CA2014666C - Large-pored molecular sieves with charged octahedral titanium and charged tetrahedral aluminum sites - Google Patents

Abstract

A crystalline-titanium-aluminum-silicate molecular sieve is disclosed having both di-charged octahedrally coordinated titanium and mono-charged tetrahedrally coordinated aluminum in its framework.

Description

20~4666 ~., LARGE-PORED MOLECULAR SIEVES WITH CHARGED OCTAHEDRAL
TITANIUM AND CPARGED TETRAHEDRAr ALUMINUM SITES
QACKGROUND OF ~HE ~VENTION
1. Field of the Invention This invention relates to new crystalline titanium molecular sieve zeolite compositions, having both aluminum and titanium in the framework structure, methods for preparing the same uses thereof such as organic compound conversions therewith, especially hydrocarbon conversions and in ion exchange applications. The novel materials of this invention owe their uniqueness to the fact that the framework titanium is octahedrally coordinated whereas the framework aluminum is tetrahedrally coordinated.

2. ~ackground of the Invention and Prior Art Since the discovery by Milton and coworkers (U. S. 2,882,243 and U. S. 2,882,244) in the late 1950's that aluminosilicate systems could be induced to form uniformly porous, internally charged crystals, analogous to molecular sieve zeolites found in nature, the properties of syn~hetic aluminosilicate zeolite molecular sieves have formed the basis of numerous commercially important catalytic, adsorptive and ion-exchange applications. This high degree of utility is the result of a unique combination of high surface area and uniform potosity dictated by the "framework" structure of the zeolite crystals coupled with the electrostatically charged sites --~
induced by tetrahedrally coordinated Al . Thus, a large ., ' .
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~ 2~1~666 ---number of ~active~ charqed sites are readilv accessible to molecules of the DroDer size and geometrv for adsorDtive or catalytic interactions. Further, since charqe comDensatina cations are electrostaticallv and not covalentlY bound to the aluminosilicate framework, they are qenerally exchanaeable for other cations with different inherent DroDerties. This offers wide latitude for modification of active sites wherebv sDecific adsorbents and catalvsts can be tailormade for a aiven utilitv.
In the Dublication ~Zeolite Molecular Sieves~, ChaDter 2, 1974, D. W. Breck hvDothesized that DerhaDs 1,000 aluminosilicate zeolite framework structures are theoreticallv Dossible, but to date onlv aDDroximatelv 150 have been identified. While comDositional nuances have been described in Dublications such as U. S. 4,524,055, U. S. 4,603,040 and U. S.
4,606,899, totallv new aluminosilicate framework structures are beina discovered at a nealiqible rate. Of Darticular imDortance to fundamental Droaress in the catalvsis of relativelv larqe hvdrocarbon molecules, especiallv fluid crackina operations, is the fact that it has been a aeneration since the discoverv of anv new larqe Dored aluminosilicate zeolite.
With slow Droaress in the discoverv of new wide Dored aluminosilicate based molecular sieves, researchers have taken various aDDroaches to reDlace aluminum or silicon in zeolite svnthesis in the hoDe of aeneratinq either new zeolite-like framewor~ structures or inducina the formation of qualitativelv different active sites than are available in analoaous aluminosilicate based materials. While Droaress of academic ~ 201~666 interest has been made from different aDDroaches, little success has been achieved in dis~overina new wide Dore molecular sieve zeolites.
It has been believed for a aeneration that DhosDhorus could be incorDorated, to varvina dearees, in a zeolite tyDe aluminosilicate framework. In the more recent Dast (JACS 104 DD. 1146 (1982) Proceedinqs of the 7th International Zeolite Conference, DD. 103-112, 1986) E. M. Planiaan and coworkers have demonstrated the DreDaration of oure aluminoDhosDhate based molecular sieves of a wide variety of structures.
However, the site inducina Al 3 is essentiallv neutralized by the P+5, imDartina a +l charae to the framework. ThUs, while a new class of ~molecular sieves~ was created, thev are not zeolites in the fundamental sense since they lack ~active~
charaed sites.
Realizina this inherent utilitv limitina deficiencv, for the Dast few vears the molecular sieve research community has emDhasized the synthesis of mixed aluminosilicate-metal '~
oxide and mixed aluminophosDhate-metal oxide framework systems. While this aDDroach to overcomina the slow Droaress in aluminosilicate zeolite synthesis has qenerated aDDroximately 200 new com w sitions, all of them suffer either from the site removina effect of incorDorated P 5 or the site dilutina effect of incorDoratina effectively neutral tetrahedral +4 metals into an aluminosilicate tvDe framework.
As a result, extensive research by the molecular sieve research communitv has failed to demonstrate sianificant utility for any of these materials.

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~- 20~666 A series of zeolite-like ~framework~ silicates have been synthe~ized, some of which llave larger uniform pores than are observed for aluminosilicate zeolites. (W. M. Meier, Proceedinas of the 7th International Zeolite Conference, DD. 13-22 (1986).) While this particular synthe-ci~ approach oroduces materials which, bv definition, totallv lack active, charaed sites, back imDlementation after svnthesis would not aDDear out of the question althou~h little work apDears in the open literature on this topic.
Another and most straiahtforward means of Dotentiallv aeneratina new structures or qualitativelv different sites than those induced bv aluminum would be the direct substitution of some other charae inducina sDecies for aluminum in zeolite-like structures. To date the most notablv successful examole of this aDDroach aoDears to be boron in the case of ZSM~ 5 analoas, althouah iron has also been claimed in similar materials. (EPA
68,796 (1983), Taramasso et al; Proceedinas of the 5th International Zeolite Conference: oo. 40-48 (1980)); J. w. 3all et al: Proceedinas of the 7th International Zeolite Conference:
DD. 137-144 (1986) U. S. 4,280,305 to Kouenhowen et al.
Unfortunatelv, the low levels of incorporation of the species substitutina for aluminum usually leaves doubt if the species are occluded or framework incorporated.
In 1967, Youna in U. S. 3,329,481 reDorted that the svnthesis of charae béariria (exchanaeable) titanium silicates under conditions similar to aluminosilicate zeolite formation was possible if the titanium was Dresent as a "critical reaaent~ +III Deroxo soecies. While these materials were ._ ~

20~666 called ~titanium zeolites~ no evidence was Dresented bevond some questionable X-ray diffraction ~XRD) Datterns and his claim has qenerally been dismissed bv the zeolite research communitv. (D. W. 3reck, Zeolite Molecular Sieves, D. 322 ~1974); R. M. Barter, Hvdrothermal Chemistrv of Zeolites, D. 293 (1982); G. Pereao et al, Proceedinas of 7th International Zeolite Conference, D. 129 (1986). ) For all but one end member of this series of materials (denoted TS
materials), the Dresented XRD Datterns indicate Dhases too d?nse to be molecular sieves. In the case of the one questionable end member (denoted TS-26), the XRD Dattern miqht Dossiblv be interDreted as a smaIl Dored zeolite, althouah without additional suDDortina evidence, this aDDears extremelv questionable.
A naturallv occurrina alkaline titanosilicate identified as ~Zorite~ was discovered in trace quantities on the Kola Peninsula in 1972 ( A. N. Mer'kov et al; ZaDiski Vses Mineraloq. Obshch., Paaes 54-62 (1973), The Dublished XRD
Dattern was challenaed and a DroDosed structure reDorted in a later article entitled ~The OD Structure of Zorite", Sandomirskii et al, Sov. Phvs . Crvstallocr. 24 ( 6), Nov-Dec 1979, Daaes 686-693.
No further reDorts on ~titanium zeolites~ apDeared in the open literature until 1983 when trace levels of tetrahedral Ti(IV) were reDorted in a ZSM-5 analoq. (M. Taramasso et al;
U. S. Patent 4,410,501 (1983); G. Pereao et al; Proceedinas of the 7th International Zeolite Conference; D. 129 (1986).~ A
similar claim aDDeared from researchers in mid-1985 (EPA

