AU633567B2 - Large-pored molecular sieves with charged octahedral titanium and charged tetrahedral aluminum sites - Google Patents

Description

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AUSTRALIA

PATENTS ACT 1952 COMPLETE SPECIFICATION 633567.- Form

(ORIGINAL)

FOR OFFICE USE Short Title: Int. Cl: Application Number: Lodged: Complete Specification-Lodged: Accepted: Lapsed: Published: Priority: Related Art: TO BE COMPLETED BY APPLICANT Name of Applicant: ENGELHARD CORPORATION Address of Applicant: 7- MENLO PARK CN

EDISON

NEW JERSEY 08818

USA

Actual Inventor: Address for Service: GRIFFITH HACK CO., 601 St. Kilda Road, Melbourne, Victoria 3004, Australia.

Complete Specification for the invention entitled: LARGE-PORED MOLECULAR SIEVES WITH CHARGED OCTAHEDRAL TITANIUM AND CHARGED TETRAHEDRAL ALUMINUM SITES.

The following statement is a full description of this invention including the best method of performing it known to me:- ENG-89-9 LARGE-PORED MOLECULAR SIEVES WITH CHARGED OCTAHEDRAL TITANIUM AND CHARTRD TETRAHEDRAL ALUMINUM SITES BACKGROUND OF T-HE INVENTION 1i Field of the Invention This invention relates to new crystalline titanium molecular sieve zeolite compositions, having both aluminum and l titanium in the framework structure, methods for preparing the same; uses thereof such as organic compound conversions 1 therewith, especially hydrocarbon conversions and in ion i. exchange applications. The novel materials of this invention owe their uniqueness to the fact that the framework titanium is Soctahedrally coordinated whereas the framework aluminum is tetrahedrally coordinated.

2. Background of the Invention and Prior Art SISince the discovery by Milton and coworkers 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 synthetic Saluminosilicate zeolite molecular sieves have formed the basis of numerous commercially important catalytic, adsorptive and ion-exchange applications. This high degree of utility is the i| result of a unique combination of high surface area and uniform porosity dictated by the "framework" structure of the zeolite Scrystals coupled with the electrostatically charged sites +3 induced by tetrahedrally coordinated Al Thus, a large "9

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number of "active" charged sites are readily accessible to molecules of the proper size andaeometrv for adsorptive or Scatalytic interactions. Further, since charae comoensatinq Ications are electrostatically and not covalentlv bound to the aluminosilicate framework, they are aenerally exchanceable for other cations with different inherent orooerties. This offers wide latitude for modification of active sites whereby specific Sadsorbents and catalysts can be tailormade for a aiven utility,., In the oublication "Zeolite Molecular Sieves", Chaoter 2, 1974, D. W. Breck hvoothesized that oerhaos 1,000 Saluminosilicate zeolite framework structures are theoretically possible, but to date only aoproximately 150 have been identified. While comoositional nuances have been described in oublications such as U. S. 4,524,055, U. S. 4,603,040 and U. S.

4,606,899, totally new aluminosilicate framework structures are beina discovered at a nealiaible rate. Of Darticular imoortance to fundamental oroaress in the catalysis of i relatively large hydrocarbon molecules, esoecially fluid Scracking operations, is the fact that it has been a aeneration Ssince the discovery of any new larae oored aluminosilicate zeolite.

With slow proaress in the discovery of new wide oored aluminosilicate based molecular sieves, researchers have taken various aooroaches to replace aluminum or silicon in zeolite I synthesis in the hope'of aeneratina either new zeolite-like framework structures or inducina the formation of qualitatively different active sites than are available in analoaous Saluminosilicate based materials. While oroaress of academic 2 interest has been made from different approaches, little success has been achieved in disQoverind new wide Dore molecular sieve zeolites.

It has been believed for a aeneration that PhosPhoruv could be incororated, to varvina dearees, in a zeolite type I aluminosilicate framework. In the more recent oast (JACS 104 Do. 1146 (1982); Proceedinas of the 7th International Zeolite Conference, Do. 103-112, 1986) E. M. Flaniaan and coworkers Y_ have demonstrated the oreparation of oure aluminoohosohate based molecular sieves of a wide variety of structures.

However, the site inducina Al 3 is essentially neutralized by +5 the P imoartina a +1 charae to the framework. Thus, while a new class of "molecular sieves" was created, they are not zeolites in the fundamental sense since they lack "active" charaed sites.

Realizina this inherent utility limitina deficiency, for the oast few years the molecular sieve research community has emphasized the synthesis of mixed aluminosilicate-metal oxide and mixed aluminoohosohate-metal oxide framework systems. While this aoproach to overcomina the slow oroaress in aluminosilicate zeolite synthesis has qenerated approximately 200 new compositions, all of them suffer either +5 from the site removina effect of incorporated P or the site Sdilutina effect of incorooratina effectively neutral tetrahedral +4 metals'intd an aluminosilicate type framework.

As a result, extensive research by the molecular sieve research community has failed to demonstrate sianificant utility for any of these materials.

3- Ii A series of zeolite-like ramework" silicates have been synthesized, some of which .avelaraer uniform oores than i are observed for aluminosilicate zeolites. M. Meier, Si Proceedinas of the 'th International Zeolite Conference, ID jo. 13-22 (1986).) While this particular synthesis aooroach I oroduces materials which, by definition, totally lack active, Scharaed sites, back imolementation after synthesis would not SaPear out of the question althouah little work appears in theA open literature on this topic.

i Another and most straightforward means of ootentially aeneratinq new structures or qualitatively different sites than j those induced by aluminum would be the direct substitution of I some other charae inducina soecies for aluminum in zeolite-like Sstructures. To date the most notably successful examole of Sthis aooroach aDoears to be boron in the case of ZSM-5 analoas, althouah iron has also been claimed in similar materials. (EPA S68,796 (1983), Taramasso et al; Proceedinas of the S.i International Zeolite Conference; Do. 40-48 (1980)); J. W. Ball i i! et al; Proceedinas of the 7th International Zeolite Conference; SD 137-144 (1986); U. S. 4,280,305 to Kouenhowen et al.

