TITANIUM-ALUMINUM-SILICON-OXIDE MOLECULAR SIEVE COMPOSITIONS

Abstract: Titanium-aluminum-silicon-oxide molecular sieves having three-dimensional micoporous crystalline framework structures of tetrahedral oxide units TiO2, AlO2 and SiO2 are disclosed having use as molecular sieves and as catalyst compositions in hydrocarbon conversion and other processes.

Description: TITANIUM- LUMINUM-SILICON-OXIDE MOLECULAR SIEVE COMPOSITIONS FIELD OF THE INVENTION The pcesent invention relates to a new class of molecular sieve compositions containing titanui . aluminum and silicon in the form of framework tetrahedral oxide units. These compositions are prepared hydrothermally from reaction mixtures containing reactive sources of titanuim, aluminum and silicon and preferably at least one organic tem lating agent. DISCUSSION OF MOLECULAR SIEVES Molecular sieves having crystalline structures and of the alu inosilicate type are well known to those familiar with molecular sieve technology. Both naturally occurring and synthetic alu inosilicates are known to exist and literally hundreds of such have been reported in the literature. Although hundreds of aluminosilicates (binary molecular sieves) are known, the reports relating to ternary molecular sieves have been relatively few. Further, the reported ternary molecular sieves having titanium as a component have been even fewer and in those instances where titanium has been reported the amount contained in the molecular sieve has been relatively small or present as a deposition or surface modifying agent. One early report of crystalline titano-silicate zeolites (Of course, these compositions are not zeolites as the term "zeolite" is commonly employed today.) is found in U.S. Patent No. 3,329,481. The crystalline titaπo-silicates are described in U.S. Patent No. 3,329,481 by the formula: D 2/n ) χ :Ti0 2 (Si °2 ) y wherein D is a monovalent metal, divalent metal, ammonuim ion or hydrogen ion, "n" is the valence of D, "x" is a number from 0.5 to 3 and y is a number from about 1.0 to 3.5. The crystalline titano-silicate zeolites are characterized by X-ray powder diffraction patterns including all the d-spacings of one of the patterns selected from the group: Pattern A: Pattern B: Pattern C: 7.6 - 7.9A 4.92 + 0.04A 2.82 + 0.03A 3 .2 +. 0 . 05A 3 . 10 + 0. 04A 1 . 84 +. 0 . 03A The difficulty in obtaining compositions containing titanuim is evidenced by the disclosure of U.S. Patent No. 4.358.397 which discloses modified aluminosilicates. The aluminosilicates are modified by treating an aluminosilicate with a compound derived from one or more elements of titanium, zirconium or hafnium. The resulting compositions are said to contain a minor proportion of an oxide of such elements. It is clear that in the disclosed compositions the oxides of titanuim, zirconium and hafnium were present as deposited oxides and were present in a minor proportion. As above mentioned, although there has been an extensive treatment in various patents and in the published literature of aluminosilicates and recently, aluminophosphates, there has been little information available on molecular sieves other than such materials. This is particularly true in the " area of titanium containing compositions. Molecular sieve compositions wherein titanium is present in the framework of the molecular sieve or is so intimately related as to change the physical and/or chemical characteristics of the molecular sieve have not been extensively reported. This is understandable in the question of aluminosilicates, as indicated by the article, "Can Ti 4+ replace Si4+ in silicates?", Mineralogical Magazine, September vol 37, No. 287, pages 366-369 (1969). In this article it is concluded that substitution of framework silicon by titanium does not usually occur in aluminosilicates owing to the preference of titanium to be octahedrally bound rather than tetrahedrally bound. Even in the formation of crystalline "titanosilicate zeolites", as disclosed in U.S. Patent No. 3,329,481 and discussed above, wherein a metallo-silicate complex is formed and treated to give the titano silicate product the evidence for the claimed titanosilicate is based on the X-rray powder diffraction pattern data which are somewhat suspect as to whether such show substitution of titanium into the silicate framework inasmuch as the same claimed X-ray patterns are also observed for the zirconium silicates. Further, similar X-ray patterns showing similar interplanar distances for the two values in pattern B have been reported for silicalite. (see GB 2.071,071 A). The incorporation of titanium in a silicalite-type structure is disclosed in GB 2.071,071 A. published December 21, 197^. The -amount of titanium claimed to be substituted into the silicalite-type structure is very small, being no more than 0.04 mole percent, based on the number of moles of silica, and may be as low as 0.0005. The titanium content was determined by chemical analysis and was not determined to be greater than 0.023 in any of the reported examples. As indicated by a comparison of Fig. la and Fig. lb of GB 2,071,071 A. the amount of titanium present is so small that no significant change in the X-ray diffraction pattern of silicalite was observed and the minor changes observed may simply be due to occluded titanium dioxide. (Thus, in the absence of other analytical data the results are not well defined.) No comparison data for titanium dioxide ace disclosed. In view of the above, it is cleat that the substitution of titanium into a zeolitic-type framework although conceived to be possible wherein titanium substitutes for silicon, has been viewed by those skilled in the art as most difficult to achieve. The difficulty which is met in pcepacing titanium-containing molecular sieve compositions is further demonstrated by the failure of European Patent Application No. 82109451.3 (Publication No. 77.522. published April 27. 1983) entitled ■ Titanium-containing zeolites and method for theic production as well as use of said zeolites.", to actually prepare titanium-containing molecular sieve compositions. Although the applicants claim the preparation of titano-aluminosilicates having the pentasil structure, it is evident from an analysis of the products of the examples that titanium was not present in the form of a framework tetrahederal oxide. The product of the example of European patent Application No. 82109451.3 will be discussed in detail in a comparative example hereinafter. DESCRIPTION OF THE FIGURES ' FIG. 1 is a ternary diagram whersin parameters relating to the instant compositions are set forth as mole fractions. FIG. 2 is a ternary diagram wherein parameters relating to preferred compositions are set forth as mole fractions. FIG. 3 is a ternary diagram wherein parameters relating to the reaction mixtures employed in the preparation of the compositions of this invention are set forth as mole fractions. FIG. 4 is an SEM (Scanning Electron Micrograph of the product of European Application No. 82109451.3. FIG. 5 is an SEM of TASO-45 prepared in accordance with the instant invention. Summary of the Invention New molecular sieve compositions are claimed having three-dimensional microporous crystalline framework structures of TiO_. A10_ and SiO. tetrahedral oxide units. These new molecular sieves have a unit empirical formula on an • anhydrous basis of: mR: (Ti χ Al y Si 2 )O z where "R" denominates an organic templating agent pcesent in the intcaccystalline poce system; "i" cepcesents the moles of "R" pcesent pec mole of (TixAlySz)0_2, and has a value of fcom zeco to about 0.3; and *x"» "y" and "z" cepcesent the mole fcactions of titanium, aluminum and silicon, respectively, pcesent as fcamewock tetcahedcal oxide units, said mole fcactions being such that they ace within the tetcagonal acea defined by points A, B. C and D of Fig. 1, whece points A. B. C and D have the following values foe "x". "y" and "z": Mole Fcaction Point x _£ z_ A .39 . 