CA2111358C - Synthetic crystalline zeolite, its synthesis and use - Google Patents

Abstract

A synthetic crystalline zeolite, MCM-49, has in its as-synthesized form an X-ray diffractian pattern including values sub-stantially as set forth in table (1).

Description

sTlc cRYST~zNE zEO~TE, ITS s~szs ~rrn vsE
This invention relates to a synthetic crystalline zeolite, to a method for its synthesis and to its use in catalytic conversion of organic compounds.

Zeolitic materials, both natural and synthetic, have been demonstrated in the past to have catalytic properties for various types of hydrocarbon conversion.

certain zeolitic materials are ordered, porous crystalline aluminosilicates having a definite crystalline structure as determined by X-ray diffraction, within which there are a large number of smaller cavities which may be interconnected by a number of still smaller channels or pores. These 1.5 cavities and pores are uniform in size within a specific zeolitic material. Since the dimensions _of these pores are such as to accept for adsorption molecules of certain dimensions while rejecting those of larger dimensions, these materials have come to be known as "molecular sieves" and are utilised in a variety of ways to take advantage of these properties.

Such molecular sieves, both natural and synthetic, .include a wide variety of positive ion-containing crystalline silicates. These silicates~can be described as a rigid three-dimensional framework of Si04 and Periodic Table Group IIIA element oxide, e.g.

Al~4, in which the tetrahedra are cross-linked by the sharing of oxygen atoms whereby the ratio of the total Group IIIA element, e.g. alum~.num, and silicon atoms to oxygen Moms is 1:2. The electrovalence of the tetrahedra containing the Group IIIA element, e.g.

aluminum, is balanced by the inclusion in the crystal of a cation, for example an alkali metal or an alkaline earth metal canon. This can be expressed wherein the ratio of the Group IIIA element, e.g. aluminum, to the number of various canons, such as Ca/2, Sr/2, Na, K or WO 92/22498~ ~ ~ ~ ~ -2 P~.T/US92/p5198 Li, is equal to unity. One type of ration may be exchanged either entirely or partially with another type of ration utilizing ion exchange techniques in a conventional manner. By means of such ration exchange, it has been possible to vary the properties of a given silicate by suitable selection of the ration. The .

spaces between the tetrahedra are occupied by molecules of water prior to dehydration.

Prior art techniques have resulted in the formation of a great variety of synthetic zeolites..

Many of these zeolites have come to be designated by letter or other convenient symbols, as illustrated by zeolite A (U. S. Patent 2,882,243): zeolite X (U. S.

Patent 2,882,244); zeolite Y (U. S. Patent 3,130,007);

zeolite ZK-5 (U.S. Patent 3,247,195); zeolite ZK-4 (U. S. Patent 3,314,752); zeolite ZSM-5 (U. S. Patent 3,702,886); Zeolite ZSM-11 (U. S. Patent 3,709,979);

zeolite ZSM-12 (U.S. Patent 3,832,449), zeolite Z'SM-20 (U. S. Patent 3,9.72,983); 2SM-35 (U. S. Patent 4,016,245); zeolite ZSM-23 (U. S. Patent 4,076,842);

zeolite MCM-22 (U. S. Patent 4,954,325); and zeolite MCM-35 (U.S. Patent 4,981,663).

U.S. Patent 4,439,409 refers to a zeolite named PSH-3 and its synthesis from a reaction mixture c~ntaining liexamethyleneimine. ~iexamethyleneimine is also used for synthesis of zeolite MCM-22 in U.S.

Patent 4,954,325; zeolite MCM-35 in U.S. Patent 4,981,663; and zeolite ZSM-12 in U.S. Patent 5,021,141.

The present invention is directed to a synthetic crystalline zeolite, referred to herein as MCM-49, which is structurally related to, but different from, MCM-22.

Accordingly, the invention resides in a synthetic crystalline zeolite having, in its as-synthesized form, .

an X-ray diffraction pattern including values substantially as set forth in Table I below.

WO 92/22498 PC.'T1U~92/ii5198 _3_ ~~~~a~~ , The invention will now be more particularly described with reference to the accompanying drawings, in which Figure la shows a segment of the X-ray diffraction pattern of the as-synthesized precursor of MCM-22 from a repeat of Example 1 of U.S. Patent 4,954,325, Figure 1b shows a segment of the X-ray diffraction pattern of the as-synthesized crystalline material product of Example 7 of the present invention, Figure 1c shows a segment of the X-ray diffraction pattern of the calcined MCM-22 from a repeat of Example 1 of U.S. Patent 4,954,325, Figures 2-7 are X-ray diffraction patterns of the as-synthesized crystalline material products of the present Examples 1, 3, 5, 7, 8, and 11, respectively, and, Figure 8 compares the 27A12 MAS NMR spectra of calcined MCM-22 and calcined MCM-49.
The zeolite of the present invention, MCM-49, is characterized in its as-synthesized form by an X-ray diffraction pattern including the lines .listed in Table 1 below:
TAMIaE I
Interplanar d-Spacino (A) Relative Intensity, IC~o_x 100 13.15 ~ 0.26 w-s*
12.49 ~- 0.24 vs 11.19 ~ 0.22 m-s 6.43 ~ 0.12 w 4.98 ~ p.10 w 4.69 ~ 0.09 w 3.44 ~ 0.07 vs 3.24 ~ 0.06 w shoulder.
The X-ray diffraction peak at 13.15 _+ 0.26 Angstrom Units (A) is usually not fully resolved for MCM-49 from the intense peak at 12.49 + 0.24, and is observed as a shoulder of this intense peak. For this reason, the precise intensity and position of the 13.15 WO 92/22498 ~ ' '' ' ~ -4 PCT/US92/05198 + 0.26 Angstroms peak are difficult to determine within the stated range.
On calcination, the crystalline MCM-49 material of the invention transforms to a single crystal phase with little or no detectable impurity crystal phases having an X-ray diffraction pattern which is not readily distinguished from that of MCM-22 described in U.S.
Patent 4,954,325, but is distinguishable from the patterns of other known crystalline materials. The X-ray diffraction pattern of the calcined form of .
MCM-49 includes the lines listed in Table II below:
TABLE II
I_ntert~lanar d-Soacinq ~A) Relative Intensity, IJIo x 100 12.41 0.24 ' vs 11.10 0.22 ~ s 8.89 0.17 m-s 6.89 0.13 w 6.19 0.12 m 6.01 0.12 w 5.56 D.11 w 4.96 0.10 w 4.67 0.09 w 4.59 0.09 w 4.39 0.09 w 4.1a o.0a w 4.07 0.08 W-m 3.92 o.0a w-m 3.75 ~ 0.07 w-m 3.57 0.07 w 3.43 0.07 s-ors 3.31 0.06 w 3.21 -~ 0.06 w 3.12 0.06 w 3.07 0.06 w 2.83 0.05 w 2.78 0.05 w 2.69 0.05 w 2.47 0.05 w 2.42 0.05 w .