Unfortunately, the low levels of incorooration of the soecies Ssubstitutina for aluminum usually leaves doubt if the species are occluded or framework incorporated.

In 1967, Younq in U. S. 3,329,481 reported that the synthesis of charae beariia (exchanaeable) titanium silicates under conditions similar to aluminosilicate zeolite formation was possible if the titanium was present as a "critical Sreagent" +III oeroxo species. While these materials were 4 1 called "titanium zeolites" no evidence was oresented beyond Ssome questionable X-ray diffraction _XRD) oatterns and his claim has qenerally been dismissed by the zeolite research community. W. Breck, Zeolite Molecular Sieves, o. 322 (1974); R. M. Barrer, Hvdrothermal Chemistry of Zeolites, o. 293 (1982); G. Pereao et al, Proceedinqs of 7th International Zeolite Conference, o. 129 (1986).) For all but one end member of this series of materials (denoted TS i materials), the oresented XRD oatterns indicate ohases too Sdense to be molecular sieves. In the case of the one J questionable end member (denoted TS-26), the XRD oattern miaht i ossiblv be interoreted as a small oored zeolite, althouah without additional supDortina evidence, this acoears extremely questionable.

A naturally occurrina alkaline titanosilicate identified as "Zorite" was discovered in trace quantities on the Kola Peninsula in 1972 N. Mer'kov et al; Zaoiski Vses Mineraloa. Obshch., oaaes 54-62 (1973), The oublished XRD oattern was challenaed and a orooosed structure reoorted in a Slater article entitled "The OD Structure of Zorite", Sandomirskii et al, Sov. Phys. Crvstalloar. 24 Nov-Dec 1979, oaaes 686-693.

No further reoorts on "titanium zeolites" apoeared in the open literature until 1983 when trace levels of tetrahedral STi(IV) were reported in a 'ZSM-5 analoa. Taramasso et al; U. S. Patent 4,410,501 (1983); G. Pereao et al; Proceedinas of the 7th International Zeolite Conference; o. 129 (1986).) A similar claim appeared from researchers in mid-1985 (EPA 5 S132,590 (1985).) More recently, the research community reported mixed aluminosilicate-titanium(IV) (FPA 179,876 2 (1985); EPA 181,884 (1985) structures which, along with TAPO i! i (EPA 121,232 (1985) systems, appear to have no possibility of Sactive 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 M. Kuznicki et al; J. Phys. Chem.; 84; pp.

535-537 (1980)) of TiO units in some modified zeolites.

4 David M. Chapman, in a speech before llth 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 Smineral vinogradovite is a molecular sieve nor does it have the Sx-ray diffraction pattern of Table 1 of this specification.

A major breakthrough in the field of large pored titanium silicate molacular sieves is disclosed and claimed in U.S. Serial No. 94,237, filed September 8, 1987, now U.S.

Patent L~S3,2O- The crystalline titanium silicate large -6 6 I I 2 7 pored molecular sieve of said patent, hereafter designated contains no deliberately added alumina but may contain very minor amounts of alumina due to the presence of impurities. Thus, ETS-10 typically has a molar ratio of SiO 2 /A1 2 0 3 greater than 100 or more.

SUMMARY OF THE INVENTION According to the present invention there is provided 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: (1.0±0.25 M 2 n0): Ti02: x A10 2 y SiO 2 z H 2 0 2 wherein M is at least one cation having a valence of n, y is from 2.0 to 100, x is from 0.5 to 5.0 and z is from 0 to 100, said molecular sieve being characterised by having an X-ray powder diffraction pattern as set forth in Table 1 of the specification, having mono-charged tetrahedrally coordinated aluminum in the framework, and having dicharged octahedrally coordinated titanium in the framework.

According to the present invention there is also provided a process for conversion of an organic compound which comprises contacting the same at conversion conditions with the composition described in the preceding paragraph.

According to the present invention there is provided a process for catalytic cracking of hydrocarbon which comprises contacting the same with the composition described above at elevated temperatures.

DETAILED DESCRIPTION OF THE 7NVENTION i The present invention relates to a new family of I7a stable crystalline titanium-aluminum-silicate molecular i 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: (1.0±0.25 M 2 Tio2: x A10 2 y Si0 2 z 2 wherein M is at least one cation having a valence of n, y is from 2.0 to 100, x is from 0.05 to 5.0 and z is from 0 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 The original cations M can be replacea at least in part with other cations by well known exchange techniques. Preferred replacing cations include hydrogan, ammonium, rare earth, and I mixtures thereof. Members of the family of molecular sieve Szeolites designated ETAS-10 have a high degree of thermal stability of at least 450 0 C or higher, thus rendering them effective for use in high temperature catalytic processes.

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 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: TABLE 1 XRD POWDER PATTERN OF (0 400 2 theta) SIGNIFICANT d-SPACING (ANGS.) I/I 0 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 40-60 M 20-'40 W 5-20 The above values were determined by standard x-ray diffraction techniques. The radiation was the K-alpha doublet 8

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Sof copper, and a scintillation counter spectr~"ter was used.