60 0.01 B .98 . 01 0. 01 C .01 . 01 0 . 98 D .01 . 60 0. 39 The instant titanium-aluminum-silicon- oxides will be genecally cefecced to hecein by the accony "TAS0-45" to designate the instant itanium-aluminum- silicon-oxide moleculac sieves having a fcamewock stcuctuce of TiO . A10 and SiO tetcahedcal oxide units. This designation is _£ an acbitcacy one and is not intented to denote stcuctucal relations to another material(s) which may also be characterized by a numbering system. DETAILED DESCRIPTION OF THE INVENTION The present invention .relates to titanium-aluminum-silicon-oxide molecular sieves having three-dimensional microporous crystal framework structures of TiO_. A10„ and SiO., 2 2 . 2 tetrahedral units which have a unit empirical - 1 - focmula on an anhydrous basis of: S : (TixAlySiz)02„ (1) wherein H R" cepcesents at least one organic te plating agent present in the intracrystalline pore system; "i" represents the moles of "R" present pec mole of (Ti„Al Si )0_ and has a value of between zero and about 0.3. ; and "x", "y" and "z" represent the mole fcactions of titanium, aluminum and silicon, respectively, pcesent as tetcahedcal oxides, said mole fcactions being such that they ace within the tetcagonal compositional acea defined by points A, B, C and D FIG. 1 and cepcesenting the following values fo "x", "y" and "z": Mole Fcaction Point y x z A 0. 60 0. 39 0 . 01 B ' 0 .01 0. 98 0. 01 C 0. 01 0. 01 0. 98 D 0. 60 0. 01 0 . 39 The pacametecs "x". "y" and "z" are preferably within the compositional area defined by points a. b. and c of the ternary diagram which is Fig. 2 of the dcawings, said points a, b, and c representing the following values for "x", "y" and "z": Mole Fraction Point x Y z a 0.49 ' 0.01 0.50 b 0.01 0.49 0.50 c 0.01 0.01 0.98 In a oce pcefecced subclass the value of "x" is between about 0.024 and about 0.118, "y" is between about 0.020 and about 0.051 and "z" is between about 0.831 and about 0.956. The molecular sieves of the present invention are generally employable as catalysts for various hydrocarbon conversion processes. The term "unit empirical formula" is used herein according to its common meaning to designate the simplest formula which gives the relative number of moles of titanium, aluminum and silicon which form the TiO_, A10, and SiO- tetrahedral unit within a titanium-aluminum-silicon-oxide molecular sieve and which forms the molecular framework of the TASO-45 composition(s) . The unit empirical formula is given in terms of titanium, aluminum and silicon as shown in Formula (1). above, and does not include other compounds, cations or anions which may be present as a result of the preparation or the existence of other impurities or materials in the bulk composition not containing the aforementioned tetrahedral unit. The amount of template R is reported as part of the composition when the as-synthesized unit empirical formula is given, and water may also be reported unless such is defined as the anhydrous form. For convenience, coefficient "m" for template "R" is reported as a value that is normalized by dividing the number of moles of organic by the total moles of titanium, aluminum and silicon. The unit empirical formula for a given TASO-45 can be calculated using the chemical analysis data for that TASO-45. Thus, for example, in the preparation of TASO-45 disclosed hereinafter the over all composition of the as-synthesized TASO-45 is calculated using the chemical analysis data and expressed in terms of molar oxide ratios on an anhydrous basis. The unit empirical formula for a TASO-45 may be given on an "as-synthesized" basis or may be given after an "as-synthesized" TASO-45 composition has been subjected to some post treatment process, e.g., calcination. The terra "as-synthesized" herein shall be used to refer to the TASO-45 composition(s) formed as a result of the hydrothermal crystallization but before the TASO-45 composition has been subjected to post treatment to remove any volatile components present therein. The actual value of "m" for a post-treated TASO-45 will depend on several factors (including: the particular TASO-45, template, severity of the post-treatment in terms of its ability to remove the template from the TASO-45, the proposed application of the TASO-45 composition, and etc.) and the value for "ra" can be within, the range of values as defined for the as-synthesized TASO-45 compositions although such is generally less than the as-synthesized TASO-45 unless such post-treatment process adds template to the TASO-45 so treated. A TASO-45 composition which is in the calcined or other post-treatment form generally has an empirical formula represented by Formula (1), except that the value of "m" is generally less than about 0.02. Under sufficiently severe post-treatment conditions, e.g. roasting in air at high temperature for long periods (over 1 hr.), the value of "m" may be zero (0) or, in any event, the template, R, is undetectable by normal analytical procedures. The molecular sieves of the instant invention are generally synthesized by hydrothermal crystallization from a reaction mixture comprising reactive sources of titanium, aluminum and silicon, and preferably one or more organic templating agents. Optionally, alkali metal(s) may be present in the reaction mixture. The reaction mixture is placed in a pressure vessel, preferably lined with an inert plastic material, such as polytetrafluoroethylene, and heated, preferably under the autogenous pressure, at a temperature of from about 50 β C to about 250°C, until crystals of the molecular sieve product are obtained, usually for a period of from 2 hours to 2 weeks or more. While not essential to the synthesis of the instant molecular sieves, it has been found that in general stirring or other moderate agitation of the reaction mixture and/or seeding the reaction mixture with seed crystals of either the TASO-45 to be produced. or a topologically similar composition, facilitates the crystallization procedure. The product is recovered by any convenient method such as centrifugation or filtration. After crystallization the TASO-45 may be isolated and washed with water and dried in air. As a result of the hydrothermal crystallization, the as-synthesized TASO-45 contains within its intracrystalline pore system at least one form of any template employed in its formation. Generally, the template is a molecular species, but it is possible, steric considerations permitting, that at least some of the template is present as a charge-balancing cation. Generally the template is too large to move freely through the intracrystalline pore system of the formed TASO-45 and may be removed by a post-treatment process, such as by calcining the TASO-45 at temperatures of between about 200*C and to about 700°C so as to thermally degrade the