CA1248079A - Zinc-aluminum-phosphorous-silicon-oxide molecular sieve compositions - Google Patents

Abstract

ZINC-ALUMINUM-PHOSPHORUS-SILICON-OXIDE
MOLECULAR SIEVE COMPOSITIONS
ABSTRACT

Crystalline molecular sieves having three-dimentional microporous framework structures of ZnO2, AlO2, SiO2 and PO2 tetrahedral units are disclosed. These molecular sieves have an empirical chemical composition on an anhydrous basis expressed by the formula:
mR : (ZnwAlxPySiz)O2 wherein "R" represents at least one organic templating agent present in the intracrystalline pore system: "m" represents the molar amount of "R"
present per mole of (ZnwAlxPySiz)O2; and "w", "x", "y" and "z" represent the mole fractions of zinc, aluminum, phosphorus and silicon, respectively, present as tetrahedral oxides. Their use as adsorbents, catalysts, etc. is also disclosed.

Description

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ZINC-ALUMINUM-PHOSPHORUS-SILICON-O~IDE
MOLECULAR SIEVE COMPOSITIONS
FIELD OF THE INVENTION
The instant inven~ion relates to a novel class of crystalline microporous molecular sieves, to the method of their prepaLation and to their use a6 adsorbents and catalysts. The invention-oxide relates ~o novel zinc-alumimlm-phosphorus-silicon molecular sieves having zinc, aluminum, phosphorus and silicon in the form of framework tetrahedral oxides. These com~ositions may be prepared hydrothermally from gels containing reactive compounds of zinc, aluminum, phosphorus and silicon capable of forming a 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.
BAC~GROUND OF THE INVENTION
Molecuiar 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 zeslites are formed from corner-sharing A102 and SiO2 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.

D-14,223 OtheL crystalline microporous compositions ~hich are not zeolitic, i.e. do not contain A102 tetrahed~a 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 a~e capable of reversibly adsorbing molecules having molecular diamete~s of about 6R or less, are repo~ted in U.S. Patent No. 3,941,871 issued Macch

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. Patent No.
4,061,72~ issued December 6, lg77 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. Patent No. 4,310,440 issued January 12, 198Z
to Wilson et al. These materials are formed from A102 and P02 tetrahedra and have electrovalently neutral frameworks as in the case of silica polymorphs. Unlike the silica molecular sieve, silicalite, which is hydrophobic due to the absence of extra-structural cations, the aluminophosphate molecular sieves are mode~ately hydrophilic, apparently due to the difference in electronegativity between aluminum and phosphorus.
Their intrac~ystalline pore volumes and pore diameters a~e comparable to those known for zeolites and silica Dlolecular sieves.

D-14,223 In commonly assigned Canadian Patent Serial No. 1,202,016, issued on March 18, 1986, there is described a novel class of silicon-substituted aluminophosphates which are both microporous and crystalline. The materials have a three dimensions crystal framework of PO2, AlO2 and SiO2 tetrahedral 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:
mR : (SiXAlyPz)O2 wherein "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents th0 moles of "R" present per mole of (SiXAlyPz)O2 and has a value of from zero to 0.3, the maximum value in each case depending upon the molecular dimensions of the templating agent and the available void volume of the pore system of the particular silicoaluminophosphate species involved; and "x", "y", and "z" represent the mole fractions of silicon, aluminum and phosphorus, respectively, present as tetrahedral oxides. The minimum value for each of "x", "y", and "z" is 0.01 and preferably 0.02. The maximum value for "x" is 0.98; for "y" is 0.60; and for "z" is 0.52. These silicoaluminophosphates exhibit several physical and chemical properties which are characteristic of aluminosilicate zeolites and aluminophosphates.
In copending and commonly assigned Canadian Application Serial No. 450,65%, filed March 28, 1984 .~

_ 4 '~

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:
mR:(TixAlyPz)02 wherein "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the moles of "R" present per mole of (TiXAlyPz)02 and has a value of between zero and about 5.0; and "x", "y" and "z"
represent the mole fractions of titanium, aluminum and phosphorus, respectively, present as tetrahedral oxides.
In copending and commonly assigned Canadian Application Serial No. 458,495, filed July 10, 1984, there is described a novel class of crystalline metal aluminophosphates having three-dimensional microporous framework structures of M02, A102 and P02 tetrahedral units and having an empirical chemical composition on an anhydrous basis expressed by the formula:
mR:(MxAlyPz)02 wherein "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the moles of "R" present per mole of (MXAlyPz)02 and has a value of from zero to 0.3; "M" represents at leas~ one metal of the group magnesium, manganese, zinc and cobalt;
and "x", "y" and "z" represent the mole fraction of the metal "M", aluminum and phosphorus, respectively, present as te~rahedral oxides.

D-14,223-C

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In copending and commonly assigned Canadian Application Serial No. 45~,914, filed July 13, 1984, there is described a novel class of crystalline ferroaluminophosphates having a three-dimensional microporous framework structure of FeO2, Al02 and PO2 tetrahedral units and having an empirical chemical composition on a anhydrous basis expressed by the rormula:
mR:(FexAlyPz)02 wherein "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the moles of "R" present per mole of (FexAlyPz)02 and has a value of from zero to 0.3; and "x", "y" and "z" represent the mole fraction of the iron, aluminum and phosphorous, respectively, present as tetrahedral oxides.
The instant invention relates to new molecular sieve compositions having framework ZnO22, A102, PO2+ and SiO2 as tetrahedral oxide units.
DESCRIPTION OF THE FIGURES
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 compositins 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.

D-14,223-C

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SUMMARY OF THE INVENTION
The instant invention relates to a new class of molecular sieves having a three-dimensional microporous crystal framework structures of ZnO22, A102, PO2 and SiO2 tetr,ahedral oxide unit~. These new zinc-aluminum-phosphorus-xilicon-oxide molecular sieves exhibit ion-exchange, adsorption and catalytic properties and, accordingly, find wide use as adsorbents and cataly~ts. The members of thi~s novel class of compositions have crystal framlework structures of ZnO~ , A102, PO2 and SiO2 tetrahedral units and have an empirical chemical composition on an anhydrous basis expressed by the ~ormula:
mR (ZnwAlxPySiz)02 wherein "R~ represents at least one organic templating agent present in the intracrys~alli~e pore system; "m" represents the molar amount of "R"
present per mole of (ZnwAlxPySiz)02 and has a value from zero to about 0.3 , and "w", "x", "y" and "z" represent the mole fractions of zinc, aluminum, phosphorus and silicon, ~espectively, present as tetrahedral oxides. The instant molecula~ 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 speciefi and by the existence of species heretofore unknown for binary and ternary molecular sieves.

D-14,223 The molecular sieves of the instant invention will be generally referred to by *he acronym "ZnAPS0" to designate a crystal framework of Zn2 A10z, P02, SiO2 and tetrahedral units.
Actual cla6s members will be identified as structural species by assigning a number to the species and, accordingly, are identified as Z3~PS0-i wherein "i" i5 an integer. This ~esignation is an arbitrary one and is not intended to denote ~tructural relationship to another material(s) which may also be characterized by a numbering system.
Detailed DescriPtion of the Invention The instant invention relates to a new class of three-dimensional microporous crystalline molecular sieves having a crystal framework structures f Zn2 ~ A102, P02 and SiO2 tetrahedral oxide units. These ne~ molecular sieves exhibit ion-exchanqe, adsorption and catalytic properties, and accordingly find wide use as adsorbents and catalysts.
The ZnAP80 molecular sieve6 of the instant invention comprise framework fitructu~es of Zn2 ~ A102, P02 and SiO2 tetrahedral units having an empirical chemical composition on an anhydrous basis expre~sed by the formula:
mR : (ZnwAlxPySiz)02 wherein "R" represenes at least one organic templating agent present in the intracrystalline pore system; "m" represents the molar amount of "R"
present per mole of (ZnwAlxPySiz)02 and has a value of zero to about 0.3; and "w", "x", "y"
and "z" rep3:esent the mole fractions of zinc, D-14,223 aluminum, phosphorus and silicon, respectively, present as tetrahedral oxides and each has a value of at least 0.01. The mole fractions "w", "x", "y"
and "z" are çenerally defined being within the pentagonal compositional area defined by points A, B, C, D and E of the ternary diagram of Fig. 1.
Points ~, B, ~, D and ~ of Fig. 1 have ~he following values for "~", "x", "y", and "z":
Mole Fraction Point _x Y (z ~ w) A 0.60 0.380.02 B 0.38 0.600.02 C 0.01 0.600.39 D 0.01 0.010.98 E 0.60 0.010.39 In the preferred subclass of ZnAPS0 molecular sieves the values "w", "x", "y" and "z" in the above formular are within the tetragonal compositional area defined by points a, b, c and d of the ternary diagram which is Fig. 2 of the drawings, said points a, b, c and d representing the following values for "w", "x", "y" and "z".
Mole Fraction Point x y (z ~ w) a 0.55 0.430.02 b 0.43 0.550.02 c 0.10 ~.550.35 d 0.55 0.100.35 The ZnAPSOs of this invention are useful as adsorbents, catalysts, ion-exchangers, and the like in much the ~ame fashion as aluminosilicates have been employed heretofore, although their chemical and physical properties are not necessarily 6imilar to those observed for aluminosilicates.

D-14,223 ZnAPSO compositions are generally synthesized by hydrothelmal crystallization at effective process conditiens from a reaction mixture containing active sources of zinc, 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, prefe~ably lined wi~h an inert plastic material such as polytetrafluoroethylene and heated, preferably under autogenous pressure at a temperature between 50C and 250C, and preferably between 100C and 200C until crystals of the ZnAPS0 product are obtained, usually a period of from several hours to several weeks. Generally ~he effective crystallization period is from about Z
hours to about 30 days with typical periods of from about 4 hourR to about 20 days being employed to obtain ZnAPS0 products. The product is recovered by any convenient method such as centrifugation or filtration.
In synthesizing ~he ZnAPS~ compositions of the instant invention, it is preferred to employ a reaction mixture composition expressed in terms of the molar ratios as follows:
aR (ZnwAlxPysi~)Q2 bHz ~herein l'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 i8 preferably an effective amount within the range of greater than zero ~0~ to about 6: "b" has a value of from zero D-14,223 - 10- ~248B79 (0) to about 500, more preferably between about Z
and about 300; and "w", "x", "y" and "z" represent the mole fractions of zinc, aluminum, phosphorus and fiilicon, respectively, and each has a value of at least 0.01. In a prèferred embodiment the reaction mixture i8 selected such that the mole fractions "~", "x", "y" and "z" are generally defined as being within the pentagonal compositional area defined by points F, G, H, I and J of the ternary diagram of FIG. 3. Points F, G, H, I and J of FIG. 3 have the following values for "w", "x", "y" and "z":
Mole Fraction Poin~ x y (z + w) F - 0.60 0.3a 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 ~.39 For reasons unknown at present, not every reaction mixture gave crystalline ZnAPS0 products when reaction p~oducts were examined for ZnAPS0 products by X-ray analysis. Those reaction mixtuces from which crystalline ZnAPS0 products were ob~ained are reported in the examples hereinafter as numbered examples and those reaction mixtures from which ZnAPS0 products were not identified by use of X-ray analysic are reported as lettered examples.
In the foregoing expression of the reaction composition, the reactants are normalized wi~h D-14,223 2~
respect to the ~o~al of "w", "x", "y" and "z" such that (w~x~y~z) = l.OQ ~ole, whereas in the examples the reaction mixtures are express~d in terms of molar Oxiae ratios and may be normalized to the moles of P205. This latter form is readily converted to the former form by Loutine calculations by dividing the number of moles of each component (including the template and water3 by the total number of moles of ~inc, alumislum, phosphoru~ and silicon which results in normalized mole fractions based on total moles of the aforemen~ioned components.
In forming reaction mixture 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 ~eolite 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 vne alkyl or aryl group having from 1 ~o 8 carbon a~oms.
Particularly preferred compounds for use as templating agents are the amines, quaternary phosphonium compounds and quaternary ammonium compounds, the latter two being repre~ented generally by the formula R4~ wherein "X" is nitrogen or phosphorus and each R i8 an alkyl or aryl group containing from 1 to 8 carbon atoms.
Polymeric quaternary ammonium salt6 such as [( 14H32N2) (OH) 2]x wherein "x" has a value of at least 2 are also suitably employed. The D-14,223 mono-, di- and tri-amines are advantageously utilized, either alone oc in combination with a quaternary a~monium compound or other templa~ing compound. Mixture~ of two or ~lore templating agents can either produce mixtures of the de~ired ZnAPSOs or the more s~rongly directing templating species may control the course of the reaction with ~he other templating ~pecies ~erving ~rimarily to establi~h the pH conditions of t~e reaction gel.
RepresentatiYe 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-di~ethyle~hanolamine:
choline; N,N'-dimethylpiperazine; 1,4-diazabicyclo (2,2,2,) octane; N-methyldiethanolamine, N-methylethanolamine; N-methylpiperidine;

3-methylpipe-idine; 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; e~hylenediamine;
pyrrolidine and 2-imidazolidone. Not every templating agent will direct the formation of every species of ZnAPSO, i.e., a single templating agent can, with prope~ manipulation of the reaction condition6, direct the formation of 6everal ZnAPSO
compo~itions, and a given ZnAPSO composition can be p~oduced using several different templating agent~.