The oeak 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 I/I where I is the intensity of the strongest line or o 0 peak, and d the interplanar spacing in anastroms, I corresponding to the recorded lines, were calculated. These interplanar d-spacings define the crystalline structure of the i oarticular composition. It has been determined that the X-ray Spowder diffraction peaks characteristics of ETS-10 are systematically altered by the inclusion of increasing amounts i of aluminum addition in ETAS-10. Such systematic alterations are taken as prima facie evidence of framework incorporation of ii some newly introduced species much akin to classical zeoliLe Ssynthesis. As cointed out in U.S. Patenti<.~ 3 2 ETS-10 contains the most sianificant lines which are set forth as follows: TABLE 2 CHARACTERISTIC d-SPACINGS d-SPACING (ANGS.) I/I o I 14.7 0.35 W-M S7.20 0.15 W-M i 4.41 0.10 W-M 3.60 7 0.05 VS 3.28 T 0.05 W-M

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I It has been found that as the decree of aluminum incorporation increases in ETAS-10, the larqest d-soacing o analoaous to 14.7 A in ETS-10 and the stronaest characteristic d-soacing analoaous to 3.60 A in ETS-10 markedly increase. In -9- I Li i 1 1 C b fact, as hiaher levels of aluminum incorporation are attained, the increase of these lines falls outside the claim limits for Additionally, one of the characteristic d-spacinas i 7.20 A disapoears. However, it is not known at this time if the disappearance reoresents a structural change or if it is morDholoaically induced.

Althouqh ETAS-10 is structurally related to Sintroduction of substantial quantities of hiahlv polar 1 mono-charaed tetrahedral aluminum sites into the zeolitic framework profoundly alters the character of the sieve, imoactina adsorotive, ion-exchange and catalytic orooerties.

can be clearly and easily differentiated from ETS-10 by Sstandard analytical techniques such as NMR and in some cases by SX-ray diffraction.

While structurally related to ETS-10, incorooration of Saluminum into the framework structure of ETAS-10 systematically expands the lattice planes and oore ooeninas. This in turn allows ETAS-10 to sorb molecules somewhat laroer than those Ssorbed by ETS-10. Additionally, the sorbtive properties are Stransformed from a relatively weak to a stronaer sorbant and much more powerful ion-exchancer. The ion exchanae oroperties are altered in such a manner that certain heavy metals, esoecially lead, are evacuated from aqueous solutions essentially on contact. The incorporation of aluminum into the Sframework also makes the catalytic acidity of substantially different than that of ETS-10 in that it is very strona, capable of crackina alkanes as would be exoected from Szeolitic aluminum sites but the hiah alkene yield Sj characteristic of relatively weak octahedral sites is retained.

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It is to be immediately undersLuod that applicants are i not maintaining to be the first to have prepared a molecular sieve containing titanium, aluminum and silicon in significani amounts. Materials of this type have previously been reported Sin the TASO work of Lok, EPO 181,884 and EPO 179,876 previously I 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 oi the other hand, have di-charged octahedrally coordinated titanium in combination with mono-chargee tetrahedrally coordinated aluminum sites.

rnm by -the m, Akob se- out molecular sieves GaBbe preparedl frem herein-fedy -ro" ireaction mixture containing a titanium source such as titanium Strichloride 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 composition in terms of mole ratios falling within the following ranges.

TABLE 3 Broad Preferred Most Preferred SiO 2 /Al 1-200 2-100 2-20 SiO2/Ti 2-20 3-10 4-7

H

2 0/SiO 2 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 In corcnce. WAt -the rekoe ihee e I to the invention. UT-reaction mixture is heated to a s 1 11 I_ I c-

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i8 ;3 I:i 3 i i:i i i I

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i 1

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i I 'i temperature of from about 100°C to 250 0 C for a period ot 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, filtered 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 sources of titanium which are solids, stirring is beneficial.

The preferred temperature range is 150 0 C to 225 0 C for a period of time ranging from 4 hours to 4 days. Crystallization is performed in a continuous or batchwise manner under autogenous 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 meth -nrlr preparing ETAS-10 compositions b e-

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mpf iss thiU r L a- rLeact on m xtI.LULrle consL LULtU Uy 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 Ti203. However, when titanium aluminum silicates are prepared from gels, its value is diminished.

The silica source include most any reactive source of silicon such as silica, silica hydrosol, silica gel, silicic acid, alkoxides of silicon, alkali metal silicates, preferably sodium or potassium, or mixtures of the foregoing.

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~i i J m.1.1 be The Litanim oxide source ,i trivalent or tetravalent Sand compounds such as titanium trichloride, TiC13, or titanium tetrachloride, TiC1 can be used.

The aluminum source can include sodium aluminute,

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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_ I the reaction mixture within the range of 10.0 to 11.5. As Sshown 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.

SI The crystalline titanium-aluminum-silicates as synthesized can have the original components thereof replaced j by a wide variety of others according to techniques well known I in the art. Typical replacing components would include li i:-i ji 1

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j ii 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, hydrogen and/or decationized form. Of the replacing metals, preference is accorded to metals of Groups II, IV and VIII of the Periodic Table, preferably the rare earth metals.

13 S!The crystalline titanium-alm-linum-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°P 1 for periods of time ranging from 1/2 to 48 hours or more.

Regardless of the synthesized 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 Si in the initial reaction mixture of metals in addition to I1 Isodium, as determined by an X-ray powder diffraction pattern of the resulting titanium silicate. The X-ray diffraction i i\ patterns of such products are essentially the same as those set Sforth in Table I above (with the exception that the 7.20 .15 A line is sometimes not observed).

I The crystalline titanium-aluminum-silicates prepared I in accordance with the invention are formed in a wide variety i 'of particular sizes. Generally, the particles can be in the 4 form of powder, a granule, or a molded product such as an i| extrudate having a particle size sufficient to pass through a 2 1 ij mesh (Tyler) screen and be maintained on a 400 mesh (Tyler) screen in cases where the catalyst is molded such as by i extrusion. The titanium silicate can be extruded before drying 4j or dried or partially dried and then extruded.

