ZSM-51, method of preparing same and catalytic conversion therewith

Abstract

A novel crystalline zeolite identified as zeolite ZSM-51 and its method of preparation is disclosed. The use of the material as a catalyst is also disclosed.

Description

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to a novel porous crystalline material, hereinafter referred to as zeolite ZSM-51, to a method for its preparation and to its use in catalytic conversion of organic compounds and combustion of carbon monoxide.

2. Description of the Prior Art

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 SiO.sub.4 and AlO.sub.4 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 tetrahedra 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 another type of cation utilizing ion exchange techniques in a conventional manner. By means of such cation exchange, it has been 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 aluminosilicates. The aluminosilicates have come to be designated by letter or other convenient symbols, as illustrated by zeolite A (U.S. Pat. No. 2,882,243), zeolite X (U.S. Pat. No. 2,882,244), zeolite Y (U.S. Pat. No. 3,130,007), zeolite ZK-5 (U.S. Pat. No. 3,247,195), zeolite ZK-4 (U.S. Pat. No. 3,314,752), zeolite ZSM-5 (U.S. Pat. No. 3,702,886), zeolite ZSM-11 (U.S. Pat. No. 3,709,979), zeolite ZSM-12 (U.S. Pat.No. 3,832,449), zeolite ZSM-20 (U.S. Pat. No. 3,972,983), ZSM-35 (U.S. Pat. No. 4,016,245), zeolites ZSM-21 and ZSM-38 (U.S. Pat. No. 4,046,859), and zeolite ZSM-23 (U.S. Pat. No. 4,076,842), merely to name a few.

The SiO.sub.2 /Al.sub.2 O.sub.3 ratio of a given zeolite is often variable. For example, zeolite X can be synthesized with SiO.sub.2 /Al.sub.2 O.sub.3 ratios of from 2 to 3; zeolite Y, from 3 to about 6. In some zeolites, the upper limit of the SiO.sub.2 /Al.sub.2 O.sub.3 ratio of unbounded. ZSM-5 is one such example wherein the SiO.sub.2 /Al.sub.2 O.sub.3 ratio is at least 5, up to infinity. U.S. Pat. No. 3,941,871 now U.S. Pat. No. Re. 29,948, discloses a porous crystalline silicate made from a reaction mixture containing no deliberately added alumina in the recipe and exhibiting the x-ray diffraction pattern characteristic of ZSM-5 type zeolites. U.S. Pat. Nos. 4,061,724, 4,073,865 and 4,104,294 describe crystalline silicates or organosilicates of varying alumina and metal content.

SUMMARY OF THE INVENTION

The present invention is directed towards a novel porous crystalline material which has been designated as zeolite ZSM-51, a method for its preparation and catalytic conversion utilizing the same as a catalyst.

ZSM-51 is a novel crystalline zeolitic material prepared from a reaction mixture containing certain organic complexes. While not wishing to be bound by any theory of operation, nevertheless, it appears that certain organic complexes function as templates for the synthesis of said zeolite ZSM-51. What is meant by the above is that said organic complexes are absolutely necessary for the crystallization of ZSM-51. It has often been desirable in the prior art to include complexes in the conventional forming solution for the preparation of various zeolites, particularly zeolites of the ZSM-5 type. In this connection, typical prior art patents such as U.S. Pat. Nos. 4,100,262; 3,941,871; 3,709,979; 3,702,886 and 3,373,102 generally teach the incorporation of metallic complexes into zeolites including ZSM-5. However, in all the above-mentioned procedures, the complex was not used as a template but was merely at most added to the conventional crystallization mix which contained a quaternary ammonium cation or precursor thereof. In other words, in the prior art techniques for the formation of zeolites wherein metals were introduced into the forming solution, the forming solution itself would have produced the same zeolite irrespective of the presence or absence of the metal complex. Thus, it is clear that the complex was not acting as a template for the formation of the zeolite; but the organic cation was, in fact, a template. As has heretofore been indicated in the preparation of ZSM-51 of this invention, the specific organic complexes appear to function as templates.

The organic complexes which are useful in carrying out this invention include the following:

1. Cobalticinium cation ##STR1##

The cobalticinium cation hereafter referred to as [Co(C.sub.5 H.sub.5).sub.2 ]+ is conveniently supplied by cobalticinium hexafluorophosphate.

