CA1248507A - Titanium-aluminum-phosphorous-silicon-oxide-molecular sieve compositions - Google Patents

Abstract

TITANIUM-ALUMINUM-PHOSPHORUS-SILICON-OXIDE
MOLECULAR SIEVES COMPOSITIONS
ABSTRACT
Crystalline molecular sieves having three-dimensional microporous framework structures of TiO2, 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 : (TiwAlxPySiz)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 (TiwAlxPySiz)O2; and "w", "x", "y" and "z" represent the mole fractions of titanium, aluminum, phosphorus and silicon, respectively, present as tetrahedral oxides. Their use as adsorbents, catalysts, etc. is also disclosed.

Description

12~35S~7 TITANIUM-ALUMINUM-PHOSPHORUS-SILICON-OXIDE
MOLECUL~R SIEVES
FIEL~ OF THE INVENTION
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 novel titanium-aluminum-phosphorus-silicon-oxide molecular sieves having titanium, aluminum, phosphorus and silicon in the form of framework tetrahedral oxides. These compositions may be prepared hydrothermally from gels containing reactive compounds of titanium, 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.
ACKGROUND OF THE INVENTION
Molecular sieves of the crystalline aluminosilicate zeolite type are well known in the art and now comprise over 150 species of both naturally occurring and synthetic compositions. In general the crystalline zeolites are formed from corner-sharing 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.

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, lZ'~8S'~7 Other crystalline microporous compositions which are not zeolitic, i.e. do not contain AlO2 tetrahedra as essential framewo~k 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 6A or less, are reported in U.S. Patent No. 3,941,871 issued March

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 di&closed in U.S. Patent No.
4,061,724 is~ued December 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. Patent No. 4,310,4q0 issued January 12, 1982 to Wilson et al. These materials are formed ~rom AlO2 and PO2 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 bydrophilic, 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.

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~Z~8S~7 In commonly assigned Canadian Patent ~o.
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 op~ionally 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 the moles of "R" present per mole of (SiXAlyPz)O2 and has a value of from zero to 0.3; the maximum value in each case depending upon the molecular dimensions of ~he templating agent and the available void volume of the pore system of the particular silicoaluminophos-phate 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. 450,658, filed March 28, 1984 there is described a novel class of titanium-D-14,219-C

lZ485~7 containing molecular sieves whose chemicalcomposition in the as-synthesized and anh~drous 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 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 least one metal of the group magnesium, manganese, æinc and cobalt;
and "x", "y" and "z" represent the mole fraction of the metal "M", aluminum and phosphorus, respectively, present as tetrahedral oxides.
In copending and commonly assigned Canadian application Serial No. 458,914, filed ~uly 13, 1984, D-14,219-C

12~85U'7 there is described a novel class of crys~alline ferroaluminophosphates having a three-dimensional microporous framework structure of FeO2, A102 and PO2 tetrahedral units and having an empirical chemical composition on a anhydrous basis expressed by the formula mR:(FexAlyPz)02 wherein "R" represents at least one organic templating agent present in the intracrystalline pore system: "m" represents the moles of "~" 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 tetrahedral oxide units of Tio2. A102, PO2 and SiO2.
DESCRIPTION OF THE PIGURES
PIG. 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 ,composition6 are set forth as mole fractions.
PIG. 3 is a ternary diagram wherein parameters relating to the reaction mixtures employed in the preparation of this compositions of this inven~ion are set forth as mole fractions.
SummarY of the Invention The instant invention relates to a new class of molecular sieves having a three-dimensional .

~24~3S5~7 microporous crystal framewor~ structures of TiO2, A102, Po2 and SiO2 tetrahedral oxide units. These new titanium-aluminum-phosphorus-silicon-oxide molecular sieves exhibit ion-exchange, adsorbtion 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 TiO2, A10z, P02 and SiO2 tetrahedral units and have an empirical chemical composition on an anhydrous basis expressed by the formula:
mR (TiwAlxPySiz)2 wherein "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the molar amount of "R"
present per mole of (TiwAlxPySiz)02 and has a value of from zero to about 0,3: and "w", "x", "y" and "z" represent the mole fractions of titanium, 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 ~hermal stability of certain species and by the e~istence 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 "TiAPSO" to designate a crystal framework of TiO2, A102. P02 and sio2 tetrahedral oxide units, 12~3S(}7 Actual class members will be identified as structural species by assigning a number to the species and, accordingly, are identified as "TiAPSo-i" wherein "i'~ is an integer. This designation is an arbitrary one and is not intended to denote structural relationship to another material(s) which may also be cha~acterized 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 structure of TiO2, A102, PO2+and SiO2 tetrahedral units. These new molecular sieves exhibit ion-exchange, adsorption and catalytic properties, and accordingly, find wide use as adsorbents and catalysts.
. The TiAPSO molecular sieves of the instant in~ention have three-dimensional microporous framewor~ structure~ of TiO2, A102, PO2 and SiO2 tetrahedral oxide units having an empirical chemical composition on an anhydrous basis expressed by the formula-mR : (TiwAlxPySiz)02 wherein "R" represents at least one organic templating agent present in the intracrystalline pore system: "m" represents the molar amount of "R"
present per mole of (TiwAlxPySiz)02 and has a value of from zero to about 0.3: and "w", "x", "y" and "z"
represent the mole fractions of titanium, aluminum, D-1~219 .., ~248S(37 phosphorus and silicon, respectively, present as tetrahedral oxides and each has a value of at least 0.01. The mole fractions "~", "x". "y" and "z" are generally defined being within the pentagonal compositional area defined by points A, B, C, D and E of the ternary diagram of Fig. 1. Points A, B, C, D and E of Fig. 1 have the followi~g values for llwll, "x", I'y", and " 2 ":
Mole Fraction Point x y (z+w) A 0.600.38 0.02 B 0.380.60 0.02 C 0.010.60 0.39 D 0.010.01 0.98 E 0.600.01 0.39 In the preferred subclass of TiAPSO
molecular sieves the values "w", "x", "y" and "z" in the above formular are within the tetragonal compo~itional area defined by points a, b, c and d of the ternary diagram which is Fig. Z of the drawing~, said points a, b, c and d representing the following values for "w", "x", "y" ana "z~.
Mole Fraction Point x _y~ L
a 0.550.43 0.02 b 0.430.55 0.02 c 0.100.55 0.35 d 0.550.10 0.~5 The TiAPSOs of this invention are useful as adsorbents, catalysts, ion-exchangers, and the like in much the same fashion as aluminosilicates have been employed heretofore, although their chemical and physical properties are not necessarily similar to those observed for aluminosilicates.

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124~S~7 TiAPSo compositions are generally synthesized by hydrothermal crystallization from a reaction mixture containing active resources of titanium, silicon, aluminum and phosphorus, and preferably an organic templating, i.e., structure-directing, agent, preferably a compound of an element or Group VA of thè Periodic Table, andior optionally an alkali or metal 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 50C and 250C, and preferably between 100C and Z00C until crystals of the TiAPSO
product are obtained. usually a period of from hours to several weeks. Generally, the crystallization time is from about 2 hours to about 30 days and typically from about 4 hours to about 20 days. The produc~ is recovered by any convenient method such as centrifugation or filtration.
In synthesizing the TiAPSo compositions of the instant invention, it is preferred to employ a reaction mixture composition expressed in terms of the molar ratios as follows:
w x y z 2 2 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 ~ and is preferably an effective amount within the range of greater than zero (0) to about 6; "b" has a value o from zero (0) to about S00, preferably between about 2 and about 300; and "w", "x", "y" and "2" represent the ~248~(~7 ~ole fracticns of titanium, alu~inu~, phosphorus and coD, respectiYely and each has D value of at least 0 01 In ~ preferred embodiment the raaction mixture ic ~elected such that t~e mole fract~on~
~ x~, ~y~ and ~z~l are ~enerally defined as being within t~e pentagonal eompo~itionsl area definéd by points F, G, H, I and J o~ the ternary aiagram of PIG 3 Pointc F, G, H, I and J of PIG ~ have ~e following ~alues ~or ~wu, Uxn~ ~y~ and ~z~;
Mole Fraction Po~nt x ~ ( ~ 0 60 0 3B 0 02 O Ol 0 60 0 39 I O Ol O Ol 0 98 J 0 60 O Ol 0 39 For rea60n6 un~nown at present, no~ every reaction ~ixture gave crystalli~e TiAPso product~ when rcaction product6 ~ere examine~ for ~i~PS0 products by X-ray analy6i6 Sho6e reaction ~ixturcc from wbic~ cry6tall~ne TiAPS0 pcoduct6 were obtained are teported in the Qxample6 here~na~ter a~ numbered xamplec vith the TiAPS0 product6 iden~ified and tho~e reaetion ~ixture6 ~roa vhich ~iAPS0 products ~ere not identified by u~e of ~-ray analy~i~ are l~o r-ported In tbe ~oregoinç e~pre6~ion of the r~action co~po6ition, the reactant~ are noraalized v~th recpect to t~e total of ~yu, ~x~ ~y~ .na ~z~
~uc~ tbat (~ ~ s ~ y ~ z~ .1 00 ole, vberea~ in tbe xa~ples tbe seact~on ~ixtures are xpresced in t~r~ of aolar oxiae ra~os and l~ay be nor~alized to S~e ~olec f ~25~ Thi~ latter ~ora ic re-dily ~ 219 lZ~35(~'7 converted to the former form by routine calculations by dividing the number of moles of each component (inc uding the template and water) by the total number of moles of titanium, aluminum, phosphorus and silicon which results in normalized mole fractions based on total moles of the aforementioned components. In forming the reaction mixture from which the instant molecular sieves are formed the organic templating agent can be any of those heretofore proposed for use in thé synthesis of conventional zeolite aluminosilicates. In general these compounds contain elements of Group VA of the Periodic Table of ~lements, 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 oarbon atoms.
Particularly preferred compounds for use as templating agents are the amines, quaternary phosphonium compounds and quaternary ammonium compounds, the latter two being represented generally by 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.
Polymeric quaternary ammonium salts such as t(C14H32N2) (OH) 2]x wherein ''x'l has a v31ue 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 agents can either produce mixtures of the desired TiAPSos . ~..

