JP3030056B2 - Large hole molecular sieves with charged octahedral titanium and charged tetrahedral aluminum sites. - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a novel crystalline titanium molecular sieve zeolite composition having both aluminum and titanium in the framework structure, a process for preparing the same, organic compounds, and especially hydrocarbon compounds. It relates to their use in conversion and ion exchange applications. The uniqueness of the novel material of the present invention lies in the fact that the framework titanium is octahedrally coordinated while the framework aluminum is tetrahedral.

The present invention is summarized as follows: a crystalline titanium-aluminum-silicate having both a dicharged octahedral coordinated titanium and a monocharged tetrahedral coordinated aluminum in the skeleton. A molecular sieve is disclosed.

The ability to form uniform, porous, internally charged crystals, similar to naturally-occurring molecular sieve zeolites, including the aminosilicate system, was widely demonstrated by Milton and collaborators in the 1950s. (U.S. Pat. No. 2,882,243 and U.S. Pat.
No. 44), the molecular sieve properties of synthetic aluminosilicate zeolites have set the standard for many commercially important catalyst adsorption and ion exchange applications. This high degree of practicality is attributed to the unique combination of high surface area and uniform porosity dominated by the "framework" of zeolite crystals, as well as electrostatically induced by tetrahedral coordinated Al ^{+ 3} This is the result of the part charged to the surface. Thus, a number of "active" charged sites are readily accessible to microcrystallites of appropriate size and geometry for adsorption or catalytic interaction. Furthermore, since the cations that compensate for the charge are not covalently bonded to the aluminosilicate backbone, but are electrostatically bonded, they are generally interchangeable with other cations having different intrinsic properties. This provides a wide latitude of active site denaturation, so that certain adsorbents and catalysts can be manufactured for a given utility.

Publication "Molecular sieve of zeolite (Zeolite
Molecular Sieves), Chapter 2, 1974, DW
Breck hypothesizes that perhaps a 1,000-aluminosilicate zeolite framework structure is theoretically possible, but to date only nearly 150 have been identified. Although the nuances of composition are described in publications such as U.S. Pat.No. 4,524,055, U.S. Pat.No. 4,603,040 and U.S. Pat.No.4,606,899, a completely new aluminosilicate skeleton has been discovered in negligible proportions. I have. Catalytic decomposition of relatively large hydrocarbon molecules,
Of particular importance to the basic progress in fluid cracking operations, in particular, is the fact that it has been a generation since the discovery of the new large pore aluminosilicate zeolite.

Because progress has been slow in discovering novel wide pore aluminosilicate-based molecular sieves, researchers have taken a variety of approaches to generate novel zeolite-like framework structures or to use similar aluminosilicate-based structures. Aluminum or silicon was substituted in the zeolite synthesis in hopes of inducing the formation of a different active site than is available in the material. Although academically interesting advances have been made from different approaches, little success has been achieved in the discovery of new wide-pore molecular sieve zeolites.

It has been believed for some generations that phosphorus could be incorporated into the zeolite-type aluminosilicate framework to varying degrees. More recently (JACS, 104 , pp.
1146 (1982); Bulletin of the 7th International Zeolite Conference (Proc
eedings of the 7th International Zeolite Conferenc
e), pp. 103-112, (1986), EM Flaniga (Flaniga
n) and co-workers have demonstrated the preparation of molecular sieves based on pure aluminophosphates of a wide variety of structures. However, the site that induces Al ⁺³ is P
^{It is} essentially neutralized by ⁺⁵ , giving the skeleton a charge of +1. Thus, a new class of "molecular sieves" was created, but they are basically not zeolites because they lack "active" charged sites.

Realizing this inherent utility of limiting disadvantages, during the past few years, the molecular sieve research community has emphasized the synthesis of mixed aluminosilicate-metal oxide and mixed aluminophosphate-metal oxide framework systems. This approach to overcoming the synthesis of aluminosilicate zeolites has generated almost 200 new compositions, all of which either suffer from sites that eliminate the effects of the incorporated P ^{+ 5} , or aluminosilicate It is plagued by sites that dilute the effect of effectively incorporating a neutral four-sided +4 metal into the mold skeleton. As a result, more extensive research in the molecular sieve research community has failed to demonstrate significant utility for any of these materials.

A series of zeolite-like "skeleton" silicates have been synthesized, some of which have larger and more uniform pores than those observed for aluminosilicate zeolites. [WM Meier, Proceedings of the 7th Inter
national Zeolite Conference), pp.13-22, (198
6)]. This particular synthetic approach, by definition,
It produces a material that is completely devoid of active charged sites, but has a post-synthesis back implementation.
tation) may not be possible, but few studies are described in well-known literature on this topic.

The other most direct means of potentially generating new structures or qualitatively different sites than those induced by aluminum is to directly replace aluminum in zeolite-like structures with certain other charge-inducing species Will.
To date, the most notably successful example of this approach is ZS
Although likely to be boron in the case of the M-5 analog, iron has also been claimed in similar materials. [European Patent Application (EPA) No. 68,796 (1983), Taramasso et al .; Proceedings of the 5th International Zeolite C
onference), pp. 40-48, (1980); JW Bar (Bal
l) et al. Proceedings of the 7th International Zeolite Conference
of the 7th International Zeolite Conference), p
137-144, (1986); U.S. Patent No. 4,280,305 (Kouen
howen et al.]]. Unfortunately, when the species is incorporated into the occlusion or framework, the incorporation of lower levels of the species that replace aluminum usually leaves doubt.

In 1967, US Patent No. 3,329,481 (Toung)
It was reported that the synthesis of charged (exchangeable) titanium silicates under conditions similar to the formation of aluminosilicate zeolites was possible when titanium was present as a "critical reagent" + III peroxo species. Was. Although these materials were termed "titanium zeolites", no evidence has been shown beyond some problematic X-ray diffraction (XRD) patterns, and the claims are generally claimed by the zeolite research community. I have been ignored.
[DW Breck, Zeolite Molecular Sieves, p.322 (1974);
RM Barrer, hydrothermal chemistry of zeolites (Hydr
othermal Chemistry of Zeolites), p.293 (1982);
Perego et al., Proceedings of the 7th International Zeolite Con
ference), pp. 129, (1986). ] One of the materials in this series
All but one of the last members (labeled TS material) indicate that the XRD graphic represented is too dense and not a molecular sieve. In the case of one problematic member (labeled TS-26), the XRD pattern can be interpreted as a small pore zeolite, but without additional supporting evidence this could be extremely problematic. There seems to be.

A naturally occurring alkaline titanosilicate identified as "zeolite" was purchased in 1972 by Kola Peninsula (Ko
la Peninsula) [AN Mer'kov et al; Zapiski Vses Mineralog. Obshch., p.
pp. 54-62 (1973). ] The published XRD pattern is suspect, and the proposed structure is described in a later paper, "OD Stracture of Zeolite", Sandmillskiy (S
andomirskii) et al., Sov.Phys.Crystallogr.24 (6), No.
v-Dec. 1976, pp. 686-693.

