# Patent

## Title
Process for cooling crude coke oven gas

## Abstract

This application is a division of prior U.S. application Ser. No. 600,175, filing date Apr. 13, 1984, now U.S. Pat. No. 4,686,092.

## Background
The instant invention relates to a novel class of crystalline microporous molecular sieves, to the method of their preparation and to their use as adsorbents and catalysts. The invention relates to manganese-aluminum-phosphorus-silicon-oxide molecular sieves having manganese, aluminum, phosphorus and silicon in the form of framework tetrahedral oxides. These compositions may be prepared hydrothermally from gels containing reactive compounds of manganese, aluminum, phosphorus and silicon capable of forming framework tetrahedral oxides, and preferably at least one organic templating agent which functions in part to determine the course of the crystallization mechanism and the structure of the crystalline product.

Molecular sieves of the crystalline aluminosilicate zeolite type are well known in the art and now comprise over 150 species of both naturally occurring and synthetic compositions. In general the crystalline zeolites are formed from corner-sharing AlO.sub.2 and SiO.sub.2 tetrahedra and are characterized by having pore openings of uniform dimensions, having a significant ion-exchange capacity and being capable of reversibly desorbing an adsorbed phase which is dispersed throughout the internal voids of the crystal without displacing any atoms which make up the permanent crystal structure.

Other crystalline microporous compositions which are not zeolitic, i.e. do not contain AlO.sub.2 tetrahedra as essential framework constituents, but which exhibit the ion-exchange and/or adsorption characteristics of the zeolites are also known. Metal organosilicates which are said to possess ion-exchange properties, have uniform pores and are capable of reversibly adsorbing molecules having molecular diameters of about 6 .ANG. or less, are reported in U.S. Pat. No. 3,941,871 issued Mar. 2, 1976 to Dwyer et al. A pure silica polymorph, silicalite, having molecular sieving properties and a neutral framework containing neither cations nor cation sites is disclosed in U.S. Pat. No. 4,061,724 issued Dec. 6, 1977 to R. W. Grose et al.

A recently reported class of microporous compositions and the first framework oxide molecular sieves synthesized without silica, are the crystalline aluminophosphate compositions disclosed in U.S. Pat. No. 4,310,440 issued Jan. 12, 1982 to Wilson et al. These materials are formed from AlO.sub.2 and PO.sub.2 tetrahedra and have electrovalently neutral frameworks as in the case of silica polymorphs. Unlike the silica molecular sieve, silicalite, which is hydrophobic due to the absence of extra-structural cations, the aluminophosphate molecular sieves are moderately hydrophilic, apparently due to the difference in electronegativity between aluminum and phosphorus. Their intracrystalline pore volumes and pore diameters are comparable to those known for zeolites and silica molecular sieves.

In copending and commonly assigned application Ser. No. 400,438, filed July 26, 1982 (now U.S. Pat. No. 4,440,871, there is described a novel class of silicon-substituted aluminophosphates which are both microporous and crystalline. The materials have a three dimensional crystal framework of PO.sub.2.sup.+, Alo.sub.2.sup.- and SiO.sub.2 tetrahedral oxide units and, exclusive of any alkali metal or calcium which may optionally be present, an as-synthesized empirical chemical composition on an anhydrous basis of:

where "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the moles of "R" present per mole of (Si.sub.x Al.sub.y P.sub.z)O.sub.2 and has a value of from zero to 0.3, the maximum value in each case depending upon the molecular dimensions of the templating agent and the available void volume of the pore system of the particular silicoaluminophosphate species involved; and "x", "y", and "z" represent the mole fractions of silicon, aluminum and phosphorus, respectively, present as tetrahedral oxides. The minimum value for each of "x", "y", and "z" is 0.01 and preferably 0.02. The maximum value for "x" is 0.98; for "y" is 0.60; and for "z" is 0.52. These silicoaluminophosphates exhibit several physical and chemical properties which are characteristic of aluminosilicate zeolites and aluminophosphates.

In copending and commonly assigned application Ser. No. 480,738, filed Mar. 31, 1983 (now U.S. Pat. No. 4,500,651), there is described a novel class of titanium-containing molecular sieves whose chemical composition in the as-synthesized and anhydrous form is represented by the unit empirical formula:

wherein "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the moles of "R" present per mole of (Ti.sub.x Al.sub.y P.sub.z)O.sub.2 and has a value of between zero and about 5.0; and "x", "y" and "z" represent the mole fractions of titanium, aluminum and phosphorus, respectively, present as tetrahedral oxides.

In copending and commonly assigned application Ser. No. 514,334, filed July 15, 1983 (now U.S. Pat. No. 4,567,029), there is described a novel class of crystalline metal aluminophosphate having three-dimensional microporous framework structures of MO.sub.2, AlO.sub.2 and PO.sub.2 tetrahedral units and having an empirical chemical composition on an anhydrous basis expressed by the formula:

wherein "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the moles of "R" present per mole of (M.sub.x Al.sub.y P.sub.z)O.sub.2 and has a value of from zero to 0.3; "M" represents at least one metal of the group magnesium, manganese, zinc and cobalt; "x", "y" and "z" represent the mole fraction of the metal "M", aluminum and phosphorus, respectively, present as tetrahedral oxides.

In copending and commonly assigned application Ser. No. 514,335, filed July 15, 1983 (now U.S. Pat. No. 4,683,217), there is described a novel class of crystalline ferroaluminophosphates having a three-dimensional microporous framework structure of FeO.sub.2, AlO.sub.2 and PO.sub.2 tetrahedral units and having an empirical chemical composition on an anhydrous basis expressed by the formula:

wherein "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the moles of "R" present per mole of (Fe.sub.x Al.sub.y P.sub.z)O.sub.2 and has a value of from zero to 0.3; and "x", "y" and "z" represent the mole fraction of the iron, aluminum and phosphorus, respectively, present as tetrahedral oxides.

The instant invention relates to new molecular sieves comprising framework tetrahedral units of MnO.sub.2.sup.-2, AlO.sub.2.sup.- and PO.sub.2.sup.+ and SiO.sub.2.

FIG. 1 is a ternary diagram wherein parameters relating to the instant compositions are set forth as mole fractions.

FIG. 2 is a ternary 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.

The instant invention relates to a new class of molecular sieves having a three-dimensional microporous crystal framework structures of MnO.sub.2.sup.-2, AlO.sub.2.sup.-, PO.sub.2.sup.+ and SiO.sub.2 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 framework structures of MnO.sub.2.sup.-2, AlO.sub.2.sup.-, PO.sub.2.sup.+ and SO.sub.2 tetrahedral oxide units and have an empirical chemical composition on an anhydrous basis expressed by the formula:

wherein "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the molar amount of "R" present per mole of (Mn.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2 and 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 oxides. The instant molecular sieve compositions are characterized in several ways as distinct from heretofore known molecular sieves, including the aforementioned ternary compositions. The instant molecular sieves are characterized by the enhanced thermal stability of certain 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 of MnO.sub.2.sup.-2, AlO.sub.2.sup.-, PO.sub.2.sup.+ and SiO.sub.2 tetrahedral units. Actual class members will be identified 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.

The instant invention relates to a new class of molecular sieves having a three-dimensional microporous crystal framework structures of MnO.sub.2.sup.-2, AlO.sub.2.sup.-, PO.sub.2.sup.+ and SiO.sub.2 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 MnO.sub.2.sup.-2, AlO.sub.2.sup.-, PO.sub.2.sup.+, and SiO.sub.2 tetrahedral units having an empirical chemical composition on an anhydrous basis expressed by the formula:

wherein "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the molar amount of "R" present per mole of (Mn.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2 and 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. 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 and E of the ternary diagram of FIG. 1 and more preferably are generally defined as being within the tretragonal compositional area defined by points a, b, c and d of the ternary diagram of FIG. 2. Points A, B, C, D and E of FIG. 1 have the following values for "w", "x", "y", and "z": Mole Fraction Point    x            y      (w + z) ______________________________________ A        0.60         0.38   0.02 B        0.38         0.60   0.02 C        0.01         0.60   0.39 D        0.01         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 ______________________________________ p The MnAPSOs of this invention are useful as adsorbents, catalysts, ion-exchangers, and the like in much the same fashion as aluminosilicate have been employed heretofore, although their chemical and physical properties are not necessarily similar to those observed for aluminosilicates.

MnAPSO compositions are generally synthesized by hydrothermal crystallization from a reaction mixture containing reactive 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, and/or optionally an alkali or other metal. The reaction mixture 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 50.degree. C. and about 250.degree. C., and preferably between about 100.degree. C. and about 200.degree. C. until crystals of the MnAPSO product are obtained, usually a period of from several hours to several weeks. Typical effective times of from 2 hours to 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 MnAPSO compositions of the instant invention, it is preferred to employ a reaction mixture composition expressed in terms of the molar ratios as follows:

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 effective amount within 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", "y" and "z" represent the mole fractions of manganese, aluminum, phosphorus and silicon, respectively, and each has a value of at least 0.01.

In a preferred embodiment the reaction mixture is selected such that the mole fractions "w", "x", "y" and "z" are generally defined as being 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. 3 have the following values for "w", "x", "y" and "z": Mole Fraction Point    x            y      (w + z) ______________________________________ F        0.60         0.38   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         0.01   0.39 ______________________________________

For reasons unknown at present, not every reaction mixture gave crystalline MnAPSO products when reaction products were examined for MnAPSO products by X-ray analysis. Those reaction mixtures from which crystalline MnAPSO products were obtained are reported in the examples hereinafter as numbered examples. Those reaction mixtures from which MnAPSO products were not identified by use of X-ray analysis are also reported.

In the foregoing expression of the reaction composition, 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 P.sub.2 O.sub.5. This latter form is readily converted to the former form by routine calculations by dividing the number of moles of 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 sieves are formed the organic 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 least 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 R.sub.4 X.sup.+ 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 as [(C.sub.14 H.sub.32 N.sub.2) (OH).sub.2 ].sub.x wherein "x" has a value of at least 2 are also suitably employed. The 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 agent can either produce mixtures of the desired MnAPSOs or the more strongly directing templating species may control the course of the reaction with the other templating species serving primarily to establish the pH conditions of the reaction gel. Representative templating agents include: tetramethylammonium; 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; 1,4-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; di-n-butylamine, neopentylamine; di-n-pentylamine; isopropylamine; t-butylamine; ethylenediamine; pyrrolidine; and 2-imidazolidone. Not every templating agent will direct the formation of every species of MnAPSO, i.e., a single templating agent can, with proper manipulation of the reaction conditions, direct the formation of several MnAPSO compositions, and a given MnAPSO composition can be produced using several different templating agents.

Most any reactive silicon source may be employed such that SiO.sub.2 tetrahedral units are formed from a species present in situ. The reactive source of silicon may be silica, either as a silica sol or as fumed silica, reactive solid amorphous precipitated silica, silica gel, alkoxides of silicon, silicic acid or alkali metal silicate and the like.