I When used as a catalyst, it is desired to incorporate i 'the new crystalline titanium-aluminum-silicate with another material resistant to the temperatures and other conditions employed in organic processes. Such materials include active 14

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1 v Sand inactive materials and synthetic and natural' occurrino zeolites as well as inoraanic maJerials such as clays, silica Sand/or metal oxides. The latter may be either naturally occurrinq or in the form of qelatinous orecinitates or aels .I includinq mixtures of silica and metal oxides. Use of a material in conjunction with the new crystalline titanium j silicate, combined therewith which is active, tends to i improve the conversion and/or selectivity of the catalyst in certain organic conversion Processes. Inactive materials Ssuitably serve as diluents to control the amount of conversion Sin a given orocess so that oroducts can be obtained Seconomically and in an orderly manner without emplovinq other I means for controllina the rate of reaction. Normally, crystalline materials have been incoroorated into naturally Soccurrina clays, bentonite and kaolin to imDrove the Scrush strength of the catalyst under commercial ooeratina conditions. These materials, clays, oxides, etc., Sfunction as binders for the catalyst. It is desirable to i provide a catalyst havina aood crush strenoth because in a

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o etroleum refinery the catalyst is often subjected to rough handlina which tends to break the catalyst down into {i powder-like materials which cause problems in orocessin.

SThese clay binders have been emoloved for the ouroose of Simorovina the crush strength of the catalyst.

SiNaturally occurrina clays that can be comoosited with ithe crystalline titanium silicate described herein include the smectite and kaolin families, which families include the montmorillonites such as sub-bentonites and the kaolins in 15 -k I I "1__._"IIIX which the main constituent is kaolinite, hallovsite, dickite, V nacrite or anauxite. Such clavs.can.be used in the raw state after conventional qrittina or they can be subjected to additional orocessina such as calcination, acid treatment or i chemical modification.

i In addition to the foreaoina materials, the crystalline titanium silicate may be comoosited with matrix materials such as silica-alumina, silica-maqnesia, u* silica-zirconia, silica-thoria, silica-berylia, silica-titania as well as ternary compositions such as silica-alumina-thoria, silica-alumina-zirconia, silica-alumina-maanesia and silica-maanesia-zirconia. The matrix can be in the form of a I coael. The relative prooortions of finally divided crystalline I metal oraanosilicate and inoraanic oxide ael matrix can vary Swidely with the crystalline oroanosilicate content ranaina from about 1 to 90 percent by weiaht and more usually in the ranae Sof about 2 to about 50 percent by weiqht of the composite.

'I 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 exchanae with hydrogen ions or precursors thereof such as ammonium and/or metal cation, such as rare earth.

Emoloyino the catalyst of this invention, containing a hydrogenation component, heavy petroleum residual stocks, cycle stocks, and other hydrocrackable charae stocks can be Shydrocracked at temperatures between 400 0 F and 825°F usina molar ratios of hydrogen to hydrocarbon charae in the ranae I between 2 and 80. The pressure employed will vary between 16 17 and 2,500 psig and the liquid hourly space velocity between 0.1 and Employing the catalyst of this invention for catalytic cracking, hydrocarbon cracking stocks can be cracked at a liquid hourly space velocity between about and 50, a temperature between about 550°F and 1100 0 F, a pressure between about subatmospheric and several hundred atmospheres.

Employing a catalytically active form of a member of the family of zeolites of this invention containing a hydrogenation component, reforming stocks such as a naphtha can be reformed employing a temperature between 700 0 F and S1000 0 F. The pressure can be between 100 and 1,000 psig, but is preferably between 200 to 700 psig. The liquid hourly space velocity is generally between 0.1 to preferably between 0.5 and 4 and the hydrogen to Shydrocarbon mole ratio is generally between 1 and preferably between 4 and 12.

1 The catalyst can also be used for hydroisomerization of normal paraffins when provided with a hydrogenation Scomponent, platinum. Hydroisomerization is carried Sout at a temperature between 2000 and 700°F, preferably j 300°F to 550 0 F, with a liquid hourly space velocity between 0.01 and 2, preferably between 0.25 and 0.50 employing hydrogen such that the hydrogen to hydrogen mole ratio is between 1:1 and 5:1. Additionally, the catalyst can be used for olefin isomerization employing temperatures between 30°F and 500 0

F.

The catalyst can also be used for the removal of polyvalent ions such as Pb 2 from a solution containing the same by contacting the solution with the catalyst.

In order to more fully illustrate the nature of the invention and a manner of practicing the same, the

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ra.arraxenm~ 17a following examples illustrate the best mode now contemplated.

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

EXAMPLE 1 A large lot of ETS-10-type gel was prepared for attempted direct aluminum incorporation. 1,256 g of N Brand, Ssodium 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, S110 g NaC1 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 Slevel for ETS-10 formation if TiC1 is employed as the titanium source.

A small portion of the ETS-10 type gel (8-10g) was removed from the large lot and crystallized at autogenous pressure for 24 hours at 200 0 C. A crystalline product was Sobtained which, after washing and drying demonstrated a small amount of an impurity beli.eved to be ETS-4 and a dominant phase with the following characteristic XRD lines: d-spacing (Angstroms) I/I o 14.7 W-M 7.19 W-M 4.40 W-M 3.60 VS 3.28 W-M 18 EXAMPLE 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) I A mixed Al/Ti solution was prepared from the following reactants: 326.4 g Fisher TiCl 3 solution 12.8 g A1C13-6H20 To the alkaline silicate solution was slowly added the mixed Al/Ti solution while thoroughly blending using an overhead stirrer and to the resultant apparently homogeneous gel was added 30 g NaC1 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 0 C. In this example, the Al/Ti ratio in the reactant mixture was prepared to be 1/8. A crystalline product was obtained whose air-equilibrated d-spacings corresponding to those of Table 1 were: i d-spacing (Angstroms) I/I o 14.85 W-M 7.21 W-M 4.42 W-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 -19 1 EXAMPLE 3 Following the procedure of Example 2 an alkaline silicate solution was prepared f.-gm the following reactants: 502.4 g 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 TiC13 solution 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 NaCI and 4 g of calcined {seed crystals.