19 more reports on "titanium zeolite"
It did not appear in the well-known literature until 1983, and then trace levels of tetrahedral Ti (IV) were reported in ZSM-5 analogs. [M. Taramasso et al .; US Patent No. 4,41.
0,501 (1983); G. Perego et al .; Proceedings of the 7th Interna
tional Zeolite Conference), pp.129, (1986). ]
Similar claims emerged from researchers in mid-1985 [European Patent Application (EPA) 132,550 (1985). More recently, the research community reported a mixed aluminosilicate-titanium (IV) structure [European patent application (EP
A) 179,876 (1985); European Patent Application (EPA) 181,884 (1985). They are TAPO-based [European Patent Application (EPA) 12
1,232 (1985)] does not appear to have the potential for active titanium sites due to the coordination of titanium. As such, their utility is highly problematic.

The possibility of having charged, exchangeable titanium silicates is only possible from the existence of exchangeable alkali titanates and the earlier work disclosed in U.S. Pat.No. 3,329,481 on misdefined titanium silicates. Of TiO ₄ -units in unmodified and also some modified zeolites [SM Kuznicki et al .;
Journal of Physical Chemistry (J.Phy
s. Chem.) 84 , pp. 535-537 (1980)].

David M. Chapman is a member of the 11th North American Meeting of the C
Atalysis Society) (1989) states that a gel of titanium aluminosilicate crystallizes, and Chapman claims that all aluminum is aggregated into anatase (ultramicroporous aluminosilicate) and titanium. , For example, was not incorporated in his observed analogs of the mineral vinogradobvite, which is a pure titanium silicate. It should be noted that vinoguadobite has been reported to contain aluminum when found in nature. However, neither the synthetic analog of vinoguadovite nor the mineral vinoguadovite is a molecular sieve,
Also, it does not have the X-ray diffraction pattern in Table 1 of this specification.

A major notable advance in the field of large pore titanium silicates is disclosed and claimed in U.S. Patent No. 4,853,202 (U.S. Patent Application No. 94,237, filed September 8, 1987). The patented crystalline titanium silicate large pore molecular sieve, hereinafter referred to as ETS-10, does not contain actively added alumina, but contains very small amounts of alumina due to the presence of impurities. Sometimes. Thus, ETS-10 typically has a molar ratio of SiO ₂ / Al ₂ O ₃ of more than 100.

The present invention provides a new family of stable, large pore, crystalline titanium-aluminum-silicate molecular sieves, hereinafter ETAS-10, methods for their preparation and such compositions as adsorbents, a wide variety of organic Compounds, such as hydrocarbon compounds and oxygenates,
For example, it relates to its use as an ion exchanger for removing methanol and unwanted metal cations from solutions containing said cations.

The present invention relates to a new family of stable crystalline titanium-aluminum-silicate molecular sieves having a pore size of approximately 9 Angstroms. These titanium-aluminum-silicates have distinct X-ray diffraction patterns and have the following oxide molar ratios: (1 + x / 2) (1.0 ± 0.25M _{2 / n} O): TiO ₂ : xAlO ₂ : ySiO _2: zH in ₂ O formula, 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 0 to 100, by Can be identified. In a preferred embodiment, M is a mixture of sodium and potassium, and y is at least 3.0 and ranges up to about 10.

The original cation M can be at least partially replaced, and other cations can be replaced by known exchange techniques. Preferred replacing cations include hydrogen, ammonium, rare earths, and mixtures thereof.
Members of the zeolite family of molecular sieves, designated ETAS-10, have a high degree of thermal stability at least at or above 450 ° C., and are thus useful for use in high temperature catalytic processes. ETAS-10 zeolites are highly adsorbent for molecules with critical diameters up to approximately 9 Angstroms units, for example 1,3,5-trimethylbenzene. In the form of sodium, ETAS-10 is completely reversibly dewaterable and has a water volume of almost 20% by weight.

Members of the ETAS-10 group of molecular sieve zeolites have a crystalline structure and have X-ray powder diffraction patterns with the following significant lines: Table 1 X-ray powder diffraction patterns of ETAS-10 −40 ° 2θ) Significant d-spacing (angstrom) I / I ₀ 14.7-.50 + 1.0 WM 7.20 ± .15 (optional) WM 4.41-.05 + 0.25 WM 3.60-.05 + 0.05 25 VS 3.28-.05 + .2 MS 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 a copper K-alpha doublet and a scintillation counter spectrophotometer was used. Position as a function of peak height I and 2 × θ, where θ is the Bragg (Br
agg) The angle was read from the spectrophotometer chart. From these, the relative intensity, 100 I / I ₀ , where I ₀ is the intensity of the strongest line or peak, and d is (obd.)
The spacing between planes (angstroms), corresponding to the recorded lines, was calculated. The d-spacing between the planes defines the crystal structure of a particular composition. It has been determined that the X-ray powder diffraction peak characteristics of ETS-10 can be systematically altered by including increasing amounts of aluminum additives in ETAS-10. At first glance, such a systematic change,
Evidence for the incorporation of a framework of some newly introduced species very similar to classical zeolite synthesis. US Patent 4,85
As pointed out in 3,202, ETS-10 contains the most significant lines listed below: Table 2 Properties d-spacing of ETS-10 d-spacing (angstrom) I / I ₀ 14.7 ± 0.35 W -M 7.20 ± 0.15 WM 4.41 ± 0.10 WM 3.60 ± 0.05 VS 3.28 ± 0.05 WM The maximum d similar to 14.7 ° in ETS-10 as the degree of aluminum incorporation increases in ETAS-10. The strongest characteristic d-spacing, similar to 3.60 ° in spacing and ETS-10, is significantly increased. In fact, when higher levels of aluminum incorporation are achieved,
The increase in these lines is outside the limits of the claims for ETS-10. Furthermore, one of the characteristic d-intervals 7.20Å
Disappears. However, it is not known at this time whether the disappearance represents a structural change or whether it is introduced morphologically.

Although ETAS-10 is structurally related to ETS-10, the introduction of a substantial amount of highly polar, mono-charged tetrahedral aluminum sites into the zeolite framework is due to the properties of the sieve, impact adsorption, ion exchange and Significantly change the catalyst ratio. ET
AS-10 is a standard analytical technique from ETS-10, such as NMR
And in some cases by X-ray diffraction, can be clearly and easily distinguished.

Although structurally related to ETS-10, the incorporation of aluminum into the framework structure of ETAS-10 systematically widens the lattice planes and pore openings. This is then followed by ETAS-10
0 allows molecules that are slightly larger than those sorbed to be sorbed. In addition, sorption properties are transferred from relatively weak sorbents to stronger sorbents and much stronger ion exchangers. Ion exchange properties include certain heavy metals,
In particular, it is modified in such a way that lead is eliminated from the aqueous solution essentially on contact. The incorporation of aluminum into the framework also makes the acidity of the catalyst of ETAS-10 substantially different from that of ETS-10, which is very strong, as expected from the aluminum site of the zeolite. Alkane can be decomposed, but the high alkene yield characteristic of the relatively weak octahedral site is retained.

It will be readily appreciated that Applicants have not claimed that they have initially prepared molecular sieves containing significant amounts of titanium, aluminum and silicon. This type of material was previously reported in the aforementioned Lok TASO study, EPO181,884 and EPO179,876. However, in both the specification and the claims of these patents, it is expressly stated that silicon, titanium and aluminum are tetrahedral, so that titanium does not change. On the other hand, the crystal structure of the present invention has dicharged octahedral coordinated titanium in combination with monocharged tetrahedral aluminum sites.