12'185{~7 or the moee strongly directing templating species may control the course of the reaction with the other templating agents 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:
tri-n-propylamine: triethylamine: triethanolamine:
piperidine; cyclohexylamine: ~-methyl~yridine;
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-methy~pyridine; quinculidine:
N,N'-dimethyl-1,4-dia~zabicyclo ~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 TiAPSo, i.e., a single templating agent can, with proper manipulation of the reaction conditions, direct the formation of several TiAPSo compositions, and d given TiAPSo composition can be produced using several different templating agents.
The source of silicon may be silica, either as a silica sol or as fumed silica, a reactive solid amorphous precipitated silica, silica gel, alkoxides of silicon, silicic acid or alkali metal silicate and the like; such that the formation of reactive 12~8S~

silicon in situ is provided to form SiO2 tetrahedral oxide units.
The most suitable phosphorus source 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 AlP04 composition of U.S.P. 4,310,440.
Organo-pho~phorus compounds, such as tetrabutylphosphonium bromide, do not apparently ~erve as reactive sources of phosphorus, but these compound~ do 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, zuch as aluminum isoproproxide, or pseudoboehmite. The cry6talline 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 titanium can be introduced into the reaction system in any form which permits the formation in ~itu of reactive form of titanium, i.e., reactive to form the framework tetrahedral oxide unit Tio2. Compounds of titanium which may be employed ;nclude oxides, hydroxides, alkoxides, titanates, titanium chelates, nitrates, sulfates, halides, carboxylates (e.g., ace~ates) and the like.

~~lg219 . ~ .

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While not essential to the synthesis of ~iAPS0 compositions, stirring or other moderate agitation of the reaction mixture and/or seeding the reaction mixture with seed crystals of either the TiAPS0 species to be produced or a topologically similar aluminophosphate, aluminosilicate or molecular sieve composition, facilitates the crystallization procedure After crystallization the TiAPso product may be isolated and advantageously washed with water and dried in air. The as-synthesized TiAPSo generally contains within its internal pore system at least one form of any templating agent, also referred to herein as the "organic moiety~', employed in its formation. Most commonly the organic moiety 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 may be an occluded molecular species in a particular TiAPSo 6pecies. As a general rule the templating agent, and hence any occluded organic species, is too large to move freely through the pore system of the TiAPSo product and must be removed by calcining the TiAPS0 at temperatures of f~om 200C to 700C to thermally degrade the organic species. In a few instances the pores of the TiAPSo 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 12485(~

conventional desorption procedures ~uch as carried out in the case of zeolites. It ~ill be understood that the term `'as-synthesized" a~ used herein does not include the condition of the Ti~PSo species wherein any ocganic moiety occupying the intracrystalline pore system as a result of the hydeothe~mal c~y~tallization proces~ has been reduced by po~t-synthesis treatment such that ~he value of "m" in the composition formula ma : ~TiwAlxPySiz)Oz 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 source of titanium, aluminum. phosphocus oc silicon the corresponding alcohol is necessarily present in the ceaction mixture since it is a hydrolysis pcoduct of the alkoxide. It has not been determined whethec this alcohol paLticipates in the synthesis process as a templating agent. For the purposes of this application, however, this alcohol is acbitcacily omitted from the class of templating agents, even if it i~ pcesent in the as-synthesized TiAPso compositions.
Since the present TiAPSo compo~iti~ns are focmed fcom TiO2, A102, P02 and SiO2 tetcahedcal units which, respectively, have a net charge of -2, ~ 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 AlO2 tetrahedra and charge-balancing cations. In the instant ~, .

85()7 compositions, an ~10z tetrahedron can be balanced electrically eithec by as~ociation with a P02 tetrahedcon or a simple cation such as an alkali metal cation, a cation of titanium present in the ceaction mixtuce, oc an organic cation derived fcom the templating agent.
It has also been postulated that non-adiacent A102 and P02 tetrahedral pairs can be balanced by Na~ and OH cespectively rFlanigen and Gco~e, Moleculac Sieve Zeolites-I, ACS, Hashington, DC (1971)]
The TiAPSo compositions of ~he pcesent invention may exhibit cation-e~change capacity when analyzed using ion-exchange techniques heceto~oce employed with zeolitic aluminosilicates and have pore diametecs which are inherent in the lattice stcucture of each species and which ace at least about 3~ in diametec. Ion exchange of TiAPSo compositions is ordinarily possible only aftec organic moiety decived fcom the template, present as a result of synthesis, has been removed fcom the pore gystem. Dehydcation to remove water pcesent in the as-synthesized TiAPSo compositions can usually be accomplished, to some degree at least, in the usual mannec without cemoval of the ocganic moiety, but the absence of the organic species greatly facili~ates adsorption and desocption pcocedures.
As illustrated hereinaftec, the TiAPSO matecials have vacious degrees of hydcothecmal and thermal stability, ~ome being quite remackable in this regacd, and function well as molecula! sieve ~Z4~35~

adsorbents and hydrocarbon conversion catalysts or catalyst bases.
In each example the stainless ~teel reaction vessel utilized was lined with the inert plastic material, polytetrafluoroethylene, to avoid contamination of the reaction mixture. In general, the final ceaction mixture from which each TiAPSo composition is crystallized is pcepared by forming mixtures of less than all of the reagents and thereaftee incorporating into these mixtures addition reagents either singly or in the form of othec intermediate mixtures of two or more reagents. In gome instance the ceagents admixed retain their identity in ~he inte~mediate mixtu~e and in other cases $ome or all of the reagents are involved in chemical reactions to produce new reagents. The term "mixture" is applied in both cases. Purther, unless otherwise specified, each intermediate mixture as well as the final reaction mixture was stirred until substantially homogeneous.
X-ray analysis of reaction products ace obtained by X-ray analysis using standard ~-ray powder diffraction technique~. The radiation source is a high-intensity, copper target, X-ray tube operated at 50 Kv and 40 ma. The diffraction pattern f~om the copper ~-alpha radiation and ~raphite monochromator i5 suitably cecorded by an X-ray spectrometer scintillation coun~er, pulse height analyzer and strip chart recorde~. Flat co~pressed powdec samples ace scanned at 2 (2 theta) per minute, using a two second time constant. Interplanar spacings (d) in Angst~om 1248S~

units are obtained from the ~osition of t~e d i~ f racSion peaks expressed as 2~ wheee 0 is the ~ragg an~le as observed on the strip chart.
Intensities are determined fcom the heights of diff~action peaks after subtracting background, "Io" being the intensi~y of the ~trongest line o~
peak, and "I" being the intensity of each of the other peaks. Alternatively. the X-ray patte~ns are obtained from the copper K-alpha radiation by use of computer based techniques using Siemens D-500 ~-ray powder diffractometers, Siemens Type R-805 X-~ay sources, available fcom Siemens Cocpo~ation, Chercy ~ill, New Jersey, with approp~iate compute~
interface.
As will be understood by those skilled in the art the determination of the parameter 2 theta is subject to both human and ~echanical error, which in combination, can impose an uncertainty of about l0.4 on each reported value of 2 theta. This uncertainty is, of course, also manifested in the reported ralues of the d-spacings, which are calculated from the 2 theta values. This impreci~ion i8 general throughout the art and is not sufficient to preclude the differentiation of the present crystalline materials from each othe~ and from the compositions of the prior art. In some of the X-ray patterns reported, the relative intensities of the d-spacings a~e indicated by the notationfi vs. s, m, w and vw which rep~esent ve~y strong, strong, medium, weak and ve~y weak, respectively.

