CA1259978A - Zeolite and a method of its synthesis - Google Patents

Abstract

A synthetic porous zeolite, identified as ZSM-57 and a method for its preparation are disclosed. The crystalline zeolite has a molar ratio of XO2: Y2O3 of at least 4, wherein X represents silicon and/or germanium and Y represents aluminum, boron, chromium, iron and/or gallium and the characteristic X-ray diffraction shown in Table 1. The silica/alumina form of this crystalline material may be prepared with a directing agent in the form of a N,N,N,N',N',N'hexaethylpentane-diammonium compound.

Description

F-2935(2936) A ZEOLITE AND A M~TI~OD OF
ITS SYNTHESIS

This invention relates to a novel zeolite and to a method for its synthesis.
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 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 utilized 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 aluminosilicates. These aluminosilicates can be described as a rigid three-dimensional framework of SiO4 and Al04 in which the tetrahedra are cross-linked by the sharing of oxygen atoms whereby the ratio of the total aluminum and silicon atoms to oxygen atoms is 1:2. The electrovalence of the tetrahedFa containing aluminum is balanced by the inclusion in the crystal of a cation, for example an alkali metal or an alkaline earth metal cation. This can be expressed wherein the ratio of aluminum to the number of various cations, such as Ca/2, Sr/2, Na, K or Li, is equal to unity. One type of cation may be exchanged either entirely or partially with 3~ another type of cation utilizing ion exchange techniques in a conventional manner. By means of such cation exchange, it has been ~ d ~ 2~S~ 7~3 F-2935(2936) --2--possible to vary the properties of a given aluminosilicate by suitable selection of the cation. 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. The zeolites have come to be designated by letter or other convenient symbols, as illustrated by zeolite A (U. S. Patent 2,882,24~), zeolite X (U. S. Patent

2,882,244), zeolite Y (U. S. Patent 3,130,007), zeolite ZK-5 (U. 5.
Patent 3,247,195), zeolite ZK-4 (U. S. Patent 3,314,752), zeolite ZSM-5 (U. 5. Patent 3,702,886), zeolite ZSM-ll (U. S. Patent

3,709,979), zeolite ZSM-12 (U. S. Patent 3,832,449), zeolite ZSM-20 (U. S. Patent 3,972,983), ZSM-35 (U. S. Patent 4,016,245), ZSM-38 (U. S. Patent 4,0~6,859), and zeolite ZSM-23 (U. S. Patent

4,076,842).
The SiO2/A1203 mole ratio of a given zeolite is often variable. For example, zeolite X can be synthesized with SiO2/A1203 ratios of from 2 to 3; zeolite Y, from 3 to about 6. In some zeolites, the upper limit of the SiO2/A1203 ratio is unbounded. ZSM-5 is one such example wherein the SiO2/A1203 ratio is at least 5 and up to infinity. U. S.
Patent 3,941,871 (Re. 29,948) d~scloses a porous crystalline silicate made from a reaction mixture containing no deliberately added alumina and exhibiting the X-ray diffraction pattern characteristic of ZSM-5 type zeolites. U. S. Patents 4,061,724, 4,073,865 and 4,104,294 describe crystalline silicates or organosilicates of varying alumina and metal content.
A number of synthetic zeolites have been prepared which may be said to be isostructural with naturally occurring zeolites.
Zeolites ZSM-35 and ZSM-38 are, for instance, ferrierite-type zeolites. Zeolite ZK 20 (U.S. Patent 3,459,676) is described as being isostructural with the naturally occurring zeolite levynite.
Although zeolites include materials containing silica and alumina, it is recognized that the silica and alumina portions may be replaced in whole or in part with other oxides. More particularly, GeO2 is an art recognized substitute for SiO2 and ~59971~;1 F-2935(2936) --3--B203, Cr~03, Fe203, and Ga203 are art recognized replacements for Q1203. Accordingly, the term zeolite is used herein to connote not only materials containing silicon and, optionally, aluminum atoms in the crystalline lattice structu~e thereof, but also materials which contain suitable replacement atoms for such silicon and/or aluminum. On the other hand, the term aluminosilicate zeolite is used herein to define zeolite materials consisting essentially of silicon and, optionally, aluminum atoms in the crystalline lattice structure thereo~, as opposed to materials which contain substantial amounts of suitable replacement atoms for such silicon and/or aluminum.
In a first aspect, the present invention resides in a novel porous crystalline zeolite, hereinafter referrsd to as zeolite ZSM-57, having a molar ratio of X02: Y203 of at least 4, 1~ wherein X represents silicon and/or germanium and Y represents aluminum, boron, chromium, iron and/or gallium, said porous crystalline zeolite having at least the X-ray diffraction lines as set forth in Table 1 below but not having an X-ray diffraction line at an interplanar D-spacing of 6.61 + 0.15 Angstrom.
Preferably, the molar ratio of X02: Y203 is in the range of 8 to 200 and most preferably X02 is silica and Y203 is alumina.
In a second aspect, the invention resides in a method of preparing the aluminosilicate zeolite ZSM-57, comprising preparing a mixture containing sources of alkali metal ions, an oxide of silicon, an oxide of aluminum, water and an organic directing agent which is a cation of a N,N,N,N"N"N,-hexaethylpentane-diammonium compound X (C2H5)3 N (CH2)5 Nl(C2H5)3 Xl wherein X and Xl are the same or different and are anions selected ~rom fluoride, chloride, bromide, iodide, hydroxide, acetate, sulfate and carboxylate, and maintaining said mixture under crystallization conditions until the required zeolite is formed.