The reactive 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 AlPO.sub.4 compositions of U.S. Pat. No. 4,310,440. Organo-phosphorus compounds, such as tetrabutylphosphonium bromide do not, apparently, serve as reactive sources of phosphorus, but these 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 isopropoxide, or pseudoboehmite. The crystalline or amorphous aluminophosphates which are a suitable source of phosphorus are, of course, also suitable sources of aluminum. Other sources of aluminum used in zeolite synthesis, such as gibbsite, sodium aluminate and aluminum trichloride, can be employed but are not preferred.

The source of manganese can be introduced into the 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 be employed herein include oxides, alkoxides, acetates, hydroxides, chlorides briomides, iodides, sulfates, nitrates, carboxylates and the like. For example, manganese acetate, manganese bromide, manganese sulfate, and the like are employable herein.

While not essential to the synthesis of MnAPSO compositions, stirring or other moderate agitation of the reaction mixture and/or seeding the reaction mixture with seed crystals of either the MnAPSO species to be produced or a topoligically similar aluminophosphate, aluminosilicate or molecular sieve composition, facilitates the crystallization procedure.

After crystallization the MnAPSO product may be isolated and advantageously washed with water and dried in air. The as-synthesized MnAPSO generally contains within its internal pore system at least one form of the templating agent employed in its formation. Most commonly any organic moiety derived from any organic template is present, at least in part, as a charge-balancing cation as is generally the case with as-synthesized 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 species, is too large to move freely through the pore system of the MnAPSO product and must be removed by calcining the MnAPSO at temperatures of 200.degree. C. to 700.degree. C. to thermally degrade the organic species. In a few instances the pores of the MnAPSO product are sufficiently large to permit transport of the templating agent, particularly if the latter is a small molecule, and accordingly complete or partial removal thereof can be accomplished by conventional desorption procedures such as carried out in the case of zeolites. It will be understood that the term "as-synthesized" as used herein does not include the condition of the MnAPSO phase wherein the organic moiety occupying the intracrystalline pore system as a result of the hydrothermal crystallization process has been reduced by post-synthesis treatment such that the value of "m" in the composition formula:

has a value of less than 0.02. The other symbols of the formula are as defined hereinabove. In those preparations in which an alkoxide is employed as the reactive source of manganese, aluminum, phosphorus or silicon, the corresponding alcohol is necessarily present in the 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 purpose of this application, however, this alcohol is arbitrarily omitted from the class of templating agents, even if it is present in the as-synthesized MnAPSO material.

Since the present MnAPSO compositions are formed from MnO.sub.2, AlO.sub.2, PO.sub.2 and SiO.sub.2 tetrahedral units which, respectively, have a net charge of -2, -1, +1 and 0. The matter of cation exchangeability is considerably more complicated than in the case of zeolitic molecular sieves in which, ideally, there is a stoichiometric relationship between AlO.sub.2.sup.- tetrahedra and charge-balancing cations. In the instant compositions, an AlO.sub.2.sup.- tetrahedron can be balanced electrically either by association with a PO.sub.2.sup.+ tetrahedron or a simple cation such as an alkali metal cation, a cation of manganese present in the reaction mixture, or an organic cation derived from the templating agent. Similarly an MnO.sub.2.sup.-2 tetrahedron can be balanced electrically by association with PO.sub.2.sup.+ tetrahedra, a cation of manganese, organic cations derived from 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 AlO.sub.2.sup.- and PO.sub.2.sup.- tetrahedral pairs can be balanced by Na.sup.+ and OH.sup.- respectively [Flanigen and Grose, Molecular Sieve Zeolites-I, ACS, Washington, DC (1971)]

The MnAPSO compositions of the present invention may exhibit cation-exchange capacity when analyzed using ion-exchange techniques heretofore employed with zeolitic aluminosilicates and have pore diameters which are inherent in the lattice structure of each species and which are at least about 3 .ANG. in diameter. Ion exchange of MnAPSO compositions is ordinarily possible only after the organic moiety present as a result of synthesis has been removed from the pore system. Dehydration to remove water present in the as-synthesized MnAPSO compositions can usually be accomplished, to some degree at least, in the usual manner without removal of the organic moiety, but the absence of the organic species greatly facilitates adsorption and desorption procedures. The MnAPSO materials will have various degrees of hydrothermal and thermal stability, some being quite remarkable in this regard, and will function as molecular sieve adsorbents and hydrocarbon conversion catalysts or catalyst bases.

The MnAPSOs are generally 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 the reagents and thereafter incorporating into these mixtures additional 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 some 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 was stirred until substantially homogeneous.

X-ray analysis of reaction products are obtained by X-ray analysis using standard X-ray powder diffraction techniques. The radiation source is a high-intensity, copper target, X-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 X-ray spectrometer scintillation counter, pulse height analyzer and strip chart recorder. Flat compressed powder samples are scanned at 2.degree. (2 theta) per minute, using a two second time constant. Interplanar spacings (d) in Angstrom units are obtained from the position of the diffraction peaks expressed as 2.theta. where .theta. is the Bragg angle as observed on the strip chart. Intensities are determined from the heights of diffraction peaks after subtracting background, "I.sub.o " being the intensity of the strongest line or peak, and "I" being the intensity of each of the other peaks. Alternatively, the X-ray patterns are obtained from the copper K-alpha radiation by use of computer based techniques using Siemens D-500 X-ray powder diffractometers, Siemens Type K-805 X-ray sources, available from Siemens Corporation, Cherry Hill, N.J., with appropriate computer interface.

As will be understood by those skilled in the art the determination of the parameter 2 theta is subject to both human and mechanical error, which in combination, can impose an uncertainty of about .+-.0.4.degree. on each reported value of 2 theta. This uncertainty is, of course, also manifested in the reported values of the d-spacings, which are calculated from the 2 theta values. This  imprecision is general throughout the art and is not sufficient to preclude the differentiation of the present crystalline materials from each other and from 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 respectively.

In certain instances the purity of a synthesized product may be assessed with reference to its X-ray powder diffraction pattern. Thus, for example, if a sample is stated to be pure, it is intended only that the X-ray pattern of the sample is 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 patterns and such may have one of the x-ray patterns set forth in the following Tables A through K, wherein said x-ray patterns are for both the as-synthesized and calcined forms unless otherwise noted: ______________________________________ (MnAPSO-5) 2.theta.     d (.ANG.) Relative Intensity ______________________________________ 7.3-7.7      12.11-11.48 vs 14.7-15.1    6.03-5.87 m 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 ______________________________________ ______________________________________ (MnAPSO-11) 2.theta.     d (.ANG.) 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 ______________________________________ ______________________________________ (MnAPSO-16) 2.theta.     d (.ANG.) Relative Intensity ______________________________________ 11.4-11.5    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 29.7-29.8    3.008-2.998 m ______________________________________ ______________________________________ (MnAPSO-20) 2.theta.     d (.ANG.)  Relative Intensity ______________________________________ 13.904-13.998 6.3692-6.3263 m-vs 19.723-19.818 4.5011-4.4918 m 24.223-24.329 3.6742-3.6584 vs 28.039-28.163 3.1822-3.1684 w 31.434-31.560 2.8458-2.8348 w 34.527-34.652 2.5976-2.5886 w ______________________________________ ______________________________________ (MnAPSO-31) 2.theta.     d (.ANG.)   Relative Intensity ______________________________________ 8.482-9.501  10.4240-9.3084 m 20.222- 20.353 4.3913-4.3632 m 21.879-21.993 4.0622-4.0415 m 22.071-22.088 4.0272-4.0242 m 22.587-22.698 3.9364-3.9174 vs 31.724-31.836 2.8546-2.8108 m ______________________________________ ______________________________________ (MnAPSO-34) 2.theta.     d (.ANG.) Relative Intensity ______________________________________ 9.4-9.6      9.41-9.21 vs 15.9-16.2    5.57-5.47 m 20.4-20.8    4.35-4.27 m-vs 25.0-25.3    3.562-3.520 w-m 31.0-31.3    2.885-2.858 w-m 33.6-33.9    2.667-2.644 m ______________________________________ ______________________________________ (MnAPSO-35) 2.theta.     d (.ANG.) Relative Intensity ______________________________________ 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    4.08-3.99 m-vs 28.2-28.7    3.164-3.110 m ______________________________________ ______________________________________ (MnAPSO-36) 2.theta.     d (.ANG.)   Relative Intensity ______________________________________ 7.596        11.6382     m 7.628-7.981  11.5899-11.0771 vs 8.105-8.299  10.9084-10.6537 m 16.395-16.673 5.4066-5.3172 m 19.052-19.414 4.6580-4.5721 w 20.744-20.871 4.2819-4.2560 m ______________________________________ ______________________________________ (MnAPSO-44) 2.theta.     d (.ANG.)  Relative Intensity ______________________________________ 9.420-9.498  9.3883-9.3110 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 2.8999-2.8981 m ______________________________________ ______________________________________ (MnAPSO-47) 2.theta.     d (.ANG.)  Relative Intensity ______________________________________ 9.434-9.696  9.3746-9.1214 vs 15.946-16.276 5.5579-5.4457 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 ______________________________________

In the following examples of the MnAPSO compositions were prepared using numerous reagents. The reagents employed and abbreviations employed herein, if any, for such reagents are as follows: of 30 weight percent SiO.sub.2 and 0.1 weight percent Na.sub.2 O; hydroxide; hydroxide;

The following preparative examples were carried out by forming a starting reaction mixture by adding the H.sub.3 PO.sub.4 to one half of the quantity of water. This mixture was mixed and to this mixture the aluminum isopropoxide or CATAPAL was added. This 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 minutes) until a homogeneous mixture was observed. A second mixture was prepared using the maganese 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 then 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 adjusted for temperature). The mixture was then placed in a lined (polytetrafluoroethylene) stainless steel pressure vessel and digested at a temperature (150.degree. C. or 200.degree. C.) for a time or placed in lined screw top bottles for digestion at 100.degree. C. All digestions 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. H.sub.3 PO.sub.4 and MnAc are given respectively in terms of P.sub.2 O.sub.5 and MnO content of the reaction mixture.