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-132,550 (1985).) More recently, the research community reported mixed aluminosilicate-titanium(IV) (EPA 179,876 (1985); EPA 181,884 (1985) structures which, along with TAPO (EPA 121,121 (1985) systems, appear to have no possibility of active titanium sites because of the titanium coordination. As such, their utility is highly questionable.
That charge bearing, exchangeable titanium silicates are possible is inferred not only from the existence of exchangeable alkali titanates and the early work disclosed in U. S. 3,329,481 on ill defined titanium silicates but also from the observation (S.M.Kuznicki et al; J. Phys. Chem.; 84; pp. 535,537 (1980) of Tio4 - units in some modified zeolites.
David M. Chapman, in a speech before 11th North American Meeting of the Catalysis Society in Dearborn, Michigan (1989) gave a presentation wherein a titanium aluminosilicate gel was crystallized with Chapman claiming all the aluminum was segregated into analcime (an ultra-small pored aluminosilicate) and not incorporated into any titanium-bearing phase such as his observed analog of the mineral vinogradovite which was a pure titanium silicate. It is noted that vinogradovite, as found in nature, has been reported to contain aluminum. However, neither the synthetic analog of vinogradovite nor the mineral vinogradovite is a molecular sieve nor does it have the x-ray diffraction pattern of Table I of this specification.
A major breakthrough in the field of large pored titanium silicate molecular sieves is disclosed and claimed in U.S.Patent 4,853,202. The crystalline titanium silicate large pored molecular sieve of said patent, hereafter designated ETS-10, contains no deliberately added alumina but may contain very minor amounts of alumina due to the presence of impurities.
Thus, ETS-10 typically have a molar ratio of SiO2/A1203 greater than 100 or more.

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SUMMARY OF THE INVENTION
The present invention relates to a new family of stable, large pore crystalline titanium-aluminum-silicate molecular sieves, hereinafter designated ETAS-10, their method of preparation and the use of such compositions as absorbents, catalysts for the conversion of a wide variety of organic compounds, e.g., hydrocarbon compounds and oxygenates such as methanol as well as ion-exchangers for the removal of undesirable metal cations from solutions containing the same.
Another aspect of this invention is as follows:
A crystalline titanium-aluminum-silicate molecular sieve having a large pore size of approximately 9 Angstrom units and having a composition in terms of mole ratios of oxides as follows:
(l+x) (1.0 + 0.25 M2/n 0): Tio2 : x A10z : y Si02 : z H20 wherein M is at least one cation having a valence of n, y is from 2.5 to 25, x is from 0.01 to 5.0 and z is from 0 to 100, said molecular sieve being characterized by a) having an X-Ray powder diffraction pattern as hereinafter set forth:

(0 - 40~2 theta) SIGNIFICANT d-SPACING (ANGS.) I/Io 14.7 - .50 + 1.0 W-M
7.20 +.15 (optional) W-M
4.41 -.05 + 0.25 W-M

3.60 -.05 + 0.25 VS
3.28 -.05 + .2 M-S
30 wherein:
VS = 60-100 S = 40-60 M = 20-40 W = 5-20, b) having mono-charged tetrahedrally coordinated aluminum in the framework, and c) having di-charged octahedrally coordinated titanium in the framework.

Other aspects of the invention involve a process for conversion of an organic compound which comprises contacting the same at conversion conditions with the composition set out above; a process for catalytic s cracking of hydrocarbon which comprises contacting the same with the composition set out above at elevated temperatures; a process for reforming a naptha which comprises contacting the same in the presence of added hydrogen and a hydrogenation/dehydrogenation component with the composition set out above; and a process for the removal of divalent ions from a solution containing the same which comprises contacting the solution with the composition set out above.
DETAILED DESCRIPTION OF THE INVENTION
The present invention relates to a new family of stable crystalline titanium-aluminum-silicate molecular sieve which have a pore size of approximately 9 Angstrom units. These titanium-aluminum-silicates have a definite X-ray diffraction pattern and can be identified in terms of mole ratios of oxides as follows:
(l+x) (1.0 + 0.25 M2~n ~): TiOz: x A102 : y SiO2 : z H2 ~
wherein M is at least one cation having a balance of n, y is from 2 . 0 to 100, x is from 0.05 to 5.0 and z is from O
to 100. In a preferred embodiment, M is a mixture of alkali metal cations, particularly sodium and potassium, and y is at least 3.0 and ranges up to about 10.

-7a-~- 2014666 The original cations M can be replaced at least n part with other cations by well known exchange techniques. Preferred ~--replacing cations include hydrog~n, ammonium, rare earth, and mixtures thereof. ~embers of the family of molecular sieve zeolites designated ETAS-10 have a high degree ~f thermal stability of at least 450~C or higher, thus rendering them effective for use in high temperature catalytic processes.
ETAS-10 zeolites are highly adsorptive toward molecules up to approximately 9 Angstroms in critical diameter such as 1,3,5-trimethylbenzene. In the sodium form, ETAS-10 is completely reversibly dehydratable with a water capacity of approximately 20 weight percent.
Members of the ETAS-10 family of molecular sieve zeolites have a crystalline structure and an X-ray powder diffraction pattern having the following significant lines:

XRD POWDER PATTERN OF ETAS-ln (0 - 40~ 2 theta) SIGNIFICANT d-SPACING (ANGS.) I/I

14.7 - .50 + 1.0 W-M
7.20 + .15 (optional) W-M

4.41 - .05 + 0.25 w-M
3.60 - .05 + 0.25 VS
3.28 - .05 + .2 M-S

In the above table, VS = 60-100 --S 5 40-60 --~

W = 5-20 The above values were determined by standard x-ray diffraction techniques. The radiation was the K-alpha doublet - ,~ , , -of copper, and a scintillation counter spectrometer was used. The peak heights, I, and the positions as a function of 2 times theta, where theta is the Bragg angle, were read from the spectrometer chart. From these, the relative intensities, 100 I/Io, where Io is the intensity of the strongest line or peak, and d (obs.), the interplanar spacing in angstroms, corresponding to the recorded lines, were calculated. These interplanar d-spacings define the crystalline structure of the particular composition. It has been determined that the X-ray powder diffraction peaks characteristics of ETS-10 are systematically altered by the inclusion of increasing amounts of aluminum addition in ETAS-10. Such systematic alterations are taken as prima facie evidence of framework incorporation of some newly introduced species much akin to classical zeolite synthesis. As pointed out in U. S. patent 4,853,202 ETS-10 contains the most significant lines which are set forth as follows:

20ETS-10 CHARACTERISTIC d-SPACINGS
d-SPACINGS (ANGS.) I/Io 14.7 + 0.35 W-M
7.20 i 0.15 W-M
4.41 + 0.10 W-M
3.60 + 0.05 VS
3.28 + 0.05 W-M
It has been found that as the degree of aluminum incorporation increases in ETAS-10, the largest d-spacing analogous to 14.7 A in ETS-10 and the strongest characteristic d-spacing analogous to 3.60 A in ETS
markedly increase. In 201466~
,., fact, as hiaher levels of aluminum inCorDOratiOn are attained, the increase of these lines falls outside the claim limits for ETS-10. Additionally, one of the characteristic d-sDacinas 7.20 A disapDears. However, it is not known at this time if the disapDearance reDre~ents a structural chanae or if it i~
morDholoaically induced.
Althouah ETAS-10 i9 structurallv related to ETS-10, in'troduction of substantial quantities of hiahlv Dolar mono-charaed tetrahedral aluminum ~ites into the zeolitic framework Drofoundlv alters the character of the sieve, imDactina adsorDtive, ion-exchanae and 'catalytic DroDerties.
ETAS-10 can be clearlv and easily differentiated from ETS-10 by standard analytical techniques such a~ NMR and in some cases by X-ray diffraction.
While structurally related to ETS-10, incorDoration of aluminum into the framework structure Oe ETAS-10 svstematically exDands the lattice Dlanes and Dore oDeninas. This in turn allows ETAS-10 to sorb molecules somewhat laraer than those sorbed by ETS-10. Additionally, the sorbtive DroDerties are transformed from a relativelv weak to a stronaer sorbant and much more Dowerful ion-exchanaer. The ion exchanae DroDerties are altered in such a manner that certain heavv metals, esDecially lead, are evacuated from aqueous solutions essentiallv on contact. The incorporation of aluminum into the framework also makes the catalvtic acidity of ETAS-10 substantiallv difFerent than that of ETS-10 in that it is verv strona, capable of crackina alkanes as would be exDected Crom zeolitic aluminum sites but the hiqh alkene yield characteristic of relativelv weak octahedral sites is eetained.