~25~978 F-2935(2936) -4--In a third aspect, the invention resides in an N,N,N,N ,N ,N -hexaethylpentane-diammonium ion of the formula:
(C2H5)3 N (CH2)5 N (C2H5)3 As is well known in the art, the preferred method for identifying a zeolite is by means of its X-ray diffraction pattern.
Zeolites in accordance with the present invention have the characteristic X-ray difFraction lines set out in Table 1.

d + delta d(Angstrom) Intensity Range 11.36 + 0.23 M-VS
9.41 + 0.19 M-VS
7.12 + 0.15 M-S (shoulder) 6.95 ~ 0.14 M-S

5.74 ~ 0.12 M
5.68 + 0.12 W-M (shoulder) 5.42 + 0.11 M-S
4.81 + 0.10 W-M
3.98 + 0.08 VW-M
3.84 + 0.08 M-S (shoulder) 3.79 + 0.08 VS
3.64 + 0.08 W
3.55 + 0.08 S
3.48 ~ 0.08 S-VS
3.36 + 0.07 W
3.14 + 0.07 M-S
3.06 + 0.07 W
2.949~ 0.06 VW
2.316+- 0.05 VW
1.935+ 0.04 W
In particular, it is to be noted that ZSM-57 is distinguished from ferrierite-type zeolites, such as ZSM-35, by the absence o~ a line at 6.61 + 0.15 Angstrom (13.09 - 13.71 2 Theta).
The set o~ diffraction lines ~or ZSM-57 may, therefore, be considered to be a subset o~ the set of diffraction lines for ZSM-35.

F-2935(2936) __5__ Mnreover, it will be understood that not all zeolites of the ZSM-57 structure will generate exactly the same X-ray diffraction data. For example, variations can occur which are attributable to the presence of impurities, e.g., in the form oF
occluded materials or crystalline intergrowths. The sodium forms in comparison with other cationic forms of otherwise identical zeolites reveal substantially the same patterns with some minor shifts in interplanar spacing and variation in relatiave intensity. Other minor variations can occur, depending on the silicon to aluminum 1~ ratio of the particular sample, as well as its degree of thermal treatment.
The following Table 2 gives X-ray diffraction data for the uncalcined, as synthesized form of the zeolite prepared in accordance with Example 4, set forth hereafter.

Interplanar Degrees Relative D-spacing(A) 2 Theta Intens t~ I/Io 11.37 7.77 19.3 9.41 9.39 29.6 7.11 12.44 16.2

6.97 12.69 25.2 5.74 15.43 28.4 5.69 15.56 16.5 5.42 16.32 38.2 4.70 18.84 9.5 3.83 23.22 39.5 3.78 23.49 100.0 3.74 23.75 12.9 3.64 24.45 13.1 3.56 25.00 48.1 3.48 25.60 56.2 3.36 26.53 7.9 3.13 28.46 34.2 3.04 29.36 10.1 2.95 30.30 5.1 2.81 31.77 1.0 2.66 33.61 2.8 ~s9g~8 F-2935(2936) - 6--The following Table 3 gives X-ray dif~raction data for the calcined form of the zeolite prepared in accordance with Example 3, set forth hereinafter.

TAaLE 3 Interplanar Degrees Relative D-spacing(A) 2 Theta 11.25 7.85 63.2 9.97 8.86 2.7 9.37 9.46 6.41

7.04 12.56 40.0 6.91 12.80 50.2 5.70 15.53 30.0 5.64 15.69 24.3 5.39 16.44 32.6 4.78 18.55 18.7 4.68 18.94 6.3 4.58 19.36 1.5 3.91 22.78 9.9 3.81 23.34 37 9 3.76 23.64 100.0 3.71 23.95 12.0 3.62 2~.58 12.9 3.53 25.18 55.3 3.46 25.75 56.0 3.34 26.66 15.5 3.31 26.90 10.1 ~.12 28.61 42.7 3.30 29.42 13.5 3.02 29.48 17.
2.93 30.46 7.4 2.80 31.95 1.8 2.73 32.79 1.0 These values were determined by standard techniques. The radiation was the K-alpha doublet of copper and a diffractometer equipped with a scintillation counter and an associated computer was used. The peak heights, I, and the positions as a function of 2 theta, where theta is the Bragg angle, were determined using algorithms on the computer associated with the spectrometer. From these, the relative intensities, 100 I/Io, where Io is the ~ig~71~1 F-2935(2936) --7--intensity of the strongest line or peak, and d (obs.) the interplanar spacing in Angstrom units (A), corresponding to the recorded lines, were determined. In Table 2~ the relative intensities are given in terms of the strongest line being taken as lO0Ø
When synthesized, ZSM-57 will contain organic directing agent bound to the anionic sites in the crystal lattice and7 hence prior to use, the as synthesized zeolite is calcined to remove the organic material, preferably at 200-900C.
1~ The original alkali metal cations of the as synthesized zeolite ZSM-57 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 render the zeolite catalytically active, especially for hydrocarbon conversion.
Replacing cations include hydrogen, rare earth metals and metals of Groups IA, IIA, IIIA, IVA, IB, IIB, IIIB, ~VB and VIII of the Periodic Table of the Elements.
A typical ion exchange technique would be to contact the synthetic zeolite with a salt of the desired replacing cation or cations. Examples of such salts include the halides, e.g.
chlorides, nitrates and sulfates.
Zeolite ZSM-57 sorbs significant amounts of commonly used test adsorbate materials, i.e. cyclohexane9 n-hexane and water.
Sorption capacities for the zeolite of the present invention may range at room temperature as rollows:
Adsorbate Capacitx, Wt. Percent n-hexane 6 - 7 cyclohexane 3 - 6 water 5 - 8 wherein cyclohexane and n-hexane sorption are measured at 20 Torr and water sorption is measured at 12 Torr.