2. Dimethylpiperidinium ##STR2##

The dimethylpiperidinium ion is conveniently supplied by utilizing a dimethylpiperidinium halide such as dimethylpiperidinium iodide.

3. Trimethylene bis trimethylammonium ##STR3##

The trimethylene bis trimethylammonium ion is conveniently supplied by utilizing trimethylene bis trimethylammonium iodide--hereinafter referred to as diquat-3.

4. Tetramethyl piperazinium ##STR4##

The tetramethyl piperazinium ion is conveniently supplied by utilizing tetramethyl piperazinium iodide.

In the as synthesized form, ZSM-51 has a calculated composition in terms of moles of oxides after dehydration per 100 moles of silica as follows:

(X) R.sub.2 O . (Y)M.sub.2 O . 0-7 Al.sub.2 O.sub.3 . 100 SiO.sub.2 wherein R represents one of the organic complexes previously defined, M is an alkali metal cation, i.e. sodium or potassium, X is a number ranging from 0.01 to 5 and Y is a number ranging from 0.1 to 10.

As can be seen from the above, ZSM-51 includes zeolitic compositions having aluminum in the crystal framework, as well as compositions which are essentially free of alumina. Thus, a convenient way of expressing the above is to state that ZSM-51 has a silica-to-alumina ratio of from about 15 to infinity. It is to be understood that ZSM-51 may also have iron, boron, and/or chromium in positions of tetrahedral substitution within the silica lattice. To the extent that boron and/or aluminum and/or iron and/or chromium is present in the crystal lattice, it possesses a negative charge, one excess electron for each such heteroatom, which is balanced by cation. These cations may be replaced at least in part by other ions utilizing conventional ion exchange techniques and it may be necessary to precalcine the crystals prior to ion exchange. Ions introduced to replace the original alkali and/or organic cations may be any that are desired so long as they can pass through the channels within the subject crystals. Desired replacing cations are those of the hydrogen, ammonia, metals of Group I-VIII of the Periodic Table.

ZSM-51 possesses a distinctive x-ray diffraction pattern containing the following significant lines.

TABLE 1______________________________________Most significant linesInterplanar Relatived-spacing (A) Intensity______________________________________11.12 .+-. 0.17 W-M9.21 .+-. 0.14 W-VS6.85 .+-. 0.10 W5.84 .+-. 0.09 W4.61 .+-. 0.07 S-VS4.47 .+-. 0.07 W-M4.31 .+-. 0.06 VS3.98 .+-. 0.06 M-S3.77 .+-. 0.06 W3.70 .+-. 0.06 W-M3.57 .+-. 0.05 W-M3.34 .+-. 0.05 W-M3.27 .+-. 0.05 M-S3.23 .+-. 0.05 W2.69 .+-. 0.04 W2.51 .+-. 0.04 W2.31 .+-. 0.03 W______________________________________

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/I.sub.o, where I.sub.o is the intensity of the strongest line or peak, and d (obs.) the interplanar spacing in A, corresponding to the recorded lines, were determined. In Table 1, the relative intensities are given in terms of the symbols vs=very strong, s=strong, m=medium, w=weak, etc. It should be understood that this x-ray diffraction pattern is characteristic of all the species of ZSM-51 zeolite compositions. The sodium form as well as other cationic forms reveal substantially the same pattern with some minor shifts in interplanar spacing and variation in relative intensity. Other minor variations can occur, depending on the silicon to boron ratio of the particular sample, as well as its degree of thermal treatment.

ZSM-51 is prepared from a reaction mixture containing a source of silica, the organic template R, an alkali metal oxide, e.g. sodium, water, and optionally alumina, and having a composition, in terms of mole ratios of oxides, falling with the following ratios:

______________________________________REACTANTS BROAD PREFERRED______________________________________SiO.sub.2 /Al.sub.2 O.sub.3 10-.infin. 15-25,000OH.sup.- /SiO.sub.2 0.005-1.0 0.2-0.6M.sup.+ /SiO.sub.2 0.001-5.0 0.1-1.5H.sub.2 O/SiO.sub.2 10-200 20-100R/SiO.sub.2 0.01-3 0.05-1.5______________________________________ wherein R is at least one organic cation previously defined and M is alkali metal.

