560 m (d) All of the MnAPS0-36 compositions, both as-synthesized and calcined for which x-ray power diffraction data have presen~ly been obtain have pat~erns which are ~ithin the generalized pattern of Table ~ below:
TA~LE ~2 2 ~ I/Io_x 100 7.132 12.3939 5 7.596 11.63~2 21 7.628 - 7.981 11.5899 - 11.0771 100 8.105 ~ 8.2gg lO.90a4 - 10.6537 33-37 13.517 - 13.778 6.5503 - 6.4270 5-17 15.7~7 - 15.928 5.6099 - 5.56~0 10-11 D-14,221 S3~

TABLE ~X (Continuecl) 2~ d, (R2 I~Io x 100 1~.3gS-16.673 5.~066-5.3172 31-32 19.052-19.~1~ 4.6580-4.5721 14-17 20.744-20.871 4.2819-4.2560 20-35 ~1.230 4.184~ ~
21.655 ~.1037 16 21.863-21.98~ 4.0651-4.0427 8-14 22.119-2~.470 ~.018S-3.9566 15 22.713-23.408 3.9150-3.8001 5-11 23.~54-23.965 3.7301-3.7131 ~-6 27.219-27.518 3.2761-3.2412 15-16 27.86~-27.939 302014-3.193~ 2-3 28.252 3.1587 6 28.304-28.536 3.1530-3.1279 6-8 29.003-29.268 3.0786-3.0513 6-7 29.347 3.0433 5 30.144-30.230 2.9646-2.9564 4 30.291-30.526 2.9505-2.9284 31.983-32.094 2.7982-2.7888 6-9 34.640-34.968 2.5894-2.5659 7 ExamPle 76 (a~ MnAPS0-44, as prepared in example 64 was subje~ted to x-ray analysis. The MnAPS0-44 wa$
determined to have an x-ray powder diffraction pattern characterized by the following data:
2e d, (R) I~Io x lOQ

9.4 9.39 100 13.0 6.83 20 13.7 6.45 4 16.1 5.52 ~3 17.3 5.12 5 19.0 4.68 7 20.7 ~.29 84 21.7 4.09 21 22.6 3.94 8 23.1 3.86 9 24.4 3.65 5~
26.1 3.409 22 27.8 3.205 10 2~.7 3.012 5 30.1 2.969 16 D-14,221 ~2~

2~ d, (A~ I/Io x 100 30.8 2.900 50 32.5 2.753 32.9 ~.721 S
3g.8 2.577 3 35.~ 2.528 9 38.5 2.336 2 39.2 2.~99 2 40.0 2.255 2 42.2 2.143 3 42.5 2.125 3 43.6 2.076 2 47.3 1.922 2 g8.2 1.890 7 A8,7 1.870 4 50.3 1.814 7 53.9 1.701 6 (b) A portion of the as-~ynthesized MnAPS0-44 of part a) was calcined in air at 500C
for about one (1) hour. The calcined product was characterized by the following x-ray powder diffraction pattern:
2e d, (A~ I/Io x 100 9.6 9.21 100 13.1 6.79 26 1~.2 6.~6 3 16.2 5.46 12 18.0 4.93 18 lg.3 4.60 3 20.9 4.25 2 ~2.3 3.99 3 23.q 3.80 3 25.3 3.526 13 2~.3 3.387 9 28.5 3.137 3 28.6 3.123 29.9 2.990 2 30.0 2.976 2 30.6 2~921 3 31.1 2.875 7 31.~ 2.811 2 32.1 2.791 2 35.1 2.560 3 D-14,221 ~2~3~

(c) The species denominated herein as MnAPS0-44 is a molecular sie~e having a three dimensional microporous crystalline framewor~
structure of MnO2 , A102, P02 and Sio2 tetrahedral oxide units and have an empirical chemical composition on an anhydrous basis expressed by the formula:
mR: (MnwAlxPySiz)Oz wherein "R" represents at least one organic templa~ing agent present in the intracrystalline pore system, "m" represents the molar amount of "R"
present per mole of (MnwAlxPySiz)02 and has a value of zero to about 0.3; and "w", "x". "y"
and "z" represent the mole fractions of manganese, aluminum, phosphorus and silicon respectively, present as tetrahedral oxide, said mole fractions being within the pentagonal compostional area defined by points A, B, C, D and E of FIG. 1, more preferably by the tetragonal compostional area defined by points a, b, c and d of FIG. 2, said Mn~PS0-44 having a characteristic x-ray powde~
diffraction patteLn which contains at least ~he d-~pacings set forth in Table XXI as follows:
- TABLE XX I