~.25~9~78 F-2935(2936) --8--The zeolite 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 exchanged into the composition to the extent atom Y, e.g., aluminum, is in the structure, impregnated therein or intimately physically admixed therewith. Such component can also be impregnated in or on to it such as For example, by, in the case of platinum, treating the zeolite with a solution containin~ a platinum metal-containing ion. Thus, suitable platinum compounds include chloroplatinic acid, platinous chloride and various compounds containing the platinum amine complex.
The zeolite ZSM~57 when employed either as an adsorbent or as a catalyst in an organic compound conversion process should be dehydrated, at least partially. This can be done by heating to a temperature in the range of 200C to 595C in an inert atmosphere~
such as air, nitrogen, etc. and at atmospheric, subatmospheric or superatmospheric pressures for between 30 minutes and 48 hours.
Dehydration can also be performed at room temperature merely by placing the zeolite in a vacuum, but a longer time is required to obtain a sufficient amount of dehydration.
The zeolite ZSM-57 can be prepared from a reaction mixture containing sources of alkali metal ions (Z), an oxide of Y, an oxide of X, a divalent N,N,N,N',N',N'-hexaethylpentane-diammonium cation (R), and water. The reaction mixture may comprise an appropriate selection of reactants, capable oF forming the zeolite and having a composition falling within the following ranges:

5~

F-2935(2936) __9__ Reactants Broad Preferred SiO /A120~ 20-200 40-100 H20~SiO2 10-200 20-50 oH-/sio2 0-3 0.1-0.5 Z/SiO2 0-3 0.1-2 R/SiOk 0.01-2 0.1-1 where~n R and Z are as above defined. The as-synthesized zeolites may have a composition, expressed in terms of moles of oxides on an anhydrous basis, as follows:
(0-15)R0:(0-5)Z20:100SiO2:(0.5-25)A1203 1~ where R and Z are as defined above.
~he divalent N,N,N,N',N',N'-hexaet ~lpentane-diammonium (hereina~ter referred to as Hexaethyl-Diquat~-Y5) cation may be supplied by suitable compounds of the formula:
X(C2H5)3N (CH2)5N (C2 5 3 where X and X' are the same or different and are appropriate counterbalancing anions such as fluoride, chloride, bromide, iodide, hydroxide, acetate, sulfate or carboxylate. Most preferably, the dibromide is employed and is conveniently produced by reaction of 1.5-dibromopentane with triethylamine.
Crystallization of the zeolite ZSM-57 can be carried out at either static or stirred conditions in a suitable reactor vessel, suoh as for example, polypropylene jars or Teflon~lined or s~ainless steel autoclaves. A useful range of temperatures for crystallization is from 80C to 35CC for a time of 12 hours to 200 days. Thereafter, the crystals are separated from the liquid and recovered. The composition can be prepared utilizing materials which supply the appropriate oxides. Such compositions may include sodium silicate, silica hydrosol, silica gel, silicic acid, sodium hydroxide, a source of aluminum~ and an appropriate organic 3~ compound. It should be realized that the reaction mixture component oxides can be supplied from more than one source. The reaction mixture can be prepared either batchwise or continuously. Crystal size and crystallization time of the crystalline zeolite of the present invention will vary with the nature of the reaction mixture employed and the crystallization conditions.

' ~ d :1, ~L;259~713 F-2935(2936) --lO--In all cases, synthesis of the zeolite crystals is facilitated by the presence of at least O.Ol wt. percent, pre~erably O.lO wt. percent and still more preferably l wt. percent, seed crystals (based on total weight) of crystalline product.
The zeolite crystals can be shaped into a wide variety of particle ~orms. Generally speaking, the particles can be in the form of a powder, a granule, or a molded product, such as an extrudate having particle size sufficient to pass through a 2 mesh (Tyler) screen and be retained on a 400 mesh (Tyler) screen. In cases where the catalyst is molded, such as by extrusion, the crystals can be extruded before drying or partially dried and then extruded.
In the case of many catalysts, it is desired to incorporate the zeolite with another material resistant to the temperatures and other conditions employed in organic conversion processes. Such materials include active and inactive material and synthetic or naturally occurring zeolites as well as inorganic materials such as clays, silica and/or metal oxides, e.g. alumina. The latter may be either naturally occurring or in the form of gelatinous precipitates or gels including mixtures of silica and metal oxides. Use of an active material in conjunction with the zeolite crystal, i.e.
combined therewith, tends to improve the conversion and/or selectivity of the catalyst in certain organic conversion processes. Inactive materials suitably serve as diluents to control the amount of conversion in a given process so that products can be obtained economically and orderly without employing other means for controlling the rate of reaction. These materials may be incorporated into naturally occurring clays, e.g. bentonite and kaolin, 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 binders have been employed normally only for the purpose of improving the crush strength of the catalyst.