~;~485~37 In certain instances the purity of a synthesized product is 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 pat~ern 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 pa~terns set forth in the following Tables A
through V, wherein said x-ray patterns are for both the as-synthesized and calcined forms unless otherwise noted:
TABLE A (TiAPSo-5) 2~ d(A) Relative IntensitY
7.3 - 7.512.11 - 11.79 s-vs 19.7 - 19.9 4.51 - 4.46 m 20,9 - 21.0 4.25 - 4.23 m-s 22.3 - 22.5 3.99 - 3.95 m-vs 25.8 - 26.1 3.453 - 3.411 m 28.9 - 29.1 3.089 - 3.069 w-m TABLE B (TiAPS0-11) 2~ d(A) Relative Intensitv 9.4 - 9.6 9.41 - 9.21 vw-m 19.9 - 20.5 4.46 - 4.33 m 21.0 - 21.8 4.23 - ~.08 vs 22,0 - 22.1 4.04 - 4.02 m-vs 22.4 - 22.6 3.97 - 3.93 m-s 22.7 3.92 m 23.1 - 23.4 3.85 - 3.80 m-vs lZ485(37 TABLE C (TiAPSO=16 ) 2~ d(A) Relative IntensitY
ll.g 7.75 m-vs 18.7 4.75 m 21.9 - 22.1 4.05 - 4.02 m-vs 26. q - 26.5 3.370 - 3.363 m 29.6 - 29.8 3.018 - 3.002 m 29.9 2.984 m 30.1 2.971 m TABLE D (TiAPSo-34) 2~ d(A) Relative Intensitv 9.4 - 9.5 9.41 - 9.31 vs 12.9 - 13.0 6.86 - 6.81 w-m 16.0 - 16.2 5.54 - 5.47 w-m 20.5 - 20.8 4.33 - q.27 m-vs 30.5 - 30.9 2.931 - 2.894 ~
31.5 - 31.6 2.840 - 2.831 vw-m TABLE E ( TiAPSo- 35 ~
d(A) Relative IntensitY
10~9 - 11.1 8.12 - 7.97 m 13.3 - 13.7 6.66 - 6.46 m 17.3 - 17.4 5.13 - 5.10 w-m 20.8 - 21.1 4.27 - 4.21 m 21.9 - 22.2 4.06 - 4.00 m-vs 28.3 - 28.7 3.153 - 3.110 m TABLE F (TiAPSo-44 ) d(A) Relative IntensitY
9.5 9.30 s 16.1 5.49 m 20.8 4.27 vs 22.0 4.05 m 24.5 ~.63 m 30.9 2.893 m ~Z~SV7 -- Zl --The following examples are provided to further illustrate the invention and are not intehded to be limiting thereof:
PREPARATIVE REAGENTS
In the following examples the TiAPSO
compositions were prepared using numerous regents.
The reagents employed and abbreviations employed herein. if any, for ~uch reagents are as follows:
a) Al ipro: aluminum isopropoxide:
b) ~UDOX-LS: LUDOX-LS is the tradename of DuPont for an aqueous 60 lution of 30 weight percent SiO2 and 0.1 weight percent Na20;
c) H3P04: 85 weight percent aqueous phosphoric acid;
d) Ti ipro: titanium isopropoxide;
e) TEAOH: 40 weight percent aqueous solution of tetraethylammonium hydroxide;
f) Pr2NH: di-n-propylamine, ( 3 7)2 (g) Pr3NH: tri-n-propylamine, (C3H7)3N;
(h) Quin: Quinuclidine. (C7H13N);
(i) MQuin: Methyl Quinuclidine hydroxide. (C7H13NCH30H);
and (j) C-hex: cyclohexylamine.
PR~PARATIVE PROCEDURES
The following preparative examples were carried out by forming a starting reaction mixture 3.24~35S~7 by adding the H3PO4 and the water. This mixture was mixed and to this mixture the aluminum isopropoxide 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.
The titanium isopropoxide was added to the above mixture 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 o~served, i~e., about 2 to 4 minutes. When the organic templating agent was quinuclidine the procedure was modified such that the quinuclidine was dissolved in about one half the water and accordingly the H3PO4 was mixed with about one half the water. (The pH of the mixture was measured and adjusted for temperature).
The mixture was than placed in a lined (polytetrafluoroethylene) stainless steel pressure vessel and digested at a temperature (150C or 200C) for a time or placed in lined screw top bottles for digestion at 100C. All digestions were carried out at the autogenous pressure.
The molar composition for each preparation will be given by the relative moles of the components of the reaction mixture. H3PO4 and titanium isopropoxide are given respectively in terms of the P2O5 and TiO2 content of the reaction mixture.
All digestions were carried out at the autogenous pressure. The products were removed LUDOX is a Trademark of E.I. du Pont de Nemours and Company.

D-14,219-C

" ~

~Z~ 07 fcom the ~eaction vessel cooled and evaluated as set focth he~einafte~.
ExamPles 1 to 30 TiAPSo moleculac sieves were prepared accocding to the above described preparative procedu~e and the TiAPSo products determined by x-ray analysis. The results of examples 1 to 30 ace set forth in Tables I and II.

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~Z485(~7 ExamPle 31 Samples of the product of examples 4, 6, 15, 24 and 30 were subjected to chemical analysis.
The chemical analy~is for each product is gi~en hereinafter with the example in which the TiAPSo wa~
prepared being given in parenthesis after the desiynation of the TiAPSO species.
(a) The chemical analy~i~ for TiAPSO-16 (Example 4) wa~:
Component~eiqht Percent A123 27.1 P205 36.1 Ti~2 6.8 SiO2 6.7 Carbon 12.0 ~itrogen 1,9 LOI* 22.9 -*LOI = Lo6s on Ignition The above chemical analysis gives an overall product compo~ition in molar oxide ratios (anhydrous basis~ of: 0.085 TiO2 : 0.266 A12O3 0.~54 P2O5: 0.112 SiO2 and a formula (anhydrou6 ba6is) of:
0.14R(Tio 07A1o 43Po.41siO-09) 2 (b) The chemical analysi6 for TiAPSO-35 (Example 30) was:
Com~onentWeiaht Percent A123 23.4 28.3 T~i~2 17.6 Si2 4.37 Carbon 11.3 Nitrogen 1.6 LOI* 26.3 ~LOI = Loss on Ianition .

~;~485~7 The above ehemical analysis gives an overall product eomposition in molar oxide ratios tanhYdrous basis) of: 0.220 TiO2 : 0.230 A1203 : 0.199 P205 : 0.073 SiO2; and a formula ~anhydrous basis~ of:
0.12 R(Tio 19Alo~goPo~3ssiO~06)02 (e) The chemical analysis for TiAPSo-5 (Example 6) was:
ComPonent Weiqht Percent Al23 34.0 P20~ 46.9 ~i2 3.0 sio2 ~ . z Carbon 5,~
Nitrogen 0,74 LOI* 14.4 *LO$ = Los~ on Ignition The above ehemieal analysis gives an overall produet eomposition in molar oxide ratios (anhydrous basis) of: 0.03B TiO2 : 0.334 A1203 : 0.330 P205 : 0.020 SiO2: and a formula (anhydrous basis) of:
0 054R(Tio 03Alo g8Po.48sio.ol) 2 (d) The ehemieal analysis of TiAPSO-11 (Example 15) was:
ComPonent Weiaht Pereent A123 35.8 P~05 49.0 T~iO2 1.08 SiO2 3-3 Carbon s.o Nitrogen 1.0 LOI* 10.5 *LOI = Loss on Ignition .