2.38 0.05 w These X-ray diffraction data were collected with a Scintag diffraction system, equipped with a germanium solid state detector, using copper K-alpha radiation.

The diffraction data were recorded by step-scanning at 0.02 degrees of two-theta, where theta is the Bragg angle, and a counting tune of 10 seconds for each step.

The interplanar spacings, d's, were calculated in Angstrom units (A), and the relative intensities of the lines, I/I
is one-hundredth of the intensity of the o strongest line, above background, were derived with. the use of a profile fitting routine (or second derivative algorithm). The intensities are uncorrected for Lorentz and polarization effects. The relative intensities are given in terms of the symbols vs = very strong (60-100), s = strong (40-60), m = medium (20-40) and w = weak (0-20).

The significance of the differences in the X-ray diffraction patterns of as-synthesized and calcined materials can be explained from a knowledge of the structures of the related materials MCM-22 and PSH-3.

Thus MCM-22 and PSH-3 are members of an unusual family of materials because, upon calcination,~there are changes in the X-ray diffraction pattern that can be explained by a significant change in one axial dimension. This is indicative of a profound change in the bonding within the materials and not a simple loss of the organic material. The precursor members of this family can be clearly distinguished by %-ray diffraction from the calcined members. An examination of the X-ray diffraction patterns of both precursor and calcined forms shows a number of reflections with very similar position and intensity, while other peaks are different. Some of these differences are directly related to the changes in the axial dimension and bonding.

The present as-synthesized MCM-49 has an axial dimension similar to those of the calcined members of ay r' ~i.F' , k.
~ y ~ , ~.5" ., , 1. .:
,:.s ,, w ~
~ o~-~- c.:~ .. , 1, r , z. . ., h ...
a . . . ~ . .. , a.-- . . ., .a ., . . .. . . a . .. ..~_ . . ~.,~s..SL' ...:-.x ..,.... . . .s ....:::~.~-..:, . t.:.. ,:.a.
... ,. , ..t<.3.'"14.... . ". . .., .a .:~: ~".4'::::fi~r_'.i.$~. ..u~.a......
4~...4,;.~... _.. ., ~... ., .. . . , ._ 'zl~.i3~~
the family and, hence, there are similarities in their X-ray diffraction patterns. Nevertheless, the MCM-49 axial dimension is different from that observed in the calcined materials. For example, the changes in axial -dimensions in MCM-22 can be deteranined from the positions of peaks particularly sensitive to these -changes. Two such peaks occur at - 13.5 Angstroms and -~ 6.75 Angstroms in precursor MCM-22, at - 12.8 Angstroms and - 6.4 Angstroms in as-synthesized MCM-49, and at - 12.6 Angstroms and - 6.30 Angstroms in calcined MCM-22. Unfortunately, the - 12.8 Angstroms peak in MCM-49 is very close to the intense - 12.4 Angstroms peak observed for all three materials, and is frequently not fully separated from it. Likewise, the - 12.6 Angstroms peak of the calcined MCM-22 material is usually only visible ~as a shoulder on the intense 1.2.4 Angstroms peak.. Figure 1 shows the same segment of the diffraction patterns of precursor MCM-22, calcined MCM-22,. and MCM-49; the position of the -6.6-6.3 Angstroms peak is indicated in each segment by an asterisk. Because the - 5.4 Angstroms peak is unobscured in MCM-49, it was chosen as abetter means of distinguishing MCM-49 from the calcined forms of MCM-22 and PSH-3 rather than the much stronger - 12.8 Angstroms peak.

As shown in Figure 8, a difference between calcined MCM-49 and calcined MCM-22 can be demonstrated by 27A1 MAS IJMR. ?then calcined completely to remove the organic material used to direct its synthesis, (Figure 8D) MCM-49 exhibits a 27A1 MAS NMR

spectrum different from that of fully calcined MCM-22 (Figure 8A). In each case, calcination is effected at 538'C for 16 hours, The NMR spectra are obtained using a Bruker MSL-400 spectrometer at 104.25 MHz with 5.00 IQiz spinning speed, 1.0 ass excitation pulses (solution ~r/2 = 6,us,, and O.1S recycle times. The number of transients obtained for each sample is 2000 and the WO 92/22498 ~~ PGT/US92/d5198 ~~.:~1~~,~~
2~A1 chemical shifts are referenced to a 1M aqueous solution of A1(N03)2 at 0.0 ppm. As shown in Figures 8B and 8C, fully calcined MCM-22 exhibits a 2~A1 MAS

NMR spectrum in which the Td AL region can 'be simulated as comprising 3 peaks centered at 61, 55 and 50 ppm having approximate relative areas of 10:50:40.

In contrast, fully calcined MDM-49 exhibits a 2~A1 MAS

NMR spectrum in which the Td Al region can be simulated as comprising the 3 peaks center at 61, 55, and 50 ppm but having approximate relative areas of .

20:45:35, together with a fourth broad peak centered at 54 ppm (Figures 8E and 8F). Formation of the broad Td component does not appear to be dependent on the calcination environment (air or nitrogen). Calcined MCM-49 also exhibits distinctly different catalytic properties than calcined MCM-22.

The crystalline material of this invention has a composition comprising the molar relationship:

X203:(n)Y02, wherein X is a trivalent element, such as aluminum, boron, iron and/or gallium, preferably aluminum; Y is a tetravalent element such as silicon and/or germanium, preferably silicon: and n is less than 35, preferably from 11 to less than 20, most preferably from 15 to less than 20. More specifically, the crystalline material of this invention has a formula, on an anhydrous basis and in terms of moles of oxides per n moles of Y02, as follows:

(0.1-0.6)M20:(1-4)R:X203:nY02 wherein M is an alkali or alkaline earth metal, and R

is an organic directing agent. The M and R components are associated with the material as a result of their presence during crystallization, and are easily removed by post-crystallization methods hereinafter more particularly described.