~2~;9~

F-2935(2936) Naturally occurring clays which can be composited with the present zeolite include the montmorillonite and kaolin families which include the subbentonites, and the kaolins commonly known as Dixie, Mc~amee, 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 calcination, acid treatment or chemical modification. ~inders useful for compositing with the present zeolite also include inorganic oxides, notably alumina.
I0 Porous matrix materials which can be composited with the present zeolite include silica-alumina, silica-magnesia, silica-zirconia, silica-thoria, silica-beryllia, silica-titania as well as ternary compositions such as silica-alumina-thoria, silica-alumina-zirconia, silica-alumina-magnesia and silica-magnesia-zirconia. The relative proportions of finely divided crystalline material and inorganic oxide gel matrix vary widely, with the zeolite 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 zeolite ZSM-57 is useful as a catalyst component for a variety of organic, e.g. hydrosarbon, compound conversion processes. Such conversion processes include cracking hydrocarbons with reaction conditions including a temperature of from 300C to 700C, a pressure of from 10 to 3040 kPa (0.1 to 30 atmospheres) and a weight hourly space velocity of from 0.1 to 20; dehydrogenating hydrocarbon compounds with reaction conditions including a temperature of from 300C to 700C, a pressure of from 10 to 1013 kPa (0.1 to 10 atmospheres) and a weight hourly space velocity of from 0.1 to 20; converting paraffins to aromatics with reaction conditions including a temperature of from 100C to 700C, a pressure of from 10 to 6080 kPa (0.1 to 60 atmospheres), a weight hourly space velocity of from 0.5 to 400 and a hydrogen/hydrocarbon mole ratio of from 0 to 20; converting olefins to aromatics, e.g.

~5997~3 F-2935(2936) --12--benzene, toluene and xylenes, with reaction conditlnns including a temperature of from 100C to 700C, a pressure of from 10 to 6080 kPa tO.l to 60 atmospheres), a weight hourly space velocity of from 0.5 to 400 and a hydrogen/hydrocarbon mole ratio of from O to 20;
converting alcohols, e.g. methanol, or ethers, e.g. dimethylether, or mixtures thereof to hydrocarbons including aromatics with reaction conditions including a temperature of from 275C to 600C, a pressure of from Sl to 5066 kPa (0.5 to 50 atmospheres) and a liquid hourly space velocity of from 0.5 to 100; isomerizing xylene feedstock components with reaction conditions including a temperature of from 230C to 510C, a pressure of from 304 to 3546 kPa (3 to 35 atmospheres), a weight hourly space velocity of from 0.1 to 200 and a hydrogen/hydrocarbon mole ratio of from O to 100;
disproportionating toluene with reaction conditions including a temperature of from 200C to 760C, a pressure of from 101 to 6080 kPa (1 to 60 atmospheres) and a weight hourly space velocity of from 0.08 to 20; alkylating aromatic hydrocarbons, e.g. benzene and alkylbenzenes, in the presence of an alkylating agent, e.g. olefins, formaldehyde, alkyl halides and alcohols, with reaction conditions including a temperature of from 340C to 500C, a pressure of from 101 to 20265 kPa (1 to 200 atmospheres), a weight hourly space velocity of from 2 to 2000 and an aromatic hydrocarbon/alkylating agent mole ratio of from 1/1 to 20/1; and transalkylating aromatic hydrocarbons in the presence of polyalkylaromatic hydrocarbons with reaction conditions including a temperature of from 340C to 500C, a pressure of from 101 to 20265 kPa (1 to 200 atmospheres), a weight hourly space velocity of from 10 to 1000 and an aromatic hydrocarbon/polyalkylaromatic hydrocarbon mole ratio of from 1/1 to 16/1.
Particular catalytic conversions for which the zeolite ZSM-57 can be used include (i) toluene disproportionation, (ii) toluene alkylation with methanol, (iii) propane (e.g., essentially pure propane) conversion to hydrocarbon mixtures enriched in BTX and (iv) upgrading refinery off-gas to liquid products enriched in BTX.

F-2935(2936) --13--It will be understood that BTX stands for aromatic hydrocarbon mixtures composed of two or more of benzene, toluene, xylene and ethylbenzene. The refinery off-gas is composed primarily of Cl-C3 hydrocarbons and, optionally, hydrogen. This refinery off~gas will comprise at least 10% by weight of olefins (i.e.
ethylene and/or propylene).
In order to more fully illustrate the nature of the invention and the manner of practicing same, the following examples are presented. In the examples, whenever adsorption data are set 1~ forth for comparison of sorptive capacities for water, cyclohexane and/or n-hexane, they were determined as follows:
A weighed sample of the calcined adsorbant was contacted with the desired pure adsorbate vapor in an adsorption chamber, evacuated to 1 mm and contacted with 12 mm Hg of water vapor or 20 mm Hg of n-hexane, or cyclohexane vapor, pressures less than the vapor-liquid equilibrium pressure of the respective adsorbate at room temperature. 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 e~ceed about 8 hours.
As adsorbate was adsorbed by the zeolite, 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 9/100 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 the highly active silica-alumina cracking catalyst taken as an Alpha Value of 1 (Rate Constant = 0.016 sec 1). The Alpha Test is described in U.S. Patent 3,354,078 and in The Journal of Catalysis, Vol. IV, pp. 522-529 (August 1965). The Constraint Index is a '7B

F-2935(2936) --14---measure of the selectivity of the particular catalyst and it involves conversion of normal hexane and 3-methylpentane. This test is described in many U.S. patents, inclu~iing 4,231,899 and 4,288,647.

EXAMPLES 1-~

Synthesis reaction mixtures were prepared with compositions indicated in TABLE 4. The mixtures were prepared with 4-brand sodium silicate (PQ Corporation: 27.~% SiO2, 8.4% Na20), A12(S04)3 . 16H20, Hexaethyl-Diquat-5 (bromide salt) and water. The mixtures were maintained at 160C for a number of days in a stainless steel, stirred (400 rprn) autoclave when crystallization was complete. The solids were separated from any unreacted components by filtration and then water washed, followed by drying at 110C.