template or by employing some other post-treatment process for removal of at least part of the template from the TASO-45. In some instances the pores of the TASO-45 are sufficiently large to permit transport of the template, and, accordingly, complete or partial removal thereof can be accomplished by conventional desorption procedures such as carried out in the case of zeolites. TASO-45 compositions are formed from a reaction mixture containing reactive sources of Ti0 2 , Al-O-. and SiO, and an organic templating agent, said reaction mixture comprising a composition expressed in terms of molar oxide ratios of: . aR 2 0:(Ti χ Al y Si 2 )0 2 :b H..0 wherein "R" is an organic templating agent; "a" has a value large enough to constitute an effective amount of "R" said effective amount being that amount which form said TAS0-45 compositions and preferably has a value of from greater than zero to about 100 and more preferably between about 1 and about 50; "b." has a value of from zero to 400 and gceatec. pcefecably fco about 50 to about 100: "x", "y" and "z" represent the mole fcactions, respectively of titanium, aluminum and silicon in the (TixAlySiz)0_2 constituent, and each has a value of at least 0.01 and being within the tetcagonal compositional area defined by points. E. F. G and H which is Fig. 3 of the drawings, said points E. F. G and H representing the following values for "x", "y ,r and "z": Mole Fraction Point X J . z E 0.39 0. 60 0 . 01 F 0. 98 0.01 0. 01 G 0.01 0.01 0. 98 H 0.01 0. 60 0. 39 The ceaction mixtures from which TASO-45 is formed generally contain one or more ocganic templating ageαts (templates) which can be most any of those hecetofore proposed for use in the synthesis of aluminosilicates and alu inophosphates. The template preferably contains at least one element of Group VA of the Periodic Table, particularly nitrogen, phosphorus, arsenic and/or antimony, more preferably nitrogen or phosphorus and most preferably nitrogen and are of the formula R 4.X wherein X is selected from the group consisting of nitrogen, phosphorus, arsenic and/or antimony and R may be hydrogen, alkyl. aryl. araalkyl. or alkylaryl group and is preferably aryl or alkyl containing between 1 and 8 carbon atoms. although more than eight carbon atoms may be present in "R" of group of the template. Nitrogen-containing templates are preferred, including amines and quaternary ammonium compounds, the latter being represented generally by the formula R' 4 N + wherein each R' is an alkyl, aryl, alkylaryl, or araalkyl group; wherein R' preferably contains from 1 to 8 carbon atoms or higher when R' is alkyl and greater than 6 carbon atoms when R* is otherwise, as hereinbefore discussed. Polymeric quaternary ammonium salts such as [ (C. H 32 N 2 (OH), -•£]Λ wherein "x" has a value of at least 2 may also be employed. The mono-, di- and tri-amines, including mixed amines, may also be employed as templates either alone or in combination with a quaternary ammonium compound, quaternary phosphonium compound or another template. The exact relationship of various templates when concurrently employed is not clearly understood. Representative templates which may be employed include: tetramethylammonium. tetraethylammonium, tetrapropylammonium or tetrabutylammonium ions; di-n-propylamine; tripropylamine; triethylamine; triethanolamine; piperidine; cyclohexylamine; 2-methylpyridine; N.N-dimethylbenzylamine; N.N-die hylet anolamine; dicyclohexylamine; N,N-dimethylethanolamine; 1,4-diazabicyclo (2,2,2) octane; N-methyldiethanolamine, N-methyl- ethanolamine; N-methylcyclohexylamine; 3-methyl- pyridine; 4-methylpyridine; quinuclidine; N,N'-dimethyl-1.4-diazabicyclo (2,2,2) octane ion; di-n-butylamine, neopentylamine; di-n-pentylamine; isopropylamine; t-butylamine; ethylenediamine; pyrrolidine; and 2-imidazolidone. If an alkoxide is selected as the reactive aluminum, silicon or titanium source, the corresponding alcohol is necessarily present in the reaction mixture since it is a hydrolysis product of the alkoxide. It has not as yet been determined whether this alcohol participates in the synthesis process as a templating agent, or in some other function and, accordingly, is not reported as a template in the unit formula of TASO-45, although such may be acting as templates. Alkali metal cations if present in the reaction mixture may facilitate the crystallization of TASO-45, although the exact function of such cations, when present, in crystallization, if any, is not presently known. Alkali cations present in the reaction mixture generally appear in the formed TASO-45 composition, either as occluded (extraneous) cations and/or as structural cations balancing net negative charges at various sites in the crystal lattice. It should be understood that although the unit formula for TASO-45 does not specifically recite the presence of alkali cations they are not excluded in the same sense that hydrogen cations and/or hydroxyl groups are not specifically provided for in the traditional formulae for zeolitic aluminosilicates. Most any reactive titanium source may be employed herein. The preferred reactive titanium sources include titanium alkoxides. water-soluble titanates and titanium chelates. Most any reactive source of silicon can be employed herein. The preferred reactive sources of silicon are 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 'mixtures thereof. Most any reactive aluminum source may be employed herein. The prefecced ceactive aluminum soucces include aluminum alkoxides. such as aluminum isopcopoxide. and pseudoboehmite. Crystalline oc amorphous aluminosilicates which are a suitable source of silicon are. of course, also suitable sources of aluminum. Other sources of aluminum used in zeolite synthesis, such as gibbsite, sodium alu inate and aluminum trichloride, are believe employable herein. The following examples are provided to exemplify the invention and are not meant to be limiting thereof in any way. EXAMPLES 1-66 (a) Examples 1 to 66 were carried out to demonstrate the preparation of the TASO-45 compositions of this invention. The TASO-45 compositions were caccied out by employing the hydcothecmal ccystallization pcoceduce discussed supca. Reaction mixtuces wece prepared foe each example using one oc moce of the following pcepacative ceagents: (1) Tipco: Titanium isopcopoxide; (2) AA: TYZOR AA. Titanium. bis(2.4-pentanedionate-0.0' ) bis(2-pcopanolato)-; (3) TE: TYZOR TE. Ethanol, 2,2' ,2"-nitrilotris-. titanium (4+) salt; (4) LA: TYZOR LA. Titanate (2-) .dihydroxy bbiiss [[22--hhyyddrrooxxyypprrooppaannaattoo((2)-0 102]-; (5) DC: TYZOR DC. Titanium bis(ethyl-3-oxobutanolato-0 .0 )bis (2-propanolato)-; (6) ANF: TYZOR ANF, Titanium. bis(2.4-pentanediona o-0,0' )bis(2-propan olato)-; (7) LUDOX-LS: Trademark of DuPont for an aqueous solution of 30 weight percent SiO- and 0.1 weight percent Na 0; (8) Sodium aluminate; (9) Sodium hydroxide; (10) TBABr: tetrabutylammonium bromide; (11) TEABr: tetraethylammonium bromide; (12) TPABr: tetrapropyla monium bromide; (13) TPAOH: tetrapropylammonium hydroxide; (14) Kaiser alumina. The designation TYZOR in the above list is the Trademark of DuPont for the identified titanium compounds. The method of addition of the above mentioned components to the reaction mixture was done according to three methods (A, B and C) . In some of the examples seed crystals of silicalite (U.S.P. 3,941,871) were added to the reaction mixtures. Methods A, B and C are as follows: METHOD A LUDOX-LS and two-thirds of the water were blended to form a homogeneous mixture. The remaining water and sodium hydroxide were blended to form a homogeneous mixture. Sodium aluminate was dissolved in this second mixture and the two mixtures blended to form a homogeneous mixture. The titanium source was blended into this mixture after which the organic templating agent (referred to herein as "template") was added to this mixture and blended until a homogeneous mixture was observed. METHOD B LUDOX-LS and one half of the water were blended to form a homogeneous mixture. The titanium source was added to this mixture and blended to form a homogeneous mixture. The sodium aluminate was dissolved in approximately one fourth the water and added to the previous mixture until a homogeneous mixture was observed. The sodium hydroxide was dissolved in one fourth of the water and blended with the previous mixture. The organic template was added to this mixture and blended until a homogeneous mixture was observed. METHOD C LUDOX-LS and one-third of the water were blended to form a homogeneous mixture. The sodium hydroxide was dissolved in one-sixth of the water and added to this mixture and blended to form a homogeneous mixture. Kaiser alumina was dissolved in one-sixth of the water added to the NaOH solution and blended. The mixture was then added to the LUDOX solution and blended. The titanium source was added to this mixture and blended to provide a homogeneous mixture after which the organic template (in one-third of the water) was added and the mixture again blended until a homogeneous mixture was observed. (b) The X-ray patterns appearing herein were obtained using standard x-ray powder diffraction techniques or by use of copper K-alpha radiation with computer based techniques using Siemens D-500 X-ray powder diffractometers, Siemens Type K-805 X-ray sources, available from Siemens Corporation, Cherry Hill, New Jersey, with, appropriate computer interface. The standard X-ray technique employs as the radiation source a high-intensity, copper target. X-ray tube operated at 50 Kv and 40 ma. The diffraction pattern from the copper K radiation and graphite monochromator is suitably recorded by an X-ray spectrometer scintillation counter, pulse height analyzer and strip chart recorder. Flat compressed powder samples are scanned at 2°(2 theta) per minute, using a two second time constant. Interplanar spacings (d) in Angstrom units are obtained from the position of the diffraction peaks expressed as 2θ (theta) where theta is the Bragg angle as observed on the strip chart. Intensities were determined from the heights of diffraction peaks after subtracting background, "I " being the intensity of the strongest line or peak, and "I" being the intensity of each of the other peaks. When Relative Intensities are reported the following abbreviations mean: vs __ very strong; s = strong; m = medium, w __ weak; and vw = very weak. Other abbreviations include: sh __ shoulder and br = broad. As will be understood by those skilled in the art the determination of the parameter 2 theta is subject to both human and mechanical error, which in combination, can impose an uncertainty of about +0.4° on each reported value of 2 theta. This uncertainty is. of course, also manifested in the reported values of the d-spacings. which are calculated from the 2 theta values. This imprecision is general throughout the art and is not sufficient to preclude the dif erentiation of the present crystalline materials from each other and from the compositions of the prior art. (c) The preparative examples were carried out by preparing reaction mixtures having molar amounts of components expressed by: e R:f Al O :g SiO :h Ti0 2 : i NaOH: H O wherein "R" is at least one organic template as hereinbefore define; and e, f. g. h.^i and j are the number of moles of template, A1-0-, SiO_, TiO-, NaOH and H_0, respectively. The values for e, f. g, h, i and j are set forth in Table I for the TASO-45 products prepared in examples 1 to 66: TABLE I Mix Example Template β h i j Temp CO . Source Method 2 1 TPABr 15 10 14 1715 150 14 TiPro B 2 TPABr 15 10 14 1715 200 4 TiPro B 3 TPABr 15 10 14 1715 200 14 TiPro B 4 TPAOH 35 5 10 1779 150 4 AA B 5 TPAOH 35 5 10 1779 150 14 AA B 6 TPAOH 35 5 10 1779 150 20 AA B 7 TPAOH 35 5 10 1779 200 4 AA B 8 TPAOH 35 5 10 1779 200 10 AA B 9 TPAOH 35 5 10 1779 150 4 AA A 10 TPAOH 35 5 10 1779 150 10 AA A 11 TPAOH 35 5 10 1779 200 4 AA A 12 TPAOH 35 5 10 1779 200 10 AA A 13 TPAOH 35 5 10 1715 150 4 TE A 14 TPAOH 35 5 10 1715 150 10 TE A 15 TPAOH 35 5 10 1715 150 4 TE B 16 TPAOH 35 5 10 1715 150 10 TE B 17 TPAOH 35 5 10 1750 150 4 LA A 18 TPAOH 35 • 5 10 1750 150 10 LA A 19 TPAOH 35 5 10 1784 150 4 LA B 20 TPAOH 35 5 10 1784 150 10 LA B 1 All amounts are given in moles. The value of "e" was 3.6 and the value of "f" was 1.0. 2 S S_e»Ae.d 1 rcrr-yi.suttaA!lαs o ntf • • s«iillii.c«allii 1 it- Ae lwιfAelr-1e added after formation of the reaction mixture in examples 1 to 20. The seed crystals were present in an amount of five wt. percent based on the weight of the soLld oxides of the reaction mixture, exclusive of the seed crystals. TABLE I (continued) Mix Example Template e i j Temp < • (_•) Time (days) Ti Source , Method 2 21 TPAOH 3.6 14 1715 150 4 Tipro B 22 TPAOH 3.6 14 1715 150 11 Tipro B 23 TPAOH 3.6 14 1715 200 4 Tipro B 24 TPAOH 3.6 14 1715 200 11 Tipro B 25 TPAOH 3.6 14 1715 150 4 DC A 26 TPAOH 3.6 14 1715 150 11 DC A 27 TPAOH 3.6 14 1715 200 4 DC A 28 TPAOH 3.6 14 1715 200 11 DC A 29 TPAOH 25.2 3.6 1800 200 21 Tipro A 30 TPAOH 3.6 7 1715 150 18 Tipro A 31 TPAOH 3.6 7 1715 200 10 Tipro A 32 TPAOH 3.6 7 1715 200 18 Tipro A 33 TPAOH 3.6 14 1715 150 5 Tipro A 34 TPAOH 3.6 14 1715 150 10 Tipro A 35 TPAOH 3.6 14 1715 200 5 Tipro A 36 TPAOH 3.6 14 1715 200 10 Tipro A 37 TPAOH 3.6 14 1715 200 4 Tipro A 38 TPAOH 3.6 14 1715 200 4 Tipro A 39 TPAOH 3.6 14 1715 150 4 Tipro A 1 All amounts are given In moles. The value of "f" was 1.0, "g° was 35 and "h" was 5. 2 Seed crystals of silicalite were added after formation of the reaction mixture In examples 21 to 28 and 37 to 39. The seed crystals were present In an amount of five wt. percent based on the weight of the solid oxides of the reaction mixture, exclusive of the seed crystals. TABLE 1 (continued) Mix Example Template j Temp (*C) Tlme(days) Tl Source Method? 40 TPAOH 1.0 35 5 14 1715 150 3 Tipro A 41 TPAOH 1.0 35 5 14 1715 150 7 Tipro A 42 TPAOH 1.0 35 5 14 1715 150 10 Tipro A 43 TPAOH 1.0 35 5 14 1715 125 4 Tipro B 44 3 TPABr 0.71 80 2. 10. 5 1912 150 4 TE C 53 TPABr 0.71 80 2 10. 5 1912 150 10 TE C 63 TPABr 0.71 80 2 10. 5 1912 200 4 TE C / TPABr 0.71 80 2 10. 5 1912 200 10 TE C 4&3 TPABr 0.71 80 2 10. 5 1717 150 4 Ti ro C 9 TPABr 0.71 80 2 10. 5 1717 150 10 Tipro C 503 TPABr 0.71 80 2 10. 5 1717 200 4 Tipro C 513 TPABr 0.71 80 2 10. 5 1717 200 10 Tipro C 52 TPAOH 1.0 35 5 14 1715 150 4 DC B 53 TPAOH 1.0 35 5 14 1715 150 II DC B fO 54 TPAOH 1.0 35 5 14 1715 200 4 DC B 55 TPAOH 1.0 35 5 14 1715 200 11 DC B 56 TPAOH 1.0 35 5 14 1715 150 4 ANF A 57 TPAOH 1.0 35 5 14 1715 150 10 ANF A 58 TPAOH 1.0 35 5 14 1715 200 4 ANF A 59 TPAOH 1.0 35 5 14 1715 200 10 ANF A 60 TPAOH 1.0 35 5 14 1715 150 4 ANF B 61 TPAOH 1.0 35 5 14 1715 150 10 ANF B 62 TPAOH 1.0 35 5 14 1715 200 4 ANF B 63 TPAOH 1.0 35 5 14 1715 200 10 ANF B 64 TPAOH* 1.0 35 5 10 1779 200 9 AA B 65 TBΛOH 1.0 15 5 14 1715 200 7 Tipro B 66 TPAOH 1.0 35 5 10 1779 200 10 Tipro B 1 All amounts are given in moles. The value of "β" was 3.6. 