The following examples are provided to further illustrate the invention and are not intended to be limiting thereof:

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. ______________________________________ Temp    Time Example.sup.1 Template (.degree.C.) (days) MnAPSO Product.sup.2 ______________________________________ 1      TEAOH    150     4      MnAPSO-34; MnAPSO-5 2      TEAOH    150     11     MnAPSO-5; MnAPSO-34 3      TEAOH    200     4      MnAPSO-5; MnAPSO-34 4      TEAOH    200     11     MnAPSO-5; MnAPSO-34 5      TEAOH    100     2      --.sup.3 6      TEAOH    100     7      MnAPSO-34 7      TEAOH    150     2      MnAPSO-34; MnAPSO-5 8      TEAOH    150     7      MnAPSO-34; MnAPSO-5 9      TEAOH    200     2      MnAPSO-5; MnAPSO-34 10     TEAOH    200     7      MnAPSO-5; MnAPSO-34 11     TEAOH    100     14     MnAPSO-34 12     TEAOH    150     14     MnAPSO-34; MnAPSO-5 13     TEAOH    200     14     MnAPSO-5; MnAPSO-34 ______________________________________ .sup.1 The reaction mixture comprised: 1.0 TEAOH: 0.2 MnO: 0.9 Al.sub.2 O.sub.3 : 0.9 P.sub.2 O.sub.5 : rSiO.sub.2 : 50 H.sub.2 O where "r" was 0.2 for examples 1 to 4 and was 0.6 for examples 5 to 13. .sup.2 Major species as indentified by xray powder diffraction pattern of product, except that when two species where indentified the first species listed is the predominant species observed. .sup.3 No MnAPSO products were observed by xray analysis. ______________________________________ Temp    Time Example.sup.1 Template (.degree.C.) (days) MnAPSO Product.sup.2 ______________________________________ 14     Quin     150     4     MnAPSO-16; MnAPSO-35 15     Quin     150     11    MnAPSO-16; MnAPSO-35 16     Quin     200     4     MnAPSO-16; MnAPSO-35 17     Quin     200     11    MnAPSO-16; MnAPSO-35 18     Quin     100     4     MnAPSO-35 19     Quin     100     11    MnAPSO-35 20     MQuin    150     2     MnAPSO-35; MnAPSO-16 21     MQuin    150     7     MnAPSO-35 22     MQuin    200     2     MnAPSO-35 23     MQuin    200     7     MnAPSO-35 24     Pr.sub.2 NH 150     4     MnAPSO-11 25     Pr.sub.2 NH 150     11    MnAPSO-11 26     Pr.sub.2 NH 200     4     MnAPSO-11; MnAPSO-39 27     Pr.sub.2 NH 200     11    MnAPSO-11; MnAPSO-39 28     Pr.sub.2 NH 100     4     --3 29     Pr.sub.2 NH 100     11    --3 ______________________________________ .sup.1 The reaction mixture comprised: 1.0 R: 0.2 MnO: 0.9 Al.sub.2 O.sub.3 : 0.9 P.sub.2 O.sub.5 : 0.2 SiO.sub.2 : 50 H.sub.2 O where "R"is the template, as indentified in Table II .sup.2 Major species as indentified by xray powder diffraction pattern of product, except that when two species where identified the first species listed is the predominant species observed. .sup.3 No MnAPSO products were observed by xray analysis. ______________________________________ Temp    Time Example.sup.1 Template (.degree.C.) (days) MnAPSO Product .sup.2 ______________________________________ 30     Pr.sub.3 N 150     4     MnAPSO-5 31     Pr.sub.3 N 150     11    MnAPSO-5 32     Pr.sub.3 N 200     4     MnAPSO-5 33     Pr.sub.3 N 200     11    MnAPSO-5 34     Pr.sub.3 N 100     4     --3 35     Pr.sub.3 N 100     11    --3 36     TBAOH    150     4     --3 37     TBAOH    150     10    --3 38     TBAOH    200     4     MnAPSO-5 39     TBAOH    200     10    MnAPSO-5 40     C-hex    150     3     MnAPSO-13 41     C-hex    150     9     MnAPSO-44; MnAPSO-13 42     C-hex    200     3     MnAPSO-5; MnAPSO-44 43     C-hex    200     9     MnAPSO-5; MnAPSO-44 ______________________________________ .sup.1 The reaction mixture comprised: (a) Examples 30 to 35: 1.0 Pr.sub.3 N; 0.2 MnO; 0.9 Al.sub.2 O.sub.3 ; 0. P.sub.2 O.sub.5 ; 0.2 SiO.sub.2 ; 50 H.sub.2 O (b) Examples 36 to 39: 2.0 TBAOH; 0.4 MnO; 0.8 Al.sub.2 O.sub.3 ; 1.0 P.sub.2 O.sub.5 ; 0.4 SiO.sub.2 ; 50 H.sub.2 O (c) Examples 40 to 43: 1.0 Chex; 0.2 MnO; 0.9 Al.sub. 2 O.sub.3 ; 0.9 P.sub.2 O.sub.5 ; 0.6 SiO.sub.2 ; 50 H.sub.2 O .sup.2 Major species as identified by xray powder diffraction pattern of product, except that when two species where identified the first species listed is the predominant species observed. .sup.3 No MnAPSO products were observed by xray analysis. ______________________________________ Temp    Time Example.sup.1 Template (.degree.C.) (days) MnAPSO Product.sup.2 ______________________________________ 44     TPAOH    150     2     MnAPSO-5 45     TPAOH    200     2     MnAPSO-5 46     TMAOH    150     4     MnAPSO-20 47     TMAOH    200     4     MnAPSO-20 48     DEA      150     9     MnAPSO-47 49     DEA      150     18    MnAPSO-47 50.sup.4 Pr.sub.2 NH 150     4     MnAPSO-31 51.sup.4 Pr.sub.2 NH 150     10    MnAPSO-31; MnAPSO-46 52.sup.4 Pr.sub.2 NH 200     4     MnAPSO-31; MnAPSO-11 53.sup.4 Pr.sub.2 NH 200     10    MnAPSO-31; MnAPSO-11 54.sup.4 Pr.sub.2 NH 150     2     MnAPSO-31 55.sup.4 Pr.sub.2 NH 150     2     MnAPSO-31 56.sup.4 Pr.sub.2 NH 200     2     MnAPSO-31; MnAPSO-11 57     Pr.sub.2 NH 200     25    MnAPSO-11; MnAPSO-5; MnAPSO-39; MnAPSO-46 58     Quin     225     5     MnAPSO-16; MnAPSO-35 59.sup.5 Pr.sub.3 N 150     2     MnAPSO-36 60.sup.5 Pr.sub.3 N 150     7     MnAPSO-36; MnAPSO-5 61.sup.5 Pr.sub.3 N 200     2     MnAPSO-36; MnAPSO-5 62.sup.5 Pr.sub.3 N 200     7     MnAPSO-36; MnAPSO-5 63     C-hex    225     5     MnAPSO-5; MnAPSO-44 64     C-hex    200     4     MnAPSO-44 ______________________________________ .sup.1 reaction mixtures comprised: 1.0 R; 0.2 MnO: 0.9 Al.sub.2 O.sub. 3 : 0.9 P.sub.2 O.sub.5 : 0.6 SiO.sub.2 : 50 H.sub.2 O where R is as above identified and except than in examples 48, 49, 57 and 64 moles of "R"was 2.0 and in example 58 the coefficient for P.sub.2 O.sub.5 was 1.0 instead of 0.9. .sup.2 Major species as identified by xray powder diffraction pattern of product, except that when two species where identified the first species listed is the predominant species observed. .sup.3 No MnAPSO products were observed by xray analysis. .sup.4 Seed crystals of AlPO.sub.431 were employed (U.S. Pat. No. 4,310,440). .sup.5 Seed crystals MnAPO36 were employed, as disclosed in U.S. Ser. No. 514,334, filed July 15, 1983.

(a) Samples of the MnAPSO products were calcined in air or nitrogen to remove at least part of the organic templating agent of the product. The example in which a given MnAPSO product was prepared is given in parenthesis. The adsorption capacities of each calcined sample were measured using a standard McBain-Bakr gravimetric adsorption apparatus. The samples were activated in a vacuum (less than 0.04 torr) at 350.degree. C. prior to measurement. The McBain-Bakr data for the aforementioned MnAPSO molecular sieves are set forth hereinafter:

(a) MnAPSO-5 (Example 31): Kinetic    Pressure  Temp   Wt. % Adsorbate Diameter, .ANG. (Torr)    (.degree.C.) Adsorbed* ______________________________________ O.sub.2  3.46       102       -183   8.9 O.sub.2  3.46       750       -183   10.8 n-butane 4.3        504       23.0   4.4 cyclohexane 6.0        65        23.4   5.4 H.sub.2 O 2.65       4.6       23.0   8.1 H.sub.2 O 2.65       19.5      23.0   17.1 ______________________________________ *MnAPSO-5 was calcined at 600.degree. C. in air for 4 hours.

The above data demonstrate that the pore size of the calcined MnAPSO-5 product is greater than 6.2 .ANG..

(b) MnAPSO-11 (Example 24): Kinetic    Pressure  Temp   Wt. % Adsorbate Diameter, .ANG. (Torr)    (.degree.C.) Adsorbed* ______________________________________ O.sub.2  3.46       106       -183   7.0 O.sub.2  3.46       744       -183   11.1 neopentane 6.2        741       25.3   2.5 isobutane 5.0        740       24.2   3.5 cyclohexane 6.0        82        23.9   10.7 H.sub.2 O 2.65       4.6       24.9   5.1 H.sub.2 O 2.65       19        24.8   14.9 ______________________________________ *MnAPSO was calcined at 600.degree. in air for 2 hours.

The above data demonstrate that the pore size of the calcined MnAPSO-11 product is about 6.0 .ANG..

(c) MnAPSO-20 (Example 46): Kinetic    Pressure Temp   Wt. % Adsorbate Diameter, .ANG. (Torr)   (.degree.C.) Adsorbed* ______________________________________ O.sub.2  3.46       102      -183   0.7 O.sub.2  3.46       744      -183   1.2 H.sub.2 O 2.65       4.6      23.3   9.0 H.sub.2 O 2.65       19       23.2   13.7 ______________________________________ *MnAPSO calcined at 500.degree. C. in air for 1 hour.

The above data demonstrate that the pore size of the calcined MnAPSO-20 product is greater than about 2.65 .ANG. and less than about 3.46 .ANG..

(d) MnAPSO-31 (Example 55): Kinetic    Pressure Temp   Wt. % Adsorbate Diameter, .ANG. (Torr)   (.degree.C.) Adsorbed* ______________________________________ O.sub.2  3.46       105      -183   5.6 O.sub.2  3.46       741      -183   9.7 Neopentane 6.2        739      23.5   4.6 H.sub.2 O 2.65       4.6      23.8   5.8 H.sub.2 O 2.65       20       24.0   15.5 ______________________________________ *MnAPSO-31 calcined at 500.degree. C. in air for 1.5 hours.

The above data demonstrate that the pore size of the calcined MnAPSO-31 product is greater than about 6.2 .ANG..

(e) MnAPSO-34 (Example 11): Kinetic    Pressure Temp   Wt. % Adsorbate Diameter, .ANG. (Torr)   (.degree.C.) Adsorbed* ______________________________________ O.sub.2  3.46       103      -183   11.4 O.sub.2  3.46       731      -183   15.6 isobutane 5.0        741      24.5   0.8 n-hexane 4.3        103      24.4   4.6 H.sub.2 O 2.65       4.6      24.4   15.2 H.sub.2 O 2.65       18.5     23.9   24.4 ______________________________________ *MnAPSO-34 was calcined at 425.degree. C. in nitrogen for 2 hours.

The above data demonstrate that the pore size of the calcined MnAPSO-34 product is about 4.3 .ANG..

(f) MnAPSO-35 (Example 21): Kinetic    Pressure Temp   Wt. % Adsorbate Diameter, .ANG. (Torr)   (.degree.C.) Adsorbed* ______________________________________ O.sub.2  3.46       103      -183   1.8 O.sub.2  3.46       731      -183   2.6 n-hexane 4.3        103      24.4   0.8 H.sub.2 O 2.65       4.6      24.4   9.9 H.sub.2 O 2.65       18.5     23.9   15.9 ______________________________________ *MnAPSO-35 was calcined at 500.degree. C. in nitrogen for 2 hours.