TABLE 4. Synthesis of Zeolite Samples Mixture Composition (Mole Ratios)a SiO2 H2o OH Na~ Rb Time, Example No. ~ ~ SiO2 ~ ~ Days 1 90 40 0.40 0.59 0.10 5 2 90 40 0.30 0.59 0.10 6 3 60 40 0.30 0.59 0.10 7 4 60 40 0.30 0~59 0.08 5 0.20 0.59 0.10 6 6 60 40 0.30 0.59 0.10 4 7 50 40 0.30 0.59 0.10 4

8 40 40 0.30 0.59 0.15 5 a Q-brand sodium silicate, A12(S04)3 . 16H20.
R=(C2H5)3N~(CH2)5N~(C2Hs)3=Hexaethyl-Diquat-5 (bromide salt).

~ 7i~

F-2935(2936) --15--The zeolite ZSM-57 was produced in each of Examples 1-8, although Examples 1 and 2 also produced a detectable amount of alpha quartz, the amount of alpha quartz in the Example 1 zeolite being merely a trace.
The directing agent N,N,N,N ,N ,N -hexaethylpentane-diammonium dibromide employed in crystallizing the zeolite of the present invention was prepared by refluxing overnight 1,5-dibromopentane with excess triethylamine in absolute ethanol.
Analytical data for zeolite samples are compiled in Table 5.
Siû2/A1203 ratios for the zeolite range From 41-69. Aluminum present in the zeolite appears to be present as framework aluminum.
Also in Table 5, the compositions of the samples have been calculated on the basis of lOO~SiO2+A102 ) tetrahedra. If it is assumed that the diquaternary cation employed to direct the crystallization is trapped intact within the structure during synthesis~ then, from the analytical data, one can calculate an average of 2-3 Hexaethyl-Diquat-5 cations per 100 tetrahedra in the zeolite structure.

TABLE 5. Analytical Data for Zeolite Samples Compositiona C Moles per mole A1203 Al Na+ N Rb Sample N N20 Na2U SiU2 I00 r~ T- ~ 100 ~d 1 10.2 1.3 0.84 69 2.8 2.4 3.6 2.2 2 8.6 1.3 0.53 68 2.9 1.5 3.7 1.9 3 8.7 1.2 0.28 43 4.4 1.2 5.4 2.7 4 10.1 1.2 0.63 45 4.3 2.7 5.2 3.1 8.6 1.5 0.33 48 4.0 1.3 6.1 3.1 6 7.3 1.4 0.31 41 4.6 1.4 6.4 2.8 7 10.8 1.0 0.21 43 4.4 0.92 4.6 2.9 8 7.7 1.5 0.98 36 5.3 5.2 7.9 3.6 . . _ a. Calculated on the basis of lOO(SiO2+A102~)tetrahedra b. R = (c2Hs)3N+(cH2)sN (C2H5)3-F-2935(2936) --16--As indicated previously herein, Table 2 sets forth the X-ray powder diffraction pattern data for the uncalcined, as synthesized form of the zeolite prepared in accordance with Exarnple 4. Table 3 sets forth the X-ray powder diffraction pattern data for the calcined zeolite prepared in accordance with Example 3. This Example 3 sample was calcined in air for six hours at 550C.
Clearly, the framework structure of this zeolite is stable to high temperature air calcination.
From SEM photomicrographs the zeolite crystals produced 1~ under these conditions appear to have a pla~elet morphology.
Characterization data for the Example 3 zeolite are set forth in Table 6. The H-form of the zeolite sorbed 7.1 wt%
n-hexane, 4.7 wt% cyclohexane, and 6.7 wt% water at 25C. Catalytic data is also set forth in Table 6. More particularly, Table 6 shows that the Example 3 zeolite (Sin2/A1203 = 43) in the H-form also showed molecular shape selectivity (Constraint Index =
6.3 at 343C [650F]) and high cracking activity ( alpha = 225).
TABLE 6. Characterization Data for Example 3 Zeolite ~e~ Example 3 Form: Hydrogen; SiO2/A1203 = 43 I. Sorptions Wt~Yo; 2soca N-hexane 7.1 Cyclohexane 4.7 Water 6.7 a. Hydrocarbons, 20 mm; water, 12 mm II. Catalytic Data Alpha = 225 Constraint Index = 6.3b Ea = 13.8 Kcal/mole b. 343C (650F) ~:2S~97i~

F-2935(29~6) --17--The zeolite preparation procedure of Examples 1-8 was repeated except that sodium aluminate was used in place of A12(S04)3 . 16 ~0 and silica sol (30% SiO2) was used in place of Q-brand sodium silicate. As shown in the results set forth in Table 7, only about 10% by wei~ht of the zeolite of the present invention was obtained after 3 days.

TA~LE 7. Synthesis of Zeolite of the Present Invention (160C~ stirred) Mixture Composition tMole Ratios)a SiO2 H2o OH Na Rb Time Example No- A123 Si2 Si2 SiO2 S 2 Y Product .

9 60 40 0.30 0.33 0.10 3 10% Crystn.

a. Silica sol (30% SiO2); NaA12-b- R = (C2H5)3N+(CH2)5N+(C2H5)3 = Hexaethyl-Diquat-5 (bromide salt).