ETAS-10 molecular sieves have a composition with a molar ratio in the following range: a titanium source, for example, titanium trichloride and an aluminum source, for example, aluminum chloride, a silica source, an alkaline source, for example, an alkali metal hydroxide, It can be prepared from a reaction mixture containing water and, if desired, an alkali metal fluoride mineralizer.

Table 3 Wide preferred and most preferred _{SiO 2 / Al 1-200 2-100 2-20 SiO} 2 / Ti 2-20 3-10 4-7 H 2 O / SiO 2 2-100 5-50 10-25 Mn / SiO ₂ 0.1-20 0.5-5 1-3 where M is the cation of valence n derived from the alkali metal hydroxide and potassium fluoride and / or alkali metal salt used in the preparation of the titanium silicate according to the present invention. Show. The reaction mixture is heated to a temperature of about 100C to 250C for a period of about 2 hours to 40 days or more. The hydrothermal reaction is carried out until crystals form, then the resulting crystalline product is separated from the reaction mixture, cooled to room temperature, filtered and washed with water. The reaction mixture can be stirred, but it is not required. When using a gel, it was discovered that stirring was unnecessary, but could be used. Agitation is beneficial when using a solid titanium source. A preferred temperature range is 150 ° C to 225 ° C for a period of 4 hours to 4 days. The crystallization is carried out continuously or in a batchwise manner at autogenous pressure in an autoclave or a stationary cylinder reactor. After washing with water, the crystalline ETAS-10 is dried at 100-600 ° F (37.8 ° C-316 ° C) for a period of up to 30 hours.

The method of preparing the ETAS-10 composition is as follows: a silica source, an alumina source, a titanium source, an alkaline source, such as sodium and / or potassium oxide and water, having the composition of the molar ratio of the reagents listed in Table 3. Consisting of preparing a reaction mixture to be constituted. If necessary, especially solid titanium source, for example, to facilitate solubilization of Ti ₂ O _3, a fluoride source, for example, it can be used potassium fluoride. However, when titanium aluminum silicate is prepared from a gel, its value decreases.

The silica source can be almost any reactive source of silicon, for example, silica, silica hydrosol, silica gel, silicic acid, silicon alkoxide, alkali metal silicate,
Preferably, it includes sodium or potassium, or a mixture thereof.

The titanium oxide source is trivalent or tetravalent, and compounds such as titanium trichloride, TiCl ₃ , or titanium tetrachloride, TiCl ₄ can be used.

Aluminum sources can include sodium aluminate, aluminum salts such as aluminum chloride and the like.

The alkalinity source is preferably an aqueous solution of an alkali metal hydroxide, e.g., sodium hydroxide, to maintain the ionic value neutral and to control the pH of the reaction mixture within the range of 10.1 to 11.5. Provide an ion source.
As shown in the examples below, pH is critical for the formation of ETAS-10. The alkali metal hydroxide serves as a source of sodium oxide, which can also be provided by an aqueous solution of sodium silicate.

The synthesized crystalline titanium-aluminum-silicate can have a wide variety of others and their original components according to techniques well known in the art. Typical substitution components include hydrogen, ammonium, alkylammonium and arylammonium and metals, and mixtures thereof. Hydrogen forms can be prepared, for example, by replacing the original sodium with ammonium or using a weak acid. The composition is then calcined, for example, at a temperature of 538 ° C. (1000 ° F.) to evaporate the ammonia in the composition and retain the hydrogen, ie, retain the hydrogen and / or decationized form. To do. In the replacement of metals, metals of groups II, IV and VIII of the periodic table, preferred rare earth metals are preferred.

The crystalline titanium aluminum silicate is then preferably washed with water, and from about 37.8 ° C to about 316 ° C (about 1 ° C).
Dry in the temperature range of 00 ° F to about 600 ° F) and then in air or other gas at 260 ° C to 816 ° C (500 ° F to 1500 ° F)
Calcination at temperatures ranging from 0.5 to 48 hours or more.

Regardless of the synthesized form of the titanium silicate, the spatial arrangement of the atoms forming the basic crystal lattice, as determined by the X-ray powder diffraction pattern of the resulting titanium silicate, is due to the substitution of sodium or other alkali metal, or Due to the presence of the metal in addition to the sodium in the initial reaction mixture, it remains essentially unchanged. The X-ray diffraction pattern of such a product is essentially identical to that described in Table 1 above, except that the 7.20 ± 0.15 ° line is sometimes not observed.

In accordance with the present invention, crystalline titanium aluminum silicate is formed with a wide variety of pore sizes. Generally, the particles can be in the form of a powder, granules, or a shaped product, eg, an extrudate, and have a pore size sufficient to pass through a two mesh (Tyler) sieve; When the catalyst is shaped, for example, by extrusion, it has a pore size maintained on 400 mesh (Tyler). The titanium silicate can be extruded before drying or partially dried and then extruded.

When used as a catalyst, it is desirable to add other materials to the novel crystalline titanium aluminum silicate that are resistant to temperature and other conditions used in organic processes. Such materials include active and inert materials and synthetic and naturally occurring zeolites and inorganic materials such as clays, silicas and / or metal oxides. The latter can occur naturally or can be in the form of a gelatinous precipitate or gel, including mixtures of silica and metal oxides. In combination with a new crystalline titanium silicate,
That is, the use of the combination of the material with it tends to improve the conversion and / or selectivity of the catalyst in certain conversion processes. Since the inert material acts as a diluent and controls the amount of conversion even in a given process, the product can be obtained in an economical and orderly manner without using other means to control the reaction rate Can be. Usually, crystalline materials are naturally occurring clays, for example,
In addition to bentonite and kaolin, the crush strength of the catalyst has been improved under commercial operating conditions. These materials, ie, clays, oxides, etc., function as binders for the catalyst. It is desirable to provide a catalyst having excellent crush strength. Because in oil refining,
Catalysts are often handled poorly because they break down into powder-like materials that cause problems in the process.
These clay binders have been used to improve the crush strength of the catalyst.

Naturally occurring clays that can be complexed with the crystalline titanium silicates disclosed herein include the green clay and kaolin families, which include montmorillonite, for example, sub-bentonite. And kaolin (where the main constituents include kaolinite, halloysite, dickite, nekrite or anauxite. Such clays can be used in the raw state after ordinary grinding) Alternatively, they can be subjected to additional treatments, such as calcination, acid treatment or chemical modification.

In addition to the foregoing materials, crystalline titanium silicates can be complexed with matrix materials, such as silica-alumina, silica-magnesia, silica-zirconia, silica-tria, silica-beryllia, silica-titania, and ternary components. Compositions such as silica-alumina-tria, silica-alumina-zirconia, silica-
It can be alumina-magnesia and silica-magnesia-zirconia. The matrix is cogel (co
gel). The relative proportions of the matrix of the fine crystalline organosilicate and inorganic oxide gel are from about 1 to 90% by weight of the composite, more usually from about 2 to about
In the range of 50% by weight, it can vary widely with the crb organosilicate content.

As is known in the art, it is often desirable to limit the alkali metal content of the materials used for acid catalyzed reactions. This is usually achieved by ion exchange with hydrogen ions or their precursors, for example ammonium and / or metal cations, for example rare earths.