The crystalline material of the invention is thermally stable and in the calcined form exhibits high WO 92/22498 . 8 PCTlUS92/05i98 '~ 11158 ~ .
surface area (greater than 400 m2/gm) and an Equilibrium Adsorption capacity of greater than 10 wt.%
for water vapor, greater than 4.3 wt.%, usually greater than 7 wt.%, for cyclohexane vapor and greater than 10 wt . % f or n-hexane vapor .
The present crystalline material can be prepared from a reaction mixture containing sources of alkali or alkaline earth metal (M), e.g. sodium or potassium, cation, an oxide of trivalent element X, e.g. aluminum, an oxide of tetravalent element Y, e.g. silicon, organic directing agent (R), and water, said reaction mixture having a composition, in terms of mole ratios of oxides, within the following ranges:
Reactants Broad Preferred Z5 YO2/X203 Z2 to <35 15 to 25 H20/Y02 10 to 70 15 to 40 OH-/Y02 0.05 to 0.50 0.05 to 0.30 M/Y02 0.05 to 3.0 0.05 to 1:0 R/Y02 . 0.2 to 1.0 0.3 to 0.5 In the present synthesis method, the source of Y02 should predominately be solid YO2, for example at least about 30 wt.% solid Y02, in order to obtain the crystal product of the invention. Where YO~ is silica, the use of a silica source containing at least about 30 wt.%
solid silica, e.g. Llltrasil (a precipitated, spray dried silica containing about 90 wt.% silica) or HiSil (a precipitated hydrated SiO2 containing about 87 wt.%
silica, about 6 wt.% free H2O and about 4.5 wt.% bound H20 of hydration and having a particle size of about 0.02 micron) favors crystalline MCM-49 formation from the above mixture. Preferably, therefore, the Yc~2, e.g. silica, source contains at least about 30 wt.%
solid YO2, e.g. silica, and more preferably at least about 40 wt.% solid Y02, e.g. silica.
The directing agent R is selected from the group consisting of cycloalkylamine, azacycloalkane, diazacycloalkane, and mixtures thereof, alkyl V1~0 92/22498-g PCTlUS92/OSt98 )~

comprising from 5 to 8 carbon atoms. Non-limiting examples of R include cyclopentylamine, cyclohexylamine, cycloheptylamine, hexamethyleneimine, heptamethyleneimine, homopiperazine, and combinations thereof. However, in the case of hexamethyleneimine, it is found that pure MCM-49 can only be produced within the narrow silica/alumina range of 15 to less than 20, since above this range the product contains at least some MCM-22. Thus when R is hexamethyleneimine, the Y02/X203 range in the reaction mixture composition tabulated above should be 15 to 25.

The R/M ratio is also important in the synthesis of MCM-49 in preference to other crystalline phases, such as MCM-22, since it is found that MCM-49 is favored when the R/M ratio is less than 3 and preferably is less than ~l.

Crystallization of the present crystalline material can be carried out at either static or 'stirred conditions in a. suitable reactar vessel, such as for example, polypropylene jars or teflon lined or stainless steel autoclaves. Crystalli2ation is generally performed at a temperature of'~80C to 225C

for a time of 24 hours to 60 days. Thereafter, the crystals are separated from the mother liquid and recovered.

It should be realized that the reaction mixture components can be supplied by more than one source. The reaction mixture can be prepared either batchwise or continuously. Crystal size and crystallization time of the new crystalline material will vary with the nature of the reaction mixture employed and the crystallization conditions.

Synthesis of the new crystals may be facilitated by the presence of at least 0.01 percent, preferably 0.10 percent and still more preferably 1 percent, seed crystals (based on total weight) of crystalline WO 92/22498 ~ ~ ~ ~ ~ ~ ~ ' lo- PCT/US92/U5198 product. Useful seed crystals include MCM-22 and/or MCM-49.
To the extent desired, the original sodium cations of the as-synthesized material can be replaced in accordance with techniques well known in the art, at least in part, by ion exchange with other cations.

Preferred replacing cations include metal ions, hydrogen ions, hydrogen precursor, e,g. ammonium, ions and mixtures thereof. Particularly preferred cations are those which tailor the catalytic activity for certain hydrocarbon conversion reactions. These include hydrogen, rare earth metals and metals of Groups IIA, IIIA, IVA, I8, IIB, IIIB, IVB and VIIT of the Periodic Table of the Elements.

Then used as a catalyst, the crystalline material of the invention may be~subjected to treatment to remove part or all of any organic constituent.

Typically this treatment involves heating at a temperature of 370 to 925'C for at least 1 minute and generally not longer than 20 hours. The crystalline material can also be used as a catalyst in intimate combination with a hydrogenating component such as tungsten, vanadium; molybdenum, rhenium, nickel, cobalt, chromium, manganese, or a noble metal such as platinum or~palladium where a hydrogenation-dehydrogenation function is to be performed. Such component can be in the composition by way of cocrystallization, exchanged into the composition to the extent a Group IIIA element, e.g.

aluminum, is in the structure, impregnated therein or intimately physically admixed therewith. Such component can be impregnated in or on to it such as, for example, by, in the case of platinum, treating the silicate with a solution containing a platinum metal-containing ion. Thus, suitable platinum compounds for this purpose include chloroplatinic acid, platinous ~ .~. ~ J J O
chloride and various compounds containing the platinum amine complex.
The crystalline material of this invention can be used to catalyze a wide variety of chemical conversion processes including many of present commercial/industrial importance. Examples of chemical conversion processes which are effectively catalyzed by the crystalline material of this invention, by itself or in combination with one or more other catalytically active substances including other crystalline catalysts, include those requiring a catalyst with acid activity. Specific examples include:
(1) alkyiation of aromatic hydrocarbons, e.g.
benzene, with long chain olefins, e.g. C14 olefin, with reaction conditions including a temperature of 340'C to 500°C, .a pressure of 100 to 200'00 kPa (1 to 200 atmospheres), a weight hourly space velocity of 2 hr ~' to 2000 hr 1 and an aromatic hydrocarbon/olefin mole ratio of 1/1 to 20/1, to provide long chain alkyl aromatics which can be subsequently sulfonated to provide synthetic detergents;
(2) alkylation of aromatic hydrocarbons with gaseous olefins to provide short chain alkyl aromatic compounds, e.g. the alkylation of benzene with propylene to provide cumene, with reaction conditions including a temperature of 10°C to 125°C, a pressure of 100 to 3000 kPa (1 to 30 atmospheres), and an aromatic hydrocarbon weight hourly space velocity (WgiSV) of from 5 hr-1 to 50 ~hr-1<

(3) alkylation of reformats containing substan-tial quantities of benzene and toluene with fuel gas containing C5 olefins to provide, inter alia, mono- and dialkylates with reaction conditions including a temperature of 315°C to 455°C, a pressure of 2850 to 5600 kPa (400 to 800 psig), a WO 92/22498 -12 PC:T/US92/05~98 WHSV-olefin of 0.4 hr-1 to 0.8 hr ~, a WHSV-reformate of 1 hr~1 to 2 hr-1 and a gas recycle of 1.5 to 2.5 vol/vol fuel gas feed;

(4) alkylation of aromatic hydrocarbons, e.g.
benzene, toluene, xylene and naphthalene, with long chain olefins, e.g. C14 olefin, to provide alkylated aromatic lube base stocks with reaction conditions including a temperature of 160°C to 260°C and a pressure of 2500 to 3200 kPa (350 to 450 psig); and .