D-14,223 - 13~

The source of silicon may be silica, either as a silica sol or as fumed silica, a reactive solid amorphous precipitated silica, silica ~el, a~koxides of silicon, silicic acid or alkali metal silicate and the like: such that the focmation of reactive silicon in situ is provided to form sio2 tetrahedral units.
The most suitable phosphorus soucce yet found for the present process is phosphoric acid, but organic phosphates such as triethyl phosphate have been found satisfactory, ,and so also have crystalline or amorphous aluminophosphates such as the ~lPO4 composition Of U.S.P. 4,310,440.
Organo-phosphorus compounds, such as tetrabu~ylphosphonium bromide do not, apparently, secve as reactive sources of phosphoru6, but these compounds do function as templating agents.
Con~entional phosphorus salts such as sodium metaphosphate, may be used, at least in part, as the phosphorus source, but are not preferced.
The preferred aluminum source is either an aluminum alkoxide, such as aluminum isoproproxide, 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 u~ed in zeolite synthesis, such as gibbsite, sodium aluminate and aluminum trichloride, can be employed but are not preferred.
The source of zinc can be introduced into the reaction system in any form which permits the formation in situ of reactive form of zinc, i.e., D-14,223 - 14~

reactive to form the framework tet~ahedral unit Zn2 - Compounds of zinc which may be employed include oxides, hyd~oxides, alkoxides, nitcates, sulfates, cacboxylates (e.g., acetatas), o~ganometallic zinc compounds and the like, and mixtu~es the~eof.
While not essential ~o the synthesis of ZnAPS~ compositions, stirring or other moderate agitation of the reaction mixture and/or seeding the reaction mixture with seed crystals of either the ZnAPSO species to be produced or a topologically similar aluminophosphate, aluminosilicate or molecular sieve composition, facilitates the crystallization procedure.
After crystallization the ZnAPSO p~oduct may be isolated and advantageously washed with water and dried in air. The as-synthasized ZnAPSO
generally contains within its internal pore system at least one form of the ~emplating agent employed in its formation. Most commonly any organic moiety derived from an organic template is present, at least in pa~t, 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 ZnAPSO species. As a general rule the templating agent, and hence the occluded organic species, is too large to move fceely through the pore system of ~he ZnAPSO product and must be removed by calcining the Zn~PSO at tempe~atures of D-14,223 - 15- 3L2~

Z00C to 700C to the~mally degrade the organic species. In a few instances the pores of the ZnAPS0 product are sufficiently large to permit transpo~t 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 tlhe ZnAPS0 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 I'm" in the composition formula mR : (Zn~AlxPySiz)02 has a value of le~s than 0.02. The othee symbols of the formula are as defined hereinabove. In tho~e prepacations in which an alkoxide i6 employed as the source of zinc, aluminum, phosphorus or ~ilicon, the corre6ponding alcohol is necessarily present in the reaction mixture since ie is a hydrolysis product of the alkoxide. I~ has not been determined whether this alcohol participates in the syntheses process as a templaeing agent. For the ~urposes of this application, however, this alcohol is arbitrarily omitted from the class of templating agents, even if it is present in the as-synthesized ZnAPS0 material.
Since the present ZnAPS0 compositions are formed from ZnO2, A102, P02 and SiO2 tet~ahedral units which, respectively, have a net charge of -2. -1, ~1 and 0. The matter of cation D-14,223 exchangeability is considerably more complicated than in the case of zeolitic ~olecular sieves in which, ideally, there i6 a stoichiometric relationship between A102 tetrahedra and charge-balancing cations. In the instant compositions, an A102 tetrahedron can be balanced electrically either by a6socia~ion with a P02 tetrahedron or a simple cation such as an alkali metal cation, a eroton (H~), a cation of zinc present in the reaction mixture, or an organic cation derived from ~he templating agent. Similarly an ZnOz tetrahedron can be balanced electrically by association with POz tetrahedra, a simple cation such as an alkali metal cation, a proton (H ), a cation of the zinc present in the reaction mixture, organic cations derived from the templating agent, or other divalent or polyvalent metal cations introduced from an extraneous 60urce. It has also been postulated that non-ad3acent A102 and P02 tetrahedral pairs can be balanced by Na+ and OH
respectively [Flanigen and Grose, Molecular Sieve Zeolites-I, ACS, Washington, DC (1971)]
The ZnAPSO composition~ of the present invention exhibit cation-exchange capacity when analyzed using ion-exchange techniques heretofore employed with zeolitic aluminosilicates and have uniform pore diameters which aIe inherent in the lattice structure of each species and which are at least about 3A in diameter. Ion exchange of ZnAPSO compositions i6 ordinarily possible only after the organic moiety present as a result of synthesis ha~ been removed from the pore system.

D-14,223 ~ 17- ~a~

Dehydration to remove water present in the as-synthesized ZnAPS0 compositions can usually be accomplished, to some degree at least, in the usual manner withcut rQmoval of the organic moiety, but the absence of the organic species greatly facilitates adsorption and desorption procedures.
The ZnAPS0 materials have va~ious degrees of hydrothermal and thermal stability, some being quite remarkable in this regard, and function well as molecular ~ieve adsorbents and hydrocarbon conversion catalysts or catalyst bases.
In each example a stainless steel reaction vessel was utilized and was lined with ~he ineLt plastic material, polytetrafluoroethylene, to avoid csntamination of the reaction mixture. In genecal, the final reaction mixture from which each ZnAPS0 composition is crystallized is prepa~ed by forming mixtures of less than all of the reagent6 and thereafter incorporating into these mixtures additional reagents either singly or in the form of other intermediate mixtures of two or more reagent~. In some instancas the reagents admixed retain their identity in the intermediate mixture and in other cases some or all of the reagents ace 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.
~ -ray analysis of reaction p~oduc~s are obtained by ~-ray analysis, u~ing standard X-ray powder diffraction techniques. The radiation 60urce D-14,223 - 18~

is a high-intensity, copper target, ~-ray tube operated at 50 Kv and 40 ma. The diffraction pattern from the copper K-alpha radiation and graphite ~onochromator i~ ~uitably recorded by an ~-ray spectrometer scintillation counter, pulse height analy2er and strip chart recorder. Flat compressed powder samples are ~canned at 2 (2 theta) 2er minute, using a two second time constant. Interplanar spacings (d) in Angstrom units are obtained from the position of the diffraction peaks expressed as 2e where ~ i8 the Bragg angle as obserYed on the strip chart.
Int~nsities are determined from the heights of diffraction peak6 after subt~acting bac~g~ound, "Io" 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 R-alpha radiation by use of computer based techniques using Siemens D-500 ~-ray powder diffractome~ers, Siemens Type K-805 X-ray sources, available from Siemens Corporation, Cherry ~ill, New Jersey, with appLoeriate 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, ~hich in co~bination, can impose an uncertainty of abou~
*0.4 on each reported value of 2 theta. This uncertainty i6, of course, 3180 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 i~ not D-14,223 - L9- ~ 2~80 79 sufficisnt to preclude the differentiation of the present crystalline mate~ials from each other and from the compositions of the prior art. In some of the ~-ray patterns reported, the relative intensities of the d-spacings iare 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 refecen~e to its X-ray powder diffraction pattern. Thus, for example, if a sample is stated to be pure, it is intended only that the ~-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 theic x-ray powder diffraction patterns and such may have one of the x-ray patterns set forth in the following Tables A
through N, wherein said x-ray patterns are for both the as-synthesized and calcined forms unless otherwise noted:
TABLE A (Zn~PS0-5) 2~ d (R~ Relative Intensity 7.2 - 7.412.~8 - 11.91 vs 19.4 - 19.84.58 - 4.48 m 21.0 - 21.24.23 - 4.19 m 22.3 - 22.53.971 - 3.952 m-s 25.7 - 26.03.466 - 3.427 w-m D-14,223 TABLE B (ZnAPSO-ll) 2e d(A2 Relative Inte~sity 9.35 - 9.459.44 - 9.35 m 13.15 - 13.356.67 - 6.63 ~
21.1 - 21.254.21 - 4.19 s-Ys 22.75 - 22.853.911 - 3.8~6 s-vs 23.15 - 23.33 r 839 - 3.8l9 w-m 26.8 - 26.93.327 - 3.313 w-m TAB~E C (Zn~PSO-20~
2e d~A) Relative Intensitv 13.85 - 14.0 6.39 - 6.33 m 19.65 - 19.8 4.52 - 4.48 m 24.15 - 24.3 3.685 - 3.663 vs 28.0 - 28.15 3.187 - 3.170 w 31.35 - 31.5 2.853 - 2.840 w 34.5 - 34.65 2.600 - 2.589 w-m TABLE D (ZnAPS0-31) 2e d(R) Relative IntensitY
8.4 - 8.510.53 - 10.40 ~
20.2 - 20.34.40 - 4.37 m 21.3 4.171 w 22.0 4.036 m 22.5 - 22.63.952 - 3.934 vs 31.6 - 31.752.831 - 2.820 w-m TABLE E (ZnAPS0-34) 2e d~A) Relative IntensitY
9.4 - 9.8 9.41 - 9.03 m-vs 12.7 - 13.2 6.97 - 6.71 w-m 15.8 - 16.2 5.61 - 5.47 w-m 20.5 - 20.9 4.33 - 4.25 m-vs 25.0 - 25.3 3.562 - 3.520 vw-m 30.5 - 30.9 2.931 - 2.894 w-m D-14,223 TABLE P ~ZnAPS0-351 2e d(A) Relative Intensit~
10.8 - 11.08.19 - 8.04 m-vs 13.30 - 13.56.66 - 6.56 m-vs 17.2 - 17.455.16 - 5.08 m 20.95 - 21.24.24 - 4.19 ~
21.9 - 22.154.06 - 4.01 m-vs 32.0 - 32.5 2.797 - 2.755 m TABLE G (ZnAPS0-36) 2e d~A) Relative Intensity 7.45 - 8.0 11.14 - 11.04 vs 16.45 - 16.5 5.38 - 5.36 w-m 19.1 - 19.2 4.65 - 4.62 w-m 20.8 - 20.9 4.28 - 4.25 w-m 21.75 - 21.8 4.09 - 4.08 w 22.05 - 22.15 4.027 - 4.017 w TA8LE H (ZnAPS0-39) 2e d(A) Relative Intensitv 9.35 - 9.45 9.4~ - 9.36 m 13.15 - 13.35 6.73 - 6.63 m 18.3 - 18.4 4.85 - 4.82 w-m 21.1 - 21.2 4.21 - 4.19 s-Ys 22.75 - 22.8~ 3.909 - 3.892 s-vs 26.8 - 26.3 3.389 - 3.314 w-m TABLE J (ZnAPS0-43) 2e d(~) Relative Intensitv 12.3 - 12.45 7.20 - 7.11 m-vs 16.8 - 16.95 5.28 - 5.23 vw-w 21.7 - 21.85 4.095 - 4.068 vw-m 26.95 - 27.1 3.308 - 3.291 5-VS
32.4 - 32.S5 2.763 - 2.751 w-m D-14,223 -- 22-- ~ 2L~8~7~