Using the cations of the present invention containing hydrogenation components, heavy petroleum resid stocks, cycle feeds, and other hydrocrackable general formula feeds are reduced to 204
Hydrocracking can be carried out at a temperature of 400 to 825 ° F. at a hydrogen to hydrocarbon feed molar ratio in the range of 2 to 80. The pressure used can vary between 10-2,500 psig, and the liquid hourly space velocity
It can be between 0.1 and 10.

Using the catalyst of the present invention for catalytic cracking, hydrocarbon cracking feedstocks have a liquid hourly space velocity of about 0.5 to 50, about 371
It can decompose at 550 ° C. to 593 ° C. (550-1100 ° F.), and pressures from about atmospheric to several hundred atmospheres.

Using a catalytically active form of the zeolite family member of the present invention containing a hydrogenation component, the reforming feed is reformed using a temperature of 371-538 ° C (700-1000 ° F). be able to. The pressure is between 100 and 1,000 psig, but is preferably between 200 and 700 psig. The liquid hourly space velocity is generally from 0.1 to 10, preferably from 0.5 to 4, and the molar ratio of hydrogen to hydrocarbon is from 1 to 20, preferably from 4 to 12,
It is.

The catalyst can also be used for conventional paraffin hydroisomerization when preparing the hydrogenation component, for example, platinum. Hydroisomerization is 93.3-371 ° C (200-700 ゜
F), preferably at a temperature of 149 ° -288 ° C. (300-550 ° F.), at a liquid hourly space velocity of from 0.01 to 2, preferably from 0.25 to 0.50, using hydrogen and thus hydrogen to hydrocarbon The molar ratio is between 1: 1 and 5: 1. Further, the catalyst is -1.1 to 2
It can be used for isomerization of olefins using a temperature of 60 ° C (30-500 ° F).

In order to better and more fully describe the nature of the invention and the method of producing it, the following example describes the best way conceivable here.

Due to the difficulty of measuring pH during crystallization, the term pH, as used in the specification and claims, is diluted to 100: 1 weight with water before crystallization, and 5-20 minutes It refers to the pH of the reaction mixture that has equilibrated over a range of times.

Example 1 A large lot of ETS-10-type gel was
Prepared for incorporation of luminium. 1,250g N bra
Mix the Brand's sodium silicate solution well,
And 179g of NH_FourCombined with OH and 112g KF (anhydrous)
Thus, an alkaline silicate solution was formed. This solution
816g of commercial Fisher titan chloride
Solution, mix well, and add
It was blended with the previous solution using a paddle stirrer. Mixing and
110 g of NaCl and 10 g of calcination after initial gel formation
Add ETS-10 seed crystal and mix well in gel
Was. Equilibration period after 5 minutes using standard 100: 1 dilution
The pH of the later gel was found to be approximately 10.05, and the TiCl_ThreeTo
When used as a source of titanium, this pH will cause the formation of ETS-10.
Suitable for

 Small lot of ETS-10 (8-10g)
And at autogenous pressure at 200 ° C for 24 hours
Crystallized. A crystalline product is obtained, which is
ETS-4 (<10%) after drying and incredible small amount
Demonstrates impurities and major phases with the following characteristic XRD lines
D: interval (angstrom) I / I₀ 14.7 WM 7.19 WM 4.40 WM 3.60 VS 3.28 WM Example 2 A suspension of potassium fluoride in an alkaline solution was prepared as follows:
Prepared from reaction components: 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 reaction components: 326.4 g Fisher TiCl_ThreeSolution 12.8 g AlCl_Three・ 6H_TwoO Overhead stirrer for alkaline silicate solution
While mixing well, slowly mix Al / Ti solution
30 g of N to the resulting apparently homogeneous gel.
aCl and 4 g of calcined ETS-10 seeds are added, and
Mixing was continued until the mixture was homogeneous again.

The mixture of the seeded titanium aluminum silicate reaction components was autoclaved at 200 ° C. for 24 hours without autogenous pressure stirring. In this example,
The Al / Ti ratio in the mixture of reaction components was adjusted to 1/8. A crystalline product was obtained and its air-equilibrated d-spacings corresponding to those in Table 1 were as follows: d-spacings (Angstrom) I / I ₀ 14.85 WM 7.21 WM 4.42 WM 3.61 VS 3.28 MS A general upshift in d-spacing, especially for the highest d-spacing, was noted in comparison to Table 2 (ETS-10).

Example 3 According to the procedure of Example 2, an alkaline silicate solution
Was prepared from the following reaction components: 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 reaction components: 326.4 g Fisher TiCl_ThreeSolution 25.6 g AlCl_Three・ 6H_TwoO Alkaline silicate solution and mixed Al / Ti solution
Is mixed well using an overhead stirrer, and then
The resulting gel has 20 g of NaCl and 4 g of calcined ETS-10.
Seed crystals were added.

The mixture of the seeded titanium aluminum silicate reaction components was autoclaved at 200 ° C. for 24 hours without autogenous pressure stirring. In this example,
The Al / Ti ratio in the mixture of reaction components was adjusted to 1/4. A crystalline product was obtained and its air-equilibrated d-spacings corresponding to those in Table 1 were as follows: d-spacings (Angstrom) I / I ₀ 14.88 WM 7.22 W 4.45 W -M 3.61 VS 3.285 MS Again, some of the d-spacings demonstrate a measurable upshift compared to both the previous example with less aluminum addition and the ETS-10 in Table 2.

Example 4 According to the procedure of Example 2, an alkaline silicate solution
Was prepared from the following reaction components: 502.4 g N Branded sodium silicate 96.6 g NaOH 46.4 g KF (anhydrous) A mixed Al / Ti solution was prepared from the following reaction components: 326.4 g Fisher TiCl_ThreeSolution 38.4 g AlCl_Three・ 6H_TwoO Alkaline silicate solution and mixed Al / Ti solution
Is mixed well using an overhead stirrer, and then
The resulting gel has 10 g of NaCl and 4 g of calcined ETS-10.
Seed crystals were added.

The mixture of the seeded titanium aluminum silicate reaction components was autoclaved at 200 ° C. for 24 hours without autogenous pressure stirring. In this example,
The Al / Ti ratio in the mixture of reaction components was adjusted to 3/8. A crystalline product was obtained and its air-equilibrated d-spacings corresponding to those in Table 1 were as follows: d-spacings (angstrom) I / I ₀ 14.97 WM (7.2 no longer observed 4.44 WM 3.63 VS 3.30 MS Again, some of the d-spacings show measurable upshifts compared to both the previous example with less aluminum addition and ETS-10 in Table 2. Demonstrate. The peak at 7.2 ° associated with ETS-10 is no longer observed.

Example 5 Preparation of alkaline silicate solution from the following reaction components
Done: 502.4g N Brand sodium silicate 105.0 g NaOH 46.4 g KF (anhydrous) A mixed Al / Ti solution was prepared from the following reaction components: 326.4 g Fisher TiCl_ThreeSolution 51.2 g AlCl_Three・ 6H_TwoO Alkaline silicate solution and mixed Al / Ti solution
Is mixed well using an overhead stirrer, and then
To the resulting gel was added 4 g of calcined ETS-10 seeds.
Was.

The mixture of the seeded titanium aluminum silicate reaction components was autoclaved at 200 ° C. for 24 hours without autogenous pressure stirring. In this example,
The Al / Ti ratio in the mixture of reaction components was adjusted to 1/2. A crystalline product was obtained and its air-equilibrated d-spacings corresponding to those in Table 1 were as follows: Again, some of the d-spacings demonstrate a measurable upshift compared to both the previous example with less aluminum addition and the ETS-10 in Table 2. The peak at 7.2 ° associated with ETS-10 is no longer observed again.