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It is to be immediately understood that appiicants are not maintaining to be the first to have prepared a molecular sieve containing titanium, aluminum and silicon in significant amounts. Materials of this type have previously been reported in the TASO work of Lok, EPO 181,884 and EPO 179,876 previously referred to. However, in both the specifications and claims of these patents, it is clearly stated that the silicon, titanium and aluminum are tetrahedral with the titanium being therefore uncharged. The crystal structures of the instant invention on - the other hand, have di-charged octahedrally coordinated titanium in combination with mono-charged tetrahedrally coordinated aluminum sites.
- ETAS-10 molecular sieves can be prepared frlom a reaction mixture containing a titanium source such as titanium trichloride with an aluminum source such as aluminum chloride, a source of silica, a source of alkalinity such as an alkali metal hydroxide, water and, optionally, an alkali metal fluoride mineralizer having a ComDOSitiOn in terms of mole ratios falling within the following ranges.

Broad Preferred Most Preferred SiO2/A1 1-200 2-100 2-20 SiO2/Ti 2-20 3-10 4-7 H2O/siO2 2-100 5-50 10-25 Mn/SiO2 0.1-20 0.5-5 1-3 wherein M indicates the cations of valence n derived from the -alkali metal hydroxide and potassium fluoride and/or alkali metal salts used for preparing the titanium silicate according to the invention. The reaction mixture is heated to a 4 ~
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201~666 ~, temperat re of from about 100~C to 250~C for a period of time ranging from about 2 hours to 40 days, or more. The hydrothermal reaction is carried out until crystals are formed and the resulting crystalline product is thereafter separated from the reaction mixture, cooled to room temperature, filter*d and water washed. The reaction mixture can be stirred although it is not necessary. It has been found that when using gels, stirring is unnecessary but can be employed. When using s~urces of titanium which are solids, stirring is beneficial.
The preferred temperature range is 150~C to 225~C for a period of time ranaing from 4 hours to 4 days. Crystallization is performed in a continuous or batchwise manner under a~utogenous pressure in an autoclave or static bomb reactor. Following the water washing step, the crystalline ETAS-10 is dried at temperatures of 100 to 600~F for periods up to-30 hours.
The method for preparing ETAS-10 compositions comprises the preparation of a reaction mixture constituted by sources of silica, sources of alumina, sources of titanium, sources of alkalinity such as sodium and/or potassium oxide and water having a reagent molar ratio composition as set forth in Table 3. Optionally, sources of fluoride such as potassium fluoride can be used, particularly to assist in solubilizing a solid titanium source such as Ti2O3. However, when titanium aluminum silicates are prepared from gels, its value is diminished.
The silica source-includes most any reactive source of silicon such as silica, silica hvdrosol, siiica gel, siiicic acid, alkoxides of silicon, alkali metal silicates, preferably sodium or potassium, or mixtures of the foregoing.

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The titanium oxide sour~e is trivalent or tetravalent and compounds such as titanium trichloride, TiC13, or titanium tetrachloride, TiC14 can be used.
The aluminum source can include sodium aluminate, aluminum salts such as aluminum chloride, etc.
The source of alkalinity is preferably an aqueous solution of an alkali metal hydroxide, such as sodium hydroxide, which provides a source of alkali metal ions for maintaining electrovalent neutrality and controlling the pH of the reaction mixture within the range of 10.0 to 11.5. As shown in the examples hereinafter, pH is critical for the production of ETAS-10. The alkali metal hydroxide serves as a source of sodium oxide which can also be supplied by an aqueous solution of sodium silicate.
The crystalline titanium-aluminum-silicates as synthesized can have the original components thereof replaced by a wide variety of others according to techniques well known in the art. Typical replacing components would include hydrogen, ammonium, alkyl ammonium and aryl ammonium and metals, including mixtures of the same. The hydrogen form may be prepared, for example, by substitution of original sodium with ammonium or by the use of a weak acid. The composition is then calcined at a temperature of, say, 1000~F causing evolution of ammonia and retention of hydrogen in the composition, i.e., hydrogen and/or decationized form. Of the replacing metals, pref~rence is accorded to metals of Groups II, IV ana VIII of the ~eriodic Table, preferably the rare earth metals.

' 20~666 ., The crystalline titanium-aluminum-silicates are then preferably washed with water and dried at a temperature ranging from about 100~F to about 600~F and thereafter calcined in air or other inert gas at temperatures ranging from 500~F to 1500~F
for periods of time ranging from l/2 to 48 hours or more.
Regardless of the synthesi2ed form of the titanium silicate the spatial arrangement of atoms which form the basic crystal lattices remain essentially unchanged by the replacement of sodium or other alkali metal or by the presence in the initial reaction mixture of metals in addition to sodium, as determined by an X-ray powder diffract-on pattern of the resulting titanium silicate. The X-ray diffraction patterns of such products are essentially the same as those set forth in Table I above (with the exception that the 7.20 ~ .15 A line is sometimes not observed).
The crystalline titanium-aluminum-silicates prepared in accordance with the invention are formed in a wide variety of particular sizes. Generally, the particles can be in the form of powder, a granule, or a molded product such as an extrudate having a Particle size sufficient to pass through a 2 mesh (Tyler) screen and be maintained on a 400 mesh (Tyler) screen in cases where the catalyst is molded such as by extrusion. The titanium silicate can be extruded before drying or dried or partially dried and then extruded.
When used as a catalyst, it is desired to incorporate the new crystalline titanium-aluminum-silicate with another mater-al resistant ~o the temperatures and other -onditicns employed in organic processes. Such materials include active 201~666 ~' , and inactive materials and synthetic and naturally occurring zeolites as well as inorganic materials such as clays, silica and/or metal oxides. The latter may be either naturally occurring or in the form of gelatinous precipitates or gels including mixtures of silica and metal oxides. Use of a material in conjunction with the new crystalline titanium silicate, i.e., combined therewith which is active, tends to improve the conversion and/or selectivity of the catalyst in certain organic conversion processes. Inactive materials suitably serve as diluents to control the amount of conversion in a given process so that products can be obtained economically and in an orderly manner without employing other means for controlling the rate of reaction. Normally, crystalline materials have been incorporated into naturally occurring clays, e.g., bentonite and kaolin to improve the crush strength of the catalyst under commercial operating conditions. These materials, i.e., clays, oxides, etc., function as binders for the catalyst. It is desirable to provide a catalyst having good crush strength because in a petroleum refinery the catalyst is often subjected to rough handling which tends to break the catalyst down into powder-like materials which cause problems in processing.
These clay binders have been employed for the purpose of improving the crush strength of the catalyst.
Naturally occurring clays that can be composited with the crystalline titanium silicate described herein include the smectite and kaolin families, which families include the montmorillonites such as sub-bentonites and the kaolins in which the main constituent is kaolinite, hallovsite, dickite, nacrite or anauxite. Such clays can be used in the raw state after conventional gritting or they can be subjected to additional processing such as calcination, acid treatment or chemical modification.
In addition to the foregoing materials, the crystalline titanium silicate may be composited with X