The seeded titanium-aluminium-silicate reactant mixture was autoclaved under autogenous pressure fur 24 hours at 200 0 C. In this example, the Al/Ti ratio in the reactant mixture was prepared to be 1/4. A crystalline product was obtained whose air-equilibrated d-spacings corresponding to Sthose of Table 1 were: d-spacing (Angstroms) I/Io

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14.88 W-M 7.22 W 4.45 W-M 3.61 VS 3.285 M-S

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20 Again, several of th measurable upshift in compari lower alurninum addition as we.

EX,

I Following the genera alkaline silicate solution wa Sreactants: 502.4 g P 96.6 g Na 46.4 g KF I A mixed Al/Ti soluti reactants: 326.4 g Fi i^ I .i A e d-spacings demon-trate a son to both the prior example with 11 as the ETS-10 of Table 2.

AMPLE 4 1 procedure of Example 2 an s prepared from the following brand sodium-silicate

OH

(anhydrous) on was prepared from the following sher TiCl solution 3 3O.'4 U MA.1.l O6 U o. 3 2 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 caleined seed crystals.

The seeded titanium-aluminum-silicate reactant mixture was autoclaved under autogenous pressure for 24 hours at 200 0 C. In this example, the Al/Ti ratio in the reactant r -p 21 mixture was prepared to be 3/8. A crystalline product was obtained whose air equilibrated d-spacings corresponding to those of Table 1 were: d-spacing (Angstroms) I/I o 14.97 W-M (7.2 no longer observed) 4.44 W-M 3.63 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.

0o The peak at 7.2 A associated with ETS-10 is no longer observed.

EXAMPLE An alkaline silicate solution was prepared from the following reactants: 502.4 g N brand sodium-silicate 105.0 g NaOH 46.4 g KF (anhydrous) A mixed Al/Ti solution was prepared from the following reactants: 326.4 g Fisher TiCI solution 3 51.2 g A1Cl *6H 0 3 2 The alkaline silicate and the mixed Al/Ti solution weLe thoroughly blended using an overhead stirrer and to the resultant gel was added 4 g of calcined ETS-10 seed crystals.

The seeded titanium-aluminium--ilicate reactant mixture was autoclaved, under autogenous pressure for 24 hours at 200 0 C. In this example, the Al/Ti ratio in the reactant Smixture was prepared to be 1/2. A crystalline product was 22 obtained whose air-cquili.brated d-spacings corresponding to Sthose of Table 1 were: d-spacing I/I -o 14.97 22 (7.2 no longer observed) 5.05 6 4.45 3.78 7 3.65 100 3.31 39 2.59 18 2.53 42 2.49 16 j Again, several of the d-spacings demonstrate a measurable upshift in comparison to both the prior examples Swith lower aluminum addition as well as the ETS-10 of Table 2.

o SThe peak at 7.2 A associated with ETS-10 is again no longer observed.

EXAMPLE 6 An alkaline silicate solution was prepared from the following reactants: 502.4 g M brand sodium-silicate 121.7 g NaOH 46.4 g KF (anhydrous) A mixed Al/Ti solution was prepared from the following reactants: 326.4 g Fisher TiC1 solution 3 76.8 g AlCl .6H20 The alkaline silicate and the mixed A1/Ti solution were thoroughly blended using an o-erhead stirrer and to the resultant gel was added 4 g of calcined ETS-10 seed crystals.

23 u The seeded titanium-aluminium-silicate reactant mixture was autoclaved under autogenous pressure for 24 hours o 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 Sthose of Table 1 were: d-spacing (Angstroms) I/I o 15.06 W-M (7.2 no longer observed) 4.46 W-M 3.67 VS 3.33 M-S The XRD spectrum has now upshiftec to the point where o the d-spacings for both the highest (now 15.06 A) and strongest o (now 3.67 A) peaks are no longer within the limits specified o for the ETS-10 of Table 2. The peak at 7.2 A associated with is again no longer observed.

EXAMPLE 7 An alkaline silicate solution was prepared from the following reactants: 502.4 g N brand sodium-silicate 138.4 g NaOH 46.4 g KF (anhydrous) A mixed Al/Ti solution was prepared from the following reactants: 326.4 g Fisher TiC1 solution 3 102.4 g A1C13 6H2 0 The alkaline sili.cate 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.

-24 The seeded titanium-aluminium-silicate reactant mixture was autoclaved under autogenous pressure for 24 hours at 200 0 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 were: d-spacing (Angstroms) I/I o 15.25 (7.2 no longer observed) 5.07 23 4.455 3.89 18 3.68 100 3.33 41 2.587 24 2.536 2.507 The XRD spectrum has again upshifted to the point where the d-spacings for both the highest (now 15.25 A) and o strongest (now 3.68 A) peaks are no longer within the limits o specified for the ETS-10 of Table 2. The peak at 7.2 A associated with ETS-10 is again no longer observed.

CONCLUSIONS FROM EXAMPLES 1-7 The systematic addition of aluminum to synthesis mixtures results in a systematic increase i.n the interplaner d-spacings to the point where at sufficient aluminum levels both the largest and the strongest d-spacings Srise above the limits for ETS-10 as claimed. The systematic rises are graphically portrayed for the lead and strongest peaks in Figures 1 and 2, respectively. Such systematic rises 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.

25 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 I(described and claimed in U.S. 094,233 filed September 8, 1987) would form if aluminum were not present. The pH utilized for ETAS formation is higher than the level associated with Sformation. The increased pH allowed with aluminum present m, 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.

TABLE 4 "pH" of ETAS-10 FORMING REACTANT GELS MIN. EOUILIBRATION) EXAMPLE "pH" 1 (ETS-10) 10.10 .03 2 10.30 .03 3 10.35 .03 4 10.55 .03 t 10.65 .03 (REGION OF ETS-4 6 10.80 .03 FORMATION IF NO 7 10.85 7 .03 ALUMINUM IS

PRESENT)

8 10.80 .03 4 EXAMPLE 8 In this example, all pertinent reactants (alumina, titania and silica) employed in examples 1-7 are replaced. The gross reaction ratios resemble example 7 the reactant Al/Ti 1).