(5) alkylation of phenols with olefins or equivalent alcohols to provide long chair°a alkyl phenols with reaction conditions includir,~g a temperature of 200°C to 250°C, a pressure: of 1480 to 2170 kPa (200 to 300 psig) and a total WHSV of 2 hr-1 to 10 hr-~' .
When used as a catalyst, it may be desirable to inc~rp~rate the composition of the invention with another material resistant to the temperatures and other conditions employed in organic conversion px~oeesses. Such materials include active and inactive materials and synthetic or naturally occurring zeolites as well as inorganic materials such as clays, silica and/or metal oxides such as alumina. The latter may be either naturally occurring or in the form of gelatinous precipitates or gels including mixtures of silica and metal oxides. Rise of a maternal in conjunction with the new crystal, i.e. combined therewith or present during synthesis of the new crystal, which is active, tends to change the conversion and/or selectivity of the catalyst in certain organic conversion processes.
Inactive materials suitably serve as diluents to control the amount of conversion in a given process so that products can be obtained economically and orderly withr~ut employing other means for controlling the rate of reaction. These materials may be incorporated into naturally occurring clays, e.g. bentonite and kaolin, P('T/U592105198 to improve the crush strength of the catalyst under commercial operating conditions. Said materials, i.e.

clays, oxides, etc., function as binders for the catalyst. It is desirable to provide a catalyst having good crush strength because in commercial use it is desirable to prevent the catalyst from breaking down into powder-like materials. These clay and/'or oxide binders have been employed normally only for the purpose of improving the crush strength of the to catalyst.

Naturally occurring clays which can be composited with the new crystal include the montmorillonite and kaolin family, which families include the subbentonites, and the kaolins commonly known as Dixie, McNanaee, Georgia and.Florida clays or others in which the main mineral constituent is halloysite, kaolinite, dickite, nacrite, or anauxite. Such clays can be used in the raw state as originally mined or initially .

subjected to ca~cinatir~n, acid treatment or chemical modification. Binders useful for compositing with the present crystal also include inorganic oxides, notably alumina. w In addition to the foregoing materials, the new crystal can be composited with a porous matrix material such as silica-alumina, silica-magnesia, silica-zirconia, silica-thoria, silica-beryllia, silica-titania as well as ternary compositions such as silica-aluaaina-thoria, silica-alumina-zirconia, silica-silica-alumina-magnesia and silica-magnesia-zirconia.

The relative proportions of finely divided crystalline material and inorganic oxide matrix vary widely, with the crystal content ranging from 1 to 90 percent by weight and more usually, particularly when the composite is prepared in the form of beads, in the range of 2 to 80 weight percent of the composite.

The invention will now be more particularly described with reference to the following examples.

WO 92/22498 ~ -14- PC'1'/US92/05198 In the examples, whenever sorption data are set forth for comparison of sorptive capacities for water, cyclohexane and/or n-hexane, they were Equilibrium Adsorption values determined as follows:

A weighed sample of the calcined adsorbant was contacted with the desired pure adsorbate vapor in an adsorption chamber, evacuated to less than 133 kPa (1 mm~ig) and contacted with 1.6 kPa (12 Torr) of water vapor and 5.3 kPa (40 Torr) of n-hexane or cyclohexane vapor, pressures less than the vapor-liquid equilibrium pressure of the respective adsorbate at 90C. The pressure was kept constant (within about + 0.5 mm) by addition of adsorbate vapor controlled by a manostat during the adsorption period, which did not exceed about 8 hours. As adsorbate was adsorbed by the test sample, the decrease in pressure caused the manostat to open a valve which admitted more adsorbate vapor to the chamber to restore the above control pressures.

Sorption was complete when the pressure change was not sufficient to activate the manostat. The increase in weight was calculated as the adsorption capacity of the sample in g/100 g of calcined adsorbant.

When Alpha Value is examined, it is noted that the Alpha Value is an approximate indication of the catalytic cracking activity of the catalyst compared to a standard catalyst and it gives the relative rate constant (rate of normal hexane conversion per volume of catalyst per unit time). It is based on the activity of silica-alumina cracking catalyst taken as an Alpha of 1 (Rate Constant ~ 0.016 sec-1). The Alpha Test is described in U.S. Patent 3,354,078; in the Journal of Catalysis, Vol. 4, p. 527 (1965); Vol. 6, p.

278 (1966); and Vol. 61, p. 395 (1980). The experimental conditions of the test used herein include a constant temperature of 538C and a variable flow rate as described in detail in the Journal of Catalysis, Vol. 61, p. 395.

WO 92/22498 15- PCT/US92/OS~98 ~11.~~~x~~

A 1 part quantity of A12(S04)3 ~ xH20 was dissolved in a solution containing 1.83 parts of 50%
NaOH solution and 13 parts of H20. To this were added 1.78 parts of hexamethyleneimine (HMI) followed by 6.6 parts of amorphous silica precursor (46% solids). The mixture was thoroughly mixed until uniform.
The reaction mixture had the following composition in mole ratios:
Si02/A1203 - 30 OH-/Si02 - 0.25 Na/Si02 - 0.43 HMI/Si02 - 0.35 H20/Si02 - 19.4 The mixture was crystallized in a stirred reactor at 150°C for 4 days. The crystals were filtered, washed with water and dried at 120°C. A portion of the product was submitted for X-ray analysis and identified as the new crystalline material MCM-49. The material exhibited the X-ray powder diffraction pattern as shown in Table III and Figure 2.
The chemical composition of the product was, in Wt.%:
N 1.81 Na 0.38 A1203 7.1 Si02 72.8 Ash 79.2 The Si02/A1203 molar ratio of this product was I7.4.
The sorption capacities, after calcining for F
hours at 538°C were, in wt.%:
Cyclohexane, 40 Torr 4.4 n-Hexane, 40 Torr 12.8 H20, 12 TOrr 11.1 , A portion of the sample was calcined in air for 16 hours at 538°C. This material exhibited the X-ray diffraction pattern shown in Table IV.

°~11.~~5~~ ., TABLE III

Degrees Interplanar 2-Theta d-spacing (Ay I I

3.2 27.5 11 6.75 13.09 36 sh 7.08 12.49 100 7.88 11.23 40 9.81 9.02 24 12.79 6.92 13 13.42 6.60 5*

13.87 6.38 6 14.24 6.22 7 14.64 6.05 4 15.24 5.81 2 15.81 5.61 8 17.72 5.01 2 18.91 4.69 4 19.2? 4.61 5 20.09 4.42 19 20.83 4.26 6 21.48 4.14 15 21.78 4.08 29 22.22 4.00 12 22.59 3.94 36 , 23.56 3.78 19 24.87 - 3.58 21 25.10 3.55 6 25.89 3.44 80 26.32 3.39 7 26.81 3.33 ~17 27.57 3.24 11 28.36 3.15 7 29.03 3.08 3 29.50 3.03 2 31.47 2.842 3 32.16 2.784 3 33.26 2.694 6 34.08 2.631 2 34.83 2.576 ~ 1 36.25 2.478 2 36.96 2.432 2 37.72 2.385 7 sh = Shoulder * - Impurity peaDc 8 -17- PCfi/US92/05198 ~:l:L~.~~~3 , TABLE IV