It has been found that when R is a cobalticinium ion, ZSM-51 is not produced from reaction mixtures which are essentially aluminum-free. However, when R is dimethyl piperidinium, ZSM-51 can be crystallized from reaction mixtures which are essentially aluminum-free.

DESCRIPTION OF PREFERRED EMBODIMENTS

Crystallization can be carried out at either static or stirred condition in polypropylene jars or in teflon lined or stainless steel autoclaves. The total useful range of temperatures is 80.degree. C. to about 180.degree. C. for about 2 to 10 days. Thereafter, the crystals are separated from the liquid and recovered. The composition can be prepared utilizing materials which supply the appropriate oxide. Such compositions include sodium silicate, silica hydrosol, silica gel, silicic acid, sodium hydroxide, and the organic compound. It should be realized that the oxide 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 new crystalline material will vary with the nature of the reaction mixture employed and the crystallization conditions.

The crystals prepared by the instant invention can be shaped into a wide variety of particle sizes. 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.

ZSM-51, especially in its metal, hydrogen, ammonium, alkylammonium and arylammonium forms, can be beneficially converted to another form for use as a catalyst or an adsorbant by thermal treatment. This thermal treatment is generally performed by heating one of these forms in an atmosphere such as air, nitrogen, hydrogen, steam, etc., at a temperature of at least 700.degree. F. for at least one minute and generally not more than 20 hours to remove part or all of the water and the organic constituent. While subatmospheric pressure can be employed for the thermal treatment, atmospheric pressure is desired for reasons of convenience. The thermal treatment can be performed at a temperature up to about 1700.degree. F. The thermally treated product is particularly useful in the catalysis of certain hydrocarbon conversion reactions as well as for the oxidation of carbon monoxide. Since ZSM-51 does not absorb C.sub.6 - hydrocarbons, its use in hydrocarbon conversion is limited to smaller molecules. It can be used to catalytically crack, isomerize and otherwise convert C.sub.2 -C.sub.5 olefins, paraffins, etc. The ability to oxidize carbon monoxide makes ZSM-51 useful in automobile exhaust systems.

ZSM-51 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 desired. Such component can be exchanged into the composition, impregnated therein or physically intimately admixed therewith. Such component can be impregnated in or onto it such as, for example, by, in the case of platinum, treating the subject crystalline material with a solution containing a platinum metal-containing ion. Thus, suitable platinum compounds include chloro-platinic acid, platinous chloride and various compounds containing the platinum tetraamine-platinum complex.

Simple dehydration of the crystal can also be performed at lower temperatures, such as room temperature, merely by placing the ZSM-51 zeolite type crystal in a vacuum, but a longer time is required to obtain a sufficient amount of dehydration.

In the case of many catalysts, it is desired to incorporate the new crystal 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. The latter may be either naturally occurring or in the form of gelatinous precipitates or gels including mixtures of silica and metal oxides. Use of a material in conjunction with the new boron-containing crystal, i.e. combined therewith, which is active, tends to improve the conversion and/or selectivity of the catalyst in certain organic conversion processes. Inactive materials suitably serve as diluents to control the amount of conversion in a given process so that products can be obtained economically and 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.

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, McNamee-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. Binders useful for compositing with the present crystal also include inorganic oxides, notably alumina.

In addition to the foregoing materials, ZSM-51 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-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 crystal content ranging from about 1 to about 90 percent by weight.

The catalyst can also be used for hydroisomerization of normal paraffins, when provided with a hydrogenation component, e.g. platinum. Hydroisomerization is carried out at a temperature between 200.degree. F. and 700.degree. F., preferably 300.degree. F. to 550.degree. F., with a liquid hourly space velocity between 0.01 and 2, preferably between 0.25 and 0.50, employing hydrogen such that the hydrogen to hydrocarbon mole ratio is between 1:1 and 5:1. Additionally, the catalyst can be used for olefin isomerization, employing temperatures between 30.degree. F. and 700.degree. F.

Other reactions which can be accomplished employing the catalyst of this invention, include olefin polymerization (oligomerization) and other organic compound conversion such as the conversion of alcohols (e.g. methanol) to hydrocarbon.