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2~1~666 matrix materials such as silica-alumina, silica-magnesia, silica-zirconia, silica-thoria, silica-berylia, silica-titania as well as ternary compositions such as silica-alumina-thoria, silica-alumina-zirconia, silica-alumina-magnesia and silica-magnesia-zirconia. The matrix can be in the form of a cogel. The relative proportions of finally divided crystalline metal organosilicate and inorganic oxide gel matrix can vary widely with the crystalline organosilicate content ranging from about 1 to 90 percent by weight and more usually in the range of about 2 to about 50 percent by weight of the composite.
As is known in the art, it is often desirable to limit the alkali metal content of materials used for acid catalyzed reactions. This is usually accomplished by ion exchange with hydrogen ions or precursors thereof such as ammonium and/or metal cations such as rare earth.
Employing the catalyst of this invention, containing a hydrogenation component, heavy petroleum residual stocks, cycle stocks, and other hydrocrackable charge stocks can be hydrocracked at temperatures between 400~F
and 825~F using molar ratios of hydrogen to hydrocarbon charge in the range between 2 and 80. The pressure employed will vary between 10 ~r 201g666 and 2,500 DSiq and the liquid hourlv space velocity between 0.1 and 10.
EmDloyina the catalvst of t~is invention for catalytic cracking, hydrocarbon crackina stocks can be cracked at a liquid hourly sDace velocity between about 0.5 and 50, a temDerature between about 550~F and llOn~F, a pressure between about suDatmosDheric and several hundred atmosDheres.
EmDloyina a catalytically active form of a member of the family of zeolites of this invention containina a hydroaenation comDonent, reformina stocks can be reformed emDloyina a temDeratUre between 700~F and 1000~F. The Dressure can be between 100 and 1,000 psig, but is Dreferably between Z00 to 700 Dsiq. The liquid hourlv sDace velocitv is generallv between 0.1 and 10, Dreferablv between 0.5 and 4 and the hydrogen to hydrocarbon mole ratio is generally between 1 and 20, Dreferably between 4 and 12.
The catalyst can also be used for hvdroisomerization of normal Daraffins when provided with a hydroaenation comDonent, e.g., olatinum. Hvdroisomerization is carried out at a temperature between 200~ and 700~F, preferablv 300~F to 550~F, with a liquid hourlv sDace velocity between 0.01 and 2, Dreferably between 0.25 and 0.50 employina hydro~en such that the hydrogen to hydrocarbon mole ratio is between 1:1 and 5:1.
Additionally, the catalyst can be used for olefin isomerization employina temDeratUreS between 30~F and 500~F.
In order to more fullv illustrate the nature of the invention and a manner of Dracticina the same, the following examDles illustrate the best mode now contemplated.

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Because of the difficulty of measuring pH during crystallization, it is to be understood that the term pR as used in the specification and claims refers to the p~ of the reaction mixture before crystallization diluted 100:1 by weight with water and equilibrated for periods of time ranging from 5-20 minutes.

A large lot of ETS-10-type gel was prepared for attempted direct aluminum incorporation. 1,256 g of ~ 8rand sodium silicate solution was thoroughly mixed and blended with -~' 179 g NaOH and 112 g KF (anhydrous) to form an alkaline silicate solution. To this solution was added 816 g of commercial Fisher titanous chloride solution which was thoroughly mixed and blended with the previous solution using an overhead stirrer. After mixing and initial gel formation, 110 g NaCl and 10 g of calcined ETS-10 seed crystals were added and thoroughly blended into the gel. The "pH" of the gel, using our standard 100:1 dilution, after a 5 min. equilibration period was found to be approximately 10.05, an appropriate level for ETS-10 formation if TiC13 is employed as the titanium source. ~ -~~
A small portion of the ETS-10 type gel (8-lOg) was removed from the large lot and crystallized at autogenous pressure for 24 hours at 200~C. ~ crystalline product was obtained which, after washing and drying demonstrated a small amount of an impurity believed to be ETS-4 (~15%) and a dominant phase with the following characte!istic YRD lines:
d-spacing (Angstroms) I/I

14.7 W-~
7.19 W-M
4.40 w- M
3.60 VS
3.28 W-M

.--.. . . . . ....

201~66~

EXAMPL~ 2 A suspension of potassium fluoride in an alkaline silicate solution was prepared from the following reactants: -502.4 g N~ brand sodium-silicate 80.0 g NaOH
46.4 g KF (anhydrous) A mixed Al/Ti solution was prepared from the following reactants:
326.4 g Fisher TiC13 solution 12.8 g AlC13 6H2o To the alkaline silicate solution was slowly added the mixed Al/Ti solution while thoroughly blending us ing an overhead stirrer and to the resultant apparently homogeneous gel was added 30 g NaCl and 4 g of calcined ETS-10 seed crystals and mixing continued until the mixture again appeared homogeneous.
The seeded titanium-aluminum-silicate reactant mixture was autoclaved without stirring under autogenous pressure for 24 hours at 200~C. In this example, the Al/Ti ratio in the reactant mixture was prepared to be 1/8. A crystalline product t was obtained whose air-equilibrated d-spacings corresponding to those of Table 1 were:

d-spacing (Angstroms) I/Io 14.85 W-M
.21 . W-M
4.42 ~-M
3.61 VS
3.28 M-S
A general upshift in d-spacings, especially on the highest d-spacing was noted in comparison to Table 2 (~TS-10).

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201~66~
", Following the procedure of Example 2 an alkaline silicate solution was prepared from the following reactants:
502.4 g N brand sodium-silicate 88.3 g NaOH
46.4 g KF (anhydrous) A mixed Al/Ti solution was prepared from the following reactants:
326.4 g Fisher TiCl3 solutions 25.6 g AlC13 ~ 6H20 The alkaline silicate and the mixed Al/Ti solution were thoroughly blended using an overhead stirrer and to the resultant gel was added 20 g NaCl and 4 g of calcined ETS-10 seed crystals.
The seeded titanium-aluminium-silicate reactant mixture was autoclaved under autogenous pressure for 24 hours at 200~C. In this example, the Al/Ti ratio in the reactant mixture was prepared to be 1~. A crystalline product was obtained whose air-equilibrated d-spacings corresponding to those of Table 1 were:

d-spacing (Angstroms) I/Io 14.88 W-M
7.22 W

3.61 VS
3.285 M-S

20146~6 Aqain, several of the d-spacings demonstrate a measurable upshift in comparison to both the prior example with ' lower aluminum addition as well as the ETS-10 of Table 2.

Following the general procedure of EXam~le 2 an alkaline silicate solution was prepared from the following reactants:
502.4 g ~ brand sodium-silicate 96.6 g ~aOR
46.4 g KF (anhydrous) A mixed Al/Ti solution was prepared from the following reactants:
- - 326.4 g Fisher TiC13 solution 38.4 a ~lC13~6~20 The alkaline silicate and the mixed Al/Ti solution were thoroughly blended using an overhead stirrer and to the resultant gel was added 10 g NaCl and 4 g of calcined ETS-10 seed crystals.
The seeded titanium-aluminum-silicate reactant mixture was autoclaved under autogenous pressure for 24 hours at 200~C. In this example, the Al/Ti ratio in the reactant ~.