Example 6 Alkaline silicate solution was prepared from the following reaction components
Done: 502.4g N Brand sodium silicate 121.7 g NaOH 46.4 g KF (anhydrous) A mixed Al / Ti solution was prepared from the following reaction components: 326.4 g Fisher TiCl_Three76.8 g of AlCl solution_Three・ 6H_TwoO Alkaline silicate solution and mixed Al / Ti solution
Is mixed well using an overhead stirrer, and then
The resulting gel has 20 g of NaCl and 4 g of calcined ETS-10.
Seed crystals were added.

The mixture of the seeded titanium aluminum silicate reaction components was autoclaved at 200 ° C. for 24 hours without autogenous pressure stirring. In this example,
The Al / Ti ratio in the mixture of reaction components was adjusted to 3/4. A crystalline product was obtained and its air-equilibrated d-spacings corresponding to those in Table 1 were as follows: The XRD spectrum now up-shifts to a point, at which point both the highest (here, 15.06 °) and the strongest (here, 3.67 °) peaks are within the limits specified for ETS-10 in Table 2. No longer exists. The peak at 7.2Å is no longer observed again.

Example 7 Preparation of alkaline silicate solution from the following reaction components
Done: 502.4g N Branded sodium silicate 138.4 g NaOH 46.4 g KF (anhydrous) A mixed Al / Ti solution was prepared from the following reaction components: 326.4 g Fisher TiCl_ThreeSolution 102.4 g AlCl_Three・ 6H_TwoO Alkaline silicate solution and mixed Al / Ti solution
Is mixed well using an overhead stirrer, and then
To the resulting gel was added 4 g of calcined ETS-10 seeds.
Was.

The mixture of the seeded titanium aluminum silicate reaction components was autoclaved at 200 ° C. for 24 hours without autogenous pressure stirring. In this example,
The Al / Ti ratio in the mixture of reaction components was adjusted to 1/1. A crystalline product was obtained and its air-equilibrated d-spacings corresponding to those in Table 1 were as follows: The XRD spectrum now up-shifts to a point at which both the highest (here, 15.25 °) and strongest (3.68 °) peaks are no longer within the limits specified for ETS-10 in Table 2. do not do. The peak at 7.2Å is no longer observed again.

Conclusions from Examples 1-7 Systematic addition of aluminum to the ETS-10-like synthesis mixture increases the d-spacing between planes to a point, at which point, at sufficient aluminum levels, the maximum and strongest d-spacings The spacing has risen above the limit for the claimed ETS-10; The systematic rise is shown graphically in FIGS. 1 and 2 for lead and the strongest peak, respectively. Such a systematic rise is taken as a glimpse of the incorporation of elemental frameworks in classical zeolite synthesis, as well as roughly excess potential analytical errors.

As in the case of the molecular sieve with all the other titanium we have observed, the phase formation of ETAS-10 is pH dependent. In the case of ETAS-10, the appropriate range of pH for formation depends on the degree of aluminum incorporation desired. At most levels of aluminum incorporation, EST-4 (US patent application Ser.
No., filed September 8, 1987, and claimed) would form in the absence of aluminum. The pH utilized for ETAS formation is higher than the level associated with ETS-10 formation. The increased pH due to the presence of aluminum causes ETAS-10 to grow much faster and at potentially lower temperatures than can be established for ETS-10. The pH levels for Examples 1-8 are shown in Table 4.

Example 8 In this example, all the relevant reactants (alumina, titania and silica) used in Examples 1 to 7 are replaced. The overall reaction ratio is similar to Example 7 (i.e., reaction component Al / Ti = 1).

An alkaline silicate solution was prepared by combining the following reaction components: 280 g of sodium-disilicate solution (SDS) 45.0 g of NaOH 23.2 g of KF (anhydrous) 30.0 g of deionized water To this solution was added 192.0 g of deionized water slowly added 1.27 mol of TiCl ₄ solution in HCl in 20% by weight. After compounding, a gel formed, to which 20 g of sodium aluminate was added and compounded. The resulting mixture was autoclaved at 200 ° C. under autogenous pressure for 24 hours and a crystalline product was obtained, the XRD line of which was prepared using the product of Example 7 (different silica, titania and alumina sources) ). When these figures are compared, essentially the same
3 shows the ETAS-10 product.

This example demonstrates that ETAS-10 can be prepared from various silicas.

Example 9 This example establishes that as the aluminum content of the ETAS-10 reaction mixture increases, the aluminum content of the overall product increases proportionally. As is common in the synthesis of molecular sieves, the crystalline products of Examples 1 to 8 contain a mixed phase, with the ETAS-10 phase accounting for the major proportion (Examples 2 to 8). The most common pollutant found was EST-4.

Wash some samples and dry (es1,2,
5 and 7), these samples contain most of the desired crystalline phases (estimated to be> 85%), which are analyzed by X-ray fluorescence to determine the overall product composition did.

This analysis yielded the following results: It is common in zeolite synthesis that the addition of the added element is not necessarily linear with the addition. However, contamination is often a linear function of some reaction components (li
near function). Such a tendency is shown graphically in FIGS. 3 and 4.

This example establishes that the added aluminum is substantially incorporated into the overall product of the ETAS-10 synthesis mixture. In all cases, the exchangeable cation of the reaction product was estimated to be 2 (Ti) +1 (Al).

Thus, if titanium (Ti) has a charge of −2 and aluminum (Al) has a charge of −1, the ratio of (balancing cation) / (2 × titanium content + 1 × aluminum content) is pure Will approach 1.0 for most materials.

The purest sample, the product of Example 5, was found to demonstrate the following cation / site balance when synthesized: (Na + K) / (2Ti + Al) = 0.97 For example, it is readily interchangeable with, for example, ammonium and there is little or no change in the XRD spectrum, as is evident from the following table showing the exchange of ammonium. Data for magnesium and calcium are shown below.

Example 10 The product of Example 5 was contacted with a 10% by weight solution of magnesium chloride for 0.5 hour at 100 ° C. After washing with deionized water and calcining at 500 ° C. for 1 hour and re-equilibrating in air, the crystalline product had the following d-spacings: The composition of the elements was as follows (% by weight): SiO ₂ 60.76 TiO ₂ 18.96 Al ₂ O ₃ 5.60 Na ₂ O 5.82 K ₂ O 3.62 MgO 5.47 2Mg + Na + K / (2Ti + Al) = 0.92 EXAMPLE 11 Example 7 The product was contacted with a 10% by weight solution of magnesium chloride for 0.5 hour at 100 ° C. After washing with deionized water and calcining at 500 ° C. for 1 hour and re-equilibrating in air, the crystalline product had the following d-spacings: The composition of the elements was as follows (% by weight): SiO ₂ 56.20 TiO ₂ 17.30 Al ₂ O ₃ 9.85 Na ₂ O 9.32 K ₂ O 3.09 MgO 4.64 2Mg + Na + K / (2Ti + Al) = 0.95 Example 12 Example 5 The product was contacted twice with a 5% by weight solution of calcium chloride dihydrate at 100 ° C. for 0.5 hours.
After washing with deionized water and calcining at 200 ° C. for 1 hour and re-equilibrating in air, the crystalline product had the following d-spacings: The composition of the elements was as follows (% by weight): SiO ₂ 59.93 TiO ₂ 19.23 Al ₂ O ₃ 5.69 Na ₂ O 1.61 K ₂ O 2.76 CaO 11.31 2Ca + Na + K / (2Ti + Al) = 0.92 Example 13 Coordination of aluminum Can be deduced to be four-sided from the cation balance of the previous example, but ²⁷ Al N
Using MR, whether Al is tetrahedral or octahedral, and if it is incorporated into the molecular sieve,
As expected, it can be more clearly established whether it is "skeleton" aluminum. Almost
²⁷ Al MAS of a sample of ETAS-10 containing 7.2% by weight Al ₂ O ₃
The NMR spectrum is shown in FIG. The peak at 58 ppm indicates tetrahedral framework aluminum. No octahedral aluminum was observed and the small peak at -6 ppm was interpreted as a spinning side band.