2 Seed crystals of silicalite were added after formation of the reaction mixture In examples 40 to 43 and examples 52 to 66. The seed crystals were present in an amount of five wt. percent of the solid oxides based on the weight of the reaction mixture, exclusive of the seed crystals. Kaiser alumina was employed In examples 44 to 51. EXAMPLE 67 (a) Products from examples 8, 37, 40 and 44 were calcined and treated as hereinafter described and were then employed to determine adsorption capacities of TASO-45. The adsorption capacities were measured using a standard McBain-Bakr gravimetric adsorption apparatus on samples activated in a vacuum at 350°C. The data for TASO-45 as prepared in examples 8, 37. 40 and 44 were as follows: (b) (Example 8) : Kinetic Pressure Temp. wt % Diameter. A° (Torr) (°C) Adsorbed* 3 46 105 -183 15.0 3 46 741 -183 18.7 Cyclohexane 6 0 65 23.6 4.9 Neopentane 6. 2 739 23.5 2.0 H-0 2. 65 4.6 23.8 6.6 H.O 2. 65 20.0 24.0 13.1 ""Calcined air at 500°C for 1.5 hours prior to activation. ( c ) (Exampl e 37 ) : Kinetic Pressure Temp. wt % Diameter. A e (Torr) (°C) Adsorbed* °2 3.46 106 -183 12.1 °2 3.46 744 -183 14.4 Cyclohexane 6.0 82 23.9 5.6 Isobutane 5.0 740 24.2 6.2 Neopentane 6.2 741 25.3 1.7 H 2 0 2.65 4.6 24.9 5.5 H 2 0 2.65 19 24.8 9.8 *Calcined at 600 β C in air for one hour prior to activation. (d) (Example 40): Kinetic Pressure Temp. wt % Diameter, A° (Torr) S °C) Adsorbed' -183 13.6 °2 3.65 105 °2 3.65 747 -183 17.7 Cyclohexane 6.0 71 23.5 7.3 Neopentane 6.2 750 23.5 2.7 H 2 0 2.65 4.6 23.5 7.7 H 2 0 2.65 19 23.4 15.5 *Calcined at 500 β C in air for one hour prior to activation. ( e ) (Example 44 ) : Kinetic Pressure Temp. Wt % Diameter. A° (Tocr) (°C) Adsorbe • °2 3.65 105 -183 16.7 °2 3.65 747 -183 18.3 Cyclohexane 6.0 71 23.5 0.7 Neopentane 6.2 750 23.5 0.4 V 2.65 4.6 23.5 5.3 "Calcined in air at 500°C foe one hour prior to activation. (f) From the data set forth in parts (b) (c). (d) and (e) it was determined that the pore size of TASO-45 is about 6.0A. EXAMPLE 68 (a) The as-synthesized products of examples 8. 12, 29, 37, 40. 42. 44. 51 and 66 were analyzed (chemical analysis) to detecmine the weight percent Al O . SiO , TiO , LOl (Loss on Ignition), carbon (C) and nitrogen (N) present as a result of the template. The results of these analyses were as follows: (b) (Example 8): Component Weight Percent A1 2°3 2.83 sio 2 71.8 τϊo 2 11.3 a 2 0 1.0 C 6.3 N 0.70 LOl 12.4 The above chemical analysis gives an anhydrous formula of: 0.044 R (Al nΛn Si acQ Ti n _ Λ _) 0.040 0.859 0.101 (c) (Example 12): Component Weicrht Percent A1 2°3 3.01 sio 2 74.1 τio 2 8.45 a 2 0 1.08 C 6.5 N 0.70 LOT 12.0 The above chemical analysis givesn an anhydrous formula of: 0.045 R (AT rt _- _,Si β a _,Ti Λ M \ 0.042 0. 882 0.076 (d) (Example 29): Component Weight Percent 3.7 A1 2°3 sιo 2 76.8 τio 2 6.2 a 2 0 0.95 C 7.3 N 0.75 LOl 12.3 The above chemical analysis gives an anhydrous formula of: 0.053 R (Al 0<051 Si 0 895 Ti 0 055 ) (e) (Example 37): Component Weight Percent 2.88 A1 2°3 67.0 Si0 2 τio 2 12.5 Na 2 0 4.34 C 4.7 N 0.44 LOl 12.8 The above chemical analysis gives an nhydrous formula of: 0.033 R (Al θ!θ43 Si 0>839 Ti 0>118 ) (f ) (Example 40 ) Component Weight Percent A1 2°3 2.8 sio 2 66.7 τio 2 12.3 Na 2 0 3.3 C 5.5 N 0.58 LOl 14.5 The above chemical analysis gives an anhydrous formula of: 0.038 R ( 1 Al0.042Si l 0.842Ti0.117) (g) (Example 42) : Component Weight Percent A1 2°3 2.6 sio 2 65.2 τio 2 10.7 Na 2 0 6.2 C 4.6 N 0.48 LOl 14.3 The above chemical analysis gives an anhydrous formula of: 0,032 R (Al 0<040 Si 0>854 Ti θ!l06 ) (h) (Example 44 Component Weight Percent 1.4 A1 2°3 80.3 Si °2 Tio 2.7 1.8 Na 2° C 6.0 N 0.64 LOl 13.0 The above chemical analysis gives an anhydrous formula of: 0.042 R (A 0>020 Si 0 956 Ti 0 024 ) (i) (Example 51) : Component Weight Percent A1 2°3 1.5 sio 2 80.5 τio 2 3.2 N 2 0 1.7 C 6.7 N 0.59 LOl 12.7 The above chemical analysis gives an anhydrous formula of: 0.047 R (Al 0-021 Si 0>951 Ti 0>029 ( i ) (Example 66 ) : Component Weight Percent 2.80 A1 2°3 Si0 2 73.1 τio 2 12.4 Na 2 0 0.92 C 6.7 N 0.63 LOl 11.1 The above chemical analysis gives an anhydrous formula of: 0.047 R (Al0 n .„0_3, 0 9Si0 rt . β 8 c 5,3Ti0 Λ ..1 n 0 o 9) (k) EDAX (energy dispersive analysis by x-ray) microprobe analysis was carried out on clean crystals on the TASO-45 products prepared in examples 8, 12 and 29. supra. The EDAX microprobe analysis showed that at least 7.1 weight percent titanium was present as an integral part of the crystal particle of each of the TASO-45 compositions. The relative amounts of SiO . Al O , and TiO , expressed as a relative weight percent was as follows: Example 29 Average of Spot Probes Ti 1.5 Si 9.7 Al 0.9 Example 8 Average of Spot Probes Ti 0.7 Si 10.0 Al 0.8 Example 12 Average of Spot Probes Ti 0.2 Si 10.0 Al 0.5 EXAMPLE 69 (a) TASO-45. as referred to in example 12. was subjected to x-ray analysis. TASO-45 was determined to have a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth in Table II, below: TABLE II 2θ .(A) 100 x I/Io 7.9 11.17 59 8.8 10.03 37 11.9 7.46 9 12.5 7.10 4 13.2 6.71 4 13.9 6.38 9 14.7 6.02 9 15.5 5.72 6 15.9 5.58 8 17.2 5.14 3 17.7 5.01 5 TABLE II (Cont ' d ) 2θ d.(A) 100 X I/IO 19.2 4.62 5 20.0 4.45 2 20.3 4.37 9 20.8 4.27 9 22.2 4.01 5 23.1 3.85 100 23.7 3.76 34 23.9 3.73 44 24.4 3.66 26 25.8 3.448 9 26.9 3.314 8 27.4 3.258 3 29.2 3.057 9 29.9 2.989 12 30.3 2.951 5 32.7 2.738 3 34.4 2.609 3 34.8 2.576 2 35.7 2.517 3 36.0 2.495 6 37.2 2.418 2 37.4 2.407 3 37.5 2.400 3 45.0 2.015 7 45.2 2.005 9 46.4 1.956 2 47.4 1.919 3 48.5 1.876 4 48.7 1.871 2 51.8 1.766 2 54.6 1.680 2 55.0 1.671 3 55.2 1.664 3 (b) All of the as-synthesized TASO-45 compositions for which x-ray powder diffraction data have been obtained to date have patterns which are " characterized by the data of Table III. below: TABLE III 2θ. d.(A) Relative Intensity 7.9-8.0 11.17-11.10 m-vs 8.8-8.9 10.03-9.97 m 23.1-23.3 3.85-3.82 m-vs 23.7-23.8 3.76-3.75 m 23.9-24.0 3.73-3.71 24.4-24.5 3.66-3.63 m (c) A portion of the as-synthesized TASO-45 of example 11 was calcined in air at 500 β C for 1.5 hours. The calcined product was characterized by the x-ray powder diffraction pattern of Table IV, below: TABLE IV 2θ d. (A) 100 X I/IO 8.0 11.10 100 8.9 9.97 59 11.9 7.46 4 13.3 6.68 4 14.0 6.34 11 14.9 5.97 13 15.6 5.69 8 16.0 5.56 10 17.8 4.97 6 19.3 4.60 4 20.4 4.36 5 20.9 4.25 8 22.3 3.99 4 23.2 3.84 62 23.3 3.82 59 23.8 3.75 24 24.0 3.71 32 24.4 3.66 21 25.7 3.474 3 25.9 3.438 4 TABLE IV (Cont . ) 2θ d.