201~6~

mixture was prepared to be 3/&. A crystalline product was obtained whose air equilibrated d-spacings corresponding to those of Table 1 were:
d-spacing ~Angstroms) I/I

14.97 W-M
(7.2 no longer observed) 4.44 ~-M
3.~3 vs 3.30 M-S
Again, several of the d-spacings demonstrate a measurable upshift in comparison to both the prior examples with lower aluminum addition as well as the ETS-10 of Table 2.
The peak at 7.2 A associated with E~S-10 is no longer observed.

An alkaline silicate solution was prepared from the following reactants:

502.4 g ~ brand sodium-silicate 105.0 9 NaOH
46.4 g KP (anhydrous~
A mixed Al/Ti solution was prepared from the following reactants:
326.4 g Fisher TiC13 solution 51.2 g AlC13~6~20 The alkaline silicate and the mixed Al/Ti solution were thoroughly blended using an overhead stirrer and to the resultant gel was added 4 g of calcined ~TS-l~ seed crvstals.
The seeded titanium-aluminium-silicate reactant mixture was autoclaveq under autogenous pressure for 24 hours at 200~C. In this example, the Al/Ti ratio in the reactant mixture was prepared to be 1/2. A crystalline product was .~

obtained whose air-equilibrated d-cpacings corresponding to those of Table 1 were:
d-spacing (A) I/I

14.97 22 (7.2 no longer observed), 5.05 6 4'45 10 3.78 7 3.~5 10 3.31 39 2.59 18 2.53 42 2.49 16 Again, several of the d-spacings demonstrate a measurable upshift in comparison to both the prior examples with lower aluminum addition as well as the ETS-10 of Table 2.
The peak at 7.2 .~ associated with ETS-10 is again no longer -observed.

An alkaline silicate solution was prepared from the following reactants:
502.4 g ~1 brand sodium-silicate 121.7 g MaOH
46.4 g K~ (anhydrous) A mixed Al/Ti solution was prepared from the following reactants:
326.4 g Fisher TiC13 solution 76.8 g AlC13.6H20 ~ he alkaline silicate and the mixed Al/Ti solution were thoroughly blended using an overhead stirrer and to the resultant gel was added 4 g of calcined ETS-10 seed crystals.

~ ~ , 201966~
.

The seeded titanium-aluminium-silicate reactan~
mixtu~e was autoclaved under autogenous pressure for 24 hours at 200 C. In this example, the Al/Ti ratio in the reactant mixture was prepared to be 3/4. A crystalline product was obtained whose air-equilibrated d-spacings corresponding to those of Table 1 were: , d-spacing (AngstromS) I/I

15.06 W-~
(7.2 no longer observed) 4.46 ~-M
3.67 vs The XRD spectrum has now upshifted to the point where the d-spacings for both the highest (now 15.06 A) and strongest (now 3.67 A) peaks are no longer within the limits specified for the ETS-10 of Table 2. The peak at 7.2 A associated with ETS-10 is again no longer observed.
EXA~PLE 7 An alkaline silicate solution was prepared from the follow ing reactants:
502.4 g ~ brand sodium-silicate 138.4 q NaOH
46.4 g KF (anhydrous) A mixed Al/Ti solution was prepared from the following reactants:
~26.4 g ~isher ~iC13 solution 102.4 g AlC13- 6H20 The alkaline 6ilicate and the mixed Al/Ti solution were thorough!y blended using an over~.ead stirrer and to the resultant gel was added 4 g of calcined ETS-10 seed crystals.

' ' ' r~

.
-The seeded titanium-aluminium-silicate reactant mixture was autoclaved under autogenous pressure for 24 hours at 200~C. In this example, the Al/Ti ratio in the reactant mixture was prepared to be 1/1. A crystalline product was obtained whose air-equilibrated d-spacings corresponding to those of Table 1 where:
d-spacing (Angstroms) I/Io 15.25 15 (7.2 no longer observed) 105.07 23 4.455 10 3.89 18 3.68 100 3.~3 41 152.587 24 2.536 40 2.507 25 The XRD spectrum has again upshifted to the point where the d-spacings for both the highest (now 15.25 A) and strongest (now 3.68 A) peaks are no longer within the limits specified for the ETS-10 of Table 2. The peak at 7.2 A associated with ETS-10 is again no longer observed.

The systematic addition of aluminum to ETS-10-like synthesis mixtures results in a systematic increase in the interplanar d-spacings to the point where at sufficient aluminum levels both the largest and the strongest d-spacings rise above the limits for ETS-10 as claimed. Such systematic increases are not only grossly in excess of potential analytical error but are taken as prima facie evidence of elemental framework incorporation in classical zeolite synthesis.

As in the case of all other titanium bearing molecular sieves that we have observed, phase formation of ETAS-10 is pH dependent. In the case of ETAS-10, the appropriate range of pH for formation is dependent on degree of desired aluminum incorporation. At most levels of aluminum incorporation, ETS-4 (described and claimed in U.S. Patent No. 4,938,939) would form if aluminum were not present. The pH utilized for ETAS formation is higher than the level associated with ETS-10 formation.
The increased pH allowed with aluminum present allows ETAS-10 to be grown much faster and potentially at lower temperatures than can be accomplished for ETS-10. The pH
levels of examples 1-8 are presented as Table 4.

"pH" of ETAS-10 FORMING REACTANT GELS
(10 MIN. EQUILIBRATION) EXAMPLE "pH"
1 (ETS-10 10.10 + .03 2 10.30 + .03 3 10.35 + .03--------4 10.55 + .03 10.65 + .03 (REGION

6 10.80 + .03 OF ETS-4 7 10.85 + .03 FORMATION
IF NO
ALUMINUM
IS PRESENT

8 10.80 _ .03 In this example, all pertinent reactants (alumina, titania and silica) employed in examples 1-7 are replaced. The gross reacion ratios resemble example 7 (i.e., the reactant Al/Ti = 1).

E

An alkaline silicate solution was prepared by blending the following reactants;
280g sodium-disilicate solution (SDS) 45.0 g NaOH
23.2 KF (anhydrous) 30.0 g D.I. H2O
To this solution is slowly added 192.0 g of a 1.27 molal TiCl4 solution in 20 wt.% HC1. After blending, a gel was formed to which 20 g sodium aluminate was added and blended. The resultant mixture was autoclaved under autogenous pressure at 200~C for 24 hours and a crystalline product was obtained whose relevant XRD lines were compared to the product of example 7, prepared using different silica, titania and alumina sources. The comparison of these patterns indicates essentially identical ETAS-10 products.

d-SPACING A (I/Io) d-SPACING (A) I/Io 15.25 W-M 15.25 W-M
20 (7.2 no longer observed) 4.45 W-M 4.45 W-M
3.68 VS 3.68 VS
3.33 M-S 3.33 M-S
This example demonstrates that ETAS-10 may be prepared from various silica, tatinum and aluminum sources.

This example establishes that as the aluminum content of the ETAS-10 reaction mixture rises, the aluminum content of the gross product rises proportion-ally. As is common in molecular sieve synthesis, the crystalline product of examples 1-8 contained mixed phases, with ETAS-10 phases predominating (examples 2-8).
The most common contaminant noted was ETS-4.

.~

Several samples washed and dried (from examples 1, 2, 5 and 7) which contained a preponderance (estimated at >85%) of the desired crystalline phase were analyzed by X-ray fluorescence to determine the composition of the gross product.
This analysis revealed:
Al/Ti AI/ti PRODUCT OF WT.%81203 (REACTANTS) GROSS PRODUCT
EXAMPLE 1 0.28 O* 0.02 EXAMPLE 2 1.26 0.125 0.10 EXAMPLE 5 3.89 0.500 0.33 EXAMPLE 7 9.70 1.00 0.88 * = other than reactant impurities It is common in zeolite synthesis that the incorpo-ration of an added element is not necessarily linear with addition. However, incorporation often appears as a linear function of the ratios of several reactants.
This example establishes that added aluminum is substantially integrated into the gross reaction product of ETAS-10 synthesis mixtures. In all cases, the exchangeable cationic content of the reaction products approximated 2 (Ti) + 1 (Al).
Thus, if titanium (Ti) bears a charge of -2 and aluminum (Al) bears a charge of -1, the ratios of counter-balancing cations to 2 times the titanium content plus 1 times the aluminum content and should approach 1.0 in a pure material.