2~ d,(R~ Rela~ive Intensitv 9.420 - 9.498 9.3883 - ~.31~0 vs 16.062 - 16.131 5.5179 - 5.4944 m 20.715 - 20.790 4.2877 - 4.2725 s 24.396 - 24.424 3.6485 - 3.6444 m 26.143 - 26.184 3.4085 - 3.4032 m 30.833 - 30.853 2.8999 - 2~89al m D-14,221 ~, 2~5~

(d~ All of the MnAPSO-44 compositions, both as-synthesized and calcined, for which x-ray power diffraction data have presen~ly been obtain ha~e pat~erns which are within the generalized pattern of Table XXII below:
TABLE ~XII
2~ d~ (A) I/Io x 100 9.4~0-9.498 9.3~3-g~3110 lQO
12.930-12.958 6.8468-6.~318 20 13.738 6.~458 4 }6.062-16.131 5.~179-5.g944 43 17.329-17.396 5.1173-5.0975 5 1~.950-18.998 4.6828-~.~713 7 20.715-20.790 4.2877-4.2725 8~
21.709-21.743 4.0937-4.OB73 21 22.366-22.~83 3.9748-3.9372 8 23.061-23.101 3.8566-3.8501 9 24.396-24.42g 3.6485-3.6444 58 26.1~3-26.184 3.4085-3.4032 22 27.837-27.881 3.2049-3.1999 10 29.661 3.0117 5 30.002-30.096 2.9783-2.9692 16 30.833-20.B53 2.8999-2.8981 50 32.520-32.562 2.7532-2.7~98 4 32.900-32.918 2.7223-2.7208 6 3~.812 2.5770 3 35.516-35.534 2.5275-2.5263 9 38.536 2.3361 2 3~.185 2.2989 2 39.991 2.Z545 2 92.162-42.177 2.1432-2.1425 3 42.533-42.541 2.1254-2.1250 3 43.607-73.621 2.0755-2.07~9 2 47.2~3 1.9224 2 48.157 ~8.177 1.8895-1.~88a 7 48.640-4B.697 1.8719-1.8698 4 50.303-50.307 1.8138-1.8137 7 53.885-53.887 1.7014-1.7013 6 Example 77 ~a) MnAPSO-97, as prepared in example 49 ~as subjected to x-ray analysis. The MnAPS0 47 was D-14,221 3~

_ determined to have an x-ray powder d:iffraction pattern characterized by the following data:
2~ d, LA) _~Io ~ 100 ~.~ 18.44 9.4 9.38 100 lZ.9 6.89 5 13.9 6.40 3 ~ 5.56 9 17.5 5.0fi 18.9 4.69 3 20.5 ~.32 30 21.8 4.08 4 22.4 3.98 22.g 3.88 3 24.6 3.61 11 25.9 3.~45 7 27.6 3.234 2 27.9 3.199 29.5 3.033 2 30.5 2.930 10 30.8 2.901 7 31.5 2.845 33.2 2.700 34.4 2.604 2 34.8 2.576 35.7 2.516 z 38.4 2.343 39.2 2.297 39.6 2.277 ~2.4 2.132 43.3 2.091 ~7.6 1.911 48.6 1.874 5 50.3 1.813 O 2 53.2 1.722 5~.0 1.698 ~b) A portion of the as-synthes;zed MnAPS0-~7 of par~ (a) was calcined in air a~ 500~C
for about o~e (1) hour. The calcined product ~as charac~erized by the following x-ray powder diffrac~ion pattern:

D-14,221 3~

d,_(A) I/Io x loO
5,0 17.80 9.7 9.12 100

10.0 8.85 13.1 6.75 5 1~.2 6.23 16.3 5.~5 2 18.0 4.92 2 19.~ 4.58 3 20.9 4.2~ 7 22.4 3.98 23.4 3.80 25.3 3.521 2 26.~ 3.3B5 2 28.1 3.176 28.6 3.125 30.0 2.977 31.1 2.~76 3 31.5 2.~37 2 33.9 2.645 35.0 2.56~ 1 49.6 1.838 (c) The species denominated herein as MnAPS0-47 i~ a molecular sieve having a three dimensional microporous crystalline framework structure of MnO22, A102, PO2 and SiO2 tetrahedral oxide units and have an empirical chemical compo~ition on an anhydrous basis expres~ed by the formula:
mR: ~MnwAlxPySiz)02 wherein "R" represents at least one organic ~emplating agent present in the intracrystalline pore system: "m" represents the molar amount of "~"
present per mole of (Mn~AlxPySiz)02 and has a value of zero to about 0~3;:and "w", "x", "y"
and "z" represent the mole fractions of manganese, aluminum, phosphorus and silicon r~spectively, pre~ent as tetrahedral oxide, sa~d mole fractions D-14,221 _~7~ ~_ being within the pentagonal compostional area defined by poin~s A, B, C, D and E of FIG. 1, more preferably by ~he tetragonal compostional area defined by points a, b, c and d of PIG. 2, ~aid MnAPS0-47 having a characteristic x-ray powder diffraction pattern which contains at least the d-spacing~ set ~orth in Table ~III as follows:
TABLE XXIII

2~ d,(Al Relative Intensitv 9.434 - 9.696 9.3746 - 9.121~ vs 15.946 - 16.276 5.5579 - 5.~457 vw 20.539 - 20.940 4.3242 - 4.2423 vw - m 24.643 3.6125 w 30.511 2.9297 w 30.820 - 31.096 2.9011 - 2.8759 vw (d) All of the MnAPS0-47 compo~itions, both as-synthesized and calcined for which x-ray power diffraction da~a have presently been obtain have patterns which are within the generalized pa~tern ~f Table X~IV below:
TABL~ XXIV
2~ I/Io x 100 ~.793 - 4.964 18.4368 - 17.8028 9.434 - 9.696 9.3746 - 9.1214 100 12.8~7 - 13.107 6.8907 - 6.7543 5 13.~40 - 14.211 6.3983 - 6.Z321 1-3 15.946 - 16.276 5.5579 - 5.4~57 2-9 17.544 - 19.032 5.0550 - 4.9191 2-~
18.941 - 19.365 4.6~51 - 4.58~6 3 20.539 - 20.940 4.3~42 - 4.242~ 6-30 21.811 4.0747 22.351 - 22.352 3.9775 - 3.9774 22.936 3.8773 3 ~3.401 3.eO13 D-14,221 653~i TABLE ~2IV (Continued2 2Q d, (A? IfIo x lQ0_ 24.643 3.61Z5 11 25.294-25.864 ~.5210 2-7 26.327-27.577 3.3851-3.2344 2 27.881-2~.093 3.1992-3.1762 28.560 3.1253 29.~48-30.019 3.0331-2.9767 1-2 30.511 2.9297 1~
30.820-31.096 2.9~11-2.8759 3-7 31.448-31.532 2.8446-2.8~72 1-2 33.186-33.894 2.6g95-2.6447 34.444 2.6037 2 34.834-35.026 2.57~5-2.561~ 1 3~.685 2.5159 2 38.412 2.3~34 39.223 2.2968 39.582 2.276~ 1 42.403 2.1316 43.278 2.0905 47.595 1.9105 48.584-49.595 l.a739-1.8380 L-5 50.327 1.8130 53.205 1.7215 54.006 1.6979 Example 78 The catalytic activity of MnAPS0 compositions, calcined samples of the MnAPSO
products of Examples 11, 21, 25, 31, 49, 55, 59 and 64 were tested for catalytic cracking.
The catalytic activity was determined using a reactor comprising a cylindrical quartz tube 254 mm. in length and 10.~ mm. I.D. In each test MnAPS0 which were 20-40 mesh (U.S. std.) in size and in an amount of from 0.5 to 5 grams, the quantity being ~elected so that the conversion of n-butane was at least 5% and not more than 90~ under the test conditions. Most of the MnAPS0 samples had been pre~iously calcined in air or nitrogen to remove D-1~,221 ~2~53~
- ~5 -organic materials from the pore system, and were activated in situ in the reactor in a Flowing stream of helium at 500C for one hour. The feedstoc~ was a helium- n-butane mixture containing 2 mole percent n-butane and was passed through the reactor at a rate of 50 cc./minute. Analysis of the feedstock and the reactor effluen~ were carried out using conven~ional ga6 chromatography techniques. The reactor effluent was analyzed after lO minutes of on-stream operation.
The p~eudo-first-order rate constant (kA~
was calculated to determine the relative catalytic activity of the MnAPS0 compositions, The kA value (cm3/g min) obtained for the MnAPS0 compositions are set forth, below, in Table ~XV:

D-14,221 .