Degrees Interplanar 2-Theta d-spacing (A) I I

o 3.4 26.0 6 6.96 12.69 45 sh 7.15 12.37 100 7.97 11.09 58 9.97 8.87 49 12.88 6.88 10 13.50 6.56 3*

14.34 6.18 26 14.76 6.00 8 15.30 5.79 1 15.96 5.55 13 17.84 4.97 1 19.03 4.66 3 19.34 4.59 2 19.67 4.51 2*

20.26 4.38 10 21.18 4.20 3 21.59 4.12 10 21.88 4.06 17 22.40 3.37 8 22.72 3.91 28 23.74 3.?5 16 24.73 ' 3.60 3 24.98 3.57 10 25.23 3.53 5 26.00 3.43 57 26.98 3.30 12 27.81 3.21 12 28.64 3.12 7 29.14 3.06 2 29.69 3.01 2 31.62 2.830 3 32.28 2.773 3 33.38 2.685 6 34.43 2.605 2 34.98 2.565 2 36.39 2.469 1 37.09 2.424 2 37.86 2.377 4 sh = Shoulder * - Impurity peak zlil'~~~~

The calcined portion of the product of Example 1 was ammonium exchanged and calcined at 538°C in air for 15 hours to provide the hydrogen form transformation product of the crystalline MCM-49. The Alpha Test proved this material to have an Alpha Value of 291.

A 1.45 part quantity of sodium aluminate was added to a solution containing 1 part of 50% NaOH solution and 53.1 parts H20. A 5.4 part quantity of HMI was added, followed by 10.3 parts of Ultrasil, a precipitated spray-dried silica (about 90% Sio2~. The reaction mixture was thoroughly mixed and transferred to a stainless steel autoclave equipped with a stirrer.
The reaction mixture had the following composition in mole ratios:
Si02/A12O3 - 25 OH-/Si02 - 0.19 Na/Si02 - 0.19 HMI/Si02 - 0.35 H20/SiO2 - 19.3 The mixture was crystallized with stirring at 150°C for 8 days. The product was identified as poorly crystalline MCM-49 and had the X-ray pattern which appears in Table V and Figure 3.
The chemical composition of the product was, in wt.%:
N 2.29 Na 0.19 A1203 6.3 SiO2 71.0 Ash 77.9 The silica/alumina mole ratio of the product was 19.2.
.,r-...>?. >,..~ r S .a,.. , ,~ ...
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'>1 ~ .: 1.:
\ .a: _ .y l . f . ... ~..v.,,, s-T.. ~ .' 1 ,ka~
1 '. f'.~,. " r.~v . ..4 .. ~ l a 'l a °~~t ..'Y
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f ' y" , ,v 1 ~7.,~.p n ~. l v . . ~. ., y. o i3 S. ~a,t~~
r'bi 3 Y ..,-:.t. .~ "...~,. ,w . , r..~
( ~.. .! . .1 ~4 i~ .;;'~'c~. n..P ' 'l. v ~ t ,"K""'>' .,.l it~a.;a\, _ ., m .,"~ - .y ' V.~ . .t.: , e-, ... _ ., :: L .. , ,. x , >, ~. , , ~.. . . > . , . . ~. r.. .... . ~r , ~ . a . . . ., t. .
,'...._.....a.t .: .... ..........,....... wm.~._.».a~..~.F?3:~..,.,~:,..x-....."~ ".,n -"........c~~roc.~....~' a~'\.~.~.....W ,..~.a...,ty.~....,.
~.::...e ~u:xs,..~R.,.,... ,.... .7;.3:~J..a...,:~"'~.. v,. . . .., WO 92/22498 -1g- PCf/US92/05198 .V
The sorption capacities, after calcining for 16 hours at 538°C were, in wt.%:
Cyclohexane, 40 Torr 9.9 n-Hexane, 40 Torr 14.6 H20, 12 Torr 15.1 A portion of the sample was calcined in air for 16 hours at 538°C. This material exhibited the X-ray diffraction pattern shown in Table VI.

WO 92/22498 . , -20- PC'T/US92/05198 ~111~~~3 ~.~:r 'r'ABLE V
Degrees Interplanar 2-Theta d-spacing~(A)_ I I
"° o 3.0 29.3 g 3.9 22.8 2+

6.66 13.27 34 710 12.45 100 7.91 11.18 39 9.24 9.57 16*

9.79 9.04 23 12.79 6.92 11 13.60 6.51 5 14.28 6.20 5 14.68 6.03 5 15.33 5.78 2 15.83 5.60 7 17.80 4.98 2 18.94 4.68 3 19.32 4.59 g 20.09 4.42 21 21.51 4.13 17 21.82 4.07 27 22:17 4.01 13 22.58 3.94 33 23.50 - 3.79 19 24.09 3.69 8*

24.96 3.57 23 25.55 3.49 11*

25:93 3.44 ' 73 26.82 3.32 20 27.54 3.24 g 28.32 3.15 9**

29.07 3.07 5**

31.50 2.840 3 32.15 2.784 3 33.31 2.690 6 3448 2.601 2 36.26 2.478 2 37.03 2.428 2 37.75 2.383 6 + - Non-crystallographic Mt'M-49 peak * - Impurity peak ** = May contain impurity peak '~.~_~37 TALE ~7I

Degrees Interplanar 2-Theta d-spacing 3.9 22.8 6+

6.88 12.84 46 sh 7.11 12.43 I00 7.97 11.10 57 9.35 9.46 25*

9.94 8.90 48 12.53 7.07 4*

12.82 6.90 13 13.41 6.60 3*

I4.30 6.19 36 14.73 6.01 6 15.93 5.56 10 17.90 4.96 2 18.9$ 4.68 3 19.34 4.59 3 20.18 4.40 11 21.56 4.12 I1 21.86 4:07 18 22.34 3.98 IO

22.67 3.92 30 23.68 3.76 17 , 24.94 3.57 15 25.20 - 3.53 6*

25.97 3.43 60 26.93 3.31 13 27.79 3.21 I1 28.56 3.13 ~ 8**

29.10 3.07 3**

29.60 3.02 1 32.58 2.83 3 32.24 2.776 3 33.34 2.688 7 34.59 2.593 3 36.33 2.473 1 37.05 2.426 2 37.79 2.380 4 sh ~ shoulder + - Non-crystallographic MCM-49 peak * - Impurity peak ** = May contain impurity peak The calcined portion of the product of Example 3 was ammonium exchanged and calcined at 538°C in air for 16 hours to provide the hydrogen form transformation product of the crystalline MCM-49. The ~ilpha Test proved this material to have an Alpha Value of 286.