This example establishes that all aluminum incorporated into the overall reaction product of the ETAS-10 reaction mixture forms as tetrahedral skeletal sites. This example does not exclude the possibility of a mixed phase, including the possibility of an alumino-silicate zeolite co-forming with ETS-10 in an ETAS-10 reaction mixture.

Example 14 The ETAS-10 sample from the previous example is subjected to a standard SEM / EDS analysis. The morphology of the major crystal species (established as ETAS-10 from XRD) was found to be a thin, flat-split soul, markedly different from the nearly cubic-shaped crystals characteristic of ETS-10 . Spot elemental analysis of the sample showed that aluminum was uniformly associated with crystals having both high titanium and high silicon levels.
No significant aluminum-containing souls or crystals were observed, which was also substantially free of the observed titanium, ie, no alumino-silicate phase was observed.

According to this example, the aluminum incorporated into the overall reaction product of the ETAS-10 reaction mixture forms as crystalline titanium-aluminum-silicate and as crystalline titanium-silicate and classical alumino-silicate zeolite. Not established.

Conclusions from Examples 9-14 Examples 9-14 establish that aluminum is incorporated as a tetrahedral framework into the crystalline titanium-aluminum-silicate phase during the crystallization of the ETAS-10 reaction mixture.

Example 15 The entire product of Examples 1, 5 and 8 is ammomium exchanged, activated at 350 ° C. under vacuum and exposed to xenon under a pressure of 530 torr. The xenon-treated sample was then subjected to ¹²⁹ Xe NMR. Although some crystallinity has been lost, the spectra of these materials are shown in FIG. ETS-10 of Example 1 shows a clear spectrum with a peak at 119.3 ppm. The incorporated aluminum dramatically shifts the position of this peak. The product of Example 5 is 13
It shows a clear single peak at 7.6 ppm,
ETAS-10 is a single crystalline phase and is established to be easily discriminated from ETS-10 of Example 1 by standard analytical techniques. When the aluminum level was substantially increased in Example 8, an additional 2 ppm primary peak was raised for the first time (to 139.8) and the characteristic peak position for ETAS-10 was reduced to the aluminum level incorporated under the stated test conditions. Regardless, it clearly demonstrates that ETS-10 covers a relatively small area, well away from the characteristic area.

Example 16 The ²⁹ Si MAS NMR spectra of ETS-10 and ETAS-10 of Example 10 are shown in FIG. The ETS-10 spectrum is -1
Shows three distinct silica environments as evidenced by peaks at 04, -96 and -94 ppm. ETAS-10
Spectra demonstrate these environments plus at least two new highly clustered environments, as evidenced by additional significant peaks at -96 and -90 ppm.
Such new environments would be expected if silica and aluminum were incorporated in the same crystal. ET
Since AS-10 was established as a single phase, the incorporation of aluminum impacted the silica sites of the structure,
Using additional standard analytical methods, ETS-10 and ETA
S-10 can be easily distinguished.

Results from Examples 15 and 16 As these examples demonstrate, the ETAS
The -10 sample represents a single distinct phase that can be easily distinguished from ETS-10 by various standard analytical methods.

Example 17 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 adsorption capacity of 6.4% by weight was observed for this synthesized and mixed Na ⁺ / K ⁺ material. The synthesized and mixed Na ⁺ / K ⁺ ETS-10 was observed to be essentially non-adsorbing to 1,3,5-trimethylbenzene, and this molecule was found in the pores of the synthesized ETS-10. It was slightly larger than the opening.

As this example demonstrates, the opening of the ETAS-10 hole is
Slightly larger than ETS-10. This is consistent with the lattice expansion observed in Examples 1-8 where aluminum is incorporated into the reaction mixture.

Example 18 The products of Examples 1 and 5 are air-equilibrated and TG
Dewatering was performed at 10 ° / min in the A apparatus. ETS-10 is a weak, mode I, moderate adsorbent for small polar molecules and loses water rapidly at slightly higher temperatures than 100 ° C. Under equivalent conditions, the ETS-10 of Example 5
Lost most of the water adsorbed only after a significant drop at approximately 250 ° C. As this demonstrates, only when 3.9% by weight of Al ₂ O ₃ is incorporated does the electrostatic field inside the material change significantly and tightly bind small polar molecules such as water.

Conclusions from Examples 17 and 18 As these two examples demonstrate, ETAS-10 has a somewhat larger pore and an entirely different internal electrostatic environment than ETS-10. These two points are described in Examples 1 to
The lattice expansion observed in 8 and the well-defined xenon shift of Example 14 (possibly indicating a very strong xenon / site interaction) and the new silica environment of Example 16 are completely consistent.

Examples 19-23 In these examples, ETAS-10 was a "standard" ETS
It demonstrates that it is not as simple as adding an aluminum source to the synthesis mixture of −10 and subsequent crystallization. Depending on the desired degree of aluminum incorporation, a particular pH level must be in place during the formation of the reaction component gel. In these examples, if the addition of aluminum is performed at the wrong gel pH, the ETAS- by rebalancing to the appropriate level for the formation of ETAS-10
The formation of 10 proves to be at best difficult.

Separating the sample of 200g of ETS-10 of Example 19 Example 1 from a large lot, and AlCl ₃ · 6H reagent grade 20.8g this sample
₂ O was added so that the Al / Ti ratio was approximately 1.0 as in Examples 7 and 8. The sample was mixed well and the "pH" of the gel was approximately equal after a 10 minute equilibration period.
7.8, which is ETS-10 or ETAS-10
Significantly lower than the area associated with the formation of Three small samples (8-10 each) were withdrawn from the lot now having aluminum and crystallized under the conditions of the previous example for 1, 3 and 7 days, respectively. After washing and drying as described above, the XRD powder pattern shows that the reaction product is essentially amorphous (approximately 10% crystalline) and in all cases ETS-10, ETAS-10 or related phases It was revealed that a small amount of crystallization product was missing.

Separating the sample of 200g of ETS-10 of Example 20 Example 1 from a large lot, and the addition of AlCl ₃ · 6H ₂ O in 6.7g in this sample, the ratio of Al / Ti, Examples 7 and As in 8,
It was almost 1.0. The sample was well formulated and the "pH" of the gel was found to be approximately 10.1 after a 10 minute equilibration period, which was essentially unchanged from the starting ETS-10. Three small samples (8-10 each) were withdrawn from the lot now having aluminum and crystallized under the conditions of the previous example for 1, 3 and 7 days, respectively. After washing and drying as described above, XRD
The powder pattern revealed that the reaction product was highly crystalline EST-4 and lacked ETS-10, ETAS-10 or related phases.