3~

TABLE ~X~
Prepared in Rate MnAPSO E~ample No.: Constant ~)*
~nAPSO-5 31 0.2 Mn~PSO-ll 25 0.6 MnAPSO-20 45 0.2 MnAPSO-31 55 1.3- 0.5 MnAPSO-39 11 ~.1 MnAPSO-35 21 0.1**
~nAPSO-36 59 0.3 MnAPSO-44 64 1.5 MnAPSO-47 49 1.7 * Prior to determination of the catalystic acti~ity of a given ~nAPSO, each was calcined as follows:
a) Mn-APSO-5 was calcined at 500C in air for 2 hours;
b~ MnAPSO-ll, MnAPSO-39 and MnAPSO-36 were calcined in situ c) MnAPSO-31 was calcined in air at 500C for 1.5 hours and then at 600C for 1 hour;
d) MnAPSO-35 was calcined at 500C in nitrogen for 1 hour; and e) ~nAPSO-20, MnAPSO-94 and MnAPSO-47 were calcined at 500C in air for 1 hour.
** Less than 0.1 PROCESS APPLICATIONS
The MnAPSO compositions o~ the present invention are, in general, hydrophilic and adsorh water preferentially over common hydrocarbon molecules such as paraffins~ olefins and aromatic species, e.g., benzene, xylenes and cumene. Thu~, the MnAPSOs as a class are useful as desiccants in such ad~orption separation/ purification processes as natural gas drying, cracked gas drying. Wa~er is also preferentially adsorbed over the so-called permanent gases such as carbon dioxide, nitrogen, D~14,221 ~LZ~ 5i3~

oxygen and hydrogen. These MnAPSOs are therefore suitably employed in the drying of reformer hydrogen ~treams and in the drying of oxygen, nitrogen or air prior to liquifaction.
T~e present ~nAPSO compositions al50 exhibit novel surface selectivity characteristics which render them useful as catalyst or ca~alys~
bases in a number of hydrocarbon conversion and oxidative combustion reactions. They can be impregnated or otherwise loaded with catalytically active metals by methods well known in the art and used, ~or example, in fabricating catalys~
compositions havin~ silica or alumina bases. Of the general class, those species having pores larger than about 4A are preferred for catalytic applica~ions.
Among the hydrocarbon conversion reactions ca~alyzed by MnAPSO compositions are cracking, hydrocracking, alkylation for both the aromatic and isoparaffin ~ypes,isomeri2ation including xylene isomerization~ polymerization, reforming, hydrogenation, dehydrogenation, transalkyla~ion, dealkylation, hydrodecycli2ation and dehydrocyclization.
Using MnAPSO catalyst composi~ions which contain a hydrogenation promoter such as platinum or palladium, heavy petroleum residual stocks, cyclic stocks and other hydrocrackable charge stocks, can be hydrocracked at temperatures in the range of 400F to 8259F using molar ratios oE hydrogen to hydrocarbon in the range of between 2 and 80, pressures between 10 and 3500 p.s.i.g., and a liquid D-14,221 .