A 10.5 part quantity of gallium oxide was added to a solution containing 1.0 part sodium aluminate, 3.05 parts 50% NaOH solution and 280 parts H20. A 25.6 part quantity of HMI was added followed by 56.6 parts of Ultrasil and 1.7 parts of MCM-22 seeds. The slurry was thoroughly mixed.
The composition of the reaction mixture in mole ratios:
Si02/A1203 - 138 Si02/Ga203 - 17.9 OH /502 - 0.057 Na/Si02 - 0.057 HMI/Si02 - ' 0.30 H20/Si02 - x.8.4 The mixture was crystallized with stirring at 150°C for 10 days. The product was identified as poorly crystalline MCM-49 and had the X-ray pattern which appears in Table VII and Figure 4.
The chemical composition of the product was, in wt.%:
N 1.89 Na 0.40 ~ Ga 8.5 A1203 0.81 Si02 65.6 Ash 79.3 with silica/alumina and silica/gallia molar ratios for the product of:

WO 92/22498 -23- ~(.'T/US92/05~198 ~~_.~.:1~~~
Si02/A1203 138 Si02/Ga203 17.9 The sorption capacities, after calcining for 3 hours at 538°C were, in wt. o:
Cyclohexane, 40 Torr 13.3 n-Hexane, 40 Torr 11.3 H20, 12 Torr 12.3 A portion of the sample was calcined in air for 16 hours at 538°C. This material exhibited the X-ray diffraction pattern shown in Table VIII.
P

~~.1i~5~
TABI~ VII

Degrees I:nterplanar 2-Theta d-spacing (A) I I

p 3.9 22.8 6+

6.66 13.27 30 sh 7.08 12.48 100 7.92 11.17 43 9.27 9.54 8*

9.74 9.08 20 12,78 6.93 12 13.75 6.44 6 14.28 6.20 5 14.62 6.06 3 15.78 5.62 8 17.99 4.93 3 18.92 4.69 6 20.10 4.42 24 20.86 4 . 26 9 21.47 4.14 10 21.73 4.09 26 22.57 3.94 29 23.53 3.78 22 24.92 3.57 24 25.91 3.44 82 26.80 3.33 19 27.43 . 3.25 14 28.31 3.15 10 29.04 3.07 5 31.59 2.832 8 32.17 2.783 ~ 3 .

33.25 2.694 6 33.70 2.659 8*

35.12 2.555 4*

35.96 2.497 11*

36.29 2.476 4 37.73 2.384 7 sh = Shoulder + - Peon-crystallographic MCM-49 peak * - Impurity peak WO 92/22498 25 PCTlUS92/OS198 >:~~..~,35~
TABLE VIII

Degrees Interplanar 2-Theta d-spacing 1A) I I

3.9 22.8 11+

6.89 12.83 40 sh 7.11 12.43 100 7.96 11.11 55 9.40 9.41 10*

9.94 8.90 47 I2.81 6.91 10 1.4.31 6.19 32 14.74 6.01 4 15.94 5.56 12 17.89 4.96 <1 19.00 4.6? 3 19.39 4.58 3 20.22 4.39 9 21.56 4.12 9 21.86 4.07 17 22.70 3.92 29 23.70 '3.75 16 24.99 3.56 14 26.01 3.43 57 26.96 3.31 12 27.84 3.20 10 28.60 - 3.12 5 29.30 3.07 3 31.63 2.829 6 32.28 2.7?3 3 33.39 2.684 - 7 33.72 2.658 9*

35.07 2.559 4*

35.94 2.499 4*

36.40 2.468 1 37.13 2.422 2 37.88 2.375 3 sh d Shoulder + - Non-crystallographic MCM-49 peak * - Impurity peak W~ 92/22498 The calcined partion of the product of Example 5 was ammonium exchanged and calcined at 538°C in air for 16 hours to provide the hydrogen form transformation product of the crystalline MCM-49. The Alpha Test proved this material to have an Alpha Value of 64.

A solution containing 1 part of A12(S04)3 ~ xH20, 1.31 parts of 50% NaOH solution and 14.0 parts of H2.0 was prepared. To this were added 2.8 parts of Ultrasil precipitated silica followed by 1.48 parts of HMI. The reaction mixture was thoroughly mixed. The composition of the reaction mixture in mole ratios was:
Si02/A1203 . - 25.5 OH /Si02 - 0.15 Na/Si02 - 0.39 HMI/Si02 - 0.35 H20/SiD2 - 19.4 The mixture was crystallized for 5 days at 143°C.
The product was washed, dried at 120°C and identified by X-ray analysis as MCM-49. It exhibited an X-ray pattern as shown in Table IX and Figure 5.
The sorption capacities, after calcining for 16 hours at 538°C were, in wt.%:
Cyclohexane, 40 Torr 8.8 n-Hexane, 40 Torr 15.9 H20, 12 Torr 13.6 The chemical composition of the product was, in wt.%:
' N 1.83 Na 0.27 A1203 6.8 Si02 73.8 Ash 80.5 The silica/alumina mole ratio of the product was 18.4.

WO 92/22498 -2~- PCT/US92/05198 '~ ~. ~~ l_ :~ ~~
The surface area of this material was measured to be 459 m219~
A portion of the sample was calcined in air far 16 hours at 538°C. This material exhibited the X-ray diffraction pattern shown in Table X.

~.1 ~. '~ f~ ~
TABLE IX

Degrees Interplanar 2-Theta d-spacing (A) 3.1 28.5 17 4.0 22.2 3+

6.73 13.14 43 sh 7.08 12.48 100 7.92 11.16 42 9.69 9.13 23 12.80 6.91 13 13.76 6.44 7 14.27 6.20 6 14.65 6.05 15.85 5.59 7 17.82 4.98 2 18.92 4.69 3 19.32 4.59 8 20.13 441 20 21.48 4.14 12 21.82 4.07 31 22.56 3.94 36 23.59 377 18 24.91 3.57 22 25.91 - 3.44 ?~

.26.74 3.33 20 27.61 3.23 7 28.25 3.16 8 29.14 3.06 t 3 31.48 2.842 32.16 2.783 3 33.26 2.694 6 33.85 2.648 3 sh 34.72 25$4 Z

36.26 2.478 2 37.00 2,429 2 37,73 2,384 sh = Shoulder + - Non-crystallographic MCM-49 peak WO 92/22498 2~ PCT/US92/05198 '~~,~ 1.~.~".:a~
TABLE X
Degrees Interplanar 2-Theta d~spacing~A~