TABLE K (ZnAPS0-44) 2a d(~2 Relative IntensitY
9.4 - 9.559.41 - 9.26 vs 12.9 - 13.056.86 - 6.78 vw-m ~0.65 - 20.84.30 - 4.27 m 21.4 - 21.84.15 - 4.08 w-m 24.3 - 25.153.663 - 3.541 m 30.75 - 30.952.90B - 2.889 TABLE L (ZnAPS0-46) 2e dtA) Relative Intensitv 7.6 - 7.7511.63 - 11.42 vs 13.1 - 13.356.76 - 6.63 w-m 21.5 - 21.~4.13 - 4.12 w-m 22.6 - 22.853.934 - 3.89S m 26.75 - 27.03.333 - 3.302 w TABLE ~ (ZnAPS0-47) 2~ dtA? Relative Intensity 9.45 - 9.65 9.35 - 9.17 vs 12.85 - 13.05 6.89 - 6.78 w-m 15.95 - 16.2 5.55 - 5.46 w-m 20.55 - 20.85 4.31 - 4.26 m-vs 25.9 - 26.23.439 - 3.399 w-m 30.55 - 31.02.925 - 2.885 w-~
The following examples are provided to further illustrate ~he invention and are not intended to be limiting thereof:
PREPARATIVE REAGENTS
In the following examples the ZnAPS0 compositions were prepared using numerous reagents.
The reagents employed and abbreviations employed herein, if any, for ~uch reagents are as follows:
a) Alipro: aluminum isopropoxide;

D-14,223 ' - ~

b) LUDOX-LS: LUDOX-LS is the trade name of DuPont for an aqueous solution of 30 weight percent SiO2 and 0.1 weight percent Na20;
c) CATAPAL: Trademark of Condea Corporation for :hydrated pseudo-boehmite~
d) H3PO4: 85 weight percent aqueous phosphoric acid;
e) ZnAc: Zinc Acetate, Zn(C2H302)2 4H20;
f) TEAOH: 40 weight percent aqueous solution of tetraethylammonium hydroxide;
g) TBAOH: 40 weight percent aqueous solution of tetrabutylammonium hydroxide;
h) TMAOH: Tetramethylammonium hydroxide pentahydrate, (CH3)4NOH-5H20;
i) TPAOH: 40 weight percent aqueous solution of tetrapropylammonium hydroxide, (C3H7)4NOH;
j) Pr2NH: di-n-propylamine, (C3H7)2NH;
k) Pr3N: Tri-n-propylamine, (C3H7)3N;
1) Quin: Quinuclidine, ~C7H13N);
m) C-hex: cyclohexylamine; and n) DEEA: diethylethanolamine, ( C2H5 ) 2~C2H5H .

LUDOX is a Trademark of E. I. du Pont de Nemours and Co.

D-14,223-C

~L2~

PREPARATIVE PROCEDURE
The ZnAPSO compositions were prepared by preparing reaction mixtures having a molar composition expressed as:
eR:fZnO:gA1203:hP205:iSiO2:i~20 wherein e, f, g, h, i and j represent the moles of template R, zinc (exeressed as the oxids), 2 3~ P205 (H3PO4 eXpressed as P205), SiO2 and H20, respectively. The values for e, f, g, h, i and j were as ~e~ forth in the hereinafter discussed preparative example~ where "j" was 50 in each example, and "e" wafi 1Ø
The reaction mixtures were prepared by forming a ~tarting reaction mixture comprising the H3PO4 and a portion of the water. This mixtu~e ~as stirred and the aluminum source added. The resulting mixture was blended until a homogeneous mixture was observed. The LUDOX LS was then added to the resul~ting mixture and the new mixture blended until a homogeneous mixture was observed. The zinc source (zinc acetate) was dissolved in the remaining water and combined with the first mix~ure. The combined mixture was blended until a homogenous mixture was observed. The organic templating agent was added to this mixture and blended for about two to four minutes until a homogenous mixture was observed. The resulting mixture (final reaction ~ixture) was placed in a lined (polytetrafluo~o-ethylene) stainle6s steel pressure vessel and digested at an effective temperature for an effective time. All digestions were carried out at D-14,223 ~2~

the autogeneous pressure. The products were removed from the reaction vessel cooled and evaluated as set forth heceina~ter.
Examples 1 to 41 Zn~PS0 molecular sieves were prepared according to the above described proceduLe and the Zn~PSO products determined by x-ray analysis. The results of preparative examples 1 to 41 are set forth in Tables I and II. The reactive zinc sou~ce was zinc acetate. The reactive aluminum source was Al-ipro. The reactive phosphorus source was H3P04. the reactive silicon source was LUD0~-LS. The organic templating agents are set forth in Tables I and II.

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æ7 ExamPle 42 Samples of the pcoducts of examples 4, 17, 24, 33, 35 and 39 we~e subjected to chemical analysis. The chemical analysis for each product is given hereinafter with the example in which the ZnAPSO was prepared being given in ~aren~hesis after the desîgnation of the Zn~PSO species.
~ a) The chemical analysis Eor Zn~PSO-5 (Example 43 was:
comPonent Weiqht Percent A123 31.3 P205 ~5.7 zno 2.8 Si2 5 7 Carbon 5 5 LOI* 12.8 ~LOI = Loss on Ignition The above chemical analysis gives an overall product c~mposition in molar oxide ratios tanhYdrous basis) of: 0.17R, 0.11 ZnO; 1.0 A1203; 1-05 P2O5; 0.31 sio2; and a formula tanhYdrous basis) of:
0.04R tzn0 03A1o 44Po.47 0-07 2 (b) The chemical analysis for ZnAPSO-34 tExample 17) was:
Componen~ ~eight Percent A123 32.3 P205 35.3 Zno 2.8 SiO2 1.6 Carbon 5.0 LOI* 26.7 *LOI = Loss on Ignition D-14,223 7g The above chemi~al analysis gives an ovecall pcoduct composition in molar oxide ratio6 (anhydcous basis) of: 0.16 R; 0.11 ZnO: 1.0 A1203; 0.79 P205: 0.08 Sio2; iand a focmula (anhydrous basis) of:
0.04R (Zn0 03Alo 54]P0~4lsio~o2) 2 lc) The chemical analysis foc ZnAPSO-34 (Example 24) was:
Component Weiqh~ Peccent A123 36.2 P2O5 30.3 ZnO 3.8 SiO2 3.7 Cacbon 5.2 LOI* 24.0 *LOI = Loss on Ignition The above chemical analysis gives an overall product composition in molar oxide ratios of: 0.15-R; 0.13 ZnO; 1.0 A12O3; 0.60 P2O5:
0.07 SiO2; and a formula ~anhydcous basis) of:
0.04R (Zn0 04A10 57po~345io-o5) 2 ~d) The chemical analysis of ZnAPSO-35 (Example 33) was:
Component Weiqht Peccent P205 33.2 ZnO 5.6 SiO2 7.6 Carbon 10.1 LOI~ 22.1 ~LOI = Loss on Ignition The above chemical analysis gives an ovecall pcoduct composition in molac oxide catios D-14,223 _ 30_ ~ 7~

of: 0.40R: 0.23 ~nO; 1.0 A1203; 0.78 P205;
0.42 SiO2; and a formula (anhydrous basis) of:
0.12R (Z~O o~Alo g7P0~37siO~lo) 2 (e) The chemical analysis for ZnAPSO-44 (Example 35) was:
Component ~eiqht Percent ~123 27.5 P205 31.1 Zno 4.8 SiO2 10.6 Carbon 11.7 LOI* 25.1 ~LOI = Loss on Ignition The above chemical analysis gives an overall product composition in molar oxide ratios of: 0.60 R; 0.22 ZnO: 1.0 A1203; 0.81 P205;
0.65 SiO2; and a formula (anhydrous basis) of:
0.13R (ZnO o5Alo 44P0.3SS 0.15 2 (f) The chemical analysis of ZnAPSO-47 (Example 39) was:
ComPonent Weiqht Percent P205 32.~
ZnO 5.3 SiO2 6.5 Carbon 7.7 LOI~ Z3.4 ~LOI = Loss on Ignition The above chemical analysis gives an overall product composition in molar oxide ratios of: 0.35 R; 0.22 ZnO; 1.0 A1203; 0.77 P205;
0.36 SiO2; and a formula (anhydrous basis) of:
o~osR tznO 05Alo ~9Po~37sio~o9) 2 D-14,223 ExamPlQ 43 EDAX (energy dispersive analysis by x-ray) microprobe analysis in conjunction with SEM
(~canning electron microscope ~as carried out on clear crystals from the products of examples 4, 24.
33, 35 and 39. Analysis of crystals having a morphology characte~istic of the Zn~PSO products gave the following analysis based on relative peak heights:
a) ZnAPS0~5 (ExamPle 4):
Average of Spot Probes Zn Al 44 Si 5 bl ZnAPSO-34 (ExamPle 24~:
Average of Spot Probes Zn 3 Al Si 6 c) ZnAPSO-35 tExample 33i:
Average of Spot Probes Zn 5 Al 43 Si 6 d) ZnAPSO-36 (ExamPle 4):
Average of Spot Probes Zn 4 Al 42 si D-14,223 - 32- ~8~79 e) ZnAPS0-44 (Example 35~:
~verage of Spot Probes Zn 2 Al Si 16 f) Zn~PS0-47 (ExamPle 392:
Average of Spot Probes Zn 5 Al 42 P ~0~
si g ~ xa~Ple 44 Samples of the ZnAPS0 products of exa~ples 4, 27, 33, 35 and 39 were for adsorption capacities evaluated in the as-synthesized form or were calcined in air or nitrogen, to remove at least part of the organic templating agent, a~ hereinafter ~et forth. The ad60rption capacities of each calcined sample were measured u~ing a 6tandard McBain - Bakr gravimetric ad60~ption apparatus. The sa~ples were activated in a vacuum at 350C prior to mea~urement. The McBain-Bakr data for the aforementioned calcined ZnAPS0 eroducts were:
a) ZnAPS0-5 (Exam~le 4):
Xinetic Pressure Temp Adsorbate Diameter, A (Torr) (C) Adsorbad*
~z 3.46 99 -183 11.0 2 3.46 749 -183 14.9 neopentane 6.2 100 23.4 3.5 cyclohexane 6.0 57 Z3.4 7.4 H20 2.65 4.6 23.2 13.5 H20 2.65 16.8 23.5 17.5 calcined in air at 500C for 0.75 hours and at 600C for 1.25 hour6 erior to activa~ion.

D-14,223 7~

The above data demon~trate that the poce Rize of the calcined produc~ is greater than 6.ZA.
b) ZnAPS0-34 tExamPle 27):

Kinetic P~essure Temp ~t. ~
Adsocbate Diameter, A ~Torr) (C~ Adsorbed*
2 3.~6 ~9 -183 14.5 2 3.46 725 -183 25.8 isobutane 5.0 100 2Z.8 0.8 n-hexane 4.3 98 23.313~3 H2O 2.65 4.6 23.119.9 HzO 2.65 17.8 23.130.1 ~ calcined in air at 500C for 2 hours prior to activation The above data demonstrate that the pore si~e of the calcined product i6 about 4.3A.
c) ZnAPS0-35 (ExamPle 331:

Kinetic Pressure Temp Wt. %
Adsorbate Diameter,_A (Torr) (C) Adsorbed 2 3.46 99 -183 10.2 2 3.46 7~5 -18~ 19.1 n-hexane 4.3 98 23.3 8.6 isobutane 5.0 100 22.8 0.8 H20 2.65 4.6 23.117.2 H20 2.65 17.8 23.126.3 * calcined in air at 500C for 1.75 hours prior to activation The above data demonstra~e that the pore size of the calcined product i6 about 4.3A.