1~485(~7 The above chemical analysis gives an overall product composition in molar oxide ratios (anhydrous basis) of: 0.014 TiO2 : 0.351 A1203 : 0.345 P205 : 0.055 SiO2; and a formula ~anhydrous basi~) of:
0.~7~Tio ~ 4~P~l 47sio.04)~2 ~ e~ T~e chemical a~alys~s for TiAPSo-34 (example 24) was:
Component~ei~ht Percent A1~03 32.3 P205 37.9 Tio2 0~4 SiO2 8.2 Carbon g,~
Nitrogen 1.6 LOI~ 20.5 *LOI = Lo s on Ignition The above chemical analysis gives an o~erall product compo~ition in molar oxide ratios (anhydrous basis) of: 0.01 TiO2 : 0.32 A1203 : 0.27 P205 : 0.14 SiO2; and a formula (anhydrous ba6is~ of:
0.103R(Tio olAlo 48P0~4lsio 11)2 Exam~le 32 EDAX (energy dispersive analysis by x-ray) microprobe analysis in conjunction with S~M
(scanning electron microscope was carried out on clear crystals from the products of example g, 11, 12, and 21. Analysis of crystals having a morphology characteri~tic of TiAP50 compositions gave the ~ollowing analysis based on relative peak heights:

~2~35~37 ~9 a) TiAPSo-44/3s (Example 11):
Averaqe of S~ot Probes Ti 0.02 Al 0 97 P 0.94 Si 0.25 b) TiAPSo-16 (Example 4):
Averaqe of SPot Probes Ti 0.38 Al 0-79 p 0.~4 Si 0-33 c) TiAPSo-34/5 (Example 2~):
Averaae of SPot Probes Ti 0 005 Al 0.85 P 1.00 si o. oa d) TiAPS0-11 (Example ~2):
Averaqe of SPot Probes Ti 0.12 Al 0.88 P 0.84 Si 0.07 Example 33 Samples of the TiAPS0 products of Examples

4, 13 and 6 were evaluated for adsorption capacities in the calcined form by calcination in air to remove at least part of the organic templatin~ agent, as hereinafter set forth. The adsorption capacities of each calcined sample were measured using a standard ~cBain - Bakr gravimetric adsorption apparatus. The samples were a~ti~ated i~ a vacuu~ ~t 3S0C prior to , , .

~j 12485(~7 measurement. The McBan-Bakr data for the aforementioned calcined TiAPSo products were:
a) TiAPS0-16 (Example 4):
Kinetic Pre~sure Temp Wt. % *
Adsorbate Diameter, A (Torr) (C) Ad60rbed 2 3.46 102 -183 3.3 oz 3.46 744 -1~3 12.8*~
n-hexane 4.3 95 23.6 7.0 H20 Z.65 4.6 23.3 13.4 H20 2.65 19 23.2 25.4 * TiAPS0-16 was calcined at 500OC in air for 1.5 hours prior to being activated.
*~ Sample may not have been fully equilibrated.
The above data demon6trate that the pore size of the calcined product i6 about 4.3 A.
b) TiAPS0-11 (ExamPle 13):
Kinetic Pres~ure Temp Wt. % *
Adsorbate Diameter, R (Torr) (C) Adsorbed 2 3.~6 101 -183 9.3 2 3.46 736 -183 10.3 neopentane 5.0 742 23.0 1.1 cyclohexane 6.0 67 22.9 5.2 H2O 2.65 4.6 22.4 12.4 H20 2.65 19 22.5 23.4 ~ TiAPS0-11 was calcined at 600C in air for 1.5 hours prior to being activated.
The above data demonstrate that the pore size of the calcined product i6 about 6.0 A.

:~.

lZ485S~7 c) TiAPSo-5 tExample 6):
~inetic Pressure Temp Wt. % *
Adsorbate Diameter, A (Torr) LC) Adsorbed 0z 3.46 101 -183 13.0 2 3.46 736 -183 14.5 neopentane 6.Z 742 23.0 4.9 cyclohexane 6.0 67 22.9 7.1 H20 2.65 4.6 22.4 14.7 H20 2.65 19 22.5 23.4 ~ TiAPSo was calcined at 600C in air for Z.5 hours pcior to being activated.
The above data demonstrate that the pore size of the calcined product is greater than 6.2 A.
Example 34 (a) TiAPso-5 compositions, as referred t~
hecein in both the as-synthesized and calcined form~, have a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth in Table III below:
Table III
2~ d, (R) Relative Intensit~
7.3-7.5 12.11-11.79 ~-vs 19.7-19.9 4.51-4.46 m 20.9-21.0 4.25-4.23 m-s 2Z.3-22.5 3.99-3.95 m-vs 25.8-26.1 3.453-3.41L m 28.9-29.1 3.089-3.069 w-m (b) TiAPSo-5 compositions for which x-ray powder diffraction data have been ob~ained to date have patterns which a~e ~-ray po~der diffeaction patterns chacacterized by Table IV below.

.:

12~85~7 Table lV
2e d,(A) 100 x I/Io 7.3-7.5 12.11-11.79 g4-100 12.9-13.0 6.86-6.81 19-22 14.9-15.0 5.95-5.91 9-21 19.7-19.9 4.51-4.46 Z6-50 Z0.9-21.0 4.25-4.23 43-82 Z2.3-22.5 3.99-3.95 60-100 24.6-24.8 3.62-3.59 7-9 Z5.8-26.1 3.453-3.414 25-~0 28.9-29.1 3.089-3.069 17-Z7 30.0-30.2 2.979-2.959 18-25 33.5-33.7 2.675-2.660 6-9 34.5-34.7 2.600-2.585 L7-19 36.8-37.1 2.442-2.423 6 37.5-37.~ 2.398-2.380 L0-13 41.4-41.5 2.181-Z.176 5-6 41.7-4Z.0 2.166-2.15L 3-4 42.5-42.9 2.127-2.108 3-6 43.6-43.7 2.076-2.071 3-4 44.9-45.0 2.019-2.014 3-4 47.4-47.6 1.918-1.910 5-7 47.8-47.9 1.903-1.900 6-7 51.4-51.5 1.778-1.774 4-5 51.8-51.9 1.765-1.762 3-~
55.6 1.653 6 (c) A poction of the as-synthesized TiAPSo-5 of Example 6 was subjected to X-cay analysi~. The TiAPSo-5 p~oduct was cha~acte~ized by the x-cay powdec diffraction patte~n of Table V, belov:
Table V
2~ d.(Al 100 x I/Io 7.3 12.11 94 9.1* 9.72 3 12.9 6.86 19 13.6* 6.51 6 14.9 5.95 21 L8.2* 4.87 6 ~9.7 4.51 50 20.9 4.25 82 :~248S~

Table V (Con't) 2e d,(A~ 100 x IJIo 22.3 3.99 1~0 24.6 3.6Z 9 25.8 3.4S3 40 28.9 3.089 27 30.0 2.979 Z5 33.5 2.675 9 34.5 Z.600 19 36.8 2.44Z 6 37.5 Z.39~ 13 41.4 2.181 6 42.0 2.151 4 42.5 2.127 6 43.6 2.076 4 44.9 2.019 3 47.6 1.910 7 51.4 1.778 4 51.8 1.765 4 55.6 1.653 6 *peak may contain an impucity.
(d) The TiAPSo-5 compositions of Example 6 was calcined at 600C in aic foc 2.5 hou~s. The calcined product was characterized by the x-ray powder dif~raction pattern ~hown in Table VI, below:
Table VI
2e d,(A) 100 x I/Io 7.5 11.79 100 1~.5* 7.08 8 13.0 6.81 22 15.0 5.91 9 19.9 4.46 26 21.0 4.23 43 2Z.5 3.95 60 ~4.8 3.59 7 26.1 3.414 25 29.1 3.069 17 12485~7 Table VI (Con't~
2~ d,(A) 100 x I/Io 30.2 2.959 18 33.7 2.660 6 34.7 2.585 17 37.1 2.423 37.8 2.380 10 41.7 2.166 3 4Z.9 2.108 3 47.4 1.918 5 47.9 1.900 6 51.4 1.778 3 Sl.8 1.765 3 ~peak may contain an impu~ity.
ExamPle 35 (a) TiAPSO-ll. as referred to hecein in both the as-synthesized and calcined forms. have a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set focth in Table VII below:
Table VII
2~ d.(A) Relative IntensitY
9.4-9.6 9.41-9.21 vw-m 19.9-20.5 4.46-4.33 m 21.0-21.8 4.23-4.08 vs 22.0-22.1 4.04-4.02 m-Ys Z2.4-22.6 3.97-3.93 m-s 2Z.7 3.92 m 23.L-23.4 3.85-3.80 m-vs (b) The TiAPS0-11 compositions for which x-ray powder diffraction data have been obtained to date have patterns which ace characteeized by the x-ray powder diffraction pattern of Table VIII below:

~Z485V7 Tab le VI I I
2~ d, (A) 100 x I/Io 8.0-8.1 11.05-lo .92 23-59 9.4-9.6 9.41-9.21 sh-73 9.8 9.03 51 12.8- 13.2 6.92 - 6.71 26- 27 13.5-13.7 6.56- 6.46 9- 11 14.7-15.0 6.03-5.91 9-18 15.6-16.1 5.68-5.51 32-63 16.2-16.3 5.47-5.44 7- 1~
19. o-l9.5 4.67-4.55 20-23 19.9-Z0.5 4.46-4.33 31-68 21.0-21. B 4.23-4.08 100 22.0-22.1 4.04-4.02 57-~oo 22.4-22.6 3.97-3.93 54-82 2Z.7 3.92 73 23.1-Z3.4 3 ~ 85-3.80 63- 91 23.9-24.4 3.72-3.65 23 Z~ .7 3.60 27 26.5-26.6 3.363-3.351 17-36 27.2-27.3 3.278-3. z67 16-20 27.6-27.7 3. Z32-3.220 20-23 27.8-27.9 3.209-3.200 20-21 28.5-2~ .6 3.132-3.12~ 14-27 28.7 3. llo 11-32 29.0-29.5 3.079-3.028 27-31 29.6-29.7 3.018-3.008 23-34 30.3-30.4 2.950-2.940 20-22 31.4-31.6 2.849-2.831 14-23 32.5-32.9 ~ .755-2.722 26-32 33.g-34.2 2.644-2.622 11-23 3s .5-35.6 z .529-Z .522 17-19 36.5 2.462 18 37.2-37.5 2.417-2.398 14-23 38.7-39.4 2.327-2.287 14-17 41. o 2.201 11 42.8 2.113 14 43.6 2.076 9 44.5-44.6 2.036-2.032 9-14 45.0 2.014 14 48.7-49.2 1.870-18.52 14 49.4 1,845 11 49.6 1.838 11 50.6 1.804 7- 18 53.4 1.716 11 s3.6 1.707 9 s4.6-54.7 1.681-1.678 9-14 55.4-55.8 1.658-1.647 11-14 ~- ~24~35U7 ~ port~oa ~f the as-~ynthe~zed TiAPS0-11 of Exa~ple 13 was subjec~ed to x-ray ~naly~l~. T~e ~iAP80-11 p~oduct ~as characte~lze~
by the x-ray povde~ diffcaction patt~rn of Table I~C, belov:
Table I~
2e ~5~.
8.1 lO.g2 59 9.4 9.41 73 13. Z 6.71 27 15.0 5.91 18 15.7 5.64 50 ~6.3 S .44 18 19.~ ~.67 23 Z0.5 4. ~3 6B
21.0 ~.Z3 100 22. ~ ~ .02 73 22.6 3.93 ~2 22.~ 3.92 73 23.2 3.83 91 2~.4 3.65 23 2~ .7 3.60 27 26.5 3. ~63 36 28.5 3.132 27 28.7 3.110 32 29 0 3.079 27 29 5 3.028 23 31. ~ 2.849 23 32.9 2.722 32 3~ ~ 2 2.622 23 36.5 2. ~62 1~
37. S 2.398 23 3g . ~ 2.287 1~
42.8 2.113 14 ~4.6 2.032 14 ~S.0 2.01~ 14 .7 1. ~70 14 S0.6 1.~04 18 54.7 1.678 14 55.4 1.658 . 14 (d) ~he S~APS0-11 compoiition of Exa~ple 13 ~- c-lcin-d at SOO'C ~n ~ir ~or 2 ~ourr. T~e D~1~219 :1~48507 calcined peoduct was characte~ized by the x-~ay powde~ diff~action patte~n shown in Table X, below:
Table X
d,(A) 100 x I/Io 8.1 10.92 23 9.6 9.21 ~h 9.8 9.03 Sl 12.8 6.92 26 13.5 6.56 11 13.7 6.46 9 14.7 6.03 9 16.1 5.51 63 ~9.5 4.55 20 19.9 4.46 31 21.8 4.08 100 22.1 4.02 57 22.4 3.97 54 23.4 3.80 63 23.9 3.72 Z3 24.2 3.68 17 26.6 3.351 17 27.2 3.278 20 27.6 3.Z3Z 23 27.8 3.209 20 28.5 3.132 14 2~.7 3.110 11 29.5 3.028 31 29.7 3.008 34 30.3 2.950 20 31.6 2.831 14 32.5 2.755 26 33.9 2.644 11 3S.S 2.529 17 37.2 2.417 14 3~.7 2.327 17 41.0 2.201 11 43.6 2.076 9 44.5 2.036 9 49.2 ~.852 14 49.4 l.B45 11 49.6 l.a38 11 53.4 1.716 9 53.6 1.707 9 55.8 1.647 ~1 D-i4219 lZ~85(~7 Example 36 (a) TiAPSO-16, as ceferced to he~ein in both the as-~ynthesized and calcined form, have a chaLacte~istic x ray powder diffraction patte~n ~hich contain~ at lea~t the d-~pacings set fo~th in Table XI below:
Table XI
2e d,(A) Relative Intensit~
11.4 7.75 m-~s ~8.7 4.75 m 21.9-22.1 4.05-4.02 m-~s Z6.4-26.5 3.370-3.363 m 29.6-29.8 3.018-3.002 m Z9.9 2.984 m 30.1 2.971 m (b) The TiAPSO-16 compositions for ~hich x-ray po~der diffcaction data have been obtained to date have patterns w~ich are characte~ized by the X-ray powder diffraction patte~n of Table XII belo~:
Table ~II
2e d,(Al 100 x I/Io 10.5 8.41 5 11.4 7.75 72-100 18.7 4.75 . 25-59 2~.1 4.21 3 2~.9-22.1 4.~5-4.02 56-100 22.8-22.9 3.90-3.89 10-15 2~.3 3~818 3 25.0 3.56~ 6 25.4-25.5 3.506-3.489 13-17 26.4-26.5 3.370-3.363 20-23 26.6 3.346 1~
26.9-27.1 3.314-3.290 4-15 28.9-29.~ 3.088-3.073 12-13 29.6-29.8 3.018-3.002 22-27 29.9 2.984 24 30.~ 2.971 23 124~3S1~7 Table ~II Con't 2Q d,(A) 100 x I/Io 32.5-32.7 2.755-2.739 3-4 34.4-34.8 2.607-2.581 3-5 37.3-37.6 2.411-2.394 4-5 37.8-37.9 2.380-2.373 8-14 38.Z-38.4 2.356-2.343 5 39.5 Z.282 3-~
39.7-39.8 2.270-2.265 3-5 40.1 2.247 7 40.5 2.227 4 ~4.4 2.04~ 3 47.8-47.9 1.904-~.899 5 ~8.0-48.1 l.~g7-1.~93 6-8 48.2-48.3 1.887-1.885 7-8 48.4-48.5 1.881-L.876 7-8 48.8 l.B65 5-6 49.0 1.858 5 49.2 1.853 4 54.2 1.692 3 ~.
54-3 1.689 3 (c) A portion of the as-synthesizea TiAPS0-16 of example 4 was subiected to x-ray analysis. The TiAPS0-16 pcoauct was characterized by the x-ray powder diffraction eattern of Table XIII, below:
Table XIII
2e d, (A) 100 X I/lo 11.4 7.75 . 72 18.7 4.74 59 22.1 4.02 100 22.9 3.89 lL
25.3 3.521 15 26.4 3.376 13 26.6 3.346 16 26.9 3.314 15 29.1 3.073 13 29.8 3.002 22 29.9 2.984 24 30.1 2.971 23 34.8 2.581 3 37.6 2.395 5 2~8507 Table XIII (Cn't ?
2~ d.(A) 100 x I/Io 37.9 2.371 14 38.4 2.343 5 39.5 2.282 4 39.7 2.270 5 40.1 Z.247 7 40.5 2.227 4 47~B 1.904 5 48.~ 93 8 48.Z 1~887 8 48.5 1.876 8 48.8 1.865 6 49.0 1.858 5 4g.2 1.~53 4 *peak may contain impurity (d) The TiAPS0-16 composition of pact (c~ was calcined at 500C in air for 1.5 hour~. The calcined product was characterized by the x-ray powdec diffcaction pattecn shown in Table XIV, below:
Table XIV
d,(A~ 100 x I/Io 10.5 8.41 5 11.4 7.75 100 18.7 4.75 25 21.1 4.27 3 21.9 4.05 56 22.8 3.90 10 25.0 3.561 6 25.4* 3.506 14 25.5 3.489 13 26.4 3.370 20 2fl.9 3.088 12 29.7 3.007 27 34.6 2.594 5 37.6 2.391 5 37.9 2.373 9 ~Z4~3507 Table ~IV (Con'tl _ d,(A) 100 x I/Io 38.2 2.3s6 s 48.0 1.897 6 48.3 1.885 7 *peak may contain impu~ity ExamPle 37 (a) TiAPSo-34~ as referred to herein in both the as-synthe~ized and calcined form~, have a charactecistic x-ray powder diffraction patte~n which contains at lea~t the d-spacings set forth in Table XV below:
Table ~V
2~ d,(R~ Relative Intensity 9.4-9.5 9.41-9.31 vs 12.9-13.0 6.86-6.81 w-m 16.0-16.2 5.54-5.47 w-m 20.5-20.8 4.33-4.27 m-vs 30.5-30.9 2.931-2.894 m 31.5-31.6 2.840-2.831 w-m (b) The TiAPSo-34 compo6itions fo~ which x-ray powder diffraction data have been obtained to date have patterns which are characterized by the x-ray powder diffraction pattern of Table XVI below:
Table ~VI
2e d.tA) 100 x I/Io 9.4-9.~ 9.41-9.31 100 12.9-13.0 6.86-6.81 16-31 14.0-14.1 6.33-6.28 7-16 ~Z485U7 Table X~I (Con't) 2~ d,(~) 100 x I/Io 16.0-16.2 5.54-5.47 19-50 17.~-17.9 4.98-4.96 16-23 l9.Z 4.62 10 20.5-20.8 4.33-4.27 38-97 22.1-22.2 4.02-4.00 8-9 Z3.1-23.3 3.85-3.82 8-14 25.0-25.1 3.562-3.548 17-27 25.8-26.2 3.453-3.401 19-21 27.5-27.9 3.243-3.198 7-10 28.2-28.3 3.164-3.153 7-12 29.5-29.8 3.0Z8-2.998 8-lZ
30.5-30.9 2.931-2.894 31-39 31.1-31.3 Z.876-Z.858 Sh-Z9 31.5-31.6 Z.840-Z.831 8-3Z
32.3-3Z.4 Z.772-2.763 6-7 33.2 2.698 5 33.8 Z.65Z 5 34.4-34.9 2.607-2.571 8-9 35.0 2.564 3 36.1-36.Z Z.488-2.481 6-7 38.8 2.321 3 39.6-39.8 2.276-2.Z65 5-7 40.2 2.243 5 43.0 2.103 5 43.4 2.0~5 7 47.5 l.9L4 5 48.9-49.2 1.863-1.852 5-8 49.8 1.831 5 50.9-51.0 1.794-1.791 7-8 51.5-SL.6 1.774-L.77L 3-5 53.1-53.2 L.725-1.7Z2 7-8 54.4-54.5 1.687-1.684 5-6 55.8-55.9 1.647-1.645 6-7 (c) A portion of the as-synthesized TiAPSo-34 of exa~ple 24 was ~ubjected to x-cay analy~i~. The TiAPSo-34 product ~as characterized by the x-cay ~owder diffraction pattern of Table ~VII below:

D-~4219 - . .

lZ48S07 - 4~ -Table XVII
_ d . (R) 00 x I/Io 9.4 9.41 ~00 12.9 6.86 16 14.0 6.33 16 ~6.0 5.54 50 17.9 4.96 23 20.5 4.33 97 22.1 4.02 8 23.1 3.~5 8 25.1 3.548 27 25.8 3.453 21 27.5 3.243 ~ 7 28.3 3.153 7 29.5 3.028 8 30.5 2.931 39 31.1 2.876 29 31.6 2.831 8 32.4 2.763 7 33.2 2.698 5 33.8 2.652 5 34.4 2.607 8 35.0 2.564 3 36.2 2.481 7 38.8 2.321 3 39.6 2.276 7 43.0 2.103 5 43.4 2.085 7 47,5 1.914 5 48.9 1.863 8 49.8 1.831 5 50.9 1.794 7 51.6 1.771 3 53.1 1.725 7 54,4 1.687 5 55.8 1.647 7 (d) The TiAPS0-34 compositions of example 24 was calcined at 500C in air for 2 hours. The ealcined pcoduct was characterized by the x-ray powder difraction pattern shown in Table XVII}, below:

12~85Q'7 Table ~
2~ d.(A) 100 x I/lo 9.5 9~31 loo 13.0 6.81 31 14.1 6.28 7 16.2 5.47 19 17.9 4.96 16 19.2 4.62 10 2~.8 4.27 38 22.2 ~,oo 9 23.3 3.82 1~
25.0 3.562 17 26.2 3.401 ~ 19 27.9 3.198 10 28.2 3.164 12 29.8 2.g98 12 30.9 2.894 31 31.3 2.858 sh 32.4 2.763 9 34.9 2.571 9 36.2 2.481 7 39.8 2.265 5 40.2 2.243 5 49.2 1.852 5 51.0 1.791 7 Example 38 (a) TiAPSo-35~ as referred to herein in both the as-synthesized and calcined ~ocms, have a charactecistic x-ray powder diffraction pattern which contains at leafit the d-spacings set forth in Table XIX below:
Table XIX
2e d.(A~ Relative Intensitv 10.9-11.1 8.12-7.97 m 13.3-13.7 6.66-6.46 m L7.3-17.4 5.13-5.10 w-m 20.8-21.1 4.27-4.21 m 21.9-22.2 4.06-4.00 m-vs 28.3-Z8.7 3.153-3.110 m ~248sa~

tb) The TiAPSo-35 compositions fo~ which x-ray powder diffraction data have been obtained to date have patterns which are characterized by the x-ray powder diffcaction pattern of Table ~X below:
Table XX
2e d,(~) 100 x I/lo 8.6-8.8 10.28-10.05 13-14 10.9-11.1 8.~2-7.97 36-74 13.3-13.7 6.66-6.46 20-39 15.9-16.1 5.57-5.51 11-15 17.3-17.4 5.13-5.10 17-75 17.6-L7.7 5.04-5.OL 13-17 20.8-2L L 4.27-4.2L Z5-49 21.9-22.2 4.06-4.00 65-LOO
23.2-23.7 3.83-3.75 22-32 24.9-25.Z 3.58-3.534 19-30 26.6-26.9 3.363-3.314 19-35 28.3-28.7 3.153-3.110 30-48 29.1-29.2 3.069-3.058 11-15 29.6-29.7 3.018-3.008 6-39 31.5-31.7 2.840-2.823 9-11 32.1-32.7 2.788-2.739 30-4 34.3-34.6 2.614-2.592 11-17 35.0-35.1 2.564-2.557 4-5 35.8-35.9 2.508-2.501 5-6 37.8-38.0 2.3BO-2.368 9-13 39.5 2.281 4-5 40.9 2.206 3-4 41.9 2.156 6 4Z.1-42.6 2.146-2.122 5-6 42.7 2.118 4-6 4B.4-48.5 1.881-1.877 9-13 49.0 1.859 5-6 50.1 1.821 10-11 55.0-55.1 1.670-1.667 9-13

5~.4-55.5 1.658-1.656 9-10 (c) A portion of the as-synthesized TiAPSO-35 of example 30 was subjected to x-~ay analysis. The TiAPSo-35 product was characterized by the x-~ay powde~ diffraction pateecn of T~ble XXl belo~:

..

,, .
i~

~Z~l~SV7 Table XXI
2~ d,(~ 100 x I/Io B.6 10.28 13 10.9 8.12 36 11.4* 7.76 6 13.3 6.66 21 lS.g 5.57 11 17.3 5.13 75 17.7 5.01 13 18.6* 4.77 6 20.8 4.27 49 21.9 4.06 100 22.6* 3.93 9 23.2 ` 3.83 32 24.9 3.58 19 25.2* 3.534 28 26.9 3.314 lg 28.3 3.153 47 2g.1 3.069 11 29.7 3.008 6 31.5 2.840 9 32.1 2.788 38 34.3 2.614 11 35.0 2.564 4 35.9 2.50~ 6 37.8 2.380 9 39.5 2.2B1 4 40.9 2.206 4 41.9 2.156 6 42.6 2.122 6 42.7 2.118 6 44.7* 2.027 6 47.6~ 1.910 1 48.4 1.881 9 ~9.0 1.859 6 49.6* 1.838 7 50.1 l.B21 11 54.0* 1.698 6 55.0 1.670 9 5s.4 1.658 9 .
*pea~ may contaln an lmpurlty (d) The calcined TiAPSo-35 c~mpDsitions of example 2 ~a~ calcined at 600C in air for 2 ho~rs.