3.9 22.8 6+

6.91 12.79 38 sh 7.12 12.42 100 7.96 11.10 53 9.94 8.90 39 12.84 6.90 11 14.30 6.29 39 14.71 6.02 10 15.92 5.57 12 18.00 4.93 1 18.98 4.67 3 19.34 4.59 3 20.17 4.40 10 21.55 4.12 10 21.86 4.07 17 22.67 3.92 27 23.69 3.75 15 24.96 '3.57 1'3 25.98 3.43 61 26.93 3.31 13 27.80 3.21 9-28.58 3.12 6 29.11 ' 3.07 2 29.63 3.02 1 31.57 2.834 3 32.23 2.777 3 33.35 2.687 ~ 6 34.60 2.593 3 36.34 2.472 1 37.06 2.426 1 37.83 2.378 5 sh = Shoulder + - Non-cr~rstallographic MCM-49 peak ~1~.1~~8 ~XAMpr..~ 8 A 2.24 part quantity of 45% sodium aluminate was added to a solution containing 1.0 part of 50% NaOH
solution and 43.0 parts H20 in an autoclave. An 8.57 part quantity of Ultrasil precipitated silica was added with agitation, followed by 4.51 parts of HMI:
The reaction mixture had the following composi-tion, in mole ratios:
Si02/A1203 - 23 OH /Si02 - 0.21 Na/Si02 - 0,21 HMI/Si02 - 0.35 H20/Si02 - 19.3 The mixture was crystallized at 150°C for 84 hours with stirring. The product was identified as MCM-49 and had the X-ray pattern which appears in Table'XI and Figure 6.
The chemical composition of the product was, 'in wt.%: .
N 1.70 Na 0.70 A1203 7.3 SiO2 74.5 Ash 84.2 The silica/alumina mole ratio of the product was 17.3.
The sorption capacities, after calcining at 538°C
for 9 hours were, in wt.%:
Cyclohexane, 40 Torr 10.0 n-Hexane, 40 Torr 13.1 H20, 12 Torr 15.4 A portion of the sample was calcined in air for 3 hours at 538°C. This material exhibited the X-ray diffraction pattern shown in Table XII.

~11!3~~
TABLE XI

Degrees Interplaraar 2-Theta d-spacinq~jA) 3.1 28.5 18 3.9 22.8 7+

6.81 12.99 61 sh 7.04 12.55 97 789 11.21 41 9.80 9.03 40 12.76 6.94 17 13.42 6.60 4*

13.92 6,36 17 14.22 6.23 11 14.63 6.05 2 15:81 5.61 15 17.71 5.01 4 18.86 4.71 4 19.23 4.62 6 20.09 4.42 '27 20.93 ' 4.24 8 21.44 4.14 I7 21.74 4.09 37 22.16 4.01 17 22.56 3:94 58 23.53 3.78 26 24.83 ' 3.59 22 25.08 3.55 10 25.86 3.45 100 26.80 3.33 28 27.53 3.24 21 28.33 3.15 15 28.98 3.oa 4 29.47 3.03 2 31.46 2.843 4 32.08 2.790 6 33.19 2,699 9 34.05 2.633 5 34.77 2.580 4 36.21 2.481 2 36.90 2.436 3 37,68 2.387 8 sh = Shoulder + - Non-crystallographic MCM-49 peak * - Impurity peak :,..~i. ~.f S .:.W
a~~
.K,,,. t!t9"' . '3 . .%-i , ,~W .
,~~'s..:-' :' w'. T.7 .: ..r5 a L. .', ,.~~x::Y ..
Y -;.; '~;f 1.?. c h,.e,' ..,5:;,.~~.
,~,. ,. ..: 9 .1:".,. ~. .
..,h i.. ,. ::;.r. ..
... !,- 1' , ~: 5v , i., ' Y
.a- .... . ..;5 y-. ~.. ..., ,c ,. r, .
tt. ~
:.. ~".~f~.
~~ ., : v .. , .,..,,.;t.,. 1....,'n .~4.~.
~r:,.' . I.. '.. t~i~...,-..
.aa. ~:
4r~. . . ~; ' . ~ s. ~ ».. , y. ~. ,:;-,~..... zt~, ~ :a y to . . ,..4c . ,,.: : .As :1... .1.. ~.,,; ..'fit?' ... . ~ y...., aa. .. .-..a -~ ~c ; i .. .,a -. ~~. " t, t..,.,.. : i as . ~, °61. fi , i z ..
a.
.a '., 1 w ' :; f .
s,4. a r. ... _ !~ . ..~ .:. k...w . ,. ~ .", . 1...,. 'M..:.,. S ;. : r _ :~ ~F . , S..
a~: , , ~ . .'s., S
S 4 f ! ~......
. .~'~, . , ...S ; ~ f . .. y ~ , 4 f . ~ ~ ,. , ;;..
..
5i , r ~, r1. ., S.. v S ~ , . $, Wk .' t ~ s, 0,....,......., . ,..._...._.bi~.,.:., e$iab~..._..,...:..a,.,.......i......tc:.~..~.....,.....x~A...e.~
;~9kV'.,>..w...,........_:.H,..&., .
y;\.ns...,..,....~.......,....1.~,'~i...__t..~ "~i:,:e ...,... ,.., . ....

WO 92/22498 32 PC1'/US92/U5198 TABLE XII

Degrees Interplanar 2-Theta d-spacin~(~1 I I

o 3.2 28.0 9+

3.9 22.8 7+

6.90 12.81 48 sh 7.13 12.39 100 7.98 11.08 46 9.95 8.89 53 12.87 6.88 10 14.32 6.18 36 14.74 6.01 11 15.94 5.56 17 17.87 4.96 2 19.00 4.67 5 19.35 4.59 3 20,24 4.39 14 21.06 4.22 5 21.56 4.12 .15 21.87 . 4.06 25 22.32 3.98 12 22.69 3.92 41 23.69 3.76 23 24.95 3.57 19 25.22 3.53 4 25.99 3.43 90 26.94 3.31 20 27.73 3.22 1?

28.55 3.13 11 29.11 3.07 ~ 3 29.63 3.01 2 31.59 2.833 6 32.23 2.777 4 33.34 2.687 9 34.35 2.611 4 34.92 2.570 3 36.35 2.471 2 37.07 2.425 2 37.82 2.379 6 sh = ShOUlder + - Non-crystallr~graphic MCM-49 peak WO 92/22498 ~33 PCT/US92/05198 1.~. .~. ~ '~ ~ , The calcined portion of the product of Example 8 was ammonium exchanged and calcined at 538°C in air for 3 hours to provide the hydrogen form transformation product of the crystalline MCM-49. The Alpha Test . proved this material to have an Algha Value of 308.