(A) 100 X I/Io 26.7 3.334 4 29.3 3.048 7 29.9 2.989 9 30.4 2.943 5 32.8 2.731 3 36.1 2.487 4 37.5 2.400 3 45.1 2.010 5 45.6 1.991 8 48.6 1.873 4 48.8 1.868 3 53.5 1.713 5 (d) All of the as-synthesized and calcined TASO-45 compositions for which x-ray powder diffraction data have been obtained to date have patterns which are characterized by the .data of Table V. below: TABLE V 2Θ d. (A) 100 X l/Io 7.9 -8.0 11.17-11.10 36-100 8.8-8.9 10.03-9.97 25-60 9.0-9.1 9.83-9.72 14-18 11.8-12.0 7.50-7.38 2-11 12.5-12.6 7.10-7.03 3-6 13.2-13.3 6.71-6.68 4-7 13.9-14.0 6.38-6.34 6-12 14.7-14.9 6.02-5.97 7-16 15.5-15.6 5.72-5.69 6-12 15.9-16.0 5.58-5.56 6-14 16.5-16.6 5.37-5.34 2-3 17.2-17.3 5.14-5.13 2-5 17.7-17.8 5.01-4.97 4-6 19.2-19.3 4.62-4.60 4-8 19.9-20.0 4.46-4.45 2-3 20.3-20.5 4.37-4.33 5-9 20.8-21.0 4.27-4.23 8-13 TABLE V (Cont. ) 2θ d, (A) 100 x I/Io 21.7-21.8 4.10-4.08 1-3 22.1-22.3 4.02-3.99 3-7 23.1-23.3 3.85-3.82 62-100 23.7-23.8 3.76-3.75 24-34 23.9-24.0 3.73-3.71 32-50 24.4-24.5 3.66-3.63 21-31 25.4-25.7 3.507-3.47-4 3-5 25.7-26.0 3.474-3.427 3-9 26.3-26.7 3.389-3.334 sh-8 26.7-27.1 3.339-3.290 4-16 27.3-27.7 3.267-3.220 3-8 28.0-28.4 3.187-3.143 2-3 29.2-29.4 3.057-3.038 7-10 29.9-30.1 2.989-2.969 9-16 30.3-30.4 2.951-2.943 5-6 32.7-32.8 2.738-2.731 3-4 34.3-34.6 2.614-2.592 3-7 34.6-35.0 2.592-2.5-64 2-3 35.6-35.8 2.522-2.508 2-4 36.0-36.3 2.495-2.475 3-9 37.1-37.3 2.423-2.411 2-3 37.4-37.7 2.407-2.386 3-5 41.3-41.5 2.186-2.176 2-3 45.0-45.2 2.015-2.005 5-9 45.3-45.6 2.002-1.991 6-11 46.4-46.5 1.956-1.953 2-3 47.3-47.6 1.922-1.910 2-3 48.4-48.6 1.881-1.873 3-4 48.7-48.8 1.871-1.868 2-3 51.8-52.0 1.766-1.759 1-3 53.5 1.713 5 54.4-54.7 1.687-1.678 2-3 54.9-55.1 1.672-1.667 3-5 55.2-55.5 1.664-1.656 3-4 EXAMPLE 70 In order to demonstrate the catalytic activity of the TASO-45, calcined samples of the products of Examples 8. 29 and 37 were then tested for catalytic cracking. The test procedure employed was the catalytic cracking of premixed two (2) mole X n-butane in helium stream in a 1/2" O.D. quartz tube reactor over up to about 5 grams (20-40 mesh) of the TASO-45 sample to be tested. The sample was _> activated in situ for 60 minutes at 500°C under 200 cm /min dry helium purge. Then the two (2) mole (percent) n-butane in helium at a flow rate of 50 cm /min was passed over the sample for 40 minutes with product stream analysis being carried out at 10 minute intervals. The pseudo-first-order rate constant (k„) was then calculated to determine the catalytic activity of the TASO-45 composition. The k A value (cm /g min) obtained for the TASO-45 compositions are set forth, below: Sample Rate Constant (k ) Ex. 8 5.6 EX. 29 16.8 Ex. 37 0.2 EXAMPLE 71 This is a comparative example wherein example 1 of European Patent Application No. 82109451.3 was repeated and the product evaluated by several techniques as hereinafter discussed: (a) Example 1 of European Patent Application No. 82109451.3 was repeated with the starting reaction mixture having a composition based on molar ratios of: 1 A1 2 0 3 : 47 SiO : 1.32 i0 2 : 11.7 NaOH: 28 TPAOH: 1498H 2 0 The reaction mixture was divided and placed in two digestion vessels. At the end of the procedure set forth in example 1 of the European Application a sample of the product from each digestion vessel was analyzed and gave the following chemical analyses: Weight Percent Sample 1 Samp! l e 2 SiO 75.3 75 . 9 A1 2 0 3 3.02 2 , . 58 TiO 3.91 4 , . 16 Na 2 0 3.66 3 , . 46 C 6.3 6 . , 7 N 0.62 0 . , 65 LOl 14.0 14 . 0 The two samples were then analyzed by SEM (scanning electron microscope) and EDAX (energy dispersive analysis by X-ray) micropiope. The SEM probe of the two samples showed four morphologies to be present and such are shown in FIG. 4 (which should be compared with FIG. 5 which shows the single morphology of crystals of. TASO-45 as prepared by the instant invention). The four morphologies of the two samples prepared in accordance with the aforementioned European Application and the EDAX microprobe analysis for each were as follows: (1) Smooth, intergrown hexagonal particles (at B in FIG. 4) which are associated with a ZSM-5 morphology had an EDAX microprobe of: Average of Spot Probes .Ti 0 Si 1.0 Al 0.05 (2) Flat, smooth plates (at A in FIG. 4) had an EDAX microprobe of: Average of Spot Probes Ti 0.13 _> Si 1.0 Al 0.05 (3) Spheres and elongated bundles (at C in FIG. 4) had an EDAX microprobe of: . Average of Spot Probes Ti 0.22 Si 1.0 Al 0.05 Na 0.10 (4) Needles or f.ine rods (at D in FIG. 4) had an EDAX microprobe of: Average of Spot Probes Ti 0.05 Si 0.8 Al 0.13 Na 0.05 Cl 0.10 The above SEM and EDAX data demonstrate that although 2SM-5 type crystals were formed that these crystals contained no detectable titanium. The only detectable titanium was present as impurity phases and not in crystals having the characteristic x-ray diffraction pattern of ZSM-5. The X-ray diffraction patterns of the as-synthesized materials were obtained and the following X-ray patterns were observed: Table VI ( Sample 1 ) 5.577 15.8467 5.950 14.8540 6.041 14.6293 6.535 13.5251 7.154 12.3567 7.895 11.1978 8.798 10.0504 9.028 9.7946 9.784 9.0401 11.846 7.4708 12.453 7.1079 12.725 6.9565 13.161 6.7267 13.875 6.3821 14.637 6.0518 14.710 6.0219 15.461 5.7310 15.881 5.5802 16.471 5.3818 17.218 5.1498 17.695 5.0120 19.212 4.6198 19.898 4.4619 20.045 4.4295 20.288 4.3770 20.806 4.2692 21.681 4.0988 22.143 4.0145 23.091 3.8516 23.641 3.7632 Table VI (Sample 1) (Continued) 23.879 3.7263 24.346 3.6559 24.649 3.6116 25.548 2.4865 25.828 3.4494 26.228 3.3976 26.608 3.3501 26.887 3.3158 27.422 3.2524 28.048 3.1812 28.356 3.1473 29.191 3.0592 29.912 2.9870 30.295 2.9502 32.736 2.7356 33.362 2.6857 34.355 2.6102 34.640 2.5894 34.887 2.5716 35.152 2.5529 35.551 2.5252 35.660 2.5177 36.031 2.4926 37.193 2.4174 37.493 2.3987 45.066 2.0116 45.378 1.9985 46.514 1.9523 47.393 1.9182 - 41 - Tabl e VI I ( Sampl e 2 ) 5.801 15.2353 6.012 14.7012 6.169 14.3265 7.970 11.0926 8.875 9.9636 9.118 9.6981 9.879 8.9532 11.933 7.4163 12.537 7.0605 12.808 6.9115 13.242 6.6860 13.957 6.3452 14.718 ' 6.0186 14.810 5.9813 15.542 5.7014 15.954 5.5551 16.563 5.3521 17.316 5.1211 17.788 4.9862 19.291 4.6009 20.119 4.4134 20.382 4.3571 20.879 4.2544 21.735 4.0887 22.220 4.0007 23.170 3.8387 23.730 3.7494 23.964 3.7133 24.425 3.6442 24.722 3.6011 Table VI I ( Sample 2 ) (Con ' td ) 25.900 3.4399 26.734 3.3345 26.979 3.3047 27.251 3.2724 27.494 3.2440 28.175 3.1671 28.450 3.1371 29.287 3.0493 29.970 2.9814 30.371 2.9430 30.694 2.9127 31.312 2.8566 32.825 2.7283 33.457 2.6782 34.426 2.6051 34.723 2.5834 34.879 2.5722 35.709 2.5143 ' 36.125 2.4863 37.248 2.4139 37.490 2.3988 45.156 2.0078 45.453 1.9954 46.462 1.9544 46.608 1.9486 Tables VI and VII show an X-ray pattern typical of a ZSM-5 type product and can be attributed to the smooth, integrown hexagonal particles which contained no titanium. The X-ray patterns of Tables VI and VII show three peaks (2θ = 5.6-5.8. 12.45-12.54 and 24.5-24.72) which could not be explained. The two samples were calcined according to the conditions set forth in the European application with a portion of both samples being calcined at 540°C for sixteen hours. The X-ray patterns of the calcined samples were as follows: - 44 - Table VIII (Sample 1) 6.141 14.3908 6.255 14.1303 8.011 11.0355 8.913 9.9209 9.144 9.6705 9.930 8.9068 11.979 7.3876 12.440 7.1152 13.289 6.6625 14.007 6.3224 14.874 5.9557 15.613 5.6757 15.995 5.5408 16.609 5.3373 17.353 5.1103 17.884 4.9597 19.335 4.5905 20.177 4.4008 20.463 4.3401 20.940 4.2422 21.845 4.0685 22.291 3.9880 23.186 3.8361 23.362 3.8076 23.817 3.7359 24.031 3.7031 24.510 3.6317 24.908 3.5747 25.699 3.4664 25.969 3.4309 Table VIII (Sample D(Cont'd) 26.371 3.3796 26.698 3.3389 27.022 3.2996 27.487 3.2449 28.184 3.1662 28.513 3.1303 29.369 3.0411 30.017 2.9769 30.468 2.9338 31.333 2:8548 32.877 2.7241 34.490 2.6003 35.062 2.5592 35.800 2.5082 36.186 2.4823 37.324 2.4092 37.654 2.3888 45.195 2.0062 45.631 1.9880 46.639 1.9474 47.547 1.9123 48.765 1.8674 - 46 - Table IX (Sample 2) 6.092 14.5084 6.295 14.0403 7.941 11.1328 