D-14,223 7~

d) ZnAPS0-44 (ExamPle 35):

Kinetic Pressure Temp Wt. ~
Adsolbate Diame~er, R tTorr) (C) Ad~orbed*
2 3.46 99 -183 10.3 2 3.46 7~5 -183 19.8 n-hexane 4.3 98 23.3 9.7 i~obutane 5.0 100 22.8 0.8 H20 2.65 4.6 23.114.0 HzO 2.65 17.B 23.124.0 ~ calcined in air at 500C for 67 hours prior ~o activation The above data demonstrate that ~he pore size of ~he calcined product is about 4.3A.
e~ ZnAPS0-47 (Example 39):
Kinetic Pressure Temp Wt. ~
Adsorbate Diameter, A tTorr) (C) Adsorbed*
2 3.46 99 -183 13.9 2 3.~ 725 -183 23.0 isobutane 5.0 100 23.8 0.7 n-hexane ~.3 98 23.3 7.8 H20 2.65 4.6 23.118.8 H20 2.65 17.8 23.127.0 ~ calcined in air at 500C for 1.75 hours prior to activation The above data demonstrate that the pore 8ize of the calcined product is about 4.3A.
Example 45 ~ a) Zn~PS0-5, as prepared in example 4, was subjected to x-Eay analysis. ZnAPS0-5 was determined to have a chaIacteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth below:

D-14,223 2e d. ~A) 100 x I~Io 7.4 11.91 100 7.9~* 11.17 29 12.85 6.88 lo 13.5* 6.56 14.85 5.96 19 15.85** 5.60 3 16.4~** 5.39 8 19.1*~ 4.65 9 19.7 4. Sl 38 20.3** 4.38 4 20.8~* 4.27 10 21.05 4.22 30 21.5~* 4.1~ 5 21.65~ 4.10 5 22.4 3.973 73 22. g5~* 3.876 3 23.85~* 3.730 24.75 3.59~ 2 25.9 3.442 25 27. ~** 3.279 4 27.75** 3.212 28.3** 3.154 2 29.0 3.078 1~
29. ~5 2.981 15 30.35** 2.947 2 32.0** 2.798 3 33.6 2.666 4 34.45 2.602 12 34.8** 2.577 35.45~* 2.532 2 35.9 2.501 36.95 2.434 3 37.7 2.38~ 7 41.45~ 2.177 2 42.2 2.141 3 42.8 2.112 43.4 Z.085 45.0 2.013 47.6 1.910 4 Sl .4 1.778 2 51.95 1.760 55.6* 1.654 2 ....
* peak may contain impu~ity ** impur ity peak D~14,223 - 36- ~ ~9 (b) A portion of the as-synthesized ZnAPS0-5 of part (a) was calcined in air at 500C
for about 0.75 hours and then in air at 600C for about 1.5 hours. The calcined produc~ was characteri2ed by the x-ray po~der diffrac~ion pattern below:
2~ d, ~ 100 x I/Io 7.~5 11.91 100 7.85~ 11.23 21 8.2* 10.79 7 12.9 6.87 20 13.45* ~.57 3 14.9 5.95 6 16.5* 5.37 5 19.35~ ~.58 5 19.75 4.49 24 20.3 4.38 10 20.7 4.2g 4 21.1 4.21 28 21.4 4.14 11 22.4 3.9~2 69 22.75* 3,907 5 24.85 3.584 2 26.0 3.430 24 27.25* 3.275 27.45* 3.252 2 27.8~ 3.207 2 28.15* 3.168 3 28.35* 3.146 2 29.1 3.068 16 30.1 2.97~ 14 33~7 ~.658 3 34.6 2.5g2 13 35,45* 2.532 4 37.05 2.42~ 3 37.85 2.378 6 42.4 Z.132 2 47.8 1.903 2 51.5 1.774 3 55.8 1.~47 _ * Impurity Peak D-14,223 (c) The Zn~PS0-5 compositions ace gene~ally characteri~ed by the data of Table III
below.
Table III
2e d tR) Relative IntensitY
7.Z-7.4 12.28-11.91 v~
19.4-19.8 4.58-4.48 m 21.0-21.2 4.23-4.19 ~
22.3-Z2.5 3.971-3.952 m-s 25.7-26.0 3.466-3.427 w-m (d3 The Zn~PS0-5 compositions for which x-ray powde~ diffraction data have been obtained ~o date h~ve patterns which a~e characterized by the x-ray powder diffraction patteln shown in Table IV, below.
Table IV
2~ d, (~1 100 x I/Io 7.2-7.4 12.28-11.91 100 12.6-13.0 7.03-6.81 8-21 14.6-14.9 6.07-5.95 g-20 19.4-19.8 4.5~-4.48 24-38 21.0-21.2 4,23-4.19 20-35 22.3-22.5 3.971-3.952 47-8Z
24.7-2~.9 3.604-3.576 l-Z
25.7-26.0 3.466-3.427 18-27 28.9-2g.1 3.V89-3.069 10-20 29.9-30.1 2.9~8=2.969 12-17 33.6-33.8 2.667-2.652 3-4 34.4-34.S Z.607-2.592 10-14 36.9-37.0 2.436-2.430 2-3 37.6-37.9 2.392-2.374 5-8 41.45 2.177 0-2 42.2-42.4 2.141-2.132 Z-3 42.8 2.113 0-1 ~3.4 2.090 0-1 45.0 2.014 0-1 47.5-47.8 1.914-1.903 2-4 51.3-51.6 1.781 2-3 51.95 1.760 0-1 55.5-55.8 1.656-1.647 0-2 D-14,223 Example 46 (a) ZnAP5~-11, as prep~red in example 10 ~a6 subjected to x-ray analysis. ZnAPS0-11 wa~
determined to have a charactecistic x-ray powder diffraction pattern which contains at least the d-spacings set forth below:
2e d, (A~ 100 x I~Io 6.6** 13.44 10 7.7** 11.46 97 8.1 10.89 26 8.~5~* 10.44 6 9 4~* 9.35 60 13.3* 6.66 22 13.8** 6.43 4 14.9** 5.94 5 15.3** 5.80 8 15.7 5.64 24 16.2 5.47 3 16.65** 5.33 7 18.35** 4.83 16 19.0 4.66 4 19.8** 4.49 4 20.45* 4.35 29 21.1* 4.20 100 21.55** 4.123 24 22.2* 4.008 32 22.75 3.905 85 23.2 3.~30 45 24.2** 3.674 24.45** 3.643 3 24.a 3.590 5 26.55 3.355 14 26.8* 3.327 12 27.8~* 3.212 4 28.7~ 3.109 20 29.05* 3.075 5 29.8* 3.000 11 30.15* 2.966 11 ~0.75** 2.909 3 31.1~* 2.874 5 31.6 2.832 6 32.85* 2.725 11 34.3* 2.615 7 34.5** 2.598 5 D-14,223 7~3 d~ (A) 100 x I/Io 35.9* 2.501 6 36.55* 2.4S~ 5 37.85* 2.377 10 39.7~ 2.~70 43.0* 2.103 4 44.85 2.022 3 48.85~ 1.864 3 50.8 1.797 54.8 1.675 * Peak may contain impurity *~ Impurity Peak (b) The ZnAPS0-11 compositions aee generally characterized by the data of Table V below.
Table V
2e d (R~ Relative IntensitY
9.35-9.45 9.44-9.35 m 13.15-13.35 6.67-6.63 m 21.1-21.25 4.21-4.19 8-VS
22.75-22.8S 3.911-3.896 6-VS
23.15-23.3 3.839-3.819 w-m 26,8-26.9 3.327-3.313 w-m ~c) The Zn~PS0-11 compositions for which x-ray powder diffraction data have been obtained to date have patterns which are characterized by the x-ray powder diffraction pattern shown in Table VI, below:
Table VI
2e d, tA? 100 x I/Io 8.05-8.1 10.98-10.92 8-26 9.35-9.45 9.~4-9.35 5~-72 13.15-13.35 6.67-6.63 22-40 15.65-15.75 5.66-5.62 10-27 16.05-16.2 5.53-5.47 0-3 19.0 4.66 0-4 19.85 4.49-4.46 4-14 20.4-20.5 4.35-4.33 19-38 D-14,223 2e d, (R) 100 x I/Io 21.1-21.25 4.21-4.19 83-100 22.~-22.25 4.018-3.998 12-32 22.75-2Z.85 3.911-3.896 85-100 23.15-23.3 3.83~-3.819 12-45 26.45-26.55 3.369-3.354 8-14 26.8-26.9 3.327-3.313 1~-40 28.7-28.8 3.111-3.100 20-36 29.75-29.85 3.005-2.993 11-Z3 31.6-31.8 2.832-2.813 0-10 32.8-32.95 2.731-2.719 7-15 3~.2-34.3 2.620-2.615 6-9 35.B5-36.0 2.503-2.495 6-12 36.45-36.55 2.46~-2.~59 4-8 37.65-37.7 2.3~9-2.387 0-7 37.~5 2.377 0-10 39.7 2.271 0-1 43.0-43.05 2.103-2.100 0-4 44.85-~4.9 2.022-2.018 0-3 48.75-48.85 1.867-1.864 0-3 50.8-50.9 1.797-1.794 0-3 54.8 1.675 0-1 Example 47 (a) ZnAPS0-20, as prepared in example 29, was subjected to x-ray analysis. ZnAPS0-20 was determined to have a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set for~h below:
2e d, (A~ 100 x IJIo 12.35* 7.17 6 13.9 6.37 47 14.35* 6.16 2 14.5~ 6.10 14.65~ 6.04 14.85~ 5.96 19.75 4.50 40 20.8* 4.27 21.05* 4.22 21.7* 4.09 3 22.1 4.024 2 24.25 3.672 100 24.~5* 3.582 D-14,223 2e d, tA) 100 x IiIo 27.0* 3.302 5 28.05 3.181 12 28.65* 3.116 31.45 2.845 12 32.4~* 2.758 34.55 2.596 Zo 37.45 2.~02 2 38.~* 2.248 40.1 2.344 4 42.65 2.1Z1 4 45.13* 2.009 47.4 1.917 5 49.35* 1.846 51.8 1.765 9 _ ~Impurity peak (b) The ZnAPS0-20 compo~i~ions are generally characterized by the data of Table VII
below:
Table VII
2e d, (A~ Relat;ve Intensit~
13.85-14.0 6.39-6.33 m 19.65-19.8 4.52-4.48 m 24.15-24.3 3.685-3.663 vs 28.0-28.15 3.187-3.170 w 31.35-31.5 2.853-2.840 w 34.5-34.65 2.600-2.589 w-m (c~ The ZnAPSO-Z0 compositions for ~hich x-ray powder diff~action data have been obtained to date have patterns ~hich are ~haracterized by the x-ray powder diffraction pattern shown in Table ~III, below:

D-14,223 37~

Table VIII
2e d, (A) 100 x I/To 13.85-14.0 6.39-6.33 45-47 19.65-19.8 4.52-4.48 40-41 22.0-22.15 4.040-4.013 2-3 24.15-24.3 3.685-3.663 100 28.0-28.15 3.187-3.170 12-13 31.35-31.5 2.853-2.840 11-12 34.~-34.65 2.60g-2.589 16-20 37.35-37.5 2.408-2.398 2 40.0-40.2 2.254-2.243 4 42.55-~2.7 2.125-2.118 4 47.35-47.5 1.920-1.914 5 51.75-51.9 1.767-1.762 8-9 ExamPle 48 (a) Zn~PS0-31, as p~epa~ed in example 14, was subjected to x-~ay analysis. ZnAPS0-31 was dete~mined to have a characte~istic x-~ay powder diffraction patte{n which contains at leas~ the d-spacings set fo~th balow:
2~ d~ 100 x I/Io 6.6~ 13.~0 14 7.7** 11.45 10 8.1** 10.94 11 8.5 10.40 50 9.5* 9.32 8 9.85~ a.96 2 1~.45*~ 7.12 25 13.4 6.60 10 17.05 5.21 5 1~.4*~ 5.10 3 18.25 ~.86 8 20.3 4.38 52 21.3* 4.17 16 21.6~* 4.11 10 22.0 4.036 30 22.6 3.394 100 23.55~ 3.779 2 24.25** 3.66B 3 D-14,223 2e d. (A) 100 x I/Io 25.15* 3.543 4 2~.0** 3.302 3 ~7 75* 3~3 12 27.95 3.192 13 28.2* 3.162 4 28.7** 3.109 3 29.75 3.004 10 30.3 2.g50 4 31.75 2.81~ 20 32.~5 2.71~ 4 34.2** 2.623 3 35.15 2.554 12 35.7* 2.515 3 35.9* 2.500 3 36.2 2.481 4 37.~5* 2.413 3 37.~5* 2.390 Z
38.25 2.353 3 39.3 2.291 2 40.3 2.238 2 45.0* 2.014 2 46.6 1.949 4 47.4** 1.918 2 48.S 1.873 2 51.5 1.774 7 ~ peak may contain impurity **impurity peak ~b) The ZnAPSO-31 compositions are generally characterized by the data of Table IX
below:
Table IX
2e d, (A) Relative IntensitY
8.4-8.5 10.53-10.40 m 20.2-20.3 4.40-4.37 m 21.3 4.171 w 22.0 4.036 m 22.5-22.~ ~.952-3.934 ~s 31.6-31.75 2.831-2.820 w-m D-14,223 g (c) ~he ZnAPS0-31 compositions ~OI
which x-ray powdec diffrac~ion data have been obtained to date have patterns which are characterized by the x-ray powder diffraction pat~ern hown in ~able ~, below:
Table ~
2e d, (A) 100 x I/Io 8.4-a.~ 10.53-10.40 50-53 9.45-9.5 9.35-9.32 7-8 13.~-13.4 6.7~-6.60 10-11 18.2-18.25 4.87-4.8h 5-8 20.2-20.3 4.39-4.37 ~9-5Z
21.3 4.171 16-lB
22.0 4.036 30 22.5-22.6 3.952-3.934 100 26.9-27.0 3.314-3.30Z 3-7 27.95-28.25 3.192-3.529 13-17 29.6-29.7 3.018-3.008 8-10 30.2-30.3 2.959-2.950 0-~
31.6-31.75 2.831-2.820 18-20 3Z.95 2.718 4-9 35.1~-35.2 2.554-2.550 12 36.1-36.2 2.489-2.481 4-7 37.25-37.35 2.413-2.409 2-3 38.25 2.353 3 39.3 2.291 2 40.3 2.238 2 46.6-4~.65 1.949-1.948 4-6 47.4-47.45 1.918-1.916 2-4 51.5 1.774 7 ExamPle 4g (a) ZnAPS0-3~, as prepared in example 24, was subjected to x-ray analyRis. ZnAPS0-34 was determined to have a characteristic x-ray powder diffraction pattern which contains at least the d-~pacings set forth below:

D-14,223 ~2~

Table XIII
2~ d, (A) 100 x I~Io 9.~ 9~19 100 12.95 6.8~ 16 14.2 6.25 14 16.1 5.50 ~2 18.1 ~.gO 22 20.65 4.30 - 91 22.4 3.978 5 23.15 3.842 5 25.3 3.5Z1 25 25.9 3.437 18 27.7 3.218 5 28.45 3.135 6 29.~5 3.01~ 5 30.S 2.920 33 31.3 2.856 , 23 32.5 2.755 2 34.45 2.~02 7 36.4 2.468 5 38.8 2.320 4 39.75 2.2~7 5 43.15 2.097 4 43.55~ 2.077 4 47.65 1.908 5 49.10 1.856 8 49~9 1.827 4 51.0 1.791 4 53.15 1.723 3 54.~5 1.679 3 55.9 ~ 1.645 3 ~., * impurity peak (b) A portion of the as-synthesized ZnAPS0-34 of part a) was calcined in air at 500C
for about 2 hours. The calcined product was characterized by the x-ray powder diffraction pattern belo~:

D-14,223 7~

2~ d. (A~ 100 x I/Io .55 9.27 10 12.95 6.85 2 16.15 5.49 13 17.95 4.94 10 20.75 4.28 30 22.2 4.004 2 23.25 3.828 5 25.2 3.533 9 26.15 3.411 12 28.45 3.138 4 30.9 2.896 15 31.35 2.852 9 (c) The ZnAPS0-34 compositions are generally characterized by the data of Table ~1 below.
Table ~I
2~ d, (A) Relative Intensitv 9.4-9.8 9.41-9.03 m-vs 12.7-13.2 6.97-6.71 w-m 15.8-16.2 5.61-5.47 w-m 20.5-20.9 4.33-4.z5 m-vs 25.0-25.3 3.562-3.52Q vw-m 30.5-30.9 2.931-2.89~ w-m (d) The ZnAPS0-34 compositions for which x-ray powder diffraction data have been obtained to date have patterns which are charàcterized by the x-ray powder diffraction pattern shown in Table ~II, belov:
Table XII
2~ d, (A~ 100 x I/Io 9.4-9.8 9.41-9.03 77-100 12.7-13.2 6.97-6.71 16-31 14.0-1~.3 6.33-6.19 0-22 15.8-16.2 5.51-5.47 16-47 17.8-18.2 4.98-4. a7 13-29 20.5-20.9 4.33-4.25 36-100 D-14,223 2e d. (A) loO x IJIo 22.2-22.5 4.004-3.952 5.8 23.0-23.3 3.8~7-3.~18 5-6 ~5.0-~5.3 3.562-3.~20 9-3Z
2~.7-26.25 3.466-3.395 12-20 27.4~-27.7 3.249-3.220 5-8 28.1-28.45 3.175-3.137 4-8 29.4-29.8 3.03~-2.998 0-5 30.5-30.9 -2.931-2.894 16-35 31.0-~1.65 2.~85-2.827 9-25 32.2-32.5 2.780-~.755 o-Z
3~.3-34.8 2.614-2.578 5-8 36.1-36.4 2.488-2.468 0-5 38.65-38.8 2.330-~.321 0-4 39.5-39.8 2~2al-2~26~ 4-7 43.0-43.4 2.103-2.085 4 47.5-48.0 1.914-1.895 3-6 48.8-49.1 1.8~-1.855 49.9 1.859 0_4 50.8-51.0 1.797-1.791 0-4 53.1-53.15 1.725-1.723 0-3 54.5-54.8 1.684-1.675 0-3 55.8-55.9 1.647-1.645 0-4 ExamPle 50 (a) 2nAPS0-35, as prepared in example 33, was subjected to x-ray analysis. ZnAPS0-35 was dete~mined to have a characteri~tic x-ray powder diffraction pattern which contains at least the d-spacings set forth below:
2e d, (R) lOo x I/Io 8.6 10.27 20 10.5* 8.44 sh 10.95 8.08 47 11.35 7.80 4 13.30 6.66 39 1~.9 5.57 10 17.3 5.13 72 17.8 4.98 sh 21.15 4.20 48 21.9 4.06 100 23.15 3.841 19 23.65 3.762 3 D-14,223 ~L2~

2~ d, ~A) 100 x I/Io 25.05 3~52 4 26.~ 3.325 22 28.7 3.107 30 29.1 3.069 sh 32.1 2.788 43 34.75 2.582 9 3~.5 2.530 3 35.8 2~507 5 37.75 2.382 5 39.35 2.889 4 ~2.35 2.134 6 43.15 2.096 48.6 1.~73 11 49.4 1.845 8 51.55 1.773 6 55.3 1.661 6 ~impurity peak (b) A portion of the as-~ynthesized ZnAPS0-35 of part a) ~as calcined in air at 500~C
for about 1.75 hours. The calcined pEoduct was characterized by the x-~ay powder diffraction patte~n below:
2~ d,_(A) 100 x I~'Io 7.45* 11.~5 10 8.7 10.15 22 11.0 ~.04 91 13.5 6.55 100 17.45 5.08 35 Zl.0 4.23 21 22.15 4.011 60 23.5 3.782 19 ~5.15 3.542 13 27.2 3.278 20 28.6 ~.122 28 29.35 3.041 1~
32.~5 2.759 28 .
*impurity peak D-14,223 ~c) The ZnAPS0-35 composition~
obtained to date have pattelns which ar~ generally characte~ized by ~he data of Table XIII below.
Table ~III
2e d, (A) Relative Intensi~Y
10.8-11.0 8.19-8.04 m-vs 13.30-13.5 6.66-6.56 m-vs 17.2-17.45 5.16-5.08 m 20.95-21.2 4.24-4.1g m 21.9-22.15 4.06-4.01 m-vs 32.0-32.5 2.797-2.755 m - (d) The ZnAP50-35 compositions fo~
which x-~ay powder diffraction data have been obtained to date have patte~n~ which a~e characte~ized by the x-ray powder diff~action pattern shown in Table XIV belo~:
2~ d. fA) 100 x I/Io 8.6-8.7 10.27-10.16 18-2Z
10.8-11.0 8.19-8.0~ 43-91 11.35 7.80 0-4 13.30-13.5 6.66-6.56 39-100 15.8-15.9 5.61-5.57 0-10 17.2-17.45 5.16-5.08 35-75 17.8-17.9 4.98-4.96 0-sh 20.95-21.2 ~.24-4.19 21-~9 21.~-22.15 4.06-4.01 60-100 23.0-23.5 3.867-3.786 0-19 23.65 3.762 0-3 24.85-25.li 3.583-3.541 4-13 26.6-27.2 3.351-3.278 20-22 28.5-28.8 3.132-3.100 26-30 29.1-29.35 3.069-3.043 sh-14 32.0-32.5 2.797-2.755 28-43 34.55-34.9 2.596-2.57} 0-9 35.7-35.8 2.515-2.507 0-5 37~75 2.382 0-5 39.35 2.889 0-4 42.1-42.35 2.146-2.13~ 0-6 43.0-43.2 2.103-2.094 0-4 48.5-48.7 1.877-1.870 0-11 D-14,223 ~ ~$~

2e d, (A) 100 x I~Io 49.35-49.4 1.847-1.845 0-8 51.4-51.6 1.778-1.771 0-7 55.3-55.4 1.661-1.658 0-6 ExamPle 51 (a) Z~APS0-36, as prepared in example 1, was subjected to x-ray analysis. ZnAPS0-36 was de~e~mined to have a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth below:
2e d, (A2 100 x I/Io 7.45~* 11.85 76 7.95 11.13 100 8.2 10.76 sh 12.9** 6.87 3 13.6 6.52 4 14.9** 5.95 10 15.9 5.58 10 16.45 5.38 Z5 19.1 4.64 16 19.75** ~.50 15 20.8* 4.27 32 21.0S** 4.22 sh 21.75 4.09 14 22.1 4.025 14 22.4* 3.966 24 23.0 3.863 3 23.95 3.716 5 25.9** 3.440 9 27.3 3.269 11 28.35 3.147 7 29.05~ 3.074 9 30.0~* 2.978 8 30.35 2.944 4 32.0 2.796 8 33.2 2.~98 33.65** 2.663 34.5** 2.599 6 34.8 2.575 7 35.9 2.500 2 37.75 2.383 2 40.3 2.237 2 D-14,223 2e d/ (A2 100 x I/Io 41.45 2.178 2 42.2 2.142 4~.6* 1.910 2 51.35 1.779 2