, , ~ ~

The calcined product was charactecized by the x-cay powde~ diffraction patte~n shown in Ta~le X~II, below.
Table XXII
2e d!(A) 100 x I/Io 8.8 .10.05 13 11.1 7.97 74 ll.S* 7.69 ~oo 13.7 6.4~ 39 17~6 5.04 17 18.9* 4.70 26 21.1 4.Z~ 26 22.2 4.00 65 Z3.1* 3.85 26 23.7 3.75 22 25.2 3.S34 30 26.6 3.363 35 27.4* 3.255 26 28.7 3.1~0 35 29.6* 3.018 39 29.8* 2.998 . 44 32.7 2.739 30 34.6 2.592 17 38.0 2.368 13 48.5 1.877 13 55.1 1.667 13 *peak may contain an impucity Exam~le 39 (a) TiAPSo-44, as cefe~ced to herein in both the as-synthesized and calcined fo~ms, have ~ charactecistic x-cay powdec diffcaction pattecn which contains at least the d-6pacings set focth in Table XXIII below:
Table XIX
_ d,(A~ Relative IntensitY
9. 5 9 . 30 B
16.1 5.49 m 20.8 4 . 27 vs 12485~

2~ d,~A) Relative Inten~itv 22.0 4.05 m 24.5 3.63 m 30.9 2.893 m (b) The TiAPS0-44 compo6itions ~OL which x-cay powder diff~action data have been obtained to date have patte~n~ which a~e characte~ized by the x-~ay powde~ diff~action patte~n of Table XXIV below:
Table XXIV
2~ d.(~) 100 x I/Io 9.5 9.30 83 11.0 8.06 45 13.0 6.79 24 13.4 6.62 30 13.9 6.40 3 16.1 5.49 51 17.4 5.11 48 19.0 4.66 5 20.8 4.27 100 21.L 4.22 36 22.0 4.05 77 22.7 3.92 7 2~.2 3.83 19 24.5 3.63 52 26.2 3.400 20 Z7.0 3.307 Ll 27.9 3.195 10 28.6 3.123 28 29.8 3.000 6 30.3 Z.954 14 30.9 2.893 57 31.7 2.820 6 32.2 2.777 30 32.6 2.745 5 33.1 2.708 4 35.0 2.567 4 35.7 2.519 11 38.7 2.328 3 4~.1 2.145 4 42.6 2.122 5 43.7 2.073 4 47.4 1.920 3 " ~, .

~248507 Table XXIV (Cont.) 2e d,(A) 100 x I/Io 48.2 1.898 12 48.8 1.867 8 51.5 1.775 6 54.1 1.696 7 tc) A po~tion of the as-synthe~ized TiAPS0-44 of Example 11 ~as sub jec~ed to X-~ay analysis. The TiAPSo-44 ploduct was chacactecized by the x-cay powdec diffcaction pattecn of Table XXV, below:
Table XgV
2e d, (R) 100 x I~Io 8.7* 10.21 14 9.5 9.30 83 ~1.0 8.06 45 11.7~ 7.57 3 13.0 6.79 24 13.4 6.62 .30 13.9 6.40 3 16.1 5.49 51 17.4 5.11 48 17.8* 4.9~ 7 19.0 4.66 5 20.8 4.27 100 21.1 4.22 3 21.5* 4.13 19 22.0 4.05 77 22.7 3.92 7 ~3.2 3.83 19 23.6* 3.78 3 24. 5 3.63 52 25.1~ 3.554 8 z5.4~ 3.501 4 25.6~ 3.481 3 26.2 3.400 20 27.0 3.307 11 27~9 3.195 10 2B.6 3.123 28 29.2~ 3.062 5 29.8 3.~00 6 30.3 2.954 ~4 ~Z485t~7 Table XXV ~Cont.) 2e d,(A~ _0 x I~Io 30.9 Z.893 s7 31.7 2.820 6 32.2 2.777 30 32.6 Z.745 5 33.1 2.708 4 34.6~ 2.595 7 35.0 2.567 4 35.1~ 2.559 3 35.7 2.519 11 37.9* 2.372 3 38.7 2.328 3 42.1 2.145 4 42.4~ 2.134 5 42.6 2.122 5 43.0* 2.103 6 43.7 2.073 4 47.4 1.920 3 48.2 L.888 L2 48.7* ~.87~ 8 48.8 l.867 49.7~ 1.8~6 4 50.4~ 1.809 9 51.5 L.775 6 54.1 1.696 7 .

* peak may contain an impurity Example 40 In o~der to demonstrate the catalytic acti~ity of the TiAPSo compositions, calcined sample~ of the TiAPSo p~oducts of Examples 6, 13.
and 24 we~e te~ed for catalytic cracking of n-butane.
The ~eactor was a cylind~ical quaLtz tube 254 ~m. in length and 10.3 mm. I.D. In each test the reactor was loaded with particles of the test TiAPSo which were 20-40 mesh (U.S. std.) in size and in an amount of from O.S to 5 grams, the quantity .. ..

lZ485(~7 being ~elected so that the conversion of n-butane was at least 5S and not ~oee than 90~ under the test condition~. The TiAPSo samples wece calcined in air rTiAPSO-5 at 600C foc 2.5 hours: TiAPSO-ll at 600C
for 1.5 houcs: and TiAPSo-34 at 500C for 2 hours) to remove o{ganic mate~ials from the poLe system, and were activated in situ in the reactor in a flowing stream of helium at 5000C fo~ one hour. The feedstock was a helium-n-butane mixture containing 2 mole peccent n-butane and was passed through the reactor at a rate of 50 cc./minute. ~nalysis of the feedstock and the ceactoc effluent were carcied out usinq conventional gas chcomotog~aphy techniques.
The ceacto~ effluent was analyzed after 10 minutes o~ on-~tceam opecation. The pseudo-fi~st-order rate con~tant (kA) was calculated to determine the relative catalytic activity of the Ti-APSo compositions. The kA value (cm /g min) obtained ~for the TiAPSo compositions are set forth, below, in Table XXVI:
Table X~VI
TiAPSO A
TiAPSo-s 0.6 TiAPSO-ll 0.5 TiAPSo-34 1.3 PROCESS APPLICATIONS
The TiAPSo compositions of the present invention are, in general, hydrophilic and adsorb water prefecentially over common hydrocarbon molecules such as paraffins, olefins and aromatic species, e.g., benzene, xylenes and cumene. Thus, the TiAPSOs as a class ace useful as desiccants in iZ4~35~'7 such adsorption separation/pucification processes as natucal gas dcying, ccacked gas dcying. Watec is also prefecentially ad~ocbed ove~ the so-called pecmanent gases such as carbon dioxide, nitrogen.
oxygen and hydrogen. These TiAPSOs ace therefoce suitably employed in the dcying o~ Lefocmec hydrogen stceams and in the dcying o~ oxygen, nitcogen o~ air pcior to liquifaction The pcesent TiAPSo compo~itions also exhibit novel su~face selectivity chacacteristics ~hich cendec them useful as catalyst o~ catalyst bases in a number of hydcocacbon convecsion and oxidati~e combustion reactions. They can be impcegnated or otherwise loaded with catalytically active metals by methods well known in the art and .
used, foc example, in fabcicating catalysts compositions having silica oc alumina bases. Of the genecal class, those species having poces lacgec than about 4A ace prece~ed foc catalytic applications.
Among the hydrocacbon convecsion ceactions catalyzed by TiAPS0 compo~itions are ccacking, hydcoccacking, alkylation for both the acomatic and isoeacaf~in tyees,isomecization including xylene isomecization, polymecization, cefocming, hydcogenation, dehydrogenation, tcansalkylation, dealkylation, hydcodecyclization and dehyd~ocyclization.
Using TiAPS0 catalyst compositions which contain a hydcogenation pcomotec such as platinum o~
palladium, hea~y pet~oleum ~esidual stocks, cyclic 1~85~

stocks and other hydcocra~kable chalge stocks can be hydrocracked at temperatures in the range of 400F
to 825F using mola~ ratios of hyd~ogen to hyd~ocarbon in the ~ange of between 2 and ~0, eressures between 10 and 3500 p.s.i.g., and a liquid hourly space velocity (LHSV) of f~om 0.1 to 20, p~efecably 1.0 to 10.
The TiAPSo cataly6t compositions employed in hyd~occacking are also suitable fo~ use in re~o~ming proces~es in which the hydrocarbon feed~tocks contact the catalyst at tempecatures of fcom about 700P to 1000F, hydrogen pre~sures of from 100 to 500 p.~.i.g., LHSV values in the range of 0.1 to 10 and hydcogen 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 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 I the reacto~ in admixture with the hyd~ocarbon feedstock in molar proportions (hydrogen to hydrocarbon) of between 1 and 5.
At somewhat higher temperatures, i.e. from about 650F to 1000F, preferably B50F to 950F and usually at somewhat lowe~ pressures within the cange of about 15 to 50 p.s.i.g., the same catalyst ~ D-14219 ;~
. !

"

1~' .