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. 26 :i -i

I

ii i: i1 i -ii i: i i i i: :-i i -i i;i i:i i i

B

'f i 3 iii lu Y

""B

To this solution is slowly added 192.0 g of a 1.27 molal TiC14 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 2000 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.

PRODUCT OF EX MPLE 7 PRODUCT OF E AMPLE 8 d-SPACING A(I/Io) d-SPACING 15.25 W-M 15.25 W-M (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, titanium and aluminum sources.

EXAMPLE 9 This example establishes that as the aluminum content of the ETAS-10 reaction mixture rises, the aluminum content of the gross product rises proportionally. As is common in molecular sieve synthesis, the crystalline product of examples 1-8 contained mixed phases, with ETAS-10 phases predominating (examples The most common contaminant noted was ETS-4, Several samples washed and dried (from examples 1, 2, and 7) which contained a preponderance (estimated at of 27 i it the desired crystalline phase were analyzed by X-ray ifluorescence to determine the composition of the gross product.

This analysis revealed: PRODUCT OF WT.%Al 0 Al/Ti (RFACTANTS) Al/Ti GROSS PRODUCT EXAMPLE 1 0.28 0* 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 incorporation of an added element is not necessarily linear with addition. However, incorporation often appears as a linear function of the ratios of several reactants. Such trends are graphically portrayed in Figures 3 and 4.

This example establishes that added aluminum is substantially integrated into the gross reaction product of synthesis mixtures. In all cases, the exchangeable cationic content of the reaction products approximated 2(Ti) 1(Al).

Thus, if tit.anium (Ti) bears a charge of -2 and aluminum (Al) bears a charge of the ratios of counterbalancing cations to 2 times the titanium content plus 1 times the aluminum content and should approach 1.0 in a pure material.

28 1 The purest sample, the product of Example 5, was found to demonstrate the following cation/site balance as synthesized: (Na+K)/(2Ti+.Al) .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 preser.ted.

29

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A

11

A

4

I

4

V

T AR I.

COMPOSITION ANT) 541 PFAK POSITTINS OF NS-SYNTHFSIZEP AND Hlr.NI,Y AMiMONIUM FCHAM. FD ETS-10 NMI THF PRODUCTS OF EXAMPLE'S 5 AND 7 ETS- I0 ELFMDITAL COMPOSITION NW7'% AS-SYNTHESIZED 'IH4 EXCHANGED 510 61.40 70 .12 TiG 22.72 27.12 Al 2 0.28 0.26 Na 20 13.75 1.58 K 0 3.3 0.07 (Ha+K)/2Ti= 0.89 (as synthesized) (Na+K)/2Tl= .08 (after excharnqe) 5511 PFAX O.SITiOni tAI AS SYNT4F'Sl2FD NN"4 F'KCNAMCFD d-spacing A 1/10 d-spacina 14 .7 7 .20 4. 41 7.60 3 .28 14 .7c 7 .20 4 .4 15 3.60 3.,28

W-M

W-M

PXAMPUF ELFMFNTAF, COMPOSITION (WT'k) A-9-SYNTH4ESIZrD '(44 E.XCHANGFD AS 510 2 58.74 67.77 TiS 18.48 21.83 Al 20 3 3.89 6.71 Na 20 12.51 2.80 4 2 0 5.56 1.24 (Na+K)/(2Ti4A1) 0 .47 (as synthesized) (Ha4KM/2TiIA1I 0. 17 (after exr~hanqe) XP D PFAK POSITMrN (A) SYN~SI2~D N4 FYCNANGED di-spacnq A I/T0 d-spacing I/To 14 .97 4,4 5 3 .6 5 3.31 14,491 W-M .2 1-M 4 .43 14-1 3.52 VS 3. 30 N-S (AMPLE, I ELFMFNTAL COMPOITTION (WTk) AS-SYNTHF.SI7,ED 1444 EXC)IANC.ED '(F0 PFAK POSITIODN (A) AS S;YNTNPSI7E) 1N4 Py'XCNONED d-sra-ing I/10 d-spactng SiL 2 54.S2 61 .7 TIO 2 17 23 19 .72 Al 0 2 0 .70 .1.30 Na 20 14 .9 3 5 .25 Y. 0 4 .18 1 .78 (lla44(/2Ti+AI( 0,92 (as synthesized) (Na4KI/(2Ti4A11 n0.29 (after exchange) 16. 25 4 .4; 3.48 3.33 W-H 10.,30 W-M

L

EXAMPLE The product of Example 5 was contacted with a 10% by weight solution of magnesium chloride for 1/2 hour at 100 0

C.

After washing with deionized water and calcining at 500 0 C for S1 hour, and re-equilibrated in air, the crystalline product had i the following d-spacings: i o d-spacings I/Io 14.97 23 7 .20 (no longer observed) 5.01 6 4.43 3.78 6 3.63 100 3.31 28 2.540 26 2.479 .The elemental composition was as follows Si02 60 .76 Ti0 2 18.96 Al1203 5.60 5 .82 3.62 MgO 5.47 -2Mg+NaK/(2Ti+A) 0.92 1 2Mg+Na+K/(2Ti+A) 0.92

I

31 EXAMPLE 11 The product of Example 7 was contacted with a 10% by weight solution of magnesium chloride for 1/2 hour at 100 0

C.