In order to more fully illustrate the nature of the invention and the manner of practicing same, the following examples are presented.

EXAMPLES 1-3

These examples will illustrate that ZSM-51 cannot be prepared utilizing a cobalticinium ion when the reaction mixture is essentially free of alumina. In each of Examples 1-3, crystallization was attempted utilizing a reaction mixture containing cobalticinium hexafluorophosphate, water, Q-brand sodium silicate (27.8% SiO.sub.2 ; 8.4% Na.sub.2 O; 63.8% H.sub.2 O). The attempted crystallizations were carried out at 160.degree. C. while stirring at autogenous pressure. In each of Examples 1-3, H.sub.2 O/SiO.sub.2 molar ratio was 40, and the Na+/SiO.sub.2 molar ratio was 0.6. Additional reaction compositions and the results obtained are shown in the following Table 2:

TABLE 2______________________________________Crystallizations with ComplexesMixture Mole Ratios SiO.sub.2 OH.sup.- REx. Al.sub.2 O.sub.3 SiO.sub.2 SiO.sub.2 Days Product______________________________________1 .infin. 0.40 0.10 4 Amorphous, mainlycristobalite .alpha.2 .infin. 0.40 0.1 4 Amorphous, mainlycristobalite .alpha.3 .infin. 0.40 0.02 3 Amorphous, mainlycristobalite .alpha.______________________________________

As can be seen from the above table, none of Examples 1-3 resulted in a successful preparation of ZSM-51 due to the fact that there was no deliberate addition of alumina and that a cobalticinium ion was employed as a template.

EXAMPLES 4-8

The procedure of Examples 1-3 was repeated with the exception that Al.sub.2 (SO.sub.4).sub.3.16 H.sub.2 O was added to the reaction mixture. Additional reaction compositions and the results obtained are shown in the following Table 3:

TABLE 3______________________________________Crystallizations with ComplexesMixture Mole Ratios SiO.sub.2 OH.sup.- REx. Al.sub.2 O.sub.3 SiO.sub.2 SiO.sub.2 Days Product______________________________________4 360 0.40 0.10 4 100% ZSM-515 90 0.40 0.10 3 100% ZSM-516 90 0.40 0.02 3 10% ZSM-517 90 0.40 0.10 3 part. crystalline ZSM-518 60 0.40 0.10 4 100% ZSM-51______________________________________

EXAMPLE 9

The procedure of Examples 4-8 was repeated with the exception that silica sol and sodium aluminate was substituted for the Q-brand sodium silicate and the aluminum sulfate.

The reaction mixture had a silica-to-alumina ratio of 60, a water to silica ratio of 40, an OH- to silica ratio of 0.4, an Na+/SiO.sub.2 ratio of 0.4 and an R/SiO.sub.2 ratio of 1.0. Crystallization was carried out for five days after which a product was obtained which was 100% ZSM-51.

EXAMPLE 10

This example will demonstrate the use of potassium in the forming solution. In this example, crystallization was again carried out at 160.degree. C. while stirring at autogenous pressure but the reaction mixture contained potassium silicate manufactured by the Philadephia Quartz Company under their tradename "KASIL-88", Al.sub.2 (SO.sub.4).sub.3.16 H.sub.2 O, water, and the cobalticinium hexafluorophosphate.

The mole ratio of the reaction mixture was as follows:

silica-to-alumina: 60 water to silica: 40 OH-/SiO.sub.2 : 0.4 K+/SiO.sub.2 : 0.6 R/SiO.sub.2 : 0.10

Crystallization was carried out for three days after which the product obtained was 100% ZSM-51.

EXAMPLES 11-12

The procedure of Examples 4-8 was repeated with the exception that the concentration of the various components of the reaction mixture was varied. In each of Examples 11 and 12 the water to silica ratio was 40. Additional reaction compositions and the results obtained are shown in the following Table 4:

TABLE 4______________________________________Crystallizations with ComplexesMixture Mole Ratios SiO.sub.2 OH.sup.- R Na.sup.+Ex. Al.sub.2 O.sub.3 SiO.sub.2 SiO.sub.2 SiO.sub.2 Days Product______________________________________11 30 0.40 0.10 0.6 2 100% ZSM-5112 15 0.40 0.10 0.93 2 ZSM-51 + unident. component______________________________________