~485Q7 compositions are used to hydroisomerize nocmal paraff ins. P~eferably the paraffin feedstock comprise6 no~mal paEaffins having a carbon number range of C7-C20. Contact ~ime between the feedstock and the catalyst is generally relatively short to avoid undesireable side ~eaction~ such as olefin polymerization and paraffin ccacking. LHSV
values in the ~ange of 0.1 to 10, p~eferably 1.0 to

6.0 ace suitable.
The unique crystal structure of the present TiAPSO catalysts and theic availability in a form totally void of alkali metal content favor their use in the conve~ion of alkylaromatic compounds, particularly the catalytic disproportionation of toluene, ethylene, trimethyl benzenes, tet~amethyl benzenes and the like. In the disproportionation process, isomerization and transalkylation can also occur. Group VIII noble metal ad~uvants alone or in conjunction with Group VI-B metals such as ~ungsten, molybdenum and chromium are preferably included in the catalyst composition in amounts of from about 3 to 15 weiqht-% of the overall composition.
Ext~aneous hydrogen can, but need not, be present in the ceaction zone which is maintained at a temperature of from about 400 to 750F, pressures in the range of 100 to 2000 p.s.i.g. and LHSV values in the range of 0.1 to 15.
Catalytic cracking processes are preferably carried out with TiAPSo compositions using feedstocks such as gas oils, heavy naphthas, deasphalted crude oil residua, etc., with gasoline . ~24~35t~7 being the principal desired ~coduct. Tem~eratu~e condition6 of 850 to 1100F, LHSV values of 0.5 to 10 and pressu~e conditions of from about 0 to 50 p . 6 . i . g. are suitable.
Dehydrocyclization reactions employing paraffinic hydrocarbon feedstocks, preferably normal earaffins having more than 6 carbon atoms, to form benzene, xylenes, toluene and the like a~e ca~Lied out using essentially the 6ame reaction conditions as for catalytic cracking. For these ~eactions it i~ preferred to u~e the TiAPSo cataly~t in conjunction with a Group ~III non-noble metal cation such as titanium and nickel.
In catalytic dealkylation wherein it is desired to cleave paraffinic side chains f~om a~omatic nuclei without substantially hydrogenating the ring structure, relatively high temperatures in the ~ange of about 800-1000F are employed at moderate hydrogen pressures of about 300-1000 p.s.i.g., other conditions being similar to those desc~ibed above fot catalytic hydroc~acking Prefe~ed cataly~ts are of the same type described above in connection with catalytic dehyd~ocyclization. Particula~ly desirable dealkylation reactions contemplated herein include the conversion of methylnaphthalene to naphthalene and toluene and/oc xylenes to benzene.
In catalytic hydrofining, the primary objective i8 to promote the selective hydrodecomposition of organic sulfur and/o~ nitrogen compounds in the feed, without substantially 12~85~

affecting hydcocarbon molecules thecein. Foc this pu~pose it is p~efe~ced to employ the sa~e general ~onditions desc~ibed above fo~ catalytic hydroceacking, and cataly&ts of the same genecal natu~e desc~ibed in connection with dehydrocyclization opecations. Feedstocks include gasoline fractions, kerosenes, jet fuel fcactions, diesel f~actions, light and heavy gas oils, deasphalted ccude oil cesidua and the like any of which may contain up to about 5 weight-eeccent of sulfur and up to about 3 weight-peccent of nitrogen.
SimilaL conditions can be employed to effect hyd~ofining, i.e., denitcogenation and desulfurization, of hydroca~bon feeds containing substantial pro~o~tions of organonitcogen and ocganosulfur compounds. It is geneLally recognized that the p~esence of substantial amounts of such constituents ma~kedly inhibits the activity of catalysts of hydrocracking. Consequently, it ifi necessacy to operate at moce extreme conditions when it is desiced to obtain the same degcee of hydrocracking conversion pec pass on a celatively nitcogenous feed than are ~equired with a feed containing less organonitrogen compounds.
Consequently, the conditions unde~ which denitrogenation, desulfurization and/or hydroccacking can be most expeditiously accomplished in any given situation ace necessarily dete~mined in view of the characteristics of the feedstocks in particular the concentration of organonitcogen compounds in the feedstock. As a result of ~he lZ48S07 .

effect of oeganonit~ogen compounds on the hyd~ocracking activity of the~e compo~i~ions it is not at all unlikely that the conditions most suitable for denit~ogenation of a given feed~tock having a ~elatively high organonitrogen content with minimal hydrocracking, e.g., less than 20 volume peccent of fresh feed per pass, might be the same as those ereferred for hydrocracking another feedstock having a lowec concentration of hydrocracking inhibiting constituents e.g., organonitcogen 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 de~ccibed above for Leforming, using somevhat mo~e acidic catalysts. Olefins a~e preferably isome~ized at temperatures of 500-900F, while paraffins, naph~henes and alkyl aromatics are isomerized at temperatuces of 700-1000F. Particularly desirable isomeri2ation reactions con~emplated 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 oftho-xylene to paraxylene, l-butene to 2-butene and/or isobutene, n-hexene to isohexene, cyclohexene to methylcyclopentene etc. The preferred form of the catalyst i8 a combination of the TiAPSo with polyvalent metal compounds (such as .

lZ~85S~7 sul~ides) of me~als of Gcoup lI-A, Gcoup Il-B and ra~e earth metals. For alkylation and dealkylation processes the TiAPSo compositions having eores of at least 5A are p~efe~ed. When em~loyed for dealkylation of alkyl aromatics, the temperature is usually at least 350F and ~anges up to a temperature at which substantial cracking of the feedstock or convecsion products occurs, gene ally up to about 700F. The temperature i8 preferably at least 450F and not greater than the critical temperatu~e of the compound undergoing dealkylation. Pressure conditions are applied to retain at least the aromatic feed in the li~uid state. For alkylation the tempecature can be as low as 250P but i8 pre~erably at least 350F. In the alkylation of benzene, toluene and xylene, the preferred alkylating agents ace olefins such as ethylene and propylene.

D-142~9

Claims (36)

1. Crystalline molecular sieves having a three-dimensional microporous framework structures of TiO2, AlO2, PO2 and SiO2 tetrahedral units having an empirical chemical composition on an anhydrous basis expressed by the formula:
mR : (TiwAlxPySiz)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 (TiwAlxPySiz)O2 and has a value of zero (0) to about 0.3: and "w", "x", "y" and "z" represent the mole fractions of titanium, 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. Molecular sieves according to claim 1 wherein the mole fractions of titanium, 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. Process for preparing the crystalline molecular sieves of claim 1 having three-dimensional microporous framework structures wherein said process comprises reacting for an effective time at an effective temperature a mixture composition expressed in terms of molar oxide ratios as follows:
aR: (TiwAlxPySiz) wherein "R" is an organic templating agent: "a" is the amount of "R" and may have a value of zero or is an effective amount greater than zero to about 6:

"b" has a value of from zero to 500; and "w", "x", "y" and "z" represent the mole fractions, respectively, of titanium, aluminum, phosphorus and silicon in the (TiwAlxPySiz)O2 constituent, and each has a value of at least 0.01, whereby the molecular sieves of claim 1 are prepared.

10. Process of claim 9 wherein "w", "x", "y" and "z" are within the pentagonal area defined by points F, G, H, I and J of FIG. 3.

11. Process according to claim 9 wherein the source of phosphorus in the reaction mixture is orthophosphoric acid.

12. Process according to claim 9 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.

13. Process according to claim 12 wherein the aluminum alkoxide is aluminum isopropoxide.

14. Process according to claim 12 wherein the source of silicon is silica.

15. Process according to claim 12 wherein the source of titanium is titanium acetate.

16. Process according to claims 9 or 10 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.

17. Process according to claim 9 wherein the organic templating agent is an amine.

18. Process according to claim 9 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-diaziabicyclo-(2,2,2) octane;
N-methyldiethanolamine; N-methylethanolamine;
N-methylpiperidine; 3-methylpiperidine;
N-methylcyclohexylamine; 3-methylpyridine;
4-methylpyridine; quinculidine;
N,N '-dimethyl-1,4-diazabicyclo (2,2,2) octane ion;
tetramethylammonium ion; tetrabutylammonium ion;
tetrapentylammonium ion; di-n-butylamine;
neopentylamine; di-n-pentylamine; isopropylamine;
t-butylamine; ethylenediamine; pyrrolidine;
2-imidazolidone; di-n-propylamine; and a polymeric quaternary ammonium salt [(C14H32N2)(OH)2]x vherein x is a value of at least 2.

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

20. 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.

21. 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.

22. 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.

23. Process according to claim 20 or 21 wherein the more polar molecular species is water.

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

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

26. Process according to claim 24 or 25 wherein the hydrocarbon conversion process is cracking.

27. Process according to claim 24 or 25 wherein the hydrocarbon conversion process is hydrocracking.

28. Process according to claim 24 or 25 wherein the hydrocarbon conversion process is hydrogenation.

29. Process according to claim 24 or 25 wherein the hydrocarbon conversion process is polymerization.

30. Process according to claim 24 or 25 wherein the hydrocarbon conversion process is alkylation.

31. Process according to claim 24 or 25 wherein the hydrocarbon conversion process is reforming.

32. Process according to claim 24 or 25 wherein the hydrocarbon conversion process is hydrotreating.

33. Process according to claim 24 wherein the hydrocarbon conversion process is isomerization.

34. Process according to claim 25 wherein the hydrocarbon conversion process is isomerization.

35. Process according to claim 33 or 34 wherein the isomerization conversion process is xylene isomerization.

36. Process according to claim 24 or 25 wherein the hydrocarbon conversion process is dehydrocyclization.