The above data demonstrate that the pore size of the calcined MnAPSO-35 product is about 4.3 .ANG..

(g) MnAPSO-44 (Example 64): Kinetic    Pressure Temp   Wt. % Adsorbate Diameter, .ANG. (Torr)   (.degree.C.) Adsorbed* ______________________________________ O.sub.2  3.46       102      -183   18.2 O.sub.2  3.46       744      -183   20.1 n-hexane 4.3        .95      23.6   1.3 isobutane 5.0        746      24.1   0.5 H.sub.2 O 2.65       4.6      24.8   22.7 H.sub.2 O 2.65       19       29.8   27.7 ______________________________________ *MnAPSO-44 was calcined at 500.degree. C. in air for 1.0 hour.

The above data demonstrate that the pore size of the calcined MnAPSO-44 product about 4.3 .ANG..

Samples of the as-synthesized products of certain examples were subjected to chemical analysis. The example in which a given MnAPSO was prepared is noted in parenthesis. The chemical analysis for these MnAPSOs was as follows:

(a) The chemical analysis for MnAPSO-5 (Example 31) was: Component     Weight Percent ______________________________________ Al.sub.2 O.sub.3 31.8 P.sub.2 O.sub.5 46.4 MnO           4.1 SiO.sub.2     3.0 Carbon        5.2 LOI*          14.5 ______________________________________ *LOI = Loss on Ignition

The above chemical analysis gives an overall product composition in molar oxide ratios (anhydrous basis) of: 0.058 MnO; 0.312 Al.sub.2 O.sub.3 : 0.327 P.sub.2 O.sub.5 : 0.050 SiO.sub.2 ; and a formula (anhydrous basis) of:

(b) The chemical analysis of MnAPSO-11 (Example 24) was: Component     Weight Percent ______________________________________ Al.sub.2 O.sub.3 32.5 P.sub.2 O.sub.5 46.7 MnO           4.3 SiO.sub.2     2.1 Carbon        4.1 LOI*          14.0 ______________________________________ *LOI = Loss on Ignition

The above chemical analysis gives an overall product composition in molar oxide ratios (anhydrous basis) of: 0.061 MnO; 0.319 Al.sub.2 O.sub.3 ; 0.329 P.sub.2 O.sub.5 ; 0.035 SiO.sub.2 ; and a formula (anhydrous basis) of:

(c) The chemical analysis for MnAPSO-20 (Example 46) was: Component     Weight Percent ______________________________________ Al.sub.2 O.sub.3 27.3 P.sub.2 O.sub.5 39.6 MnO           4.6 SiO.sub.2     8.0 Carbon        8.4 LOI*          19.4 ______________________________________ *LOI = Loss on Ignition

The above chemical anslysis gives an overall product composition in molar oxide ratios (anhydrous basis) of: 0.065 MnO; 0.268 Al.sub.2 O.sub.3 ; 0.279 P.sub.2 O.sub.5 : 0.133 SiO.sub.2 ; and a formula (anhydrous basis) of:

(d) The chemical analysis of MnAPSO-31 was: Component     Weight Percent ______________________________________ Al.sub.2 O.sub.3 31.8 P.sub.2 O.sub.5 43.8 MnO           3.2 SiO.sub.2     2.6 Carbon        2.9 LOI*          16.7 ______________________________________ *LOI = Loss on Ignition

The above chemical analysis gives an overall product composition in molar oxide ratios (anhydrous basis) of: 0.058 MnO; 0.312 Al.sub.2 O.sub.3 ; 0.309 P.sub.2 O.sub.5 ; 0.043 SiO.sub.2 ; and a formula (anhydrous basis) of:

(e) The chemical analysis of MnAPSO-34 (Example 6) was: Component     Weight Percent ______________________________________ Al.sub.2 O.sub.3 25.0 P.sub.2 O.sub.5 35.8 MnO           7.9 SiO.sub.2     11.6 Carbon        3.3 LOI*          19.7 ______________________________________ *LOI = Loss on Ignition

The above chemical analysis gives an overall product composition in molwar oxide ratios (anhydrous basis) of: 0.11 MnO; 0.25 Al.sub.2 O.sub.3 ; 0.19 P.sub.2 O.sub.5 ; 0.19 SiO.sub.2 ; and a formula (anhydrous basis) of:

(f) The chemical analysis of MnAPSO-35 (Example 23) was: Component     Weight Percent ______________________________________ Al.sub.2 O.sub.3 25.2 P.sub.2 O.sub.5 41.3 MnO           7.1 SiO.sub.2     4.2 Carbon        12.8 LOI*          21.3 ______________________________________ *LOI = Loss on Ignition

The above chemical analysis gives an overall product composition in molar oxide ratios (anhydrous basis) of: 0.100 MnO; 0.247 Al.sub.2 O.sub.3 ; 0.291 P.sub.2 O.sub.5 ; 0.07 SiO.sub.2 ; and a formula (anhydrous basis) of:

(g) The chemical analysis of MnAPSO-36 (Example 59) was: Component     Weight Percent ______________________________________ Al.sub.2 O.sub.3 27.7 P.sub.2 O.sub.5 37.2 MnO           4.6 SiO.sub.2     9.5 Carbon        3.0 LOI*          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 Al.sub.2 O.sub.3 ; 0.262 P.sub.2 O.sub.5 ; 0.158 SiO.sub.2 ; and a formula (anhydrous basis) of:

(h) The chemical analysis of MnAPSO-44 (Example 64) was: Component     Weight Percent ______________________________________ Al.sub.2 O.sub.3 25.8 P.sub.2 O.sub.5 36.6 MnO           4.4 SiO.sub.2     9.7 Carbon        2.5 LOI*          23.1 ______________________________________ *LOI = Loss on Ignition

The above chemical analysis gives an overall product composition in molar oxide ratios (anhydrous basis) of: 0.062 MnO; 0.253 Al.sub.2 O.sub.3 ; 0.258 P.sub.2 O.sub.5 ; 0.161 SiO.sub.2 ;; and a formula (anhydrous basis) of:

(i) The chemical analysis of MnAPSO-47 (Example 49) was: Component     Weight Percent ______________________________________ Al.sub.2 O.sub.3 27.6 P.sub.2 O.sub.5 36.2 MnO           5.0 SiO.sub.2     5.7 Carbon        9.9 LOI*          25.1 ______________________________________ *LOI = Loss on Ignition

The above chemical analysis gives an overall product composition in molar oxide ratios (anhydrous basis) of: 0.071 MnO; 0.271 Al.sub.2 O.sub.3 ; 0.255 P.sub.2 O.sub.5 ; 0.095 SiO.sub.2 ; and a formula (anhydrous basis) of:

EDAX (energy dispersive analysis by x-ray) microprobe analysis in conjunction with SEM (scanning electron microscope) was carried out on clear crystals from the products of certain examples, as identified in parenthesis hereinafter. Analysis of crystals having a morphology characteristic of each MnAPSO product gave the following analysis based on relative peak heights:

(a) MnAPSO-5 (Example 4): Average of Spot Probes ______________________________________ Mn        0.5 Al        8.0 P         9.5 Si        0.7 ______________________________________

(b) MnAPSO-11 (Example 24): Average of Spot Probes ______________________________________ Mn        1.0 Al        8.0 P         9.5 Si        1.5 ______________________________________

(c) MnAPSO-20 (Example 46): Average of Spot Probes ______________________________________ Mn        0.8 Al        8.2 P         9.4 Si        1.7 ______________________________________

(d) MnAPSO-34 (Example 6): Average of Spot Probes ______________________________________ Mn        1.3 Al        7.0 P         9.0 Si        1.5 ______________________________________

(e) MnAPSO-35 (Example 23): Average of Spot Probes ______________________________________ Mn        1.0 Al        7.0 P         10.0 Si        1.2 ______________________________________

(f) MnAPSO-36 (Example 59): Average of Spot Probes ______________________________________ Mn        0.8 Al        9.3 P         9.9 Si        1.6 ______________________________________

(g) MnAPSO-44 (Example 42): Average of Spot Probes ______________________________________ Mn        0.7 Al        9.0 P         10.0 Si        1.7 ______________________________________

(h) MnAPSO-44 (Example 64): Average of Spot Probes ______________________________________ Mn        1.1 Al        8.7 P         10.0 Si        5.6 ______________________________________

(i) MnAPSO-47 (Example 49): Average of Spot Probes ______________________________________ Mn        1.0 Al        9.0 P         9.5 Si        1.9 ______________________________________

(a) The MnAPSO-5, prepared in Example 31, was subjected to x-ray analysis. The MnAPSO-5 was impure but the major phase was determined to have an x-ray powder diffraction pattern characterized by the following data: 2.theta.      d, (.ANG.) I/Io .times. 100 ______________________________________ 6.9*          12.81   13 7.5           11.79   100 8.0*          11.05   5 9.1*          9.72    4 9.3*          9.51    4 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          3.440   42 29.0          3.079   18 30.0          2.979   34 33.6          2.667   8 34.5          2.600   21 36.9          2.436   4 37.7          2.386   10 41.5          2.176   5 42.1          2.146   5 42.2          2.141   5 42.6          2.122   5 43.5          2.080   3 44.9          2.019   3 47.5          1.914   7 51.4          1.778   5 51.9          1.762   3 55.5          1.656   5 ______________________________________ *Peak may contain an impurity

(b) A portion of the as-synthesized MnAPSO-5 of part (a) was calcined in air at 500.degree. C. for about two (2) hours. The calcined product was characterized by the following x-ray powder diffraction pattern: 2.theta.       d, (.ANG.) I/Io .times. 100 ______________________________________ 7.4            11.95   100 *7.8           11.33   4 12.9           6.86    25 15.0           5.91    21 *16.5          5.37    3 *16.7          5.31    3 *17.5          5.07    5 19.8           4.48    40 21.2           4.19    40 22.5           3.95    43 26.0           3.427   30 29.1           3.069   11 30.1           2.969   35 33.7           2.660   5 34.6           2.592   19 37.1           2.423   4 37.9           2.374   6 42.5           2.127   4 43.1           2.099   3 46.0           1.973   3 47.9           1.899   5 55.8           1.647   4 ______________________________________ *Peak may contain an impurity