After washing with deionized water and calcining at 5000 for 1 hour, and re-equilibrated in air, the crystalline product had i .I the following d-spacings: 0 d-spacings I/ o 15.06 16 7.20 (no longer observed) 5.08 26 4.43 8 3.66 100 3.32 2.564 24 2.535 2.493 11 The elemental composition was as follows Si0 2 Ti0 2 Al 0 203 Na 0 2 K 0 2 MgO 56.20 17 9.85 9 .32 3.09 4.64 2Mg+Na+K/(2Ti+Al) 0.95 32 E. -e EXAMPLE 12 The product of example 5 was contacted with a 5% by weight solution of calcium chloride dihydrate for 1/2 hour at 100 0 C a total of 2 times. After washing with deionized water and calcining at 200 0 C for 1 hour, and re-equilibrated in air, the crystalline product had the following d-spacings: o d-spacings I/I o 14.9 W-M 7.2 (not observed) 4.42 W 3.615 VS 3.290 M-S The elemental composition was as follows Si0 2 59 .93 Ti02 19 .23 A120 3 5.69 1.61

K

2 0 2.76 CaO 11.31 2Ca+Na+K/(2Ti+Al) 0.92 EXAMPLE 13 While the aluminum coordination may be inferred to be tetrahedral from the cation balance of the previous examples, 27 Al NMR may be employed to more definitively establish 33 -r I Swhether Al is tetrahedral or octahedral anud v'heher it is "framework" aluminum as would be expected if it were integrated 27 into a molecular sieve. The Al MAS NMR spectrum of a sample of ETAS-10 containing approximately 7.2 wt.% Al20 3 I 2 3 is presented as Figure 5. The peak at 58 ppm is indicative of !i tetrahedral framework aluminum. No octahedral aluminum was observed, the small peak at -6 ppm being interpreted as a i spinning side band.

SThis example establishes that essentially all aluminum incorporated into the gross reaction product of 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 Szeolite co-forming with ETS-10 in ETAS-10 reaction mixtures.

EXAMPLF 14 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 Swas 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 Stitanium observed, i.e. no alumino-silicate phases were observed.

34

I

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.

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

EXAMPLE 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 i 129 samples were then subjected to Xe NMR. While some crystallinity was lost, the spectra of these materials are presented as Figure 6. The ETS-10 of example 1 shows a clean spectrum with a peak a 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 differentiated from the ETS-10 of example 1 by a S^ standard analytical technique. Substantially increasing the Saluminum level in example 8 only raises the primary peak an additional 2 ppm (to 139.8), clearly demonstrating that the 35 characteristic peak locations for ETAS-10 cover a relatively narrow region, far removed from that characteristic for irrespective of incorporated aluminum level under the test conditions stated.

EXAMPLE 16 29 fI The Si MAS NMR spectrum of ETS-10 and the Sof example 10 are presented as Figure 7. The ETS-10 spectrum indicates three distinct silica environments as manifested by peaks at -104, -96 and -94 ppm. The ETAS-10 spectrum I demonstrates these three environments plus at least two new Sheavily 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 CONCLUSIONS FROM EXAMPLES 15 16 These two examples demonstrate that the samples of the previous examples represent a single distinct i phase which can be readily differentiated from FTS-10 by a variety of standard analytical techniques.

EXAMPLE 17 The ETAS-10 sample of example 13 was activated under o 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 /K material.

36i c *So. '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 pore opening.

This example demonstrates that the pore opening of is somewhat larger than ETS-10. This is consistent with the lattice expansion noted in examples 1-8 as aluminum is incorporated into the reaction mixture.

FXAMPLE 18 I The products of examples 1 and 5 were air equilibrated and dehydrated in a TGA apparatus at 100 /riin. ETS-10 is a Sweak, type I moderate adsorbent towards small polar molecules and began rapidly losing water at a temperature slightly above i 1000C. Under equivalent conditions, the FTAS-10 of example lost the preponderance of adsorbed water only after a Spronounced drop-off point at approximately 250 0 C. This demonstrates that the incorporation of even 3.9 wt.% Al 0 Sprofoundly alters the internalAfield of the material, binding small polar molecules such water much more tightly.

CONCLUSIONS FROM EXAMPLES 17 AND 18 These two examples demonstrate that ETAS-10 has a somewhat larger pore and grossly different internal electrostatic environment than ETS-10. These two points are completely consistent with the lattice expansion observed in examples 1-8 and the distinct xenon shift (probably indicative Sof much stronger xenon/site interactions) of example 14 and the new silica environments of example 16.

37 FXAMPLES 19-23 These examples demonstrate that the preparation of is not as simple as the addition of an aluminum source to a "standard" ETS-10 synthesis mixture followed by' crystallization. Specific pH levels, depending u Dn desired 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, Sformation of ETAS-10 by rebalancing pH to the level appropr.iate for ETAS-10 formation is difficult at best.

FXAMPLE 19 A 200 g sample of the ETS-10 gel of example 1 was segregated from the larger lot and to this sample was added 20.8 g of reagent grade AlCl *6H 0 such that the ratio of 3 2 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 min. equilibration period, was found to be approximately 7.8, well below the region associated with ETS-10 or formation. 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 essentially amorphous (approximately 10% crystallinity) with the small amount of crystallized product devoid of ETS-10, ETAS-10 or related phases in all cases.

38 EXAMPLE 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 Al 0 6H 0 such that the ratio of Al/Ti was 2 3 2 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, i 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 Sdevoid of ETS-10, ETAS-10 or related phases.

SFXAMPLE 21 i A 200 g sample of the ETS-10 gel of example 1 was i segregated from the larger lot and to this sample was added .7.g of NaAlO such that the ratio of Al/Ti was approximately 2 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 Sreaction products to be highly crystalline ETS-4, essentially devoid of ETS-10, ETAS-10 or related phases.

-39 I EXAMPLE 22 To the remainder of the relatively low (for formation) alkalinity mixture of example 20 was added 3.5 g of NaOH with the resultant mixture thoroughly blended by over-head Sstirrer. The resultant "pH" was raised to approximately 10.75. A small portion of the sample (8-10 g) was crystallized i. 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 phase observed.