3~
- 7a -hourly space velocity (LH5V) of from 0.1 ~o 20, preferably 1.0 to 10.
The MnAPS0 catalyst composi.tions employed in hydrocracking are also suitable for use in reforming processes in which the hydrocarbon Peedstocks contact the catalyst at temperatures of from about 700F to 1000F, hydrogen pressures o~
rom 100 to 500 p.s.i.g., LHSV values in the range of 0.1 to 10 and hydrogen to hydrocarbon molar ratios in the ran~e of 1 to 20, preferably between 4 and 12.
These same catalysts, i.e. those containing hydrogenation promoters, are also useful in hydroisomerizations processes in which feedstocks such as normal paraffins are converted to saturated branched chain isomers. Hydroisomerization is carried out at a temperature of from about ~00F to 600F, preferably 300F to 550F with an LHSV value of from about 0.2 to 1Ø Hydrogen is supplied to the reactor in admixturc with the hydrocarbon feedstock in mo}ar proportions (hydrogen to hydrocarbon) of between 1 and 5.
At somewhat higher temperatures, i.e. from about 650F to 1000F, preferably a5ooF to 950F and usually at somewhat lower pressures within the range of about 15 to 50 p.s.i.g., the same catalyst compositions are used ~o hydroisomerize normal paraffins. Preferably ~he paraffin feedstock comprises normal paraffins having a carbon number range of C7-C20. Contac~ time bet~een the feedstock and the catalyst is generally relatively short to avoid undesireable side reactions such as D-14,221 ~z~

olefin polymerization and paraffin crac~ing. ~SV
values in the range of 0.1 to 10, preferably 1.0 to 6.0 are suitable.
The unique crystal structurle of the present MnAPS0 catalysts and ~heir availability in a form totally ~oid of alkali ~etal content favor their use in the conversion of alkylaromatic compounds, particularly the catalytic disproportionation of toluene, ethylene, ~rimethyl benzenes, tetramethyl benzenes and the like. In the disproportiGnation process, isomerization and transalkylation can also occur. Group VIII noble metal adjuvants alone or in coDjunction with Group VI-B metals such as tungsten, molybdenum and chromium are preferably included in the catalyst composition in amounts of from about 3 to 15 weight-% of the overall composition.
Extraneous hydrogen can, but need not, be present in the reaction zone which is maintained at a tempera~ure of from about 400 to 750F, pressures in the range of 100 to 2000 p.s.i.g. and LHSV values in the range of 0.1 to 15.
Catalytic crackinq processes are preferably carried out with MnAPS0 compositions using feedstocks such as gas oils, heavy naphthas, deasphalted crude oil residua, etc., with gasoline being the principal desired product. Temperature conditions of 850 to 1100F, LHSV values of 0.5 to 10 and pressure condi~ions of from about 0 to S0 p.s.i.g. are suitable.
Dehydrocyclization reactions employing paraffinic hydrocarbon feedstocks, preferably normal paraffins having more than 6 carbon atoms, to form D-14,221 53~9 benzene. xylenes, toluene and the like ars carried out using essentially the same reaction conditions as for catalytic cracking. For these reactions it is preferred to use the MnAPS0 catalyst in conjunction wi~h a Group VIII non-noble metal cation such as cobalt and nickel.
In catalytic dealkylation wherein it is desired to cleave paraffinic side chains from aromatic nuclei without substantially hydrogenating the ring structure, relatively high temperatures in the range of about 800-1000F are employed at moderate hydrogen pressures of about 300-1000 p . 8 . i . g ., other conditions being similar to t~ose described above for catalytic hydrocracking.
Preferred catalysts are of She same type described above in connection with catalytic dehydrocyclization. Particularly desirable dealkylation reac~ions contemplated herein include the conversion of methylnaphthalene to naphthalene and toluene and/or xylenes to benzene.
In catalytic hydrofining, the primary objective is to promote the selective hydrodecomposition of organic sulfur and/or nitrogen compounds in the feed, without subs~antially affecting hydrocarbon molecules therein. For this purpose it is preferred to employ the same general conditions described above for catalytic hydrocracking, and catalysts of the same general nature described in connection with dehydrocyclization operations. Feedstocks include ga~oline Practions, kerosenes, je~ fuel frac~ions, diesel fractions, light and heavy gas oils, D-14,221 . . , i3q3 , deasphalted crude oil residual and ~he like any of which may contain up to about 5 weight-percent of sulfur and up to abou~ 3 weight-percent of nitrogen.
Similar conditions can be employed ~o effect hydrofininq, i.e., denitrogenation and desulfurization, of hydrocarbon feeds containing substantial proportions of organonitrogen and organosulfur compounds. It is generally recognized that the presence of substantial amounts of such constituents markedly inhibits the activity of hydrocracking catalysts. Consequently, it is necessary to operate at more extreme conditions when it is desired to obtain the same degree of hydrocracking conversion per pass on a relatively nitrogenous feed than are required with a feed containing less organonitrogen compounds.
Consequently, the conditions under which denitrogenation, desulfurization and~or hydrocracking can be most expeditiously accomplished in any given situation are necessarily determined in view of the characteristics of the feedstocks in par~icular the concentration of orsanoni~rogen compounds in the feedstock. As a rssult of the effect of organonitrogen compounds on the hydrocracking activity of these compositions it is not at all unlikely that the conditions most suitable for denitrogenation of a given feedstock having a relatively high organonitrogen content with minimal hydrocrackin~, e.g., less than 20 volume percent of fresh feed per pass, might be the same as those preferred for hydrocracking ano~her feedstock having a lower concentration of hydrocracking D-14,221 3~
- ~2 -inhibiting constituents e.g.. organonitrogen compounds. Consequently, it has become the practice in this art to establish the conditions under which a certain feed is to be con~acted on the basis of preliminary screening tests with the ~pecific catalyst and feedstock.
I~omerizati~n reactions are carried out under conditions ~imilar to those described above for reforming, using somewhat more acidic catalys~s. Olefins are prePerably isomerized at temperatures of 500-900F, while paraffins, naphthenes and alkyl aromatics are isomerized at temperatures of 700~-1000P. Particularly desirable i~omerization reactions contemplated herein include the conversion of n-heptene and/or n-octane to i60heptanes, iso-octanes, butane to iso-butane, methylcyclopentane to cyclohexane, meta-xylene and/or ortho-xylene to paraxylene, l-butene to 2-butene and/or isobutene, n-hexene to isohexene, cyclohexene to methylcyclopentene etc. The preferred form of the catalyst i8 a combination of the MnAPS0 with poly~alent ~etal compounds (such as sulfide6) of metals of Group II-A, Group II-~ and rare earth metals. For alkylation and dealkylation processes the MnAPSO compositions having pores of at least 5A are preferred. When employed for dealkylation oP alkyl aromatics, the temperature is usually at least 350F and ranges up to a temperature at which substantial cracking of the feed~tock or conversion products occurs, generally up to about 700F. The te~perature is preferably at leas~ 450~ and not greater than the critical D-14,221 53~
- ~3 -~emperature of the compound undergoing dealkylation. Pressure conditions are applied to retain at least the aromatic feed in the liquid state. For alkylation the temperature can be as low a~ 250~ but is preferably at lsast -~50F. In the alkylation of benzene, toluene and xylene, the preferred alkylating agents are olefins such as ethylene and propylene.