(c) The species denominated herein as MnAPSO-5 is a molecular sieve having a three dimensional microporous crystalline framework structure of MnO.sub.2.sup.-2, AlO.sub.2.sup.-, PO.sub.2.sup.+ and SiO.sub.2 tetrahedral oxide units and have an empiracal chemical composition on an anhydrous basis expressed by the formula:

wherein "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the molar amount of "R" present per mole of (Mn.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2 and 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 MnAPSO-5 having a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth in Table V as follows: ______________________________________ 2.theta.    d, (.ANG.) Relative Intensity ______________________________________ 7.3-7.7     12.11-11.48 vs 14.7-15.1   6.03-5.87 m 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) All of the MnAPSO-5 compositions, both as-synthesized and calcined, for which x-ray power diffraction data have presently been obtain have patterns which are within the generalized pattern of Table VI below: ______________________________________ 2.theta.      d, (.ANG.) I/Io .times. 100 ______________________________________ 7.3-7.7       12.11-11.48 100 12.7-13.0     6.97-6.81 14-27 14.7-15.1     6.03-5.87 20-60 19.6-19.9     4.53-4.46 36-51 20.8-2l.3     4.27-4.17 29-58 22.1-22.6     4.02-3.93 30-75 24.5-24.7     3.63-3.60 4-6 25.7-26.1     3.466-3.414 25-42 28.8-29.2     3.100-3.058 10-30 29.8-30.2     2.998-2.959 34-50 33.4-33.8     2.683-2.652 4-10 34.3-34.7     2.614-2.585 19-44 36.7-37.2     2.449-2.417 3-4 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     2.151-2.141 3-5 42.4-42.6     2.132-2.122 3-5 43.1-43.5     2.099-2.080 3-5 44.7-44.9     2.027-2.019 3-5 46.0-46.1     1.973-1.969 3-4 47.3-47.6     1.922-1.910 5-7 47.9-48.0     1.899-1.895 4-5 51.2-51.4     1.784-1.778 5-7 51.7-51.9     1.768-1.762 3-5 55.3-55.9     1.661-1.645 2-7 ______________________________________

(a) MnAPSO-11, as prepared in example 24, was subjected to x-ray analysis. The MnAPSO-11 was determined to have an x-ray powder diffraction pattern characterized by the following data: 2.theta.      d, (.ANG.) I/Io .times. 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 28.3          3.153   13 28.6          3.121   23 29.5          3.028   13 31.5          2.84    16 32.8          2.730   23 34.2          2.622   16 35.4          2.54    10 35.8          2.508   10 36.3          2.475   10 37.5          2.398   13 37.8          2.370   16 39.4          2.287   10 42.9          2.108   10 44.8          2.023   10 48.8          1.866   3 50.6          1.804   10 54.6          1.681   10 ______________________________________

(b) A portion of the as-synthesized MnAPSO-11 of part (a) was calcined in air at 600.degree. C. for about two (2) hours. The calcined product was characterized by the following x-ray powder diffraction pattern: 2.theta.      d, (.ANG.) I/Io .times. 100 ______________________________________ 8.1           10.92   33 9.8           9.03    60 11.8          7.50    13 12.8          6.92    27 13.5          6.56    13 14.8          5.99    sh 16.1          5.51    67 19.5          4.55    27 19.9          4.46    40 20.4          4.35    33 21.5          4.13    73 21.8          4.08    100 22.2          4.00    73 22.4          3.97    80 23.5          3.79    73 24.3          3.66    27 25.8          3.453   33 26.7          3.339   27 27.3          3.267   33 27.8          3.209   33 28.5          3.132   27 29.5          3.028   33 29.8          2.998   40 30.4          2.940   27 31.8          2.814   20 32.6          2.747   33 34.0          2.637   20 35.5          2.529   27 37.1          2.423   20 37.4          2.404   20 38.2          2.356   20 38.6          2.332   27 41.0          2.201   20 ______________________________________

(c) The species denominated herein as MnAPSO-11 is a molecular sieve having a three dimensional microporous crystalline framework structure of MnO.sub.2.sup.-2, AlO.sub.2.sup.-, PO.sub.2.sup.+ and SiO.sub.2 tetrahedral oxide units and have an empirical chemical composition on an anhydrous basis expressed by the formula:

wherein "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the molar amount of "R" present per mole of (Mn.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2 and has a value of zero to about 0.3; and "w", "x", "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 MnAPSO-11 having a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth in Table VII as follows: ______________________________________ 2.theta.     d, (.ANG.) Relative Intensity ______________________________________ 9.4-9.8      9.41-9.03 m 16.1-16.2    5.50-5.47 vw-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 .sup. 23.1-23.5    3.85-3.79 m ______________________________________

(d) All of the MnAPSO-11 compositions, both as-synthesized and calcined, for which x-ray powder diffraction data have presently been obtain have patterns which are within the generalized pattern of Table VIII below: ______________________________________ 2.theta.      d, (.ANG.) I/Io .times. 100 ______________________________________ 8.0-8.1       11.05-10.92 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 16.1-16.2     5.50-5.47  8-67 19.0-19.5     4.68-4.55  8-27 19.9          4.46      40 20.4-20.5     4.35-4.33 33-45 21.0-21.5     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 22.6-22.7     3.93-3.92 61 23.1-23.5     3.85-3.79 69-73 24.3-24.5     3.66-3.63 11-27 24.7-24.8     3.60-3.59 11-16 24.9-25.0      3.58-3.562 sh-13 25.8          3.453     33 26.3-26.7     3.389-3.339 25-27 27.3          3.267     33 27.8          3.209     33 28.2-28.3     3.164-3.153 11-13 28.5-28.6     3.132-3.121 22-27 29.4-29.5     3.038-3.028 11-33 29.8          2.998     40 30.4          2.940     27 31.4-31.8     2.849-2.814 14-20 32.6-32.8     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 8-10 36.2-26.3     2.481-2.475 8-10 37.1          2.423     20 37.4-37.5     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 41.0          2.201     20 42.8-42.9     2.113-2.108 8-10 44.7-44.8     2.027-2.023 8-10 48.7-48.8     1.870-1.866 3-5 50.5-50.6     1.807-1.804 8-10 54.5-54.6     1.684-1.681 8-10 ______________________________________

(a) MnAPSO-16, as prepared in example 14 was subjected to x-ray analysis. The MnAPSO-16 was determined to have an x-ray powder diffraction pattern characterized by the following data: 2.theta.       d, (.ANG.) I/Io .times. 100 ______________________________________ 8.6*           10.28   8 11.0*          8.04    23 11.4           7.76    48 13.3*          6.66    11 15.9*          5.57    5 17.3*          5.13    24 17.7*          5.01    8 18.7           4.75    40 21.1*          4.21    19 21.9**         4.06    100 23.0           3.87    13 23.2*          3.83    10 23.7*          3.75    5 25.1           3.548   5 26.6**         3.351   26 26.7*          3.339   (sh) 27.8           3.209   5 28.8*          3.100   15 29.0           3.079   15 29.8           2.998   24 32.0*          2.797   16 32.6           2.747   7 34.7**         2.585   10 35.7*          2.515   5 37.8           2.380   11 39.7           2.270   5 42.0*          2.151   5 44.2           2.049   5 48.5**         1.877   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 MnAPSO-16 of part (a) was calcined in nitrogen at 600.degree. C. for about 2 hours. The calcined product was characterized by the following x-ray powder diffraction pattern: 2.theta.       d, (.ANG.) I/Io .times. 100 ______________________________________ 11.5           7.69    100 13.3*          6.66    9 18.6           4.77    25 20.3*          4.37    44 20.5*          4.33    41 21.5*          4.13    66 21.9**         4.06    72 22.9           3.88    31 23.5*          3.79    13 26.5**         3.363   31 27.9           3.198   13 29.0           3.079   19 29.7           3.008   34 32.6           2.747   13 34.7**         2.585   13 35.6*          2.522   16 37.8           2.380   13 48.2**         1.888   9 ______________________________________ *Impurity Peak **Peak may contain impurity

(c) The species denominated herein as MnAPSO-16 is a molecular sieve having a three dimensional microporous crystalline framework structure of MnO.sub.2.sup.-2, AlO.sub.2.sup.-, PO.sub.2.sup.+ and SiO.sub.2 tetrahedral oxide units and have an empirical chemical composition on an anhydrous basis expressed by the formula:

wherein "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the molar amount of "R" present per mole of (Mn.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2 and 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 MnAPSO-16 having a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth in Table IX as follows: ______________________________________ 2.theta.     d, (.ANG.) Relative Intensity ______________________________________ 11.4-11.5    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 29.7-29.8    3.008-2.998 m ______________________________________

(d) All of the MnAPSO-16 compositions, both as-synthesized and calcined, for which x-ray power diffraction data have presently been obtain have patterns which are within the generalized pattern of Table X below: ______________________________________ 2.theta.       d, (.ANG.) I/Io .times. 100 ______________________________________ 11.4-11.5      7.76-7.69  48-100 18.6-18.7      4.77-4.75 25-40 21.9*         4.06      72-80 22.9-23.0      3.88-3.87 13-31 26.5-26.6*    3.363-3.351 26-31 27.8-27.9      3.209-2.198 5-13 29.0           3.079     15-19 29.7-29.8      3.008-2.998 24-34 32.6           2.747      7-14 34.7*         2.585      9-14 37.8           2.380     11-15 39.7           2.270     5-6 44.2           2.049     5-6 48.2-48.5*    1.888-1.877 9-12 49.4           1.845     4-5 52.4           1.746     4-5 54.7           1.678     4-5 ______________________________________ *Peak might contain an impurity

(a) MnAPSO-20, as prepared in example 46 was subjected to x-ray analysis. The MnAPSO-20 was determined to have an x-ray powder diffraction pattern characterized by the following data: 2.theta.      d, (.ANG.) I/Io .times. 100 ______________________________________ 14.0          6.35    49 19.8          4.49    43 22.1          4.02    3 23.7*         3.75    1 24.3          3.67    100 28.1          3.177   13 31.5          2.842   11 34.6          2.595   16 37.5          2.400   2 40.1          2.247   4 42.7          2.118   4 47.4          1.917   4 51.8          1.764   7 ______________________________________ *Peak may contain an impurity

(b) A portion of the as-synthesized MnAPSO-20 of part (a) was calcined in air at 500.degree. C. for about 1 hour. The calcined product was characterized by the following x-ray powder diffraction pattern: 2.theta.     d, (.ANG.) Relative Intensity ______________________________________ 7.1          12.51   2 14.0         6.33    100 19.8         4.48    40 22.2         4.00    4 24.3         3.66    99 28.2         3.168   17 31.6         2.835   15 34.7         2.589   17 40.2         2.243   3 42.7         2.116   4 47.5         1.913   4 ______________________________________

(c) The species denominated herein as MnAPSO-20 is a molecular sieve having a three dimensional microporous crystalline framework structure of MnO.sub.2.sup.-2, AlO.sub.2.sup.-, PO.sub.2.sup.+ and SiO.sub.2 tetrahedral oxide units and have an empirical chemical composition on an anhydrous basis expressed by the formula:

wherein "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the molar amount of "R" present per mole of (Mn.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2 and 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 MnAPSO-20 having a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth in Table XI as follows: ______________________________________ 2.theta.     d, (.ANG.) Relative Intensity ______________________________________ 13.904-13.998 6.3692-6.3263 m-vs 19.723-19.818 4.5011-4.1918 m 24.223-24.329 3.6742-3.6584 vs 28.039-28.163 3.1822-3.1684 w 31.434-31.560 2.8458-2.8348 w 34.527-34.652 2.5976-2.5866 w ______________________________________