8.838 10.0054 9.857 8.9730 11.921 7.4236 12.399 7.1383 13.222 6.6959 13.937 6.3539 14.811 5.9809 15.535 5.7038 15.916 5.5681 16.532 5.3620 17.262 5.1370 17.806 4.9811 19.268 4.6064 20.107 4.4160 20.389 4.3556 20.868 4.2567 21.807 4.0754 22.197 4.0047 23.116 3.8476 23.263 3.8235 23.755 3.7455 23.955 3.7147 24.432 3.6433 24.854 3.5823 25.653 3.4725 25.901 3.4398 Table IX (Sample 2)(Cont'd) 26.265 3.3929 26.648 3.3451 26.976 3.3052 27.386 3.2566 28.156 3.1692 28.495 3,1323 29.304 3.0476 29.969 2.9815 30.384 2.9417 31.283 2.8592 32.819 2.7289 34.423 2.6052 34.993 2.5641 35. ' 716 2.5138 36.146 2.4850 37.295 2.4110 37.562 2.3944 45.137 2.0086 45.523 1.9925 46.562 1.9504 47.509 1.9137 The X-ray diffraction patterns of the calcined samples show a ZSM-5 type pattern with only slight differences from the as-synthesized. When chemical analysis (bulk) of a portion of the calcined samples 1 and 2 are carried out the following is obtained: Weight Percent Sample 1 Sample 2 sio 2 79.6 81.2 A1 2°3 3.5 2.9 Na 2 0 4.4 4.1 τio 2 4.4 4.6 Carbon 0.11 0.10 LOl* 8.1 7.6 *Loss on Ignition When the molar ratio of oxides is computed for the above bulk analysis the following is obtained: 1 Si0 2 : 0.043 Ti0 2 : 0.021 A1 2 0 3 : 0.049 Na 2 0 This compares quite well with the bulk chemical analysis reported in the European application which is: 1 SiO : 0.047 TiO : 0.023 Al O : 0.051 Na 0 Si Although it is clear that the product crystals which gave the product an X-ray pattern characteristic of ZSM-5 contained no titanium, the bulk analysis of the product shows titanium to be present from crystals which do not have an X-ray diffraction pattern characteristic of ZSM-5. PROCESS APPLICATIONS The TASO-45 compositions of this invention have unique ' surface characteristics making them useful as molecular sieves and as catalysts or as bases for catalysts in a variety of separation, hydrocarbon conversion and oxidative combustion processes. The TASO-45 compositions can be impregnated or otherwise associated with catalytically active metals by the numerous methods known in the art and used, for example, in fabricating catalysts compositions containing alumina or aluminosilicate materials. TASO-45 may be employed for separating molecular species in admixture with molecular species of a different degree of polarity or having- different kinetic diameters by contacting such mixtures with a TASO-45 to allow TASO-45 to adsorb at least one but not all molecular species of the mixture based on the polarity of the adsorbed molecular species and/or its kinetic diameter. When TASO-45 is employed for such separation processes the TASO-45 is at least partially activated whereby some molecular species selectively enter the intracrystalline pore system thereof. The hydrocarbon conversion reactions catalyzed by TASO-45 compositions include: cracking; polymerization; reforming;, hydrogenation; dehydrogenation; and hydration. TASO-45 containing catalyst compositions may be employed in reforming processes in which the hydrocarbon feedstocks contact the catalyst at temperatures between about 700 β F and about 1000°F, hydrogen pressures of between about 100 and " about ' 500 p.s.i.g., LHSV values in the range between about 0.1 and about 10 and hydrogen to hydrocarbon molar ratios in the range between about 1 and about 20, preferably between about 4 and about 12. Further, TASO-45 containing catalysts which contain hydrogenation promoters, are useful in hydroisomerization processes wherein the feedstock(s) , such as normal paraffins, is converted to saturated branched-chain isomers. Hydroisomer¬ ization processes are typically carried out at a temperature between about 200 β F and about 600°F, preferably between about 300°F and about 550°F with an LHSV value between about 0.2 and about 1.0. Hydrogen is typically supplied to the reactor in admixture with the hydrocarbon feedstock in molar proportions of hydrogen to the feedstock of between about 1 and about 5. TASO-45-containing compositions similar to those employed for hydroisomerization may also be employed at between about 650°F and about 1000°F, preferably between about 850°F and about 950 β F and usually at somewhat lower pressures within the range between about 15 and about 50 p.s.i.g. for the hydroisomerization of normal paraffins. Preferably the paraffin feedstock comprises normal paraffins having a carbon number range of C 7 -C 2Q . The contact time between the feedstock and the TASO-45 containing catalyst is generally relatively short to avoid undersirable side reactions such as olefin polymerization and paraffin cracking. LHSV values in the range between about 0.1 and about 10, preferably between about 1.0 and about 6.0 are suitable. TASO-45 containing catalysts may be employed in catalytic cracking processes wherein such are preferably employed with feedstocks such as gas oils, heavy naphthas, deasphalted crude oil residues etc. with gasoline being the principal desire product. Temperature conditions are typically between about 850 and about 1100°F, LHSV values between about 0.5 and about 10 pressure, conditions are between about 0 p.s.i.g. and about 50 p.s.i.g. TASO-45 containing catalysts may be employed for dehydrocyclization reactions which employ paraffinic hydrocarbon feedstocks, preferably normal paraffins having more than 6 carbon atoms, to form benzene, xylenes. toluene and the like. Dehydrocyclization processes are typically carried out using reaction conditions similar to those employed for reforming. For such processes it is preferred to use a Group VIII non-noble metal cation such as platinum in conjunction with the TASO-45 composition. TASO-45 containing catalysts may be used in catalytic hydrofining wherein the primary objective is to provide for the selective hydrodecomposition of organic sulfur and/or nitrogen compounds without substantially affecting hydrocarbon molecules present therewith. For this purpose it is preferred to employ typical hydrotreating conditions. The catalysts are the same typically of the same general nature as described in connection with dehydrocyclization operations. Feedstocks commonly employed for catalytic hydroforming include: gasoline fractions: kerosenes; jet fuel fractions; diesel fractions; light and heavy gas oils; deasphalted crude oil residua; and the like. The feedstock may contain up to about 5 weight-percent of sulfur and up to about 3 weight-percent of _ nitrogen. TASO-45 containing- catalysts may be employed for isomerization processes under conditions similar to those described above for reforming although isomerization processes tend to require- somewhat more acidic catalysts than those employed in reforming processes. Olefins are preferably isomerized at temperatures between abou 500 β F and about 900 β F, while paraffins, naphthenes. Particularly desirable isomerization reactions contemplated herein include the conversion of n-heptane and/or n-octane to isoheptanes, iso-octanes, butane to iso-butane, methylcyclopentane to cylcohexane, I-butene to 2-butene and/or isobutene. n-hexene to isohexane, cyclohexane to methylcyclopentene etc. The preferred cation form is a combination of a TASO-45 with polyvalent metal compounds (such as sulfides) of metals of Group II-A, Group II-B and rare earth metals. The TASO-45 compositions of this invention may be employed in conventional molecular sieving processes as heretofore have been carried