D-14,221

Claims (40)

1. Crystalline molecular sieves having three-dimensional microporous framework structures of MnO2, AlO2, PO2 and SiO2 tetrahedral oxide units having an empirical chemical composition on an anhydrous basis expressed by the formula:
mR : (MnwA1xPySiz)O2 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 (MnwAlxPySiz)O2 and has a value of zero to about 0.3; and "w", "x", "y"
and "z" represent the mole fractions of element manganese, 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.

2. Crystalline molecular sieves according to claim 1 wherein said mole fractions "w", "x", "y"
and "z" are within the tetragonal compositional area defined by points a, b. c and d of FIG. 2..

3. The crystalline molecular sieves of claims 1 or 2 having a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth in Table A.

4. The crystalline molecular sieves of claims 1 or 2 having a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth in Table B.

5. The crystalline molecular sieves of claims 1 or 2 having a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth in Table C.

6. The crystalline molecular sieves of claims 1 or 2 having a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth in Table D.

7. The crystalline molecular sieves of claims 1 or 2 having a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth in Table E.

8. The crystalline molecular sieves of claims 1 or 2 having a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth in Table F.

9. The crystalline molecular sieves of claims 1 or 2 having a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth in Table G.

10. The crystalline molecular sieves of claims 1 or 2 having a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth in Table H.

11. The crystalline molecular sieves of claims 1 or 2 having a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth in Table J.

12. The crystalline molecular sieves of claims 1 or 2 having a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth in Table K.