(d) All of the MnAPSO-20 compositions, both as-synthesized and calcined for which x-ray power diffraction data have presently been obtain have patterns which are within the generalized pattern of Table XII below: ______________________________________ 2.theta.      d, (.ANG.) I/Io .times. 100 ______________________________________ 13.904-13.998 6.3692-6.3263 49-100 19.723-19.818 4.5011-4.4918 40-43 22.091-22.200 4.0236-4.0041 3-4 24.223-24.329 3.6742-3.6584 99-100 28.039-28.163 3.1822-3.1684 13-17 31.434-31.560 2.8458-2.8348 11-15 34.527-34.652 2.5976-2.5886 15-17 34.413-27.465 2.2501-2.4004 2 40.071-40.207 2.2501-2.2428 3-4 42.627-42.730 2.1209-2.1160 3-4 47.383-47.519 1.9185-1.9134 3-4 51.790-51.840 1.7652-1.7636 7 ______________________________________

(a) MnAPSO-31, as prepared in example 54 was subjected to x-ray analysis. MnAPSO-31 was determined to have an x-ray powder diffraction pattern characterized by the followiang data: 2.theta.      d, (.ANG.) I/Io .times. 100 ______________________________________ 7.9           11.22   4 8.6           10.27   61 17.2          5.17    5 18.5          4.81    4 20.4          4.36    49 21.2          4.19    4 22.0          4.04    30 22.1          4.02    32 22.7          3.92    100 25.3          3.526   5 25.8          3.459   3 28.1          3.181   12 29.8          2.995   6 31.8          2.812   22 35.2          2.548   9 36.2          2.482   3 37.3          2.411   3 37.8          2.382   3 38.3          2.353   3 38.4          2.346   3 39.4          2.285   3 39.8          2.266   3 40.3          2.241   3 46.8          1.942   3 48.8          1.866   2 51.8          1.766   5 55.6          1.654   2 ______________________________________

(b) A portion of the as-synthesized MnAPSO-31 of part (a) was calcined in air at 500.degree. C. for about 1.5 hours. The calcined product was characterized by the following x-ray powder diffraction pattern: 2.theta.      d, (.ANG.) I/Io .times. 100 ______________________________________ 8.6          10.31   58 14.8          5.98    4 17.1          5.18    9 18.5          4.81    4 20.4          4.36    52 22.1          4.03    44 22.7          3.92    100 25.3          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 35.3          2.546   11 36.3          2.477   6 37.3          2.409   3 37.8          2.383   3 38.3          2.348   3 39.4          2.289   4 40.3          2.236   3 45.4          2.000   3 46.8          1.942   5 47.6          1.909   4 48.9          1.864   3 51.7          1.767   6 ______________________________________

(c) The species denominated herein as MnAPSO-31 is a molecular sieve having a three dimensional microporous crystalline framework structure of MnO.sub.2.sup.-2, AlO.sub.2.sup.-, PO.sub.2.sup.+ and SiO.sub.2 tetrahedral oxide units and have an empirical chemical composition on an anhydrous basis expressed by the formula:

wherein "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the molar amount of "R" present per mole of (Mn.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2 and 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 MnAPSO-31 having a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth in Table XIII as follows: ______________________________________ 2.theta.     d, (.ANG.)  Relative Intensity ______________________________________ 8.482-9.501  10.4240-9.3084 m 20.222-20.353 4.3913-4.3632 m 21.879-21.993 4.0622-4.0415 m 22.071-22.088 4.0272-4.0242 m 22.587-22.698 3.9364-3.9174 vs 31.724-31.836 2.8546-2.8108 m ______________________________________

(d) All of the MnAPSO-31 compositions, both as-synthesized and calcined for which x-ray powder diffraction data have presently been obtain have patterns which are within the generalized pattern of Table XIV below: ______________________________________ 2.theta.      d, (.ANG.)  I/Io .times. 100 ______________________________________ 7.694-7.883   11.4904-11.2145 2-4 8.482-9.501   10.4240-9.3084 58-66 14.756-14.822 6.0034-5.9767 2-4 17.016-17.158 5.2105-5.1679 5-9 18.310-18.466 4.8451-4.8046 3-4 20.222-20.353 4.3913-4.3632 45-52 21.032-21.221 4.2238-4.1867 4-5 21.879-21.993 4.0622-4.0415 30-51 22.071-22.088 4.0272-4.0242 32-44 22.587-22.698 3.9364-3.9174 100 23.164-23.190 3.8398-3.8355 2-3 25.115-25.260 3.5457-3.5256 4-7 25.663-25.757 3.4712-3.4588 3-8 27.922-28.050 3.1953-3.1809 12-15 29.701-29.831 3.0078-2.9950 6-11 31.068-31.315 2.8785-2.8564 2-3 31.724-31.836 2.8564-2.8108 21-33 35.117-35.251 2.5553-2.5460 9-11 35.871        2.5033      1 36.070-36.261 2.4900-2.4730 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 2-3 38.334-38.367 2.3480-2.3461 3 39.285-39.442 2.2933-2.2845 3-4 39.654-39.772 2.2728-2.2663 2-4 40.111-40.337 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 1.8012-1.7989 2 51.588-51.766 1.7716-1.7659 4-6 55.410-55.557 1.6581-1.6541 2 ______________________________________

(a) MnAPSO-34, as prepared in example 11 was subjected to x-ray analysis. MnAPSO-34 was determined to have an x-ray powder diffraction pattern characterized by the following data: 2.theta.      d, (.ANG.) I/Io .times. 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          4.31    69 22.3          3.99    10 23.1          3.85     8 25.2          3.534   25 25.8          3.453   19 27.5          3.243   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    8 43.0          2.103    6 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 MnAPSO-34 of part (a) was calcined in nitrogen at 425.degree. C. for about 2 hours. The calcined product was characterized by the following x-ray powder diffraction pattern: 2.theta.      d, (.ANG.) I/Io .times. 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          4.65    5 20.8          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   4 28.3          3.153   5 29.7          3.008   4 30.7          2.912   17 31.3          2.849   11 32.4          2.763   3 34.6          2.592   5 36.2          2.481   4 38.8          2.321   3 39.8          2.265   3 43.1          2.099   3 43.6          2.076   3 47.8          1.903   1 49.0          1.859   3 51.0          1.791   3 53.3          1.719   4 54.6          1.681   3 ______________________________________

(c) The species denominated herein as MnAPSO-34 is a molecular sieve having a three dimensional microporous crystalline framework structure of MnO.sub.2.sup.-2, AlO.sub.2.sup.-, PO.sub.2.sup.+ and SiO.sub.2 tetrahedral oxide units and have an empirical chemical composition on an anhydrous basis expressed by the formula:

wherein "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the molar amount of "R" present per mole of (Mn.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2 and 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 MnAPSO-34 having a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth in Table XV as follows: ______________________________________ 2.theta.     d, (.ANG.) Relative Intensity ______________________________________ 9.4-9.6      9.41-9.21 vs 15.9-16.2    5.57-5.47 m 20.4-20.8    4.35-4.27  m-vs 25.0-25.3    3.562-3.520 w-m 31.0-31.3    2.885-2.858 w-m 33.6-33.9    2.667-2.644 m ______________________________________

(d) All of the MnAPSO-34 compositions, both as-synthesized and calcined for which x-ray power diffraction data have presently been obtain have patterns which are within the generalized pattern of Table XIV below: ______________________________________ 2.theta.      d, (.ANG.) I/Io .times. 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     5.57-5.47 15-44 17.9-18.1     4.96-4.90 15-32 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      5 22.9-23.2     3.88-3.83 7-16 25.0-25.3     3.562-3.520 15-36 25.8-26.0     3.453-3.427 12-19 27.3-27.7     3.267-3.220 4-28 28.2-28.5     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 33.6-33.9     2.667-2.644 23-32 34.3-34.6     2.614-2.592 5-12 36.2-36.4     2.481-2.468 4-16 38.8          2.321     3 39.8          2.265     3 43.0-43.1     2.103-2.099 3-12 43.5-43.6     2.080-2.076 3-12 47.4-47.8     1.918-1.903 1-12 48.8-49.0     1.866-1.859 3-12 50.8-51.0     1.797-1.791 3-12 52.9-53.3     1.731-1.719 4-12 54.6          1.681     3 55.6-55.8     1.653-1.647 6-12 ______________________________________

(a) MnAPSO-35, as prepared in example 22 was subjected to x-ray analysis. MnAPSO-35 was determined to have an x-ray powder diffraction pattern characterized by the following data: 2.theta.      d, (.ANG.) I/Io .times. 100 ______________________________________ 8.6          10.28   14 10.9          8.12    45 13.4          6.61    23 15.9          5.57    11 17.4          5.10    80 17.8          4.98    16 20.9          4.25    57 21.9          4.06    100 23.2          3.83    34 24.8          3.59    9 25.7          3.466   7 26.9          3.314   21 28.3          3.153   50 29.1          3.069   11 31.4          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 39.5          2.281   5 41.9          2.156   7 42.7          2.118   7 44.6          2.032   5 47.6          1.910   7 48.3          1.884   7 49.5          1.841   7 51.0          1.791   9 55.0          1.670   5 55.4          1.658   7 ______________________________________

(b) A portion of the as-synthesized MnAPSO-35 of part (a) was calcined in nitrogen at 500.degree. C. for about 2 hours. The calcined product was characterized by the following x-ray powder diffraction pattern: 2.theta.      d, (.ANG.) I/Io .times. 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    sh 20.8          4.27    64 21.9          4.06    100 23.3          3.82    32 24.8          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   18 32.2          2.780   46 34.2          2.622   18 34.8          2.578   14 35.8          2.508    9 41.9          2.156    9 42.5          2.127    9 44.6          2.032    9 47.4          1.918    9 48.2          1.888    9 49.4          1.845    9 51.0          1.791   14 55.2          1.664    9 55.7          1.650    9 ______________________________________

(c) The species denominated herein as MnAPSO-35 is a molecular sieve having a three dimensional microporous crystalline framework structure of MnO.sub.2.sup.-2, AlO.sub.2.sup.-, PO.sub.2.sup.+ and SiO.sub.2 tetrahedral oxide units and have an empirical chemical composition on an anhydrous basis expressed by the formula:

wherein "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the molar amount of "R" present per mole of (Mn.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2 and 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 MnAPSO-35 having a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth in Table XVII as follows: ______________________________________ 2.theta.    d, (.ANG.) Relative Intensity ______________________________________ 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   4.08-3.99 m-vs 28.2-28.7   3.164-3.110 m ______________________________________