EXAMPLES 13-14

The procedure of Example 9 was repeated with the exception that the molar ratio of reactants was varied. In both of these examples, the water to silica molar ratio was 40. Additional reaction composition and results obtained are shown in the following Table 5:

TABLE 5______________________________________Crystallizations with ComplexesMixture Mole Ratios SiO.sub.2 OH.sup.- R Na.sup.+Ex. Al.sub.2 O.sub.3 SiO.sub.2 SiO.sub.2 SiO.sub.2 Days Product______________________________________13 15 0.05 0.09 0.18 6 About 2% crystalline14 10 0.7 0.09 0.27 6 About 5% crystalline______________________________________

The product of Example 8 had the following x-ray diffraction pattern when dried at room temperature.

______________________________________ZSM-51 (Example 8)As Synthesized2.theta. d-spacing Intensity______________________________________ 7.98 11.08 7 9.20 9.61 2 9.60 9.21 1811.72 7.55 512.93 6.85 214.20 6.24 114.82 5.98 215.20 5.83 317.32 5.12 217.94 4.94 118.60 4.77 219.22 4.62 6919.86 4.47 2420.60 4.31 10022.32 3.98 3923.60 3.77 1324.02 3.70 1724.59 3.62 224.90 3.58 2026.00 3.43 626.65 3.34 1827.22 3.28 2827.56 3.24 1328.60 3.12 428.99 3.08 429.48 3.03 229.73 3.00 329.90 2.99 131.44 2.85 232.24 2.78 232.66 2.74 233.28 2.69 934.82 2.58 235.35 2.54 335.63 2.52 1036.55 2.458 536.90 2.436 337.53 2.396 339.00 2.309 539.30 2.292 241.20 2.191 241.95 2.154 142.75 2.115 245.45 1.996 246.65 1.947 547.65 1.908 6______________________________________

The product of Example 8 had the following x-ray diffraction pattern when calcined for four hours at 500.degree. C.

______________________________________ZSM-51 (Example 8)Calcined Four Hours at 500.degree. C.2.theta. d-spacing Intensity______________________________________ 7.95 11.12 7 9.56 9.25 2011.78 7.51 512.92 6.85 114.20 6.24 114.82 5.98 115.20 5.83 117.35 5.11 118.60 4.77 219.28 4.60 7019.85 4.47 2620.57 4.32 10022.37 3.97 3722.89 3.89 323.60 3.77 1723.98 3.71 1624.59 3.62 224.98 3.56 2226.00 3.43 826.68 3.34 1727.21 3.28 2927.57 3.24 1428.60 3.12 429.04 3.07 529.42 3.04 229.72 3.01 329.84 2.99 131.50 2.84 232.19 2.78 132.62 2.75 333.29 2.69 1033.92 2.64 234.85 2.57 235.40 2.54 435.74 2.51 1136.63 2.453 636.83 2.440 637.60 2.392 538.50 2.338 239.03 2.308 839.40 2.287 339.80 2.265 141.25 2.188 241.95 2.154 242.38 2.133 142.73 2.116 345.42 1.997 346.75 1.943 747.40 1.918 147.80 1.903 4______________________________________

The product of Example 11 had the following x-ray diffraction pattern when dried at room temperature.

______________________________________ZSM-51 (Example 11)As Synthesized2.theta. d-spacing Intensity______________________________________ 7.93 11.15 5 9.55 9.26 711.70 7.56 312.89 6.87 214.20 6.24 115.15 5.85 217.35 5.11 217.88 4.96 118.60 4.77 319.20 4.62 5019.81 4.48 2220.58 4.32 10022.30 3.99 2722.81 3.90 323.59 3.77 1223.97 3.71 1824.90 3.58 1325.99 3.43 626.63 3.35 1227.19 3.28 2227.50 3.24 1228.60 3.12 428.98 3.08 429.44 3.03 229.75 3.00 229.84 2.99 131.53 2.84 232.09 2.79 332.50 2.75 433.20 2.70 934.85 2.57 235.35 2.54 335.65 2.52 836.65 2.452 536.80 2.442 437.50 2.398 239.00 2.309 639.30 2.292 239.70 2.270 341.20 2.191 141.95 2.154 242.70 2.117 445.40 1.998 346.63 1.948 647.72 1.906 3______________________________________

EXAMPLES 15-20

Examples 15-20 will illustrate the use of dimethylpiperidinium ion in the reaction mixture for the preparation of ZSM-51.