5~.0 1.6g7 55.65 1.6~2 2 *peak may contain impurity **impurity peak (b) The ZnAPS0-36 composi~ions obtained to date have patterns which are generally characterized by the data of Table ~V below.
Table ~V
2~ d, (A) Relative IntensitY
7.45-8.0 11.14-11.04 vs 16.45-16.5 5.3B-5.36 w-m 19.1-19.2 4.65-4.62 w-m 20.8-20.9 4.28-4.25 w-m 21.75-21.8 4.09-4.08 w 22.05-22.15 ~.027-4.017 w 1c) The ZnAPS0-36 compositions for which x-ray powder diffraction data have been obtained to date have patternfi which are cha~acterized by the x-ray powder diffraction pa~tern shown in Table ~VI below:
Table XVI
2a d, (A) 100 x I/lo 7.45-8.0 11.14-11.~4 100 8.2-8.3 10.76-10.68 0-sh 13.55-13.6 S.53-6.50 3-4 15.B5-15.95 5.60-5.56 10-12 16.45-16.5 5.38-5.36 18-31 lg.l-19.2 4.65-~.62 19-22 20.8-20.9 4.28-4.25 17-39 D-14,223 2e d, ~) 100 x I/Io ~1.75-21.8 4.09-4.08 10-17 ~2.05-22.15 4.027-4.017 14-17 23.0-23.05 3.865-3.859 3_4 23.85-24.0 3.728-3.707 3-6 27.25-27.35 3.~73-3.260 9-15 ~8.3-28.~ 3.152-3.142 6-~
30.1-30.4 2.970-2.940 4-6 31.9~-32.1 2.803-2.788 ~-11 33.2-33.~ 2.698-2.665 1-2 34.75-34.~ 2.580-2.572 7-10 35.85-35.95 2.504-2.497 2-6 37.75-37.8 2.384-2.380 ~0.15-40.4 2.246-2.232 1-3 41.45-41.5 2.180-2.176 1-2 42.2-42.3 2.142-2.137 0-2 51.~-51.45 1.77~-1.776 2 54.0 1.697 0-1 55.4-55.8 1.65B-1.648 1-2 ExamPle 52 (a) Zn~PS0-39, as referred to in example 9, was subjected to x-ray analysis.
ZnAPS0-39 was determined to have a characte~istic x-Lay powde~ diff~action pattern which contains at least the d-spacings set forth below:
2~ d, (AL 100 x I/Io ~.5~* 13.59 17 7.65~ 6 173 8.05** 10.99 12 8.35*~ 10.58 4 9.35* 9.44 72 13.25* 6.67 35 13.7~* ~.46 8 14.9** 5.95 8 15.2** 5.82 12 15.65** ~.~6 12 16.6~* 5.34 13 18.3 4.85 36 19.8** 4.~8 4 20.4** 4.35 19 21.1* 4.21 83 21.5** 4.13 36 22.1~* 4.018 12 D-14,223 - 5~-2e d~ (A) - 100 x I/Io ~2.75~ 3.911 100 23.15** 3.839 19 23.95** 3.716 4 24.2*~ 3.681 9 24.8** 3.593 3 Z6.~5** 3.3~g 8 26.8~ 3.32~ 21 27.75~* 3.215 6 28.2~ 3.162 5 28.7~ 3.111 19 29.7~ 3.005 15 30.1* 2.970 2Z
30.6~* 2.922 4 31.05~* 2.~81 7 32.8* 2.731 34.3* 2.615 6 34.55~* 2.597 10 , 35.9*~ 2.502 8 36.45~ 2.464 4 38.05* a.365 5 40.7~ 2.217 4 *peak may con~ain impurity ~*impurity peak (b) The ZnAPS0-39 compositions a~e generally cha~acterized by the data of Table ~VII
belo~.
Table ~II
2~ d, (A) Relative Intensity 9.35-9.45 9.46-9.36 m 13.15-13.35 6.73-6.63 m 18.3-18.4 4.85-4.82 w-m 21.1-21.2 4.21-g.l9 s-vs 22.75-22.85 3.909-3.892 s-vs 26.8-26.9 3.389-3.314 w-m (c) The ZnAPS0-39 compositions for which x-ray powder diffraction data have been D-14,223 obtained to date ha~e patterns ~hich are characterized by ~he x-ray powder diffraction pattern shown in Table ~VIII below:
2e d, (~) 100 x I/Io 9.35-9.45 9o~-9~36 60-72 13.15-13.35 6.73-6.63 ~-40 18.3-18.~ 4.85-4.82 16-40 21.1-21.2 4.21-4.19 83-100 22.75-22.85 3.gO9-3.892 85-1~0 26.8-26.9 3.38~-3.314 12-40 28.2-28.3 3.164-3.153 5-8 28.7-28.8 3.1~0-3.100 19-20 29.7-2g.8 3.008-2.998 1~-3Z
30.1-30.2 2.979-2.959 11-25 32.8-32.95 2.730-2.718 8-12 34.5-34.65 2.600-2.~89 5-6 36.45-36.5 2.46~-2.462 4-12 37.85-38.~ 2.377-2.362 3-10 40.6-40.95 2.222-2.204 0-4 ExamPle 53 (a) ZnAPS0-43, as referred to in exa~ple 28, was subjected to x-ray analy&is. Zn~PS0-43 was deteImined to have a charac~eristic x-ray powder diffIactio~ pattecn which ~ontains at least the d-spacings set forth b~lou:
d, (A): 100 x IJIo 12.45 7.11 76 1~.0* 6.32. 194 16.95 5.~4 8 19.8* 4.4~ 160 20.95 g.24 13 21.15~ ~20 13 21.85 4.07 48 22.15* 4.010 8 24.3* 3.~59 400 27.1 3.291 100 28.15* 3.171 52 28.75 3.104 4 31.55* 2.837 49 32.5S 2.751 20 D-14,223 ~_ ~ L~

2~ d, ~R~ 100 x I/Io 32.75~ 2 733 9 34.25* 2.~20 8 34.65* 2.590 68 37.~* 2.399 8 38.5* 2.340 5 4Q.2~ 2.244 16 41.2 2.1~0 4 42,7x 2.117 16 45.1 2.010 8 47.5* 1.914 18 49.45~ 1.843 7 51.15 1.787 51.9* 1.761 36 53.8 1.704 7 Impurity peak (b) ZnAPS0-43 compo~itions are generally characterized by the data of Table ~IX below:
Table XI~
2~ d, (~? Relative Intensitv 12.3-12.45 7.20-7.11 m-vs 16.8-16.95 5.28-5.23 vw-w 21.7-21.85 4.095-4.068 vw-m ~6.95-27.1 3.30Q-3.291 s-vs 32.4-32.55 ~ 2.763-2.751 w-m (c) The ZnAPS0-43 compositions for which x-ray powder diffraction data have been obtained to date have patterns which are characterized by the x-ray powder diffraction pa~tern shown in Table ~X below:
Table X~
2e d, (A) 100 x I/Io 12.3-12.45 7.20-7.11 ~6-100 16.8-16.95 5.28-5.23 0-10 20.8-20.95 4.27-4.24 10-13 D-14,223 2~ d, (R) 100 x I/Io 21.7-21.85 4.095-4.06B 0-48 26.95-27.1 3.308-3.290 82-100 28.65-28.75 3.116-3.105 11-23 32.4-32.55 2.763-2.751 18-~0 41.2 2.191 0-4 44.95-45.1 2.017-2.010 ~-15 50.9~-51.15 1.792-1.786 0-7 53.7-53.8 1.710-1.707 0-8 Example 54 ~a) ZnAPS0-44 as prepared in example 34, was subjected to x-ray analysis. ZnAPS0-44 was determined to have a characteristic x-ray powder diffrac~ion pattsrn which contains at least the d-spacings set forth below:
2e d, rA) 100 x I/Io 4.95~ 17.93 11 8.75* 10.09 sh 9.25* 9.56 sh g.55 9.25 10 13.05 6.77 13 13.8 6.41 3 lS.15 5.49 21 17.4 5.10 3 19.05 4.65 7 19.6* 4.53 2 20.8- 4.27 4 21.8- 4.08 18 22.65 3.923 4 23.15 3.845 5 2~.45 3.638 47 26.25 3.395 14 27.3* 3.266 27.9 3.197 7 29.8 2.999 3 30.15 2.962 13 30.9 2.8gS 31 32.hS 2.745 2 33.0 2.716 6 3~.9 2.571 2 35.15 2.553 2 35.6 2.523 9 D-14,223 ~2~

2~ d, (~) 100 x I/lo 38.7 2.329 2 39.2~ 2.295 2 40.1 2.247 42.25 2.139 3 42.55 2.124 2 43.7 2.072 48.2 1.887 3 48.8 1.866 4 50.4 l.Bll 5 52.0 1.759 54.0 1.698 7 Impurity peak ~ (b) A por~ion of the as-synthesized ZnAPS0-44 of part a) ~as calcined in air at 500C
for about 67 hours. The calcined product was characterized by the x-ray powder diffraction pattern below:
2e d, (A) 100 x I/Io 9.6 9.23 100 13.0 6.81 34 14.05 6.29 5 16.2 5.48 1~
17.95 4.95 30 20.3~ 4.37 22 20.8 4.27 52 21.4 4.15 32 22.3 3.987 7 22.75* 3.906 7 23.25 3.~26 10 24.~5** 3.599 5 25.15 3.538 2Z
26.15 3.406 11 28.4 3.142 9 28.75*~ 3.107 7 30.95 2.888 23 D-14,223 7~

2~ d, (R) 100 x I/Io 31.3~* 2.852 15 35.3* ~.542 9 * Peak may contain impurity Impurity peak (c) The ZnAPSO-44 compositions are generally characterized by the data of Table ~XI
below:
Table ~I
2~ d, tA) Relative Intensity 9.~-9.55 9.41-9.~6 vs 12.9-13.05 6.86-6.78 vw-m 20.65-20.8 4.30-4.27 m 21.4-21.8 4.15-4.08 w-m 24.3-25.15 3.6S3-3.541 m 30.75-30.95 2.908-2.889 m (d3 The ZnAPS0-44 compo~itions for which x-ray powder diffraction data have been obtained to date have patterns which are characterized by the x-ray powder diffraction pattern shown in Table ~II below:
2~ d, (A~ 100 x I/Io 9.4-9.55 9.41-9.25 100 12.9-13.05 6.86-6.78 ~-34 13.6-14.05 6.51-6.30 3-5 16.0-16.2 5.54-5.~7 14-21 17.25-17.95 5.14-4.94 0-6 18.95-19.05 4.68-4.66 0-5 20.65-20.8 4.30-4.27 35-5Z
21.4-21.8 4.15-4.08 18-32 22.55-22.65 3.943-3.926 4 23.15-23.25 3.842-3.826 5-10 24.3-25.15 3.663-3.54~ 22-47 D-14,223 ~ 2~
- 59~