2~1466~

iv~ ~ ~

The purest sampie, the product of Example 5, was found to demonstrate the following cation/site balance as synthesized:
(~a+K)/(2Ti+~l) = .97 These materials are easily exchangeable with cationic species such as ammonium, with little or no change in XRD
spectrum as is obvious from the following table which shows ammonium exchange. Magnesium and calcium data will be later presented.

',~ .

TABLE
COMPOSITION AND XRD PEAK POSITIONS OF AS-SYNTHESIZED AND

ELEMENTAL COMPOSITION (WT%) XRD PEAK POSITION (A) d-spacing A I/Io d-spacing I/Io SiO261.4070.12 14.7 W-M 14.75 W-M
TiO222.7227.12 7.20 W-M 7.20 W-M
Al2O3 0.28 0.26 4.41 W-M 4.415 VS
Na2O13.751.58 3.60 VS 3.60 W-M
K2O3.30.07 3.28 W-M 3.28 W-M
(Na+K)/2Ti= 0.89 (as synthesized) (Na+K)/2Ti= .08 (after exchange) ELEMENTAL COMPOSITION (WT~) XRD PEAK POSITION (A) d-spacing A I/Io d-spacing I/Io SiO258.74 67.77 14.97 W-M 14.91 W-M
TiO218.48 21.83 --- --- 7.24 W-M
Al2O33.89 6.71 4.45 W-M 4.43 W-M
Na2O12.51 2.80 3.65 VS 3.62 VS
K2O 5.56 1.24 3.31 M-S 3.30 M-S
(Na+K)/(2Ti+Al) = 0.97 (as synthesized) (Na+K)/(2Ti+Al) = 0.17 (after exchange) ELEMENTAL COMPOSITION (WT%) XRD PEAK POSITION (A) d-spacing A I/Io d-spacing I/Io SiO254.52 61.77 15.25 W-M 15.30 W-M
TiO217.23 19.72 --- --- ---Al2O39.70 11.30 4.45 W-M 4.40 W-M
Na2O14.93 5.25 3.68 VS 3.68 VS
K2O 4.18 1.78 3.33 M-S 3.33 M-S
(Na+k)/(2Ti+Al) = 0.92 (as synthesized) (Na+K)/(2Ti+Al) = 0.29 (after exchange) X

2ol~666 EXAMP~E lO
The product of Example 5 was contacted with a lO~ by weight solution of magnesium chloride for l/2 hour at 100~C.
After washing with deionized water and calcining at 500~C for 1 hour, and re-equilibrated in air, the crystalline product had the following d-spacings:

o d-spacing~ (A) I/Io 14.97 23 7.20 (no longer observed) 5.01 6 4.43 10 3.78 6 3.63 lO0 3.31 28 2.540 26 2.479 lO
The elemental composition was as follows ~wt.~):
SiO2 60.76 TiO2 18.96 A12n3 5.60 Na20 5.~2 K20 3.62 MgO 5 47 2~g+Na+K/(2Ti+Al) = 0.~2 - ..... . _ .
.

.

The product of Example 7 was contacted with a 10~ by weight solution of magnesium chloride for 1/2 hour at 100~C.
After washing with deionized water and calcining at 500~ for 1 hour, and re-equilibrated in air, the crystalline product had the following d-spacings:

d-spacings (A) I/Io 15.06 16 7.20 (no longer observed) 5.08 26 4.43 8 3.66 100 3.32 30 2.564 24 2.535 20 2.493 11 ' The elemental composition was as follows (wt.~):

SiO2 56.20 TiO2 17.30 A12~3 9.85 Na20 9.32 K20 3.09 MgO 4.64 2Mg+Na+K/(2Ti+Al) = 0.95 .: ~ ",~'' 20146~
., The product of example 5 was contacted with a 5% by weight solution of calcium chloride dihydrate for 1/2 hour at 100~C a total of 2 times. After washing with deionized water and calcining at 200~C for 1 hour, and re-equilibrated in air, the crystalline product had the following d-spacings:

o d-~pacinqs (A) I/I

14.9 W-M

7.2 (not observed) 4.42 3.615 VS

3.290 M-S

The elemental composition was as follows (wt.~):

SiO2 59 .93 TiO2 19.23 A12~3 5.69 Na20 1.61 g2~ 2.76 CaO 11.31 2Ca+Na+~/(2Ti+Al) = 0.92 While the aluminum coordination may be inferred to be tetrahedral from the cation balance of the previous examples, ~1 ~IMR may be employed to more definitively establish '~L

-whether Al is tetrahedral or octahedral and whether it is "framework" aluminum as would be expected if it were integrated into a molecular sieve. The 27 AI MAS NMR
spectrum of a sample of ETAS-10 containing approximately 7.2 wt. % A1203 was obtained and shows a peak at 58 ppm which is indicative of tetrahedral framework aluminum.
No octahedral aluminum was observed, the small peak at -6 ppm being interpreted as a spinning side band.
This example establishes that essentially all aluminum incorporated into the gross reaction product of ETAS-10 reaction mixtures forms as tetrahedral, framework type sites. This example does not eliminate the possibility of mixed phases, including the possibility of an alumino-silicate zeolite co-forming with ETS-10 in ETAS-10 reaction mixtures.

The ETAS-10 sample of the previous example was subjected to standard SEM/EDS analysis. The morphology of the dominant crystal species (established from XRD to be ETAS-10) was found to be platy masses, notably different than the nearly cubic crystals characteristic for ETS-10. Spot elemental analysis of the sample indicated that aluminum was uniformly associated with crystals bearing both high titanium and high silicon levels. No masses or crystals containing significant aluminum were observed which did not also contain substantial titanium observed, i.e. no alumino-silicate phases were observed.

., This example establishes that aluminum incorporated into the gross reaction product of ETAS-10 reaction mixtures forms as crystalline titanium-aluminum-silicates and not as a mixture of crystalline titanium-silicates and classical alumino-silicate zeolites.

Examples 9-14 established that aluminum is incorporated as a tetrahedral framework atom in a crystalline titanium-aluminum-silicate phase during the crystallization of ETAS-10 reaction mixtures.

The gross products of examples 1, 5 and 8 were ammonium exchanged, activated under vacuum at 350~C and exposed to xenon at 530 torr pressure. The xenon treated samples were then subjected to 129Xe NMR. Some crystal-linity was lost. The spectra of the ETS-10 of example 1 shows a clean spectrum with a peak at 119.3 ppm.
Aluminum incorporated dramatically upshifts this peak position. The product of example 5 shows a clear single peak at 137.6 ppm, establishing that the ETAS-10 of example 5 is a single crystalline phase, easily differen-tiated from the ETS-10 of example 1 by a standard analytical technique. Substantially increasing the aluminum level in example 8 only raises the primary peak an additional 2 ppm (to 139.8), clearly demonstrating that the characteristic peak locations for ETAS-10 cover a relatively narrow region, far removed from that characteristic for ETS-10, irrespective of incorporated aluminum level under the test conditions stated.