A reaction mixture was prepared containing water, dimethylpiperidinium iodide, silica, and alkali metal and in some examples added alumina. In Examples 15 and 16 no alumina was added. In Examples 17-20 deliberate additions of alumina were made utilizing Al.sub.2 (SO.sub.4).sub.3.16 H.sub.2 O. In Examples 15, 16 and 20 sodium hydroxide was added whereas in Examples 17, 18 and 19 potassium hydroxide was added. Crystallization was carried out at 160.degree. C. while stirring at autogenous pressures. The mole ratio of the reaction mixture and the crystallization time, as well as the results obtained are shown in the following Table 6.

TABLE 6______________________________________Crystallizations with DimethylpiperidiniumMixture Mole Ratio SiO.sub.2 H.sub.2 O OH.sup.- Na.sup.+ K.sup.+ R Time,Ex. Al.sub.2 O.sub.3 SiO.sub.2 SiO.sub.2 SiO.sub.2 SiO.sub.2 SiO.sub.2 Days Product______________________________________15 .infin. 40 0.1 0.1 -- 0.10 3 100% ZSM-5116 .infin. 40 0.2 0.2 -- 0.10 3 100% ZSM-5117 90 40 0.3 -- 0.39 0.10 3 100% ZSM-5118 60 40 0.2 -- 0.33 0.10 3 100% ZSM-5119 60 40 0.2 -- 0.33 0.10 4 100% ZSM-5120 60 40 0.2 0.33 -- 0.10 3 100% ZSM-51______________________________________ R = Dimethylpiperidinium Iodide

From the above, it can be seen that utilizing dimethylpiperidinium iodide as a template for the crystallization of ZSM-51, it was possible to utilize reaction mixtures which did not contain any added alumina, i.e. see Examples 15 and 16, as well as reaction mixtures which did contain alumina, i.e. see Examples 17-20.

The product of Example 19 had the following x-ray diffraction pattern when dried at room temperature.

______________________________________ZSM-51 (Example 19)As Synthesized2.theta. d-Spacing Intensity______________________________________ 7.99 11.06 24 9.61 9.20 4811.71 7.56 212.96 6.83 614.22 6.23 514.79 5.99 1015.29 5.79 715.92 5.57 117.46 5.08 118.49 4.80 219.22 4.62 7119.84 4.47 2820.64 4.30 10022.34 3.98 3923.59 3.77 1224.01 3.71 1924.92 3.57 1826.07 3.42 626.73 3.34 2427.32 3.26 3727.59 3.23 1228.67 3.11 729.07 3.07 429.49 3.03 429.79 3.00 830.64 2.92 131.52 2.84 332.22 2.78 232.72 2.74 333.31 2.69 1034.22 2.62 134.92 2.57 235.44 2.53 235.77 2.51 1136.56 2.458 536.86 2.438 437.64 2.390 339.07 2.305 539.42 2.286 340.39 2.233 141.32 2.185 242.09 2.147 142.82 2.112 245.59 1.990 146.49 1.953 146.79 1.941 447.49 1.914 147.82 1.902 148.89 1.863 149.64 1.836 2______________________________________

EXAMPLES 21-22

The procedure of Examples 15-20 was repeated with the exception that trimethylene bis trimethylammonium ion was used as a template. This ion was conveniently supplied by utilizing in the reaction mixture trimethylene bis trimethylammonium iodide. In addition to the iodide, the reaction mixture contained a silica sol, water, Al.sub.2 (SO.sub.4).sub.3.16 H.sub.2 O and sodium hydroxide, for Example 21, and potassium hydroxide for Example 22. Crystallization was carried out at 160.degree. C. in a stirred autoclave. The results obtained as well as the molar ratio of reaction mixtures is shown in the following Table 7.