2~ dr (~) 100 x_ I/Io 26 ~ 1-26 ~ 25 3 ~ 414-3 ~ 395 8-14 27 ~ 7-28 ~ 4 3 ~ 220-3 ~ 143 7~9 29~8 ~998- 0_3 30 ~ 05~30 ~ 15 2 ~ 974 0-13 30~75~30~95 2~908-2~889 23-31 ~2 ~ 65-32 ~ 8 2 ~ 743-2 ~ 730 0~3 33~0 2~714 0-6 34 ~ ~ 2 ~ 571 0-2 35 ~ 15 2 ~ 553 0-2 35 ~ 3~35 ~ 6 2 ~ 543-2 ~ 522 9-10 38 ~ 7 2 ~ 327-2 ~ 327 0-2 39 ~ 3~~0 ~ 2 2 ~ 2~2-2 ~ 243 0-2 40~1 2~249 0-1 4~ ~ 1-42 ~ 3 2 ~ 146-2 ~ 137 0~3 42 ~ 55 2 ~ 127 0-2 43~7 2~071 0-1 48 ~ 2 1 ~ 888 0~3 48 ~ 65-48 ~ 8 1~ 872-1~ 866 0~5 50~2-50~4 1~817-1~811 0~5 52~0 1~759 0-1 53 ~ 8-54 ~ 0 1 ~ 704-1 ~ 698 0-7 ExamPle 55 (a) ZnAPSO-46. as referred to in example 8 ~as subjec~ed to x-ray analysis.
ZnAPSO-46 was determined to have a characteristic x-ray powder diffraction pattern which contains at least the.d-~pacings set forth below:
2~ d, ~A~ 100 x I~Io fi.6 13~39 8 7 ~ 75 11 ~ 42 100 ~ * 10 ~ 90 3 9,45*x 9 ~ 34 18 10~2 8~67 13 ~ 35~ 6 ~ S3 10 13~8 6~41 4 14~95 5~92 4 15 ~75~ 5 ~ 62 3 16~7 5~31 7 1~5 5~07 18.4** 4. 83 10 D-14, 223 2e d, (A~ 100 x I/Io 19.85 4.47 3 20.5* ~.33 6 Zl.Z5*~ 4.19 25 21.6 ~.lZ 18 22.25*~ 3.998 3 22.8 3.~96 32 23.3** 3.818 4 Z4.05 3.700 3 24.25* 3.669 5 25.3~ 3.523 26.55*~ 3,354 3 26.9 3.313 10 27.8 30207 3 28.3 3.152 2 2~.~* 3.100 8 29.85* 2.993 6 30.~** Z.961 7 31.15 2.870 3 31.8* 2.813 32.95* 2.719 3 34.3~ 2.612 2 34.65** 2.~90 3 36.0* 2.495 3 36.55 2.459 2 36.8* 2.442 37.3 2.410 38.1~* 2.361 39.7~ 2.271 40.95~ 2.204 43.2** 2.093 44.1* 2.054 46.1* 1.969 47.65* 1.908 49.45*~ 1.844 49.65* 1.83S
51.55* ~.772 5~.45~ 1.745 * Peak may contain impu~ity *~ Impurity peak (b) The ZnAPS0-46 compositions are cha~actarized by the data of Table X~III below:

D-14,223 - 61~

Table XXIII
2e d, lA) Relative Inten~ity 7.6-7.75 11.63-11.42 vs 13.1-13.35 6.76-6.63 w-m 21.5-21.6 4.13-4.12 w-m 22.6-22.85 3.934-3.896 m 26.75-?7.0 3.333-3.302 w (c~ Th~ ZnAPS0-46 compositions for vhich x-~ay powd~r diffraction data have been obtained to date have pattern~s which are cha~acte~ized by the x-ray polwde~ diffra~tion pattern shown in Table XXIV below:
Tabl~ XXIV
2~ d, (A~ 100 x I/Io

6.5-6.7 13.60-13.19 7-10

7.6-7.75 11.63-11.42 100 10.2 8.67 0-1 13.1-13.35 6.76-6.63 10-Z0 13.7-13.8 6.46-6.41 4-5 14.9-15.0 5.95-5.91 4-5 15.2-15.35 5.83-5.77 5-7 16.6-16.8 5.34-5.28 7 17.~5-17.5 5.11-5.07 0-1 19.7-20.0 4.51-4.44 2-3 20.3-20.5 4.37-~.33 6-11 21.5-21.6 4.13-4.12 18-21 22.S-22.85 3.934-3.896 32-58 23.9-24.05 3.723-3.700 2-3 2~.1-25.3 3.548-3.520 0-1 26.75-27.0 3.333-3.302 10-12 27.7-2~.0 3.220-3.187 3-4 28.2-28.3 3.175-3.1~2 Z-3 28.6-28.9 3.121-3.089 8-11 29.7-29.9 3.008-2.988 6-9 31.0-31.15 2.885-2.B70 3-4 31.6-31.8 2.~31-2.813 0-1 32.8-33.2 2.730-2.706 3-4 34.15-34.4 2.626-2.607 2-4 D-14,223 2e d, ~R~ 100 x I/Io 35.8-36.0 2.508-2.495 3-4 3~.45-36.55 2.464-2.~59 2-3 37.3-37.7 2.410-2.386 0-2 39.7 ~.2~1 0-1 40.~-41.1 2.206-2.196 0-1 43.85-44.1 2. 065-2 . 054 0-1 46.1 1.969 0-1 47.4-47.7 1.918-1.908 0-1 49.7-49.~ 1.834-1.831 0-1 51.4-51.7 1.77~-1.768 0-1 52.2-52.45 1.752-1.745 0-1 Exam~le 56 (a) ~nAPS0-47, as ~efe~red to in example 38, was subjec~ed to x-~ay analysis.
ZnAPS0-47 was determined to have a cha~actecistic x-~ay powdec diff~action pattern which contains at least the d-spacings set fo~th below:
2~ d, (A) 100 x I/Io 7.45* 11.88 2 9.45 9.35 93 12.9 6.87 17 13.9 6.38 7 16.0 5.5~ 42 17.65 5.03 11 19.0* 4.67 3 20.6 4.31 100 21.85 4.07 7 22.4~ ~.97 6 23.0 3.867 11 24.75 3.S00 21 25.9 3.43~ 23 27.65 3.228 10 28.0 3.1~8 3 29.5 3.029 5 30.6 2.922 49 30.9 2.894 sh 31.5 2.839 3 32.3 2.772 2 33.3 2.689 3 34.5 2.600 10 34.9 2.573 2 D-14,223 ~2~8~

2e d, (A~ 100 x I/Io 35.7 2.516 4 38.4 2.344 3 39.65 2.273 4 42.5 2.126 3 43.3 2.089 2 44.9 2.019 Z
47.6 1.909 4 48.6 1.873 5 50.5 1.807 5 53.Z5 ~ 1.7Z1 5 5~.~ 1.684 2 56.0 1.64Z 5 Impurity peak ~b) A portion of the as-synthesized ZnAPS0-47 of part a) was calcined in air at 500C
for about 1.75 hou~s. The calcined product was characterized by the x-~ay po~der diffraction pattern below:
2e d, (~) lOO x I/Io 7.5* 11.78 11 9.65 9.17 100 13.05 6.7B Z5 14.15 6.26 16.Z 5.46 10 18.0 4.93 8 19.25 4.61 3 19.~* 4.4g 2 2~.85 ~ 4.26 27 21.25* 4.18 sh 22.5* 3.950 8 23.3 3.816 4 25.2 3.533 8 26.2 3.399 10 28.0 3.187 2 28.55 3.126 3 29.8 2.998 2 31.0 2.885 18 D-14,223 ~L2.d~

2e d, (R) 100 x I/Io 31.4 2.849 sh 34.9 2.571 2 * Impurity,peak (c) The ZnAPS0--47 compositions a~e characterized by the date in 'rable X~V below:
Table ~.~V
2e d. ~A) Relative Intensitv 9.45-9.65 9.35-9.17 ~s 12.85-13.05 6.89-6.78 w-m 15.95-16.2 5.55-5.46 w-m 20.55-20.85 4.31-4.26 m-vs 25.9-26.2 3.439-3.399 w-~
30.55-31.0 2.925-2.885 w-m (d) The 2nAPS0-47 composi~ions for which x-~ay powder diffracton data have been obtained to date have patterns which aLe characte~ized by the x-ray powde~ diffraction pattern ~hown in Table X~VI below:
Table X~VI
2e d, (R~ 100 x I/Io 9.45-9.65 9.35-9.17 93-100 12.85-13.05 6.89-6.78 17-Z5 13.85-14.15 ~.39-6.26 3-7 15.95-16.2 5.55-5.46 10-42 17.45-18.~ 5.0~-4.93 2-11 20.55-20.85 ~.31-4.26 27-100 21.85 4.07 0-7 22.95-23.3 3.867-3.816 4-11 24.75-25.2 3.600-3.533 8-21 25.9-26.2 3.~39-3.399 16-29 27.6-28.55 3.231-3.126 3-10 27.9-28.0 3.1g6-3.188 0-3 29.45-29.8 3.031-2.998 2-5 30.55-31.0 2.925-2.885 18-49 D-14,223 t;~
- ~5-2~ d, (Al 100 x I/Io 30.9-31.4 2.894-2~849 sh 31.~ 2.8~9 0-3 3~.3 2.772 0-2 33.3 Z.689 0-3 34.45-34.9 2.603-2.600 2-19 3~.9 2.573 0-~
35.7-35.9 2.516-2.503 0-5 38.4-38.55 2.344-2.336 0-3 39.6-39.65 2.273 0-~
~2.25-~2.5 2.139-2.126 0-3 43.3 2.089 0-2 44.9 2.019 0-2 47.6 1.909 0-6 48.6-4~.7 1.873-1.870 0-5 ~0.45-50.5 1.807 0_5 53.2-53.25 1.722-1.721 0-5 5~.5 1.68~ 0-2 56.d 1.642 0-5 ExamPle 57 In order to demonstrate the catalytic activity of calcined ZnAPS0 compositions wece tested for catalytic cracking of n-bu~ane using a bench-scale apparatus.
The reactor was a cylindrical quartz tube 254 mm. in length and 10.3 m~. I.D. In each test the reactor wa~ loaded with particles of the test ZnAPS0 which were 20-40 mesh (U.S. std.) in ~ize and in an amount of f~om 0.5 to 5 grams, the quantity being selected so that the conversion of n-butane was at least 5% and not more than 90g under the test conditionfi. The ZnAPS0 samples had been pLeviously calcined in air to remove organic materials from the pore system, and were activated in 6itu in the reactor in a flowing stream of helium at 500~C for one hour. The feedstock was a helium n-butane ~ixture containing 2 mole percent n-butane and was D-14,223 t~7~

passed through the ceactor at a rate of 50 cc./minute. Analysis of the feedstock and the reactor effluent were carried out using conventional gas chromatography techniques. The reactoI effluent ~as analyzed afteL 10 minutes of on-stream operation.
The p~eudo-first-order rate constant ~kA) wa~ calculated to determine the relative catalytic activity of the ZnAPSO compositions. The kA value (cm /g min) obtained for the ZnAPSO compositions are set for~h, below. in Tablle ~VII:
Table XXVII
Prepared in ZnAPSO Example No. Rate Constant (kA)*
. _ ZnAPSO-5 4 1.5 ZnAPSO-34 24 12.7 ZnAPSO-35 33 1.O
ZnAPSO-44 35 5.0 ZnAPS0~47 39 5.6 ~2nAPSO were calcined prior to ~n situ activa~ion as follows:
a) ZnAPSO-5: in air at 500C for 0.75 and at 600C
for 1.25 hours;
b) ZnAPSO-34: in air at 500C for 2 hours;
c) ZnAPSO-35: in air at 500~C for 1.75 hours;
d) ZnAPSO-~4: in air at 500C for 67 hours; and e) ZnAPSO-47: in air at 500C for 1.75 hours.
PROCES S APPLICATIONS
The ZnAPSO composition6 of the present invention are, in general, hydrophilic and adsorb water preferentially over common hydrocarbon molecules such as paraffin6, olefins and aromatic ~pecies, e.g., benzene, xylenes and cumene. Thus, the ZnAPSOs a~ a class are useful a~ desiccants in such adsorption separation/