Separating the sample of 200g of ETS-10 of Example 21 Example 1 from a large lot, and the addition of NaAlO ₂ of 7.1g in the sample, Al
/ Ti ratio was approximately 1.0 as in Examples 7 and 8.
It was made to be. The sample was well formulated and the "pH" of the gel was found to be approximately 10.7 after a 10 minute equilibration period, indicating that at this aluminum content ETAS-10
Almost ideal level for formation. Three small samples (8-10 each) were withdrawn from the lot now having aluminum and crystallized under the conditions of the previous example for 1, 3 and 7 days, respectively. After washing and drying as described above, the XRD powder pattern revealed that the reaction product was highly crystalline EST-4 and lacked ETS-10, ETAS-10 or related phases.

Example 22 To the balance of the relatively low (formation of ETAS-10) alkaline mixture of Example 20, 3.5 g of NaOH was added and the resulting mixture was well blended with an over-head stirrer. The resulting "pH" rose to approximately 10.75. A small portion (8-10 g) of the sample was crystallized for 24 hours at 200 ° C. as described above. A crystalline product is obtained, which is mainly EST-4 (estimated to be almost 80%), ETS-10 or ETA
No S-10 appearance is observed.

Example 23 To the remainder of the relatively low (formation of ETAS-10) alkaline mixture of Example 19, an additional 1.0 g of NaOH was added and the resulting mixture was better blended with an over-head stirrer. The resulting "pH" rose to approximately 10.80. A small portion (8-10 g) of the sample was crystallized for 24 hours at 200 ° C. as described above. A crystalline product is obtained, which is mainly EST
-4 (estimated to be approximately 80%) and no ETS-10 or ETAS-10 aspects are observed.

Conclusion ETAS-10 is a new wide pore titanium-aluminum-silicate molecular sieve composed of units of dicharged octahedral titanium, charged tetrahedral aluminum and neutral tetrahedral silica. Such sieves containing both charged octahedral sites and charged tetrahedral sites have not been recognized in the prior art.

Structurally titanium silicate molecular sieve ET
Involved in S-10, the incorporation of aluminum into the framework structure systematically expands the plane of the lattice and the apertures of the holes. The incorporated aluminum creates strongly polarized sites, which, in combination with the dicharged titanium sites, create a unique intercrystalline environment.

The synthesis of ETAS-10 is similar to that of ETS-10, except that a soluble aluminum source is added to the synthesis mixture and "p
"H" must be adjusted upward during gel formation depending on the aluminum level. Also, this increased alkalinity must be present at or immediately after gel formation. ETS-10 is less than the purity of the complete reactants, especially as a result of contaminants in commercial sodium silicate,
On a volatile-free basis, it contains incidental amounts of aluminum, typically 0.5% by weight of Al ₂ O ₃ . ETAS-10 as a result of deliberate aluminum incorporation into sieve in by the addition of an aluminum source to the reaction mixture, which contains substantial amounts of aluminum (about 0.5 to 10 wt% or more Al ₂ O ₃₎ .

ETAS-10 represents a new composition that can be distinguished from ETS-10 by various standard analytical techniques.

Explanation of terms Definitions, procedures and reaction components used-N Brand sodium silicate is PQ
Commercial solution obtained from Corporation. Typical
The analysis of a lot shows that almost 29% by weight of SiO_TwoAnd 9% by weight
Na_TwoO includes caustic substances, with the balance being water.

-SDS (sodium disilicate) is a sodium silicate solution that is used commercially in Engelhard FCC operations and was obtained internally. Typically, the lot analysis is approximately 27% by weight SiO ₂ and 14% by weight Na
₂ O contains caustic substances, the balance being water.

-Potassium fluoride (KF) is available from Pfaltz and Bauer, Incorporated.
c.) obtained on an anhydrous basis. The solubility of the fluoride in the silicate solution used is such that the fluoride only partially dissolves when mixed and the remainder appears to be suspended in the silicate mixture.

-CaOH (NaOH) was obtained from Fisher Scientific as an essentially anhydrous material.

-Titanium chloride solution (TiCl ₃ )
Available as Scientific 20% by weight of TiCl ₃ in the (Fisher Scientific) in 20 wt% HCl, the balance is water, produce a molar concentration of net 1.25~1.30TiCl _3.

- titanium tetrachloride (TiCl ₄₎ is alpha - Bentoron (A
lfa-Ventron) as a liquid at + 99% by weight.

- aluminum trichloride as hexahydrate salt (AlCl ₃ · 6H ₂
O) Fisher Scientific
Scientific). The aluminum trichloride is completely dissolved in the titanium (II) chloride solution, and then the mixed metal solution is incorporated into the alkaline silicate mixture.

-Sodium aluminate (NaAlO ₂ ) is available from Pfaltz and B.
auer, Inc.) on an essentially anhydrous basis. When this reactant is used as a source of aluminum, sodium aluminate is added as a solid to a freshly prepared titanium silicate gel and compounded until it clearly dissolves.

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

-The calcined seeds calcine approximately 80% ETS-10 and 15% EST-4 at temperatures above 300 ° C but below 500 ° C in a standard pilot plant run,
-4 is degraded but obtained so that ETS-10 remains intact. Species are essential for ETAS-10 formation, but appear to reduce reaction time and extend the range of acceptable gel compositions.

Well-blended refers to a gel that has been stirred by an overhead stirrer to a point where the gel appears visually homogeneous.
Although all formulations are performed at ambient temperature, acid-base reactions and base dissolution may temporarily increase the temperature of the gel.

-All the products of the examples are vacuum filtered, washed with an excess of deionized water (at least 10 cc / g) and
After drying for at least 30 minutes at, further processing or testing is performed.

-Air equilibration is performed by exposing the dried sample to ambient air for at least 1 hour.

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

-Elemental analysis is expressed on a volatile-free basis, determined by X-ray fluorescence. The X-ray fluorescence sample preparation technique used involves exposing to elevated temperatures, typically 1100 ° C. Thus, a sample represented as having been exchanged with ammonium is ideally in the hydrogen form. Because the exposure at high temperature converts the sample to the hydrogen form.

- ²⁷ Al NMR spectra (Spectra) ²⁷ Al NMR spectra MAS NMR spectroscopy, alumino - a technique using an aluminum species silicates and zeolite in order to determine characteristics. All spectra are Spectral Data Services, Inc. (Spectrum)
tral Data Services, Inc.), obtained from Campeign, Illinois. ²⁷ Al Spectra exposed the sample to a magnetic field of 8.45 tesla, and
This was done by rotating at a rate of kHz at the so-called magic angle (which reduces the anisotropy of the shield and the interaction of the two poles). Spectra averaged 3000-8000 scans, increasing resolution and signal-to-noise with a 0.3 second recycle and summing.
All samples were air-equilibrated (ie, contained adsorbed water) and then run the Spectra. Such an equilibrated sample contains 15-20% by weight of water. This equilibration creates a reproducible state of hydration and enhances the observation of ²⁷ Al MAS NMR species by increasing the sensitivity of the technique.