Samples of the zeolite of Example 6 were tested for catalytic activity. These crystals were pelletized, sized to 14/25 mesh and screened in a quartz microreactor for activity and selectivity in a variety of para selective alkylation reactions.
From SEM pictures it was es-timated that the crystal dimensions of this zeolite preparation had a shortest crystal dimension of about 0.1 microns. There~ore, for comparison, a ZSM-5 crystal which had a Si~/A1203=40 and a shortest crystal dimension of 0.1 microns was also evaluated. Comparison of these two catalysts for selective toluene disproportionation, toluene alkylation with ethylene and toluene alkylation with methanol are presented in Tables 8-10, respectively.

7~

F 2935(2936) ~-18--TABLE 8. Toluene Disproportionationl Catalyst Example 6 Zeolite HZSM-5 __ Temp. C 450 500 600 450 500 550 600 Toluene Conv., wt% 45.0 43.1 33.4 19.1 34.8 44.3 46.7 Product SelectivitY
Benzene 42.346.7 47.6 43.7 47.4 44.3 58.4 Ethylbenzene0.3 0.3 0.1 0.2 0.3 0.5 0.2 Xylene 48.348.0 48.2 54.2 49.4 41.5 37.7 Cg~ 9.0 4.8 4.2 1.8 2.7 3.6 3.7 Xylene Isomer Distribution para 24.023.9 23.4 24.1 23.6 23.5 23.3 meta 52.552.0 51.8 52.7 52.9 52.3 51.7 ortho 23.624.1 24.8 23.2 23.5 24.2 24.9 1 Toluene WHSV = 5.5 hr~

TABLE 9. Toluene Alkylation with Ethylene Catalyst Example 6_Zeolite ZSM-5 _ . _ Temp. C 400 450 400 450 Toluene Conv., wt% 23.0 17.1 17.3 19.1 Product Selectivity Benzene 20.9 18.9 20.0 32.9 Ethylbenzene/Xylenes33.2 28.6 26.5 36.5 Ethyltoluene 36.0 42.6 40.9 19.4 Cg+ 7.0 8.0 7.2 7.7 Ethyl_oluene Isomer Distribution para 30.1 30.3 28.1 29.0 meta 53.4 52.9 56.9 51.8 ortho 16.5 16.8 15.1 19.1 1 Toluene WHSV = 8.8 hr~l, C2H~ WHSV = 0.5 hr.
Toluene/C2H4 molar ratio = 5/1 ~s~

F-2935(2936) --19--TA~LE 10. Toluene Alkylation with Methanoll Catalyst Example 6 Zeolite HZSM-5 Temp. C 400 50û 6ûO ~00 500 600 Toluene Conv., wt% 31.9 35.3 30.2 21.7 ~4.2 3~.5 Product Selectiv ty Benzene 19.7 19.4 19.3 13.8 2~.5 36.8 Ethylbenzene û.4 0.1 0.1 0.9 û.5 û.3 Xylene 68.1 70.9 72.4 65.1 65.3 56.~
Cg~ 11.3 9.5 8.3 17.9 9.0 6.3 Xylene Isomer Distribution para 23.5 23.4 23.4 24.1 23.8 23.7 meta 54.0 53.0 52.0 53.0 52.3 52.1 ortho 22.6 23.6 24.6 22.8 23.8 24.2 1 Toluene/MeOH molar ratio = 4/1. Toluene WHSV = 15.8 hr~

To comparè the shape-selective characteristics of the example 6 zeolite relative to ZSM-5, a solution of phenyldodecanes 2~ in benzene was prepared. This solution was then passed over the two catalysts, the Example 6 zeolite and ZSM-5. Isomer distributions of the starting material and of the phenyldodecanes after reaction over the 0.1 micron ZSM-5 crystal and the Example 6 crystal are summarized in Table 11. As these results show, both ZSM-5 and the Example 6 zeolite pre~erentially crack the smaller 2-phenyldodecane isomer. Howevera ZSM-5 appears to be more shape-selective than the Example 6 zeolite in this reaction as it completely removes all the 2-isomer. While the Example 6 zeolite does signi~icantly reduce the amount of 2-isomer present relative to the other isomers, it does not completely remove all of the 2-isomer.

97~3 F-2935(2936) -~20--TABLE 11. Phenyldodecane Crackin~

Catalyst EF ExamE~e 6 Zeolite _ ZSM-5 Temp., C E 150 200 150 200 D

Isomer Distribution 6- 15.9 27.4 27.1 26.3 26.5 5~ .6 26.4 26.1 26.5 ~7.4 4- 14.6 23.1 22.9 25.3 24.8 3- 16.5 18.2 17.1 22.0 21.3 2- 37.4 4.8 6.7 0 0 As an additional comparison of the catalytic performance of the Example 6 zeolite and ZSM-5, the reaction of propane over these two catalysts was studied. Results are summarized in Table 12. These results show that ZSM-57 has appreciable aromatization activity, but it does not appear to be as effective as ZSM-5 in aromatization reactions.

TABLE 12. Propane Crackingl over Example 6 Zeolite and ZSM-5 Catalyst Example 6 Zeolite ZSM-5 Temp., C 500 600 500 600 Propane Conv. 28.0 46.4 35.0 94.7 Product SelectivitY
H2 1.6 3.1 1.7 3.6 Cl 23.9 23.9 26.3 44.0 C2 16.9 5.2 21.8 14.4 c2= 6.6 22.5 3.3 4.6 C3= 8.2 16.û 3.5 1.6 C4 1.6 1.9 4.4 0 C4= 11.5 0.7 11.0 0.2 C5 1.5 0.9 0.8 0 C6 0.7 0.7 0.3 0.2 BZ 3.0 6.5 5.6 17.8 Tol 5.6 6.5 10.4 9.4 C8A 5.1 4.5 8.4 2.6 CgA 2.7 2.0 1.7 0.4 C10~ 11.2 5.7 0.9 1.2 BTX Selectivity 13.7 17.5 24.4 29.8 C2=-C4=
Selectivity 26.3 39.2 17.8 6.3 1 Propane WHSV = 1.3 hr~l ~ii9~7~9 F-2935(2936) --21--In addition, the catalytic performance o~ Example 6 zeolite was compared with that of a sample o~ ZSM-35, which is known to have a ferrierite-type structure. Results of these catalytic studies are summarized in Tables 13-15. For comparison purposes, catalytic data for ZSM-5 under the same conditions are also reported.