TABLE 7______________________________________Crystallizations with Trimethylene bis trimethylammoniumMixture Mole Ratio SiO.sub.2 H.sub.2 O OH.sup.- Na.sup.+ K.sup.+ R Time,Ex. Al.sub.2 O.sub.3 SiO.sub.2 SiO.sub.2 SiO.sub.2 SiO.sub.2 SiO.sub.2 Days Product______________________________________21 60 40 0.20 0.29 -- 0.10 3 100% ZSM-5122 60 40 0.20 -- 0.29 0.10 4 100% ZSM-51______________________________________ R = Trimethylene bis trimethylammonium iodide

From the above results, it can be seen that successful crystallization of ZSM-51 was obtained utilizing trimethylene bis trimethylammonium iodide.

EXAMPLES 23-24

The procedure of Examples 21 and 22 was repeated with the exception that tetramethylpiperazinium iodide was employed as a template in the reaction mixture. Again, the reaction mixture comprised water, silica sol, Al.sub.2 (SO.sub.4).sub.3 :16 H.sub.2 O, the tetramethylpiperazinium iodide, and sodium hydroxide. A molar ratio of reactants, as well as the results obtained are shown in the following Table 8.

TABLE 8______________________________________Crystallizations with TetramethylpiperaziniumMixture Mole Ratio SiO.sub.2 H.sub.2 O OH.sup.- Na.sup.+ R Time,Ex. Al.sub.2 O.sub.3 SiO.sub.2 SiO.sub.2 SiO.sub.2 SiO.sub.2 Days Product______________________________________23 180 40 0.20 0.24 0.05 3 50% Cryst. ZSM-5124 90 40 0.20 0.29 0.05 3 100% ZSM-51______________________________________ R = Tetramethylpiperazinium iodide

From the above table, it can be seen that tetramethylpiperazinium iodide was successful in producing zeolite ZSM-51.

Some of the samples of ZSM-51 produced from the procedure of Examples 1-24 were submitted for analysis, and the following Table 9 represents analytical data obtained.

TABLE 9______________________________________Analytical Data for ZSM-51 Samples Product Formula per Mole Al.sub.2 O.sub.3 CExample Template N.sub.2 O: Na.sub.2 O: K.sub.2 O: SiO.sub.2 : Co N______________________________________ 4 A -- 3.3 -- 147 5.6 -- 5 A -- 3.1 -- 79 3.2 -- 8 A -- 1.7 -- 55 2.3 --10 A -- -- 2.2 58 2.2 -- 9 A -- 2.5 -- 53 2.1 --11 A -- 2.1 -- 27 1.2 --16 B 26.2 3.3 -- 1470 -- 9.518 B 1.2 -- 0.56 51 -- 8.319 B 1.2 -- 0.82 51 -- 8.220 B 1.6 0.57 -- 50 -- 6.221 C 1.6 1.1 -- 58 -- 4.722 C 1.5 -- 0.26 58 -- 4.924 D 2.4 0.82 -- 75 -- 3.6______________________________________ A = Cobalticinium cation B = Dimethylpiperidinium Iodide C = Diquat3 D = Tetramethylpiperazinium Iodide

EXAMPLE 25

The ZSM-51 produced by the procedure of Example 5 was evaluated for its ability to catalyze the combustion of carbon monoxide.

A ratio of air to carbon monoxide of 0.22 was employed, passed over the catalyst of Example 5 at a vapor hourly space velocity of 45,000 (on catalyst). At 600.degree. C. the catalyst combusted about 87% of the carbon monoxide and at a temperature of 650.degree. C. essentially 100% CO combustion was obtained.

Claims

1. A method of making a synthetic zeolite having an x-ray powder diffraction pattern containing the interplanar spacing set forth in Table 1 of the specification which comprises reacting a mixture containing a source of silica, an organic template R, an alkali metal oxide, water, and alumina, said mixture having a composition, in terms of mole ratios, of oxides falling within the following ranges:

SiO.sub.2 /Al.sub.2 O.sub.3 : 15-25,000

OH.sup.- /SiO.sub.2 : 0.005-1.0

M.sup.+ /SiO.sub.2 : 0.001-5.0

H.sub.2 O/SiO.sub.2 : 10-200

R/SiO.sub.2 : 0.01-3

wherein R is at least one organic cation selected from the group consisting of dimethylpiperidinium, trimethylene bis trimethylammonium and tetramethyl piperazinium and M is an alkali metal and maintaining said reaction mixture from about 80.degree. C. to about 180.degree. C. for about 2 to 10 days until said zeolite is formed.