201~666 The 29Si MAS NMR spectrum of ETS-10 and the ETAS-10 of example 10 were obtained. The ETS-10 spectrum indicates three distinct silicate environments as manifested by peaks at -104, -96 and -94 ppm. The ETAS-10 spectrum demonstrates these three environments plus at least two new heavily populated environments as manifested by additional significant peaks at -92 and -90 ppm. Such new environments would be expected if silica and alumina were integrated into the same crystal.
Having established in the previous example that ETAS-10 is a single phase, it is evident that aluminum incorporation impacts the silica sites of the structure and that an additional standard analytical method may be employed to readily differentiate ETS-10 from ETAS-10.
CONCLUSIONS FROM EXAMPLES 15 & 16 These two examples demonstrate that the ETAS-10 samples of the previous examples represent a single distinct phase which can be readily differentiated from ETS-10 by a variety of standard analytical techniques.

The ETAS-10 sample of example 13 was activated under vacuum at 200~C and exposed to 1,3,5-trimethylbenzene.
Under these conditions, an adsorptive capacity of 6.4 wt.% was observed for this as synthesized, mixed Na'/~
material.

~i i .

As synthesized, mixed Na+/K~ ETS-10 has been observed to be essentially non-adsorptive towards 1,3,5-trimethylbenzene, the molecule being slightly larger than the as synthesized ETS-10 pore opening.
This example demonstrates that the pore opening of ETAS-10 is somewhat larger than ETS-10. This is consistent with the lattice expansion examples 1-8 as aluminum is incorporated into the reaction mixture.

The products of examples 1 and 5 were air equilibrated and dehydrated in a TGA apparatus at 10~/min. ETS-10 is a weak, type I moderate adsorbent towards small polar molecules and began rapidly losing water at a temperature slightly above 100~C. Under equivalent conditions, the ETAS-10 of example 5 lost the preponderance of absorbed water only after a pronounced drop-off point at approximately 250~C. This demonstrates that the incorporation of even 3.9 wt.% Al2O3 profoundly alters the internal electrostatic field of the material, binding small polar molecules such water much more tightly.

These two examples demonstrate that ETAS-10 has a somewhat larger pore an grossly different internal electrostatic environment that ETS-10. These two points are completely consistent with the lattice expansion observed in examples 1-8 and the distinct xenon shift (probably indicative of much stronger xenon/site interactions) of example 14 and the new silica environments of example 16.

E~

201~6~

EX~MPLES 19-23 These examples demonstrate that the preparation of ETAS-10 is not as simple as the addition of an aluminum source to a "standard~ ETS-10 synthesis mixture followed by crystallization. Specific pR levels, depending upon desired ' i degree of aluminum incorporation, must be in place while the reactant gel is formed. These examples further demonstrate that if aluminum addition is made at the wrong gel pH, formation of ETAS-10 by rebalancing pH to the level appropriate for ETAS-10 formation is difficult at best.
FXAMP~E 1~
A 200 9 sample of the ETS-10 ael of example 1 was segregated from the larger lot and to this sample was added 20.8 g of reagent grade AlC13-6~20 such that the ratio of Al/Ti was approximately 1.0, as in examples 7 and 8. The sample was thoroughly blended and the "pH" of the gel, after a 10 min. equilibration period, was found to be approximately 7.8, well below the region associated with ETS-10 lor ETAS-10 formation. Three small samples (8-ln g each) were withdrawn from this now aluminum bearing lot and crystallized under the conditions of the previous example for 1, 3 and 7 days, respectively. After washing and drying as above, X~D powder patterns revealed the reaction products to be essentially amorphous (approximately 10~ crystallinity) with the small amount of crystallized product devoid of ETS-10, ETAS-10 or related phases in all cases.

~,~
.,- ,. ~

201~66~

A 200 g sample of the ETS-10 gel of example 1 was segregated from the larger lot and to this sample was added 6.7 g of Al2O3 ~ 6H2O such that the ratio of Al/Ti was approximately 1.0, as in examples 7 and 8. The sample was thoroughly blended and the "pH" of the gel, after a 10 min. equilibration period, was found to be approximately 10.1, essentially unchanged from the raw ETS-10 gel. Three small samples (8-10 g each) were withdrawn from this now aluminum bearing lot and crystallized under the conditions of the previous example for 1, 3 and 7 days, respectively. After washing and drying as above, XRD powder patterns revealed the reaction products to be highly crystalline ETS-4, essentially devoid of ETS-10, ETAS-10 or related phases.

A 200 g sample of the ETS-10 gel of example 1 was segregated from the larger lot and to this sample was added 7.1 g of NaAlO2 such that the ratio of Al/Ti was approximately 1.0, as in examples 7 and 8. The sample was thoroughly blended and the "pH" of the gel, after a 10 min. equilibration period, was found to be approximately 10.7, an apparently nearly ideal level for ETAS-10 formation at this aluminum content. Three small samples (8-10 g each) were withdrawn from this now aluminum bearing lot and crystallized under the conditions of the previous example for 1, 3 and 7 days, respectively. After washing and drying as above, XRD
powder patterns revealed the reaction products to be highly crystalline ETS-4, essentially devoid of ETS-10, ETAS-10 or related phases.

-.

TO the remainder of the relatively low (for ETAS-10 formation) alkalinity mixture of_example 20 was added 3.5 g of NaOH with the resultant mixture thoroughly blended by over-head stirrer, The resultant "pH" was raised to approximately 10.75, A small portion of the sample (8-lq g) was crystallized for 24 hours at 200~C as above. A crystalline product was obtained which was predominantly ETS-4 (estimated to be approximately 80~) with no trace of any ETS-10 or ETAS-10-like phase observed.

To the remainder of the remainder of the nearly ideal (for ETAS-10 formation) alkalinity mixture of example 19 was added an additional 1.0 g of ~aOH with the resultant mixture thoroughly blended by over-head stirrer. The resultant "pH"
was raised to approximately 10.80. A small portion of the sample (8-10 g) was crystallized for 24 hours at 200~C as above. A crystalline product was obtained which was predominantly ETS-4 (estimated to be approximately 80~) with no trace of any ETS-10 or ETAS-10-like phase observed.
CONCLUSIO~S
ETAS-10 is a new wide pored titanium-aluminum-silicate molecular sieve constructed from di-charged octahedral titanium, mono-cnarged tetrahedral aluminum and neutral tetrahedral silica units. NO such sieve containing both charged octahedral and charged tetrahedral sites is noted in ~he prior art.

201~666 While structurally related to the titanium-silicate molecular sieve ETS-10, incorporation of aluminum into the framework structure systematically expands the lattice planes and pore openings. The incorporated aluminum generates strongly polarized sites which, in concert with the di-charged titanium sites, generate a unique intercrystalline environment.
The synthesis of ETAS-10 is similar to that of ETS-10 with the exception that a soluble aluminum source is added to the synthesis mixture and the "pH" must be adjusted upward at the time of gel formation depending upon aluminum level. It also appears that this elevated alkalinity must be present at or shortly after gel formation. ETS-10 contains incidental amounts of aluminum typically 0.5 wt.~ as Al203 on a volatile free basis, as a consequence of less than perfect reactant purity, especially contamination in commercial sodium silicates. ETAS-10 contains substantial amounts of aluminum (about 0.5 to 10 wt.~ or more as Al203) as a consequence of the intentional incorporation of aluminum into the sieve by the addition of an aluminum source to the reaction mixture.
ETAS-10 represents a new composition of matter which can be differentiated from ETS-10 by a variety of standard analytical techniques.

g 201~G66 ~1 , , ~,;

~LOSSARY OF TERMS ~
;~
DEFINITION " PROCEDURES AND REACTANTS EMPLOYED

- ~ Brand Sodium Silicate is a commercial solution obtained from PQ Corporation. Typical lot analysis would .nclude approximately 29 wt.% Si02 and 9 wt.
caustic as Na20, the balance being water.