(d) All of the MnAPSO-35 compositions, both as-synthesized and calcined, for which x-ray power diffraction data have presently been obtain have patterns which are within the generalized pattern of Table XVIII below: ______________________________________ 2.theta.      d, (.ANG.) I/Io .times. 100 ______________________________________ 8.5-8.7       10.40-10.16 13-31 10.8-11.0     8.19-8.04  44-100 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 10-14 17.2-17.5     5.16-5.07 38-82 17.7-18.0     5.01-4.93 (sh)-18.sup. 20.8-21.0     4.27-4.23 44-46 21.8-22.3     4.08-3.99  56-100 23.1-23.6     3.85-3.77 31-34 24.7-25.2      3.60-3.534 13-31 25.6-25.8     3.480-3.453 4-25 26.8-27.4     3.326-3.255 19-44 28.2-28.7     3.164-3.110 50-59 29.0-29.6     3.079-3.018 10-31 31.3-31.4     2.858-2.849 9-18 32.0-32.8     2.797-2.730 31-46 34.2-34.3     2.622-2.614 11-18 34.8-34.9     2.578-2.571 4-14 35.2-35.3     2.550-2.543 5-7 35.7-35.8     2.515-2.508 4-9 37.6-37.7     2.392-2.386 4-5 39.4-39.5     2.287-2.281 4-7 41.8-42.0     2.161-2.151 6-9 42.5-42.8     2.127-2.113 5-9 44.5-44.7     2.036-2.027 5-9 47.4-47.7     1.918-1.907 6-9 48.2-48.4     1.888-1.881 6- 9 49.4-49.6     1.845-1.838 6-9 50.9-51.1     1.794-1.787 5-14 54.9-55.2     1.672-1.664 5-9 55.3-55.7     1.661-1.650 6-9 ______________________________________

(a) MnAPSO-36, as prepared in example 59 was subjected to x-ray analysis. The MnAPSO-36 was determined to have an x-ray powder diffraction pattern characterized by the following data: 2.theta.      d, (.ANG.) I/Io .times. 100 ______________________________________ 7.4           11.88   15 7.9           11.22   100 8.2           10.82   33 13.5          6.55    5 15.8          5.61    10 16.4          5.41    31 19.1          4.66    14 20.7          4.28    34 21.2          4.19    4 21.7          4.10    16 22.0          4.04    14 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 28.3          3.153   8 29.0          3.079   7 30.2          2.958   4 30.3          2.951   4 32.0          2.798   8 34.8          2.579   7 ______________________________________

(b) A portion of the as-synthesized MnAPSO-36 of part (a) was calcined in air at 500.degree. C. for about 1 hour. The calcined product was characterized by the following x-ray powder diffraction pattern: 2.theta.      d, (.ANG.) I/Io .times. 100 ______________________________________ 7.1          12.39    5 7.6          11.64   21 8.0          11.11   100 8.3          10.65   37 13.6          6.53    17 16.6          5.35    31 19.4          4.57    17 20.8          4.27    19 21.9          4.06     8 22.4          3.97    15 22.7          3.92    11 23.4          3.80     5 23.9          3.73     7 27.3          3.271   16 28.3          3.159    6 28.4          3.141    6 29.1          3.074    7 29.4          3.043    5 32.0          2.798    6 ______________________________________

(c) The species denominated herein as MnAPSO-36 is a molecular sieve having a three dimensional microporous crystalline framework structure of MnO.sub.2.sup.-2, AlO.sub.2.sup.-, PO.sub.2.sup.+ and SiO.sub.2 tetrahedral oxide units and have an empirical chemical composition on an anhydrous basis expressed by the formula:

wherein "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the molar amount of "R" present per mole of (Mn.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2 and 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 compositional area defined by points A, B, C, D and E of FIG. 1, more preferably by the tetragonal compositional area defined by points a, b, c and d of FIG. 2, said MnAPSO-36 having a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth in Table XIX as follows: ______________________________________ 2.theta.    d, (.ANG.)  Relative Intensity ______________________________________ 7.596       11.6382     m 7.628-7.981 11.5899-11.0771 vs 8.105-8.299 10.9084-10.6537 m 16.395-16.673 5.4066-5.3172 m 19.052-19.414 4.6580-4.5721 w 20.744-20.871 4.2819-4.2560 m ______________________________________

(d) All of the MnAPSO-36 compositions, both as-synthesized and calcined for which x-ray power diffraction data have presently been obtain have patterns which are within the generalized pattern of Table XX below: ______________________________________ 2.theta.      d, (.ANG.)  I/Io .times. 100 ______________________________________ 7.132        12.3939     5 7.596        11.6382     21 7.628-7.981   11.5899-11.0771 100 8.105-8.299   10.9084-10.6537 33-37 13.517-13.778 6.5503-6.4270 5-17 15.797-15.928 5.6099-5.5640 10-11 16.395-16.673 5.4066-5.3172 31-32 19.052-19.414 4.6580-4.5721 14-17 20.744-20.871 4.2819-4.2560 20-35 21.230        4.1848      4 21.655        4.1037      16 21.863-21.986 4.0651-4.0427 8-14 22.119-22.470 4.0186-3.9566 15 22.713-23.408 3.9150-3.8001 5-11 23.854-23.965 3.7301-3.7131 5-6 27.219-27.518 3.2761-3.2412 15-16 27.868-27.939 3.2014-3.1934 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 4 31.983-32.094 2.7982-2.7888 6-9 34.640-34.968 2.5894-2.5659 7 ______________________________________

(a) MnAPSO-44, as prepared in example 64 was subjected to x-ray analysis. The MnAPSO-44 was determined to have an x-ray powder diffraction pattern characterized by the following data: 2.theta.      d, (.ANG.) I/Io .times. 100 ______________________________________ 9.4           9.39    100 13.0          6.83    20 13.7          6.45    4 16.1          5.52    43 17.3          5.12    5 19.0          4.68    7 20.7          4.29    84 21.7          4.09    21 22.6          3.94    8 23.1          3.86    9 24.4          3.65    58 26.1          3.409   22 27.8          3.205   10 29.7          3.012   5 30.1          2.969   16 30.8          2.900   50 32.5          2.753   4 32.9          2.721   6 34.8          2.577   3 35.5          2.528   9 38.5          2.336   2 39.2          2.299   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 48.2          1.890   7 48.7          1.870   4 50.3          1.814   7 53.9          1.701   6 ______________________________________

(b) A portion of the as-synthesized MnAPSO-44 of part (a) was calcined in air at 500.degree. C. for about one (1) hour. The calcined product was characterized by the following x-ray powder diffraction pattern: 2.theta.      d, (.ANG.) I/Io .times. 100 ______________________________________ 9.6           9.21    100 13.1          6.79    26 14.2          6.26    3 16.2          5.46    12 18.0          4.93    18 19.3          4.60    3 20.9          4.25    28 22.3          3.99    3 23.4          3.80    3 25.3          3.526   13 26.3          3.387   9 28.5          3.137   3 28.6          3.123   4 29.9          2.990   2 30.0          2.976   2 30.6          2.921   3 31.1          2.875   7 31.8          2.811   2 32.1          2.791   2 35.1          2.560   3 ______________________________________

(c) The species denominated herein as MnAPSO-44 is a molecular sieve having a three dimensional microporous crystalline framework structure of MnO.sub.2.sup.-2, AlO.sub.2.sup.-, PO.sub.2.sup.+ and SiO.sub.2 tetrahedral oxide units and have an empirical chemical composition on an anhydrous basis expressed by the formula:

wherein "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the molar amount of "R" present per mole of (Mn.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2 and 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 compositional area defined by points A, B, C, D and E of FIG. 1, more preferably by the tetragonal compositional area defined by points a, b, c and d of FIG. 2, said MnAPSO-44 having a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth in Table XXI as follows: ______________________________________ 2.theta.     d, (.ANG.) Relative Intensity ______________________________________ 9.420-9.498  9.3883-9.3110 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 2.8999-2.8981 m ______________________________________

(d) All of the MnAPSO-44 compositions, both as-synthesized and calcined, for which x-ray power diffraction data have presently been obtain have patterns which are within the generalized pattern of Table XXII below: ______________________________________ 2.theta.     d, (.ANG.) I/Io .times. 100 ______________________________________ 9.420-9.498  9.3883-9.3110 100 12.930-12.958 6.8468-6.8318 20 13.738       6.4458     4 16.062-16.131 5.5179-5.4944 43 17.329-17.396 5.1173-5.0975 5 18.950-18.998 4.6828-4.6713 7 20.715-20.790 4.2877-4.2725 84 21.709-21.743 4.0937-4.0873 21 22.366-22.583 3.9748-3.9372 8 23.061-23.101 3.8566-3.8501 9 24.396-24.424 3.6485-3.6444 58 26.143-26.184 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 30.833-20.853 2.8999-2.8981 50 32.520-32.562 2.7532-2.7498 4 32.900-32.918 2.7223-2.7208 6 34.812       2.5770     3 35.516-35.534 2.5275-2.5263 9 38.536       2.3361     2 38.185       2.2989     2 39.991       2.2545     2 42.162-42.177 2.1432-2.1425 3 42.533-42.541 2.1254-2.1250 3 43.607-73.621 2.0755-2.0749 2 47.283       1.9224     2 48.157-48.177 1.8895-1.8888 7 48.640-48.697 1.8719-1.8698 4 50.303-50.307 1.8138-1.8137 7 53.885-53.887 1.7014-1.7013 6 ______________________________________

(a) MnAPSO-47, as prepared in example 49 was subjected to x-ray analysis. The MnAPSO-47 was determined to have an x-ray powder diffraction pattern characterized by the following data: 2.theta.      d, (.ANG.) I/Io .times. 100 ______________________________________ 4.8           18.44   1 9.4           9.38    100 12.9          6.89    5 13.9          6.40    3 16.0          5.56    9 17.5          5.06    4 18.9          4.69    3 20.5          4.32    30 21.8          4.08    4 22.4          3.98    1 22.9          3.88    3 24.6          3.61    11 25.9          3.445   7 27.6          3.234   2 27.9          3.199   1 29.5          3.033   2 30.5          2.930   10 30.8          2.901   7 31.5          2.845   1 33.2          2.700   1 34.4          2.604   2 34.8          2.576   1 35.7          2.516   2 38.4          2.343   1 39.2          2.297   1 39.6          2.277   1 42.4          2.132   1 43.3          2.091   1 47.6          1.911   1 48.6          1.874   5 50.3          1.813   2 53.2          1.722   1 54.0          1.698   1 ______________________________________

(b) A portion of the as-synthesized MnAPSO-47 of part (a) was calcined in air at 500.degree. C. for about one (1) hour. The calcined product was characterized by the following x-ray powder diffraction pattern: 2.theta.      d, (.ANG.) I/Io .times. 100 ______________________________________ 5.0           17.80   1 9.7           9.12    100 10.0          8.85    1 13.1          6.75    5 14.2          6.23    1 16.3          5.45    2 18.0          4.92    2 19.4          4.58    3 20.9          4.24    7 22.4          3.98    1 23.4          3.80    1 25.3          3.521   2 26.3          3.385   2 28.1          3.176   1 28.6          3.125   1 30.0          2.977   1 31.1          2.876   3 31.5          2.837   2 33.9          2.645   1 35.0          2.562   1 49.6          1.838   1 ______________________________________