In two separate experiments, propylene was passed into a reactor containing catalyst at 538°C, 100 KpA.(1 atmosphere) pressure, a helium/hydrocarbon ratio of 1.1 and a weight hourly space velocity of 3.10 hr-1. The catalyst of the first experiment was hydrogen-form MCM-22 prepared as in Example 1 of U.S. Patent 4,954,325 (hereinafter Example 12). The catalyst of the second experiment was the Example 6 product. After minutes on stream, the product distribution, in weight percent, was determined to be as shown in Table XIII. Significant propylene aromatization selectivity ' to benzene is observed for the Example 6 catalyst 20 compared to MCM-22. The benzene yield over the Example 6 catalyst was 7.16 wt.%, compared to 2.64 wt.% for MCM-22.
_»,_~~._.~.._..~....~.~.. ~s.,.....~,-., u.,,. ...-.~z~, r... .....,t. . t.vaa .......,s.,..wyyt,,yaxa-~sava.~..u.-arrx.Wr:,.,y,;~;n~ zr~.-.;.~",..
v,.~:.~xlR.2,&.~:;Y ....,:.,S~t,Z,.9.J.:~.., ~,~"a~1;~f.'_thr'e~~c' Ti_ .~:~.
. ., "..'.;y,i ~_..,;;

TABLE XIII

PROPYLENE AROMATIZATION

Catalyst MCM-22 Example 6 Product Dist., wt.a C1 0.35 1.28 C2= 1.59 8.72 C2 12.82 0.00.

C3= (approx) 0.00 41.87 C3 (approx) 34.58 0.00 Iso-C4 9.28 2.73 N-C4 2.65 0.00 Iso+1-C4= 4.58 5.51 C-C4= 1.72 2.31 , 2.49 1.82 T-C4=

N-C5 0.24 0.10 Cyelo-C5 0.59 . 0.19 Iso-C~ 2.27 0.93 C5= 2.25 2.94 C6 Par. 1.04 0.52 C6= 0.18 0.22 C7 Par. + OL. 0.22 0.12 C8-C12 Par. + OL. 0.00 0.00 C13+ Par. + OL. 0.00 0.00 Benzene 2.64 7.16 Toluene 9.08 8.10 C8 Ar. 7.52 6.78 C9 Ar. 3.01 3.87 C10 C11 Ar. 0.29 0.91 C12+ Ar. 0.00 0.00 Naphthalene 0.38 0.77 M-Naphthalenes 0.26 3.16 WO 92/22498 -35- i~CT/US92/05198 ~:~1~. a~'b Sodium aluminate comprising 40 wt.% A1203, 33 wt.%
Na20, and 27 wt.% H20 was added to a solution containing NaOH and H20 in an autoclave. Ultrasil precipitated silica was then added with agitation, followed by aminocycloheptane (R) directing agent to form a reaction mixture.
This mixture had the following composition, in mole ratios:
Si02/A1203 - 33.34 OH /Si02 - 0.18 Na/Si02 - 0.18 R/Si02 _ 0.35 H20/Si02 - 18.83 The mixture was crystallized at 143°C for 192 hours with stirring. The product was identified as MCM-49 and had the X-ray pattern which appears in Table XIV and Figure 7.
The chemical.composition of the product was, in wt.%:
N 1.51 Na 0.83 A1203 4.6 Si02 74.2 Ash 79.2 The silica/alumina mole ratio of the product was 27.4.
The sorption capacities, after calcining at 538°C
for 9 hours were, in wt.%~
Cyclohexane, 40 Torr 7.5 n-Hexane, 40 Torr 14.0 H20, 12 Torr 13.5 WO 92/22498 36 ~'C'TlUS92/05198 TABLE XIV

Degrees Interpl.anar 2-Theta d-s I I
~acinct (A) , c 4.1 21.4 1 6.87 12.87 41 7.14 12.38 100 7.98 11.09 26 9.88 8.G5 18 12.85 6.89 14 14.00 6.33 10 14.31 6.19 11 14.74 6.01 2 15.88 5.58 13 17.79 4.99 4 18.95 4.68 6 19.34 4.59 7 20.20 4.40 18 21.06 4.22 7 21.51 4.13 12 21.82 4.07 27 22.63 3.93 46 23.60 3.77 19 24.90 3.58 25 25.14 3.54 7 25.92 3.44 90 26.82 _ 3.32 26 27.66 3.22 13 28.43 3.14 12 29.03 3.08 4 29.45 3.03 . 3 31.51 2.839 4 32.15 2.784 5 33.24 2.695 8 34.13 2.627 4 34.84 2.575 2 36.26 2.477 3 36.97 2.431 3 37.73 2.384 7

Claims

CLAIMS:

1. A synthetic crystalline zeolite having, in its as-synthesized form, an X-ray diffraction pattern including values substantially as set forth in Table I below:

TABLE I

Interplanar d-Spacing(A) Relative Intensity. I/Io .CHI. 100 13.15 _+ 0.26 w-s*

12.49 _+ 0.24 vs 11.19 _+ 0.22 m-s 6.43 _+ 0.12 W

4.98 _+ 0.10 w 4.69 _+ 0.09 w 3.44 _+ 0.07 vs 3.24 _+ 0.06 w *shoulder.

2. The zeolite of Claim 1 and having a composition comprising the molar relationship:
X203:(n)Y02.

wherein n is less than about 35, X is a trivalent element and Y is a tetravalent element.

3. The zeolite.of Claim 2 wherein n is 15 to less than 20.

4. The zeolite of Claim 2 having a composition, on an anhydrous basis and in terms of moles of oxides per n moles of YO2, expressed by the formula:

(0.1-0.6)M20:(1-4)R:X203:nY02 wherein M is alkali or alkaline earth metal and R
is an organic moiety selected from cyclopentylamine, cyciohexylamine, cycloheptylamine, heptamethyleneimine, and homopiperazine.

5. The zeolite of Claim 3 having a composition, on an anhydrous basis and in terms of moles of oxides per n moles of Y02, expressed by the formula:

(0.1-0.6)M20:(1-4)R:X203:nY02 wherein M is alkali or alkaline earth metal and R
is hexamethyleneimine.

6. The zeolite of any one of Claims 2 to 5 wherein X
is aluminum and Y is silicon.

7. A method of synthesizing the zeolite of Claim 4 comprising crystallizing a reaction mixture containing sources of alkali or alkaline earth metal (M), an oxide of trivalent element X, an oxide of tetravalent element Y, organic directing agent (R), and water, said reaction mixture having a composition, in terms of mole ratios of oxides, within the following ranges:

Y02/X2Q3 12 to <35 H20/Y02 10 to 70 OH/Y02 0.05 to 0.50 M/Y02 0.05 to 3.0 R/Y02 0.2 to 1.0 8. A method of synthesizing the zeolite of Claim 5 comprising crystallizing a reaction mixture containing sources of alkali or alkaline earth metal (M), an oxide of trivalent element X, an oxide of tetravalent element Y, organic directing agent (R), and water, said reaction mixture having a composition, in teams of mole ratios of oxides, within the following ranges:

Y02/X203 15 to 25 H20/Y02 10 to 70 OH/Y02 0.05 to 0.50 M/Y02 0.05 to 3.0 R/Y02 0.2 to 1.0 The method of Claim 7 or Claim 8 wherein the R/M
ratio is less than 3.

10. A process for converting a feedstock comprising organic compounds to conversion product which comprises contacting said feedstock at organic compound conversion conditions with a catalyst comprising an active form of the synthetic crystalline zeolite of Claim 1.