TABLE 13. Propane Cracking CatalystHZSM~35 Example 6 Zeolite HZSM-5 Temp., C 600 600 600 C3H8 WHSV 1.3 1.3 1.3 C3H8 Conv. 58.3 69.3 99.3 Product Distribution H2 3.3 3.4 3.0 Cl 38.8 28.1 41.8 C2 7.8 8.4 14.4 C2= 28.7 12.9 3.6 C3= 16.4 9.2 0.5 C4 0 11.7 0.05 C4= 3.1 0.6 0.02 Cs+ Alip. 0.4 0.6 0.05 Aroms. 1.2 25.2 36.7 TABLE 14. Toluene Disproportionation Catalyst ZSM-35Example 6 Zeolite ZSM-5 Temp., C 500 600 500 600 500 600 Toluene Conv., wt%2.7 2.7 43.1 33.4 34.8 46.7 Product Selectivity BZ 53.5 66.7 46.7 47.6 47.4 58.4 EB 0.7 2.1 0.3 0.1 0.3 0.2 Xyl 45.8 29.7 48.0 48.2 ~9.4 37.7 Cg+ 0 1.7 4.8 4.2 2.7 3.7 Isomer Distribution para 39.1 44.4 23.9 23.4 23.6 23.3 meta 43.7 39.9 52.0 51.8 52.9 51.7 ortho 17.3 19.7 24.1 24.8 23.5 24.9 Toluene WHSV = 5.5 hr~l ~25~9~
F-2935(2936) --22--TABLE 15. Toluene Alkylation with Ethylene Catalyst ZSM-35 Example 6 Zeolite ZSM-5 Temp., C 400 450 400 450 400 450 Toluene Conv., wt% 1.2 1.1 23.0 17.1 17.3 19.1 Product Selectivity, wt%
BZ 22.1 20.9 20.9 18.9 20.0 32.9 EB/Xyl 33.0 32.3 ~3.2 28.6 26.5 36.5 ET 44.9 46.8 36.0 42.6 40.9 19.4 Cg~ 0 0 7.0 8.0 7.2 7.7 Isomer Distribution -para 51.7 l~2.4 30.1 30.3 28.1 29.0 meta 37.8 44.1 53.4 52.9 56.9 51.8 ortho 10.6 13.5 16.5 16.8 15.1 19.1 Toluene WHSV = 8.8 hr~l; C2H4 = 0.5 hr~l. Toluene/C2~l4 molar ratio = 5/1 Toluene Disproportionation 2.0 gm of the Example 6 catalyst (sized to 14/25 mesh) was centered in a quartz microreactor with low surface area quartz chips being used to position the catalyst and fill void spaces. After calcination with air at 500C for one hour, the reactor was flushed with nitrogen for approximately five minutes. The temperature was maintained at 500~C and toluene passed over the catalyst at the rate of 5.1 ml/hr (Toluene WHSV = 2.2 hr 1). A liquid sample was collected for the last 5 min. of a 30 min. run and the composition of the liquid was determined by gas chromatography using a SCOT
Lentone column. The temperature was then increased rapidly and succesively to 550 and 600C. In a similar manner, liquid samples were taken for analysis during the last 5 min. of a 30 min. run.
Results of these tests conducted are provided in Table 16.

~2~

F-2935(2936) --23--TABLE 16 Toluene Disproportionation Over the Example_6 Zeoli~e Temperature, C 500 550 600 Toluene Conversion, wt%53.2 54.2 53.9 Product Selectivities, wt%
Benzene 49.1 51.3 53.2 Ethylbenzene/Xylenes 43.1 40.8 37.5 C9+ aromatics 7.7 7.9 9.3 Isomer Distribution, wt%
p-xylene 23.9 2~.6 23.6 m-xylene 53.1 52.7 51.9 o-xylene 23.0 23.7 24.4 Toluene WHSV = 2.2 hr~l Toluene Alkylation w th Methanol A similar procedure to Example 12 was followed except, after calcina-tion in air at 500C for one hour, the temperature of the microreactor was adjusted to 400C and a mixture of toluene and methanol (4:1 molar ratio toluene:methanol) is passed over the catalyst. After 25 min. on stream, a liquid sample was collected for 5 min. for analysis. The temperature was then successively increased to 500 and 600C and the same procedure repeated. The results of the tests are summarized in Table 17.

F-2935(2936) --24--TABLE 17. Toluene Alk~lation With Methanol over Example 6 Zeolite Temperature, C 400 500 600 Toluene WHSV, hr~l 15.8 15.8 15.8 Toluene Conversion, wt% 3].. 9 35.3 30.2 Product Selectivities wt%
Benzene 19.7 19.4 19.3 Xylenes 68.2 70.9 72.4 Cg+ Aromatics 11.3 9.5 8.3 Isomer Distribution, wt%
p-xylene 23.5 23.4 23.4 m-xylene 54.0 53.û 52.0 o-xylene 22.6 23.6 24.6 Prooane Conversion Again the procedure of Example 12 was followed, but propane was passed over the catalyst at 500C. Samples of reactor effluent were taken after 30 min. on stream and a~ter 2.0 hrs. on stream. The same procedure was repeated at 550C and 600C with calcination 2~ between each temperature change. Results of the tests are shown in Table 18.