D-14,223 purification ~rocesses as natural gas drying, cracked gas drying. Wa~er is also prefe~en~ially adsorbed over the so-called permanent gases such as carbon dioxide, nitrogen, oxylyen an~ hydrogen.
These ZnAPSOs 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 ZnAPSO compo~itions also exhibit novel surface selectivity characte~istics which render them useful as catalyst or catalyst bases in a number of hydrocarbon conversion and oxidative combustion reactions. They can be i~pregnated or other~ise loaded with ca~alytically active metals by methods well known in the art and used, for example, in fabricating catalyst compositions having silica or alu~ina bases. Of the general class, those species having pores larger than about 4A are preferred for catalytic applications.
Among the hydrocarbon conversion reactions catalyzed by ZnAPSO compositions are cracking, hydrocracking, alkylation for both the aromatic and isopara~fin types,isomerization including xylene isomerization, polymerization, reforming, hydrogenation, dehydrogenation, transalkylation, dealkylation, hydrodecyclization and dehydrocyclization.
Using ZnAPSO catalyst compo~itions which contain a hydrogenation promoter such as platinum or palladium, heavy pe~roleum residual stocks, cyclic stocks and other hydrocrackable charge stocks, can D-14,223 be hydrocracked at temperatures in the ranqe of 400F to 825F u~ing molar ratios of hydrogen to hydrocarbon in the range of be~ween 2 and B0, 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 ZnAPS0 catalyst compositions employed in hydrocracking are al50 suitable for use in reforming erocesses in which the hydrocarbon feed6tock~ contact the catalyst at temperatures of from about 700F to 1000F, 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 hydroisomerization~ processes in which feed~tocks such a normal paraffins are converted to saturated branched chain isomers. Hydroisomerization is carried out at a temperature of from about 200F to 600F, preferably 300F to 550F with an LHSV value of from about 0.2 to 1Ø 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 temperaturefi, i.e. from about 650P to 1000P, preferably 850F to 950F and usually at somewhat lower pressures within the range of about 15 to 50 p.s.i.g., the same catalyst composition~ are used to hydroisomerize normal paraffins. Preferably the paraffin feedstock D-14,223 - 69- '~

comprises normal pa~affins having a carbon number range of C7-C20. Contact time between the feedstock and the catalyst is generally ~elatively shoct to avoid undesireable side reactions such as olefin polyme~ization and paraEfin c~acking. LHSV
values in the range of 0.1 to 10, pceferably 1.0 to 6.0 ace suitable.
The unique c~ystal stcucture of the p~esent Zn~PS0 catalysts and thei~ availability in a fo~m totally void of alkali metal eontent favor their use in the conversion of alkyla~omatic compounds, particula~ly the catalytic disproportionation of toluene, ethylene, trimethyl benzenes, tetramethyl benzenes and the like. In the dispropo~tionation process, isomeriza~ion and transalkylation can also occur. Group VIII noble metal adjuvants alone or in conjunction with ~roup VI-B metal~ such a~ tungsten, molybdenum and chromium are p~eferably included in ehe catalyst composition in amounts of f~om about 3 to 15 veight-% of the ove~all composition.
Extraneous hyd~ogen can, but need not, be p~esent in the reaction zone which is maintained at a ~emperature of from about 400 to 750F, p~essures in the range of 100 to 2000 p.s.i.g. and LHSV values in the range of 0.1 to 15.
Catalytic cracking p~ocesses a~e p~eferably carried out with ZnAPSO compositions using feedstocks such as gas oils, heavy naphthas, deasphalted clude oil residua, etc., with gasoline being ~he principal desired produet. Temperature conditions of 850 to 1100F, LHSV values of 0.5 to 10 and pressure conditions of fcom about 0 to 50 p.s.i.g. are suitable.

D-14,2Z3 - 70~

~ ehydrocyclization reactions e~ploying pacaffinic hydrocarbon feedstocks, preferably normal paraffins having more than 6 cacbon atoms, to form benzene,-xylenes, toluene and the like are caeried out using essentially the same reaction conditions as for catalytic cracking. For these reactions it i8 prefe{red to use the ~nAPS0 catalyst in conjunction with a Group YIII non-noble metal cation such as zinc and nickel.
In catalytic dealkylcltion wherein it is desired to cleave paraffinic side ehains from aromatic nuclei without substantially hydrogenating the ring s~cucture, relatively high temperatures in the range of about 800-1000F 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.
Pref~rred catalysts are of the same type described above in connection with catalytic dehydrocyclization. Particula~ly 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 sel~ctive hydrodecomposition cf organic sulfur and/or nitrogen compound~ in the feed, without sub~antially affecting hydroearbon molecule6 therein. For thi~
purpose it is preferred to employ the same general conditions described above for catalytic hydrocracking, and catalysts of the fiame general nature de~cribed in connection with dehydrocycli-~-14,223 -- 7 ~ L~

zation operations. Feeds~ocks include gasoline fzactions, kerosene6, jet fuel fractions, diesel f~actions, light and heavy gas oils, deasphalted crude oil residua 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 condi~ions can be e~ployed to effect hydrofining, i.e., denitrogenation and desulfurization, of hydrocarbon feeds containing ~ubstantial proportions of organonit~ogen and organosulfur compounds. It is generally recognized that the presence of ~uh~tantial amounts of such constituents markedly inhibits the activity of hyd~ocracking cataly6ts. Consequently, it is necessary to operate at more extreme conditions when it is desired to obtain the sa~e deg~ee of hydrocracking conversion per pas~ 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 accompli~hed in any given situation are necessarily determined in view of the characteristics of ~he feedstocks in particular ~he concentration of organonitrogen compounds in the feedstock. As a result of the effect of o~ganonitrogen 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., le~s than 20 volume D-14,223 percent of fresh feed per pass, might be the same as those preferred for hydrocr.acking 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 catalysts. Olefins are preferably isomerized at temperatures of 500-900F, while paraffins, naphthenes and alkyl aromatics are isomerized at temperatures of 700-1000F. Particularly desirable isomerization reactions contemplated herein include the conversion of n-heptene and/or n-octane to isoheptanes, iso-octanes, butane to iso-butane, methylcyclopentane to cyclohexane, meta-xylene and/or ortho-xylene to paraxylene, l-butene to 2-butene and/or isobutene, n-hexene to isohexene, cyclohexene to methylcyclopentene etc. The preferred form of the catalyst is a combination of the ZnAPS0 ~ith polyvalent metal compound~ (such as sulfides) of metals of Group II-A, Group II-B and rare earth metals. For alkylation and dealkylation processes the ZnAPS0 compositions having pores of at least 5A are preferred. When employed for dealkylation of alkyl aromatics, the ~emperature is usually at least 350F and ranges up to a temperature at ~hich substantial cracking of the D-14,223 feedstock or conversion p~oducts occurs, generally up to about 700F. The temperature is preferably at least 450F and not greater than the critical temperature of the`compound undergoing dealkylation. Pressure conditions aIe applied to retain at laast the aromatic feed in the liquid state. For alkylation the temperature can be a6 low as 250F but is preferably at least 350F. In the alkylation of benzene, toluene and ~ylene~ the preferred alkylating agents are ol~fins such as ethylene and propylene.

D-14,223

Claims (42)

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1. Crystalline molecular sieves having three-dimensional microporous framework structures of ZnO2, AlO2, PO2 and SiO2 tetrahedral units and having an empirical chemical composition on an anhydrous basis expressed by the formula:
mR : (ZnwAlxPySiz)O2 wherein "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the molar amount of "R"
present per mole of (ZnwAlxPySiz)O2 and has a value of zero (0) to about 0.3; and "w", "x", "y" and "z" represent the sole fractions of zinc.
aluminum, phosphorus and silicon, respectively.
present as tetrahedral oxides, said mole fractions being such that they are within the pentagonal compositional area defined by points A, B, C, D and E of Fig. 1.

2. Crystalline molecular sieves according to claim l wherein the mole fractions of zinc.
aluminum, phosphorus and silicon present as tetrahedral oxides are within the tetragonal compositional area defined by points a, b. c and d of Fig. 2.

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

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

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

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

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

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

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

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

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

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

13. The crystalline molecular sieves of claims 1 or 2 having a characteristic x-ray powder diffractions pattern which contains at least the d-spacing set forth in Table L.

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

15. Process for preparing the crystalline molecular sieves of claim 1 which comprises reacting at an effective temperature and for an effective time a mixture composition expressed in terms of molar oxide ratios as follows:
aR : (ZnwAlxPySiz) : bH2O
wherein "R" is an organic templating agent: "a" is the amount of "R" and is zero or an effective amount greater than zero to about 6; "b" has a value of from zero to about 500; and "w", "x", "y" and "z"
represent the mole fractions, respectively, of zinc, aluminum, phosphorus and silicon in the (ZnwAlxPySiz)O2 constituent, and each has a value of at least 0.01, whereby the molecular sieves of claim 1 are prepared.

16. Process according to claim 15 wherein "w", "x", "y" and "z" are within the area defined by points F, G, H, I and J of FIG. 3.

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

18. Process according to claim 15 wherein the source of phosphorus in the reaction mixture is orthophosphoric acid and the source of aluminum is at least one compound selected from the group of pseudo-boehmite and aluminum alkoxide.

19. Process according to claim 18 wherein the aluminum alkoxide is aluminum isopropoxide.

20. Process according to claim 15 wherein the source of silicon is silica.

21. process according to claim 15 wherein the source of zinc is selected from the group consisting of oxides, hydroxides, alkoxides, acetates, nitrates, sulfates, carboxylates, orqanometallic zinc compounds and mixtures thereof.

22. Process according to claim 15 wherein the organic templating agent is a quaternary ammonium or quaternary phosphonium compound having the formula:
R4X+
wherein X is nitrogen or phosphorus and each R is an alkyl or aryl group containing from 1 to 8 carbon atoms.

23. Process according to claim 15 wherein the organic templating agent is an amine.

24. Process according to claim 15 wherein the templating agent is selected from the group consisting of tetrapropylammonium ion;
tetraethylammonium ion; tripropylamine;
triethylamine; triethanolamine; piperidine;
cyclohexylamine; 2-methyl pyridine;
N,N-dimethylbenzylamine; N,N-dimethylethanolamine;
choline; N,N-dimethylpiperazine;
1,4-diazabicyclo-(2,2,2) octane;
N-methyldiethanolamine; N-methylethanolamine;
N-methylpiperidine; 3-methylpiperidine;
N-methylcyclohexylamine; 3-methylpyridine;
4-methylpyridine; quinuclidine;
N,N'-dimethyl-l,4-diazabicyclo (2,2,2) octane ion;
tetramethylammonium ion; tetrabutylammonium ion;
tetrapentylammonium ion; di-n-butylamine;
neopentylamine; di-n-pentylamine; isopropylamine;
t-butylamine; ethylenediamine; pyrrolidine;
2-imidazolidone; di-n-propylamine; and a polymeric quaternary ammonium salt [(C14H32N2)(OH)2]x wherein x is a value of at least 2.

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

26. 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 composition of claim 1 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.

27. 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 composition of claim 2 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.

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

29. Process according to claim 26 or 27 wherein the more polar molecular species is water.

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

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

32. Process according to claim 30 or 31 wherein the hydrocarbon conversion process is cracking.

33. Process according to claim 30 or 31 wherein the hydrocarbon conversion process is hydrocracking.

34. Process according to claim 30 or 31 wherein the hydrocarbon conversion process is hydrogenation.

35. Process according to claim 30 or 31 wherein the hydrocarbon conversion process is polymerization.

36. Process according to claim 30 or 31 wherein the hydrocarbon conversion process is alkylation.

37. Process according to claim 30 or 31 wherein the hydrocarbon conversion process is reforming.

38. Process according to claim 30 or 31 wherein the hydrocarbon conversion process is hydrotreating.

39. Process according to claim 30 wherein the hydrocarbon conversion process is isomerization.

40. Process according to claim 31 wherein the hydrocarbon conversion process is isomerization.

41. Process according to claim 39 or 40 wherein the isomerization conversion process is xylene isomerization.

42. Process according to claim 30 or 31 wherein the hydrocarbon conversion process is dehydrocyclization.