- SDS (sodium di-silicate) is a commercially used sodium silicate solution in Engelhard FCC operations and was obtained internally. Typically lot analysis would include approximately 27 wt.% Si02 and 14 wt.%
caustic as Na20, the balance being water.

- Potassium fluoride (KF~ was obtained on an anhydrous - basis from Pfaltz and Bauer, Inc. Solubility of fluorides in the silicate solutions employed is such that they are only partially dissolved upon mixing, the balance appearing suspended in the silicate mixtures. , -: :
- Caustic (NaOH~ was obtained as an essentially anhydrous material from Fisher Scientific.
~:
- Titanous Chloride solution (TiC13 ? was obtained from Fisher Scientific as 20 wt.% TiC13 in 20 wt.% HCl, the balance being water yielding a net molality of 1.25 - 1.30 TiC13.

- Titanium tetrachloride (TiC14) was obtained as a +99 wt.% liquid from Alfa-Ventron.

- Aluminum trichloride as the hexa-aquated salt (AlC13'6~20) was obtained from Fisher Scientific. , The aluminum trichloride is completely dissolved in the titanous chloride solution before the mixed metal solution is blended into alkaline silicate mixtures.

, i~ .

.
- Sodium aluminate (NaAlO2) was obtained on an essentially anhydrous basis from Pfaltz and Bauer, Inc.
Where this reactant is employed as the aluminum source, sodium aluminate is added as a solid to freshly prepared titanium silicate gels and blended until it apparently dissolves.

- Sodium Chloride (NaCl) was obtained as an essentially anhydrous salt from Fisher Scientific.
Sodium chloride was added to mixtures of low aluminum content to increase the ion content to a level approaching that of the higher aluminum content mixtures.

- Calcined seed crystals are obtained by calcining a standard pilot plant run of approximately 80~ ETS-10 and 15~ ETS-4 to a temperature greater than 300~C but less than 500~C such that the ETS-4 decomposes while ETS-10 remains in tact. Seeds are not essential to ETAS-10 formation, but appear to shorten reaction times and broaden the range of acceptable gel compositions.

- Thoroughly blended refers to gels which have been stirred by overhead stirrers to the point where they visually appear homogeneous. All blending is done at ambient temperature although acid base reactions and base dissolution may temporarily elevate the temperature of the gel.

- All products of the examples are vacuum filtered, washed with an excess of deionized water (at least 10 cc/g) and dried at 200~C for at least 30 minutes prior to any further treatment or testing.

- Air-equilibration is carried out by exposure of dried samples to ambient air for a period of at least one hour.

_ - SEM/EDS is scanning electron microscopy and energy dispersive spectroscopy.

- Elemental analyses are presented on a volatile free basis as determined by x-ray fluorescence. The x-ray fluorescence sample preparation technique used involves exposure to elevated temperature - typically 1100~C.
Thus, the samples presented as ammonium exchanged are in reality the hydrogen form since the said exposure at elevated temperatures converts the samples to some hydrogen form.

- 27Al N.M.R Spectra 27Al N.M.R Spectra MAS NMR
spectroscopy is a technique used to characterize the aluminum species in alumino-silicates and zeolites. All spectra were obtained from Spectral Data Services, Inc., Champaign, IL. 27Al Spectra were run by standard methods exposing the sample to a magnetic field of 8.45 tesla and spinning the sample at a rate of 8 kHz at the so-called magic angle, which reduces shielding anisotropy and dipolar interaction. Spectra were an average of 3000 to 8000 scans to increase resolution and signal-to-noise with a 0.3 sec recycle and summed. All samples were air-equilibrated (i.e. contained absorbed water) before running spectra. Such equilibrated both makes a reproducible state of hydration and enhances the observation of 27Al MAS NMR species by increasing the techniques sensitivity.

- l9Si N.M.R. Spectra 29Si MAS NMR Spectroscopy is a technique used to characterize the silicon species in alumino-silicates and zeolites. All spectra were obtained from Spectral Data Services, Inc., Champaign, IL. 29Si spectra were run by standard methods exposing the sample to a magnetic field of 6.3 tesla and spinning the sample at a rate of 4kHz at the so called magic angle, which reduces shielding anisotropy and dipolar interaction. Spectra were an average of 200 to 1500 scans to increase resolution and single-to-noise with a 80 to 120 sec recycle and summed. All samples were air-equilibrated (i.e. contained adsorbed water) before running spectra. Such equilibrated samples contain 15-20 wt.9o- water. This equilibration both makes a reproducible state of hydration and enhances the observation of 23Si MAS NMR species by increasing the techniques sensitivity.

- Discharged Titanium - Titanium centers generate a charge of -2 when in octahedral coordination with oxygen.
The charge results from 6 shared oxygen atoms impacting a charge of -12/2 = -6. Ti (IV) imparts a charge of +4 such that the coordinated titanium center bears a net charge of -2.

- Monocharged aluminum - Aluminum centers generate a charge of -1 when in tetrahedral coordination with oxygen. The charge results from 4 shared oxygen atoms imparting a charge of -8/2 = -4. Al (III) imparts a charge of +3 such that the coordinated aluminum center bears a net charge of -1.

Claims (17)

1. A crystalline titanium-aluminum-silicate molecular sieve having a large pore size of approximately 9 Angstrom units and having a composition in terms of mole ratios of oxides as follows:
(1+?) (1.0 ~ 0.25 M2/n 0) : TiO2 : x AlO2 : y SiO2 : z H2O
wherein M is at least one cation having a valence of n, y is from 2.5 to 25, x is from 0.01 to 5.0 and z is from 0 to 100, said molecular sieve being characterized by a) having an X-Ray powder diffraction pattern as hereinafter set forth:

(0 - 40°2 theta) SIGNIFICANT d-SPACING (ANGS.) I/Io 14.7 - .50 + 1.0 W-M
7.20 ~.15 (optional) W-M
4.41 -.05 + 0.25 W-M
3.60 -.05 + 0.25 VS
3.28 -.05 + .2 M-S

wherein:
VS = 60-100 S = 40-60 M = 20-40 W = 5-20, b) having mono-charged tetrahedrally coordinated aluminum in the framework, and c) having di-charged octahedrally coordinated titanium in the framework.

2. The composition of claim 1 wherein y is 3.0 to 10.

3. The composition of claim 1 wherein M is a mixture of sodium and potassium.

4. The composition of claim 1 wherein at least a portion of M is hydrogen.

5. The composition of claim 1 wherein at least a portion is rare earth.

6. A process for conversion of an organic compound which comprises contacting the same at conversion conditions with the composition of claim 1.

7. A process for catalytic cracking of hydrocarbon which comprises contacting the same with the composition of claim 1 at elevated temperatures.

8. A process for reforming a naphtha which comprises contacting the same in the presence of added hydrogen and a hydrogenation/dehyrogenation component with the composition of claim 4.

9. A process for reforming a naphta which comprises contacting the same in the presence of added hydrogen and a hydrogenation/dehydrogenation component with the composition of claim 5.

10. A process for the removal of divalent ions from a solution containing the same which comprises contacting said solution with the composition of claim 1.

11. A process for the removal of polyvalent ions from a solution containing the same which comprises contacting said solution with the composition of claim 2.

12. A process for the removal of polyvalent ions from a solution containing the same which comprises contacting said solution with the composition of claim 3.

13. A process for the removal of polyvalent ions from a solution containing the same which comprises contacting said solution with the composition of claim 4.

14. The process of claim 10 wherein the polyvalent ion is Pb+2.

15. The process of claim 11 wherein the polyvalent ion is pb+2.

16. The process of claim 12 wherein the polyvalent ion is Pb+2.

17. The process of claim 13 wherein the polyvalent ion is pb+2.