~-2~35(2936) --25~-TABLE 18. Procane Conversion Over Exampre 6 ZeoIite Temp., C 500 500 550 550 600 600 C3Hg WHSV, hr~l 1.3 1.3 2.2 2.2 1.3 1.3 Time on stream, hrs 0.5 2.0 0.5 2.0 0.5 2.0 e39~9~5~3 1~b`~ YI wt%
H2 1.7 1.6 1.9 2.0 3.9 3~1 CH4 26.8 23.9 33.7 30.1 32.3 23.8 C2~6 21.5 16.9 19.0 14.1 9.6 5.2 C2H4 4.6 6.6 7.6 11.2 14.8 22.5 C3H6 4-5 8.2 7.8 12.7 10.6 16.0 C4Hlo 1.1 1.6 1.9 2.7 1.2 1.9 C4H8 10.6 11.5 6.5 5.a 0.7 0.7 Cs 1.1 1.5 0.9 1.2 0.2 0.9 C6 0.4 0.8 0.9 1.2 0.4 0.7 BZ 4.0 3.0 4.5 3.8 7.8 6.5 Tol 7.6 5.6 7.3 6.8 9.0 6.5 C8A 7.4 5.1 5.5 5.8 5.3 4.6 CgA 2.6 2.7 1.7 1.9 1.6 2.0 C10+ 6.2 11.2 0.8 o.g 2.7 5.7 C3H~ Conversion 36.5 28.0 44.0 32.3 67.0 46.4 BTX Selectivity 18.9 13.7 17.3 16.3 22.1 17.6 C2=-C4= Selec. 19.6 26.3 22.0 29.6 26.0 39.1 Upgrading of Refinery Off Gas to Liquid Product Rlch in BTX
Again the procedure of Example 12 was followed, but a synthetic refinery off gas was passed over the catalyst at 500C. Reactor effluent was sampled at 0.5 hr~ and 2.0 hrs. on stream. The catalyst was then calcined and the same procedure repeated at 600C. Product dist~ibution as well as the composition of the simulated refinery off gas are summarized in Table 19.

F-2935(2936) --26--TABLE 19. Refinery Off Gas Upgrading ~ Zeolite Temp., C 500 500 600 600 WHSV1 hr~l 1.0 1.0 1.0 1.0 Time on stream, hrs 0.5 2.0 0.5 2.0 Feed . CompositionL wt%
H~ 1.6 2.2 2.2 2.8 2.8 C~4 38.0 42.5 41.6 45.2 42.5 C2H6 22.0 24.2 23.6 24.0 23.0 C2H4 15.3 1.2 1.6 4.4 7.0 C3H8 6.6 14.7 12.7 3.2 5.8 C3H6 16.6 1.0 2.1 1.7 4.5 C4H10 0.4 0.6 0.3 0.7 C4Hg 2.6 2.9 0.2 0.3 C5 0.4 0.7 0.1 0~1 C6 0.2 0.4 0.04 0O3 BZ 2.2 1.8 5.3 3.9 Tol 4.0 3.9 5.0 4.2 C8A 3.2 3.8 2.6 2.5 CgA 0.8 1.2 0.7 0.8 Clo~ 0.3 1.0 4.6 1.6 gms BTX/100 gms feed 9.2 9.4 14.2 11.7

Claims (6)

CLAIMS:
The embodiments of the present invention in which an exclusive property of privilege is claimed, are defined as follows:

1. A synthetic porous crystalline zeolite having a molar ratio of XO2: Y2O3 of at least 4, wherein X represents silicon and/or germanium and Y represents aluminum, boron, chromium, iron and/or gallium, said porous crystalline zeolite having at least the X-ray diffraction lines as set forth in Table 1 below;

said zeolite not having an X-ray diffraction line at an interplanar D-spacing of 6.61 ? 0.15 Angstrom.

2. A crystalline zeolite according to claim 1, which is an aluminosilicate zeolite having a silica to alumina molar ratio of at least 4.

3. A crystalline zeolite according to claim 2 having a silica to alumina molar ratio of from 8 to 200.

4. A crystalline zeolite according to claim 1 and having the composition, expressed in terms of moles of oxides on an anhydrous basis, as follows:
(0-15)RO: (0-5)Z2O : 100SiO2 : (0.5-25)Al2O3 where R is a cation of the formula (C2H5)3N+(CH2)5N+(C2H5)3, and Z is an alkali metal ion.

5. A method for preparing a synthetic porous crystalline zeolite according to claim 2, which comprises preparing a mixture containing sources of alkali metal ions, an oxide of aluminum, an oxide of silicon, water and an N,N,N,N1,N1,N1-hexaethylpentane-diammonium cation of the formula (C2H5)3 N+(CH2)5 N+(C2H5)3 and maintaining said mixture under sufficient conditions until said crystalline zeolite is formed.

6. A method according to claim 5, wherein said mixture has a composition, in terms of moles, falling within the following ranges:
SiO2/A12O3 = 20 - 200 H2O/SiO2 = 10 - 200 OH-/SiO2 = 0 - 3 Z/SiO2 = 0 - 3 R/SiO2 = 0.01 - 2 where R is the organic cation and Z is the alkali metal ion.