13. Process for preparing the crystalline molecular sieves of claim 1 having a three dimensional microporous framework structures which comprises reacting at an effective temperature and for an effective time a mixture composition expressed in terms of molar oxide ratios as follows:
aR : (MnwAlxPySiz) wherein "R" is an organic templating agent: "a" is the amount of "R" and is zero or 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 manganese, alumium, phosphorus and silicon in the (MnwAlxPySiz)O2 constituent, and each has a value of at least 0.01, whereby the molecular sieves of claim 1 are prepared.

14. Process according to claim 13 where "w", "x", "y" and "z" are within the area defined by points F, G, H, I and J of FIG.3.

15. Process according to claim 13 wherein the source of phosphorus in the reaction mixture is orthophosphoric acid.

16. Process according to claim 13 wherein the source of phosphorus in the reaction mixture is orthophosphoric acid and the source of aluminum is at least one compound selected from the group of pseudo-boehmite and aluminum alkoxide.

17. Process according to claim 16 wherein the aluminum alkoxide is aluminum isopropoxide.

18. Process according to claim 13 wherein the source of silicon is silica.

19. Process according to claim 13 wherein the source of manganese is selected from the group consisting of sulfates, carboxylates, chlorides, bromides, iodides and mixtures thereof.

20. Process according to claim 13 wherein the organic templating agent is a quaternary ammonium or quaternary phosphonium compound having the formula:
R4X+
wherein X is nitrogen or phosphorus and each R is an alkyl or aryl group containing from 1 to 8 carbon atoms.

21. Process according to claim 13 wherein the organic templating agent is an amine.

22. Process according to claim 13 or claim 14 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-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; pyrrolidine;
2-imidazolidone; di-n-propylamine; and a polymeric quaternary ammonium salt [(C14H32N2)(OH)2]x wherein x is a value of at least 2.

23. Molecular sieve prepared by calcining the compositions of claim 1 or claim 2 at a temperature sufficiently high to remove at least some of any organic templating agent present in the intracrystalline pore system.

24. Process for separating molecular species from admixture with molecular species having a lesser degree of polarity which comprises contacting said mixture of molecular species with a metal aluminophosphate composition of claim 1 having pore diameters large enough to adsorb at least one of the more polar molecular species, said molecular sieve at least partially activated whereby molecules of the more polar molecular species are selectively adsorbed into the intracrystalline pore system thereof.

25. Process for separating molecular species from admixture with molecular species having a lesser degree of polarity which comprises contacting said mixture of molecular species with a metal aluminophosphate composition of claim 2 having pore diameters large enough to adsorb at least one of the more polar molecular species, said molecular sieve at least partially activated whereby molecules of the more polar molecular species are selectively adsorbed into the intracrystalline pore system thereof.

26. Process for separating a mixture of molecular species having different kinetic diameters which comprises contacting said mixture with a metal aluminophosphate composition of claim 1 or claim 2 having pore diameters large enough to adsorb at least one but not all molecular species of said mixture, said molecular sieve being at least partially activated whereby at least some molecules whose kinetic diameters are sufficiently small can enter the intracrystalline pore system thereof.

27. Process according to claim 24 or 25 wherein the more polar molecular species is water.

28. Process for converting a hydrocarbon which comprises contacting said hydrocarbon under hydrocarbon converting conditions with a molecular sieve of claim 1.

29. Process for converting a hydrocarbon which comprises contacting said hydrocarbon under hydrocarbon converting conditions with a molecular sieve of claim 2.

30. Process according to claim 28 or 29 wherein the hydrocarbon conversion process is cracking.

31. Process according to claim 28 or 29 wherein the hydrocarbon conversion process is hydrocracking.

32. Process according to claim 28 or 29 wherein the hydrocarbon conversion process is hydrogenation.

33. Process according to claim 28 or 29 wherein the hydrocarbon conversion process is polymerization.

34. Process according to claim 28 or 29 wherein the hydrocarbon conversion process is alkylation.

35. Process according to claim 28 or 29 wherein the hydrocarbon conversion process is reforming.

36. Process according to claim 28 or 29 wherein the hydrocarbon conversion process is hydrotreating.

37. Process according to claim 28 wherein the hydrocarbon conversion process is isomerization.

38. Process according to claim 29 wherein the hydrocarbon conversion process is isomerization.

39. Process according to claim 37 or 38 wherein the isomerization conversion process is xylene isomerization.

40. Process according to claim 28 or 29 wherein the hydrocarbon conversion process is dehydrocyclization.