2. A method of making a synthetic zeolite having an x-ray powder diffraction pattern containing the interplanar spacing set forth in Table 1 of the specification which comprises reacting a mixture containing a source of silica, an organic template R, an alkali metal oxide, water, and alumina, said mixture having a composition, in terms of mole ratios, of oxides falling within the following ranges:

SiO.sub.2 /Al.sub.2 O.sub.3 : 60-360

OH.sup.- /SiO.sub.2 : 0.005-1.0

M.sup.+ /SiO.sub.2 : 0.001-5.0

H.sub.2 O/SiO.sub.2 : 10-200

R/SiO.sub.2 : 0.01-3

wherein R is a cobalticinium cation and M is an alkali metal and maintaining said reaction mixture from about 80.degree. C. to about 180.degree. C. for about 2 to 10 days until said zeolite is formed.

3. A reaction mixture for use in synthesis of a crystalline silicate which comprises one or more sources of alkali metal oxide, an oxide of silicon, water, a cobalticinium cation, and an oxide of aluminum, whereby the mixture composition, in terms of mole ratios, is within the following ranges:

SiO.sub.2 /Al.sub.2 O.sub.3 : 60-360

OH.sup.- /SiO.sub.2 : 0.005-1.0

M.sup.+ /SiO.sub.2 : 0.001-5.0

H.sub.2 O/SiO.sub.2 : 10-200

R/SiO.sub.2 : 0.01-3

wherein M is at least one alkali metal cation and R is said cobalticinium.

4. A method of making a synthetic zeolite having an x-ray powder diffraction pattern containing the interplanar spacing set forth in Table 1 of the specification which comprises reacting a mixture containing a source of silica, an organic template R, an alkali metal oxide, water, and alumina, said mixture having a composition, in terms of mole ratios, of oxides falling within the following ranges:

SiO.sub.2 /Al.sub.2 O.sub.3 : 15-25,000

OH.sup.- /SiO.sub.2 : 0.005-1.0

M.sup.+ /SiO.sub.2 : 0.001-5.0

H.sub.2 O/SiO.sub.2 : 10-200

R/SiO.sub.2 : 0.01-3

wherein R is dimethylpiperidinium, and M is an alkali metal and maintaining said reaction mixture from about 80.degree. C. to about 180.degree. C. for about 2 to 10 days until said zeolite is formed.

5. The process of claim 4 wherein the reaction mixture is substantially free of alumina.

6. A method of making a synthetic zeolite having an x-ray powder diffraction pattern containing the interplanar spacing set forth in Table 1 of the specification which comprises reacting a mixture containing a source of silica, an organic template R, an alkali metal oxide, water, and alumina, said mixture having a composition, in terms of mole ratios of oxides falling within the following ranges:

SiO.sub.2 /Al.sub.2 O.sub.3 : 15-25,000

OH.sup.- /SiO.sub.2 : 0.005-1.0

M.sup.+ /SiO.sub.2 : 0.001-5.0

H.sub.2 O/SiO.sub.2 : 10-200

R/SiO.sub.2 : 0.01-3

wherein R is trimethylene bis trimethylammonium and M is an alkali metal and maintaining said reaction mixture from about 80.degree. C. to about 180.degree. C. for about 2 to 10 days until said zeolite is formed.

7. A method of making a synthetic zeolite having an x-ray powder diffraction pattern containing the interplanar spacing set forth in Table 1 of the specification which comprises reacting a mixture containing a source of silica, an organic template R, an alkali metal oxide, water, and alumina, said mixture having a composition, in terms of mole ratios, of oxides falling within the following ranges:

SiO.sub.2 /Al.sub.2 O.sub.3 : 15-25,000

OH.sup.- /SiO.sub.2 : 0.005-1.0

M.sup.+ /SiO.sub.2 : 0.001-5.0

H.sub.2 O/SiO.sub.2 : 10-200

R/SiO.sub.2 : 0.01-3

wherein R is tetramethyl piperazinium and M is an alkali metal and maintaining said reaction mixture from about 80.degree. C. to about 180.degree. C. for about 2 to 10 days until said zeolite is formed.