²⁹ Si NMR Spectra ²⁹ Si NMR Spectra MAS NMR spectroscopy is a technique used to identify silicon species in alumino-silicates and zeolites. All spectra are from Spectral Data Services, Inc.
ata Services, Inc.), obtained from Campaign, Illinois. ²⁹ Si Spectra exposes the sample to a magnetic field of 6.3 Tesla and rotates the sample at a rate of 4 kHz at the so-called magic angle (which reduces the anisotropy of the shield and the interaction of the two poles) by standard methods. It was performed by doing. Spectra averaged 200-1500 scans, increasing resolution and signal-to-noise with 80-120 second recycle and summing. All samples were air-equilibrated (ie, contained adsorbed water) and then run the Spectra. Such an equilibrated sample contains 15-20% by weight of water. This equilibration creates a reproducible state of hydration and increases the sensitivity of the technique to ²⁹ Si MAS N
Increase observation of MR species.

-Dicharged titanium-the center of titanium, when coordinated with octahedral with oxygen, generates a charge of -2. This charge arises from 6 shared oxygen atoms, and -12 / 6 =-
6 is impacted. Ti (IV) imparts a charge of +4, and the center of the titanium thus coordinated has a net charge of -2.

-Monocharged aluminum-the center of aluminum is -1 when coordinated on all sides with oxygen.
Generates a charge. This charge originates from the four shared oxygen atoms, impacting a charge of -8 / 2 = -4. Al (III) imparts a charge of +3, and the center of the titanium thus coordinated has a net charge of -1.

 The main features and aspects of the present invention are as follows.

1, having a large pore size of approximately 9 Angstroms units and a molar ratio of the following oxides: (1 + x / 2) (1.0 ± 0.25 M _{2 / n} O): TiO ₂ ; xAlO ₂ : ySiO ₂ : zH in ₂ O formula, M is at least one cation having a valence of n, y is 2.5 to 25, x is from 0.01 to 5.0, and z has a composition of 0 to 100, A) having an X-ray powder diffraction pattern as described in Table 1 of this specification, b) having one charged tetragonally coordinated aluminum in the skeleton, and c) having two A crystalline titanium-aluminum-silicate molecular sieve, characterized by having titanium coordinated on eight charged sides.

2. The molecular sieve according to the above item 1, wherein y is from 3.0 to 10.

3. The molecular sieve of claim 1, wherein M is a mixture of sodium and potassium.

4. The molecular sieve of claim 1, wherein at least a portion of M is hydrogen.

5. The molecular sieve of claim 1, wherein at least a portion is a rare earth.

6. A method for converting an organic compound, which comprises contacting the organic compound with the molecular sieve described in the above item 1 under conversion conditions.

7. A method for catalytically cracking hydrocarbons, which comprises contacting hydrocarbons with the molecular sieve described in item 1 at an elevated temperature.

8. A method for reforming naphtha, which comprises contacting naphtha with the molecular sieve according to item 4 in the presence of added hydrogen and a hydrogenation / dehydrogenation component.

9. A method for reforming naphtha, which comprises contacting naphtha with the molecular sieve according to item 5 in the presence of added hydrogen and a hydrogenation / dehydrogenation component.

10. A method for removing divalent ions from a solution, comprising bringing a solution containing divalent ions into contact with the molecular sieve according to the above item 1.

11. A method for removing polyvalent ions from a solution, comprising bringing a solution containing polyvalent ions into contact with the molecular sieve according to the above item 2.

12. A method for removing polyvalent ions from a solution, comprising contacting the solution containing polyvalent ions with the molecular sieve according to the above item 3.

13. A method for removing polyvalent ions from a solution, comprising bringing a solution containing polyvalent ions into contact with the molecular sieve according to the above item 4.

14. The method according to the above item 10, wherein the polyvalent ion is Pb ^{+ 2} .

15. The method according to the above item 11, wherein the polyvalent ion is Pb ^{+ 2} .

16. The method according to the above item 12, wherein the polyvalent ion is Pb ^{+ 2} .

17. The method according to the above item 13, wherein the polyvalent ion is Pb ^{+ 2} .

[Brief description of the drawings]

1 and 2 are graphs showing the systematic addition of aluminum to an ETS-10-like synthesis mixture. FIG. 3 and FIG. 4 are graphs showing the mixing of the added elements. FIG. 5 is a ²⁷ Al MAS NMR spectrum of a sample of ETAS-10 containing approximately 7.2% by weight Al ₂ O ₃ . FIG. 6 is a ¹²⁹ Xe NMR spectrum of the sample treated with xenon. FIG. 7 shows ²⁹ Si MA of ETS-10 and ETAS-10 of Example 10.
It is an S NMR spectrum.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI C07C 5/25 C07C 5/25 5/27 5/27 9/00 9/00 11/02 11/02 es Keruma United States Niyujiyajii York 07068 Roseland Stone gate drive 37 (72) inventor Kiyasurin TA-Suratsushiyu United States, Pennsylvania 18042 Easton Hui Tsu Tonii suberythemal you 1206 (58) investigated the field (Int.Cl. ⁷ , DB name) C01B 39/00-39/54 B01J 20/18

Claims (13)

(57) [Claims] Claims 1. A large pore size of 9 angstroms units and a molar ratio of the following oxides: (1 + x / 2) (1.0 ± 0.25M _{2 / n} O): TiO ₂ : xAlO ₂ : ySiO ₂ : zH in ₂ O formula, M is at least one cation having a valence of n, y is 2.5 to 25, x is from 0.01 to 5.0,
And z is from 0 to 100. a) Measured by a standard X-ray diffraction method (0 to 40
°, 2θ) In the table, VS = 60 to 100 S = 40 to 60 M = 20 to 40 W = 5 to 20 The powder has an X-ray powder diffraction pattern as shown in the following table. C) crystalline titanium-aluminum-silicate molecular sieves characterized in that they have di-charged octahedral coordinated titanium in the skeleton. 2. The molecular sieve according to claim 1, wherein y is 3.0 to 10. 3. The molecular sieve according to claim 1, wherein M is a mixture of sodium and potassium. 4. The molecular sieve of claim 1, wherein at least a portion of M is hydrogen. 5. The molecular sieve according to claim 1, wherein at least a part of M is a rare earth. 6. A method for converting an organic compound, comprising bringing the organic compound into contact with the molecular sieve according to claim 1 under conversion conditions. 7. A method for catalytically cracking hydrocarbons, comprising contacting a hydrocarbon with a molecular sieve according to claim 1 at an elevated temperature. 8. A method for reforming naphtha, which comprises contacting naphtha with a molecular sieve according to claim 4 in the presence of added hydrogen and a hydrogenation / dehydrogenation component. 9. A method for reforming naphtha, which comprises contacting naphtha with a molecular sieve according to claim 5 in the presence of added hydrogen and a hydrogenation / dehydrogenation component. 10. A method for removing divalent ions from a solution, the method comprising contacting the solution containing divalent ions with the molecular sieve according to claim 1. 11. A method for removing polyvalent ions from a solution, comprising contacting a solution containing polyvalent ions with a molecular sieve according to claim 2. 12. A method for removing polyvalent ions from a solution, comprising contacting a solution containing polyvalent ions with a molecular sieve according to claim 3. 13. A method for removing polyvalent ions from a solution, comprising contacting a solution containing polyvalent ions with a molecular sieve according to claim 4.