out using aluminosilicate^ aluminophosphate or other commonly employed molecular sieves. TASO-45 compositions are preferably activated prior to their use in a molecular sieve process to remove any molecular species which may be present in the intracrystalline pore system as a result of synthesis or otherwise. For the TASO-45 compositions this is sometimes accomplished by thermally destroying the organic species present in an as-synthesized TASO-45 since such organic species may be too large to be desorbed by conventional means. The TASO-45 compositions of this invention are also useful as adsorbents and are capable of separating mixtures of molecular species both on the basis of molecular size (kinetic diameters) and based on the degree of polarity of the molecular species. When the separation of molecular species is based upon the selective adsorption based on molecular size, the TASO-45 is chosen in view of the dimensions of its pores such that at least the smallest molecular specie of the mixture can enter the intracrystalline void space while at least the largest specie is excluded. When the separation is based on degree, of polarity it is generally the case that the more hydrophilic TASO-45 will preferentially adsorb the more polar molecular species of a mixture having different degrees of polarity even though both molecular species can communicate with the pore system of the TASO-45. The instant TASO-45 compositions may be further characterized and distinguished from aluminophosphates by reference to the catalytic properties exhibited by the TASO-45 compositions. When the TASO-45 compositions are tested for n-butane cracking and compared with aluminophosphate compositions having a similar topology it has been observed that the TASO-45 compositions are more active catalysts as indicated by a higher numerical value for n-butane cracking.

Claims: WHAT IS CLAIMED IS: 1. Crystalline molecular sieves comprising pores having nominal diameters of about 6 Angstroms and whose chemical composition in the as-synthesized and anhydrous form is represented by the unit empirical formula: mR:(TixAlySiz)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 (TiM Si JO, has a value of from zero and about 0.3; and "x", "y" and "z" represent the mole fractions of titanium, aluminum, and silicon, respectively, present as tetrahedral oxides, said mole fractions being such that they are within the compositional area defined by points A. B. C and D of the ternary diagram of Fig. 1 and having a characteristic x-ray pattern as set forth in Table III. 2. The crystalline molecular sieves according to claim 1 wherein the mole fractions of titanium, aluminum and silicon are within the compositional area defined by points a, b, and c of the ternary diagram of Fig. 2. 3. The crystalline molecular sieve of claim 3 wherein "x" has a value between about 0.024 and about 0.118, "y" has a value betwen about 0.020 and about 0.051 and *z" has a value between about 0.831 and about 0.956. 4. The crystalline molecular sieves of claims 1 or 2 having the characteristic X-ray powder diffraction pattern set forth in Table II. - 5. The crystalline molecular sieves of claims 1 or 2 having the characteristic X-ray powder diffraction pattern set forth in Table IV. 6. The crystalline molecular sieves of claims 1 or 2 having the characteristic X-ray powder diffraction pattern set forth in Table V. 7. The crystalline molecular sieves of claim 1 wherein the molecular sieves have been calcined to remove at least some of any organic template present. 8. Process for preparing the crystalline molecular sieves of claim 1 comprising providing at an effective temperature and for an effective time a reaction mixture composition expressed in terms of molar oxide ratios as follows: aR:(Ti χ Al y Si z ):bH 2 0 wherein "R" is an organic templating agent; "a" is an effective amount of "R"; "b" has a value of zero to greater than zero; "x", "y" and "z" represent the mole fractions of titanium, aluminum and silicon, respectively, in the (TixAlySiz) constituent, and each has a value of at least 0.01, whereby the crystalline molecular sieves of claim 1 are prepared. 9. Process according to claim 8 wherein "x", "y" and "z" are within the tetragonal compositional area defined by points E. F, G and H of FIG. 3. 10. Process according to claim 8 wherein the source of silicon in the reaction mixture is silica. 11. Process according to claim 8 wherein -- the source of aluminum in the reaction mixture is at least one compound selected from the group consisting of pseudo-boehmite and aluminum alkoxide. 12. Process -according to claim 10 wherein the aluminum alkoxide is aluminum isopropoxide. 13. Process according to claim 8 wherein the source of titanium is selected from the group consisting of alkoxides. water-soluble titanates and titanium chelates. 14. Process according to claim 8 where the organic templating agent is selected from the group consisting of quaternary ammonium or quaternary phosphonium compounds of the formula: wherein X is nitrogen or pho.sphorous and each R is alkyl containing between 1 and about 8 carbon atoms or aryl. 15. Process according to claim 8 wherein the templating agent is selected from the group consisting of tetrapropylammonium ion; tetraethylammoniύm ion; tripropyla ine; triethylamine; triethanolamine; piperidine; cyclohexylamine; 2-methyl pyridine; N.N-dimethylbenzylamine; N.N-diethylethanolamine; dicyclohexylamine; N.N-dimethylethanolamine; choline; N.N-dimethylpiperazine; pyrrolidine; l,4-diazabicyclo-(2,2,2) octane; N-methylpiperidine; 3-methylpiperidine; N-methylcyclohexylamine; 3-methylρyridine; 4-methylpyridine; quinuclidine; * .N-dimethyl-1.4-diazabicyclo (2,2,2) octane ion; tetramethylammonium ion; tetrabutylam onium ion. tetrapentylammonium ion; di-n-butylamine; neopentylamine; di-n-pentylamine; isopropyla ine; t-butylamine; ethylenediamine and 2-imidazolidone; di-n-propylamine; and a polymeric quaternary ammonium salt £ (c ι 4 H 32 N 2^ OH 2^ wiιere n x is a value of at least 2. 16. Process for separating mixtures of molecular species wherein such mixtures contain molecular species having different degrees of polarity and/or kinetic diameters comprising contacting said mixture with a composition of claim 1 or claim 2. 17. Process for converting a hydrocarbon which comprises contacting said hydrocarbon under hydrocarbon converting conditions with a crystalline molecular sieve as set forth in claim 1 or claim 2. 18. Process according to claim 17 wherein the hydrocarbon conversion process is cracking. 19. Process according to claim 17 wherein the hydrocarbon conversion process is hydrogenation. 20. Process according to claim 17 wherein the hydrocarbon conversion process is polymerization. - 53 21. Process according to claim 17 wherein the hydrocarbon conversion process is reforming. 22. Process according to claim 17 wherein the hydrocarbon conversion process is hydrotreating. 23. Process according to claim 17 wherein the hydrocarbon conversion process is dehydrocyclization.

Inventors: FLANIGEN EDITH MARIE, LOK BRENT MEI TAK, MARCUS BONITA KRISTOFFERSEN, FLANIGEN, EDITH, MARIE, LOK, BRENT, MEI, TAK, MARCUS, BONITA, KRISTOFFERSEN
Applicants: UNION CARBIDE CORP, UNION CARBIDE CORPORATION
Application year: 1985
Main classification: C01B33
IPC codes: B01J29, C01B39, C07B61, C07C1, C07C2, C07C5, C07C67, C10G11, C10G35, C10G49