SEXAMPLE 23 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 NaOH 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 0 C as above. A crystalline product was obtained which was predominantly FTS-4 (estimated to be approximately 80%) with no trace of any ETS-10 or ETAS-10-like phase observed.

CONCLUSIONS

is a new wide pored titanium-aluminum-silicate molecular sieve constructed from di-charged octahedral titanium, mono-charged tetrahedral aluminum and neutral tetrahedral silica units. No such sieve containing both charged octahedral and-charged tetrahedral sites is noted in the prior art.

40 While structurally related to the titanium-silic.te Smolecular sieve ETS-10, incorporation of aluminum into the framework structure systematically expands the lattice planes Sand pore openings. The incorporated aluminum generates I strongly polarized sites which, in concert with the di-charged titanium sites, generate a unique intercrystalline environment.

l The synthesis of ETAS-10 is similar to that of with the exception that a soluble aluminum source is added to iI the synthesis mixture and the "pH" must be adjusted upward at i the time of gel formation depending upon aluminum level. It Salso appears that this elevated alkalinity must be present at Ior shortly after gel formation. ETS-10 contains incidental amounts of aluminum typically 0.5 wt.% as Al 20 on a 23' 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.

Si

I

41 i 1;11_1111111...

i 1 j i 1 j GLOSSARY OF TERMS DEFINITIONS, PROCEDURES AND REACTANTS EMPLOYED Brand Sodium Silicate is a commercial solution obtained from PQ Corporation. Typical lot analysis would include approximately 29 wt.% Si2 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.% SiO and 14 wt.% 2 caustic as Na 0, the balance being water.

2 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 (TiCl 3 was obtained from Fisher Scientific as 20 wt.% TiC1 3 in 20 wt.% HC1, the balance being water yielding a net molality of 1.25 1.30 TiCl3 -Titanium tetrachloride (TiCi was obtained as a +99 wt.% liquid from Alfa-Ventron.

Aluminum trichloride as the hexa-aquated salt (ACl 36H 0) 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".

t 42 EL ~I 4 Sodium aluminate (Nal0 was obtained on an essentially anhydrous basis from Pfaltz and Bauer, Inc. Where thic reactant is employed as the aluminum i source, sodium aluminate._s added as a solid to freshly prepared titanium silicate gels and blended V I until it apparently dissolves.

I

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% and 15% ETS-4 to a temperature greater than 300 0 C but less thar 500 0 C such that the ETS-4 decomposes while remains in tact. Seeds are not essential to 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 cc/g) and dried at 200 0 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.

43 i^Jl

*"I

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I

i H SEM/EDS i dispersiv, -Elemental basis as fluoresce involves 1100 0

C.

exchanged said expo samples t s scanning electron microscopy and energy e spectroscopy.

analyses are p-esented on a volatile free determined by x-ray fluorescence. The x-ray nce sample preparation technique used exposure to elevated temperature typically Thus, the samples presented as ammonium are in reality the hydrogen form since the sure at elevated temperatures converts the .o some hydrogen form.

I

27 27 S Al N.M.R Spectra Al N.M.R Spectra MAS NMR spectroscopy is a technique used to characterize the aluminum species in alumino-silicates and zeolites.

All spectra were obt.ained from Spectral Data Services, 27 Inc., Champaign, IL. Al 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 adsorbed water) before running spectra.

Such equilibrated samples contain 15-20 wt water.

This equilibration both makes a reproducible state of 27 hydration and enhances the observation of Al MAS NMR species by increasing the techniques sensitivity.

29 29 Si N.M.R. Spectra Si 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. 2Si spectra were run by standard methods 44

I

exposing the sample to a magnetic field of 6.3 tesla Ind spinning the sample at a rate of 4kHz at the so called magic angle, which reduces shielding anisotrop 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.

iSuch equilibrated samples contain 15-20 wt.% water.

This equilibration both makes a reproducible state of "i hydration and enhances the observation of 2Si MAS *i iNMR species by increasing the techniques sensitivity.

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

t

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Arr 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 Al (III) imparts a charge of +3 such that the coordinated aluminum center bears a net charge of -1.

45

Claims (12)

1. 2. The composition of claim
2. 3. The composition of claim of sodium and potassium.
3. 4. The composition of claim portion of M is hydrogen. The composition of claim portion is rare earth.
4. 6. A process for conversion which comprises contacting the same at wherein wherein y is 3.0 to M is a mixture 1 wherein at least a 1 wherein at least a of an organic compound conversion conditions with the composition of claim 1.
5. 7. A process for catalytic cracking of hydrocarbon which comprises contacting the same with the composition of claim 1 at elevated temperatures. 46
6. 8. A process for reforming a naphth. ;':ich comprises contacting the same in the presence of added hydrogen and a hydrogenation/dehyrogenation comoonent with the composition of claim 4.
7. 9. A process for reforminq a naphtha which comprises contacting the same in the presence of added hydrogen and a hydrogenation/dehyrogenation component with the composition of I claim 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.
8. 11. A process for the removal of polyvalent ions from a s6ltion containing the same which comprises contacting said solution with the composition of claim 2.
9. 12. A process for the removal of polyvalent ions from a solution containing the same which comprises contacing aid solution with the composition of claim 3.
10. 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.
11. 14. The process of claim 10 wherein the- plyvalt e t ion is Pb 2 The process of claim 11 wherein the polyvalent ion is Pb 2
12. 16. The process of claim 12 wherein the polyvalent ion is pb+2 S17 The process of claim 13 wherein the polyvalent ion +2 is Pb. DATED THIS 15TH DAY OF MAY 1990 ENGELHARD CORPORATION BY ITS PATENT ATTORNEYS: GRIFFITH HACK CO., Fellows Institute of Patent l Attorneys of Australia Si 47 IB IA i