(c) The species denominated herein as MnAPSO-47 is a molecular sieve having a three dimensional microporous crystalline framework structure of MnO.sub.2.sup.-2, AlO.sub.2.sup.-, PO.sub.2.sup.+ and SiO.sub.2 tetrahedral oxide units and have an empirical chemical composition on an anhydrous basis expressed by the formula:

wherein "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the molar amount of "R" present per mole of (Mn.sub.w Al.sub.x P.sub.y Si.sub.z)o.sub.2 and 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 compositional area defined by points A, B, C, D and E of FIG. 1, more preferably by the tetragonal compositional area defined by points a, b, c and d of FIG. 2, said MnAPSO-47 having a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth in Table XXIII as follows: ______________________________________ 2.theta.     d, (.ANG.) Relative Intensity ______________________________________ 9.434-9.696  9.3746-9.1214 vs 15.946-16.276 5.5579-5.4457 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 MnAPSO-47 compositions, both as-synthesized and calcined for which x-ray power diffraction data have presently been obtain have patterns which are within the generalized pattern of Table XXIV below: ______________________________________ 2.theta.      d, (.ANG.)  I/Io .times. 100 ______________________________________ 4.793-4.964   18.4368-17.8028 1 9.434-9.696   9.3746-9.1214 100 12.847-13.107 6.8907-6.7543 5 13.840-14.211 6.3983-6.2321 1-3 15.946-16.276 5.5579-5.4457 2-9 17.544-18.032 5.0550-4.9191 2-4 18.941-19.365 4.6851-4.5836 3 20.539-20.940 4.3242-4.2423 6-30 21.811        4.0747      4 22.351-22.352 3.9775-3.9774 1 22.936        3.8773      3 23.401        3.8013      1 24.643        3.6125      11 25.294-25.864 3.5210      2-7 26.327-27.577 3.3851-3.2344 2 27.881-28.093 3.1992-3.1762 1 28.560        3.1253      1 29.448-30.019 3.0331-2.9767 1-2 30.511        2.9297      10 30.820-31.096 2.9011-2.8759 3-7 31.448-31.532 2.8446-2.8372 1-2 33.186-33.894 2.6995-2.6447 1 34.444        2.6037      2 34.834-35.026 2.5755-2.5618 1 35.685        2.5159      2 38.412        2.3434      1 39.223        2.2968      1 39.582        2.2768      1 42.403        2.1316      1 43.278        2.0905      1 47.595        1.9105      1 48.584-49.595 1.8739-1.8380 1-5 50.327        1.8130      2 53.205        1.7215      1 54.006        1.6979      1 ______________________________________

The catalytic activity of MnAPSO 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 10.3 mm. I.D. In each test MnAPSO which were 20-40 mesh (U.S. std.) in size and in an amount of from 0.5 to 5 grams, the quantity being selected so that the conversion of n-butane was at least 5% and not more than 90% under the test conditions. Most of the MnAPSO samples had been previously calcined in air or nitrogen to remove organic materials from the pore system, and were activated in situ in the reactor in a flowing stream of helium at 500.degree. C. for one hour. The feedstock 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 effluent were carried out using conventional gas chromatography techniques. The reactor effluent was analyzed after 10 minutes of on-stream operation.

The pseudo-first-order rate constant (k.sub.A) was calculated to determine the relative catalytic activity of the MnAPSO compositions. The k.sub.A value (cm.sup.3 /g min) obtained for the MnAPSO compositions are set forth, below, in Table XXV: ______________________________________ Prepared in Rate MnAPSO        Example No.: Constant (k.sub.A)* ______________________________________ MnAPSO-5      31         0.2 MnAPSO-11     25         0.6 MnAPSO-20     46         0.2 MnAPSO-31     55         1.0; 0.5 MnAPSO-34     11         3.1 MnAPSO-35     21          0.1** MnAPSO-36     59         0.3 MnAPSO-44     64         1.5 MnAPSO-47     49         1.7 ______________________________________ *Prior to determination of the catalystic activity of a given MnAPSO, eac was calcined as follows: (a) MnAPSO-5 was calcined at 500.degree. C. in air for 2 hours; (b) MnAPSO11, MnAPSO34 and MnAPSO36 were calcined in situ; (c) MnAPSO31 was calcined in air at 500.degree. C. for 1.5 hours and then at 600.degree. C. for 1 hour; (d) MnAPSO35 was calcined at 500.degree. C. in nitrogen for 1 hour; and (e) MnAPSO20, MnAPSO44 and MnAPSO47 were calcined at 500.degree. C. in ai for 1 hour. **Less than 0.1

The MnAPSO compositions of the present invention are, in general, hydrophilic and adsorb water preferentially over common hydrocarbon molecules such as paraffins, olefins and aromatic species, e.g., benzene, xylenes and cumene. Thus, the MnAPSOs as a class are useful as desiccants in such adsorption separations/purification processes as natural gas drying, cracked gas drying. Water is also preferentially adsorbed over the so-called permanent gases such as carbon dioxide, nitrogen, oxygen and hydrogen. These MnAPSOs are therefore suitably employed in the drying of reformer hydrogen streams and in the drying of oxygen, nitrogen or air prior to liquifaction.

The present MnAPSO compositions also exhibit novel surface selectivity characteristics which render them useful as catalyst or catalyst 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, for example, in fabricating catalyst compositions having silica or alumina bases. Of the general class, those species having pores larger than about 4 .ANG. are preferred for catalytic applications.

Among the hydrocarbon conversion reactions catalyzed by MnAPSO compositions are cracking, hydrocracking, alkylation for both the aromatic and isoparaffin types, isomerization including xylene isomerization, polymerization, reforming, hydrogenation, dehydrogenation, transalkylation, dealkylation, hydrodecyclization and dehydrocyclization.

Using MnAPSO catalyst compositions 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 400.degree. F. to 825.degree. F. using molar ratios of hydrogen to hydrocarbon in the range of between 2 and 80, pressures between 10 and 3500 p.s.i.g., and a liquid hourly space velocity (LHSV) of from 0.1 to 20, preferably 1.0 to 10.

The MnAPSO catalyst compositions employed in hydrocracking are also suitable for use in reforming processes in which the hydrocarbon feedstocks contact the catalyst at temperatures of from about 700.degree. F. to 1000.degree. F., hydrogen pressures of from 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 range 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 200.degree. F. to 600.degree. F., preferably 300.degree. F. to 550.degree. F. with an LHSV value of from about 0.2 to 1.0. Hydrogen is supplied to the reactor in admixture with the hydrocarbon feedstock in molar proportions (hydrogen to hydrocarbon) of between 1 and 5.

At somewhat higher temperatures, i.e. from about 650.degree. F. to 1000.degree. F., preferably 850.degree. F. to 950.degree. F. and usually at somewhat lower pressures within the range of about 15 to 50 p.s.i.g., the same catalyst compositions are used to hydroisomerize normal paraffins. Preferably the paraffin feedstock comprises normal paraffins having a carbon number range of C.sub.7 -C.sub.20. Contact time between the feedstock and the catalyst is generally relatively short to avoid undesirable side reactions such as olefin polymerization and paraffin cracking. LHSV values in the range of 0.1 to 10, preferably 1.0 to 6.0 are suitable.

The unique crystal structure of the present MnAPSO catalysts and their availability in a form totally void of alkali metal content favor their use in the conversion of alkylaromatic compounds, particularly the catalytic disproportionation of toluene, ethylene, trimethyl benzenes, tetramethyl benzenes and the like. In the disproportionation process, isomerization and transalkylation can also occur. Group VIII noble metal adjuvants alone or in conjunction 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 temperature of from about 400.degree. to 750.degree. F., pressures in the range of 100 to 2000 p.s.i.g. and LHSV values in the range of 0.1 to 15.

Catalytic cracking processes are preferably carried out with MnAPSO 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.degree. to 1100.degree. F., LHSV values of 0.5 to 10 and pressure conditions of from about 0 to 50 p.s.i.g. are suitable.

Dehydrocyclization reactions employing paraffinic hydrocarbon feedstocks, preferably normal paraffins having more than 6 carbon atoms, to form benzene, xylenes, toluene and the like are carried out using essentially the same reaction conditions as for catalytic cracking. For these reactions it is preferred to use the MnAPSO catalyst in conjunction with 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.degree.-1000.degree. F. are employed at moderate hydrogen pressures of about 300-1000 p.s.i.g., other conditions being similar to those described above for catalytic hydrocracking. Preferred catalysts are of the same type described above in connection with catalytic dehydrocyclization. Particularly desirable dealkylation reactions 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 substantially 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 gasoline fractions, kerosenes, jet fuel fractions, diesel fractions, light and heavy gas oils, deasphalted crude oil residual and the like any of which may contain up to about 5 weight-percent of sulfur and up to about 3 weight-percent of nitrogen.

Similar conditions can be employed to effect hydrofining, 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 particular the concentration of organonitrogen compounds in the feedstock. As a result 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 hydrocracking, e.g., less than 20 volume percent of fresh feed per pass, might be the same as those preferred for hydrocracking another feedstock having a lower concentration of hydrocracking 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 contacted on the basis of preliminary screening tests with the specific catalyst and feedstock.

Isomerization reactions are carried out under conditions similar to those described above for reforming, using somewhat more acidic catalyts. Olefins are preferably isomerized at temperatures of 500.degree.-900.degree. F., while paraffins, naphthenes and alkyl aromatics are isomerized at temperatures of 700.degree.-1000.degree. F. Particularly desirable isomerization reactions contemplated herein include the conversion of n-heptane and/or n-octane to isoheptanes, iso-octanes, butane to iso-butane, methylcyclopentane to cyclohexane, meta-xylene and/or ortho-xylene to paraxylene, 1-butene to 2-butene and/or isobutene, n-hexene to isohexene, cyclohexene to methylcyclopentene etc. The preferred form of the catalyst is a combination of the MnAPSO with polyvalent metal compounds (such as sulfides) of metals of Group II-A, Group II-B and rare earth metals. For alkylation and dealkylation processes the MnAPSO compositions having pores of at least 5 .ANG. are preferred. When employed for dealkylation of alkyl aromatics, the temperature is usually at least 350.degree. F. and ranges up to a temperature at which substantial cracking of the feedstock or conversion products occurs, generally up to about 700.degree. F. The temperature is preferably at least 450.degree. F. and not greater than the critical temperature 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 as 250.degree. F. but is preferably at least 350.degree. F. In the alkylation of benzene, toluene and xylene, the preferred alkylating agents are olefins such as ethylene and propylene.

## Claims

1. 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 molecular sieve having pore diameters large enough to adsorb at least one of the more polar molecular species, said molecular sieve being at least partially activated whereby molecules of the more polar molecular species are selectively adsorbed into the intracrystalline pore system thereof, said molecular sieve being a crystalline molecular sieve having three-dimensional microporous framework structures of MnO.sub.2, AlO.sub.2, PO.sub.2 and SiO.sub.2 tetrahedral units having an empirical chemical composition on an anhydrous basis expressed by the formula: wherein "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the molar amount of "R" present per mole of (Mn.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2 and 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 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. Process 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. Process according to claim 1 wherein the more polar molecular species is water.

4. Process for separating a mixture of molecular species having different kinetic diameters which comprises contacting said mixture with a molecular sieve 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, said molecular sieve being a crystalline molecular sieve having three-dimensional microporous framework structures of MnO.sub.2, AlO.sub.2, PO.sub.2 and SiO.sub.2 tetrahedral units having an empirical chemical composition on an anhydrous basis expressed by the formula: wherein "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the molar amount of "R" present per mole of (Mn.sub.w Al.sub.x P.sub.y Si.sub.x)O.sub.2 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 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.

5. Process according to claim 4 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.