This invention relates to a process for the catalytic conversion of a Cg+ aromatic feedstock. 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 silicates. These silicates can be described as a rigid three-dimensional framework of SiO. and

Periodic Table Group IIIA element oxide, e.g., A10., in which the tetrahedra are cross-linked by the sharing of oxygen atoms whereby the ratio of the total Group IIIA element, e.g., aluminum, and silicon atoms to oxygen atoms 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, e.g., an alkali metal or an alkaline earth metal cation. This can be expressed wherein the ratio of the Group IIA element, e.g., 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 silicate by suitable selection of the cation. 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 Z (U.S. Patent No. 2,882,243), zeolite X (U.S. Patent No. 2,882,244), zeolite Y (U.S. Patent No. 3,130,007), zeolite ZK-5 (U.S. Patent No. 3,247,195), zeolite ZK-4 (U.S. Patent No. 3,314,752), zeolite ZSM-5 (U.S. Patent No. 3,702,886), zeolite ZSM-11 (U.S. Patent No. 3,709,979), zeolite ZSM-12 (U.S. Patent No. 3,832,449), zeolite ZSM-20 (U.S. Patent No. 3,972,983), zeolite ZSM-35 (U.S. Patent No. 4,016,245), and zeolite ZSM-23 (U.S. Patent No. 4,076,842).

It is known from U.S. Patent 4,418,235 to effect the disproportionation of methylnaphthalene to provide a mixture of naphthalene and dimethylnaphthalenes over a catalyst having a silica to alumina ratio of at least 12 and a Constraint Index of about 1 to 12, e.g., ZSM-5, ZSM-11, ZSM-12, ZSM-23, ZSM-35 and/or ZSM-38. It is an object of the present invention to effect the catalytic disproportionation of a feedstock containing at least one methylnaphthalene with high selectivity for the 2,6-dimethylnaphthalene isomer and relatively little of the more highly substituted, e.g., tri- and tetra-, methylnaphthalenes.

Accordingly, the present invention resides in a process for effecting disproportionation of a feedstock containing at least one methylnaphthalene to provide a product containing naphthalene and at least one dimethylnaphthalene which comprises contacting the feedstock with a conversion catalyst comprising a zeolite which, in its calcined form has an X-ray diffraction pattern with the lines listed in Table 1 below:

TABLE I

more specifically the lines listed in Table II below:

TABLE II

Interplanar d-Spacing (A) Relative Intensity, I/Io x 1

30.0 +_ 2.2 W-M

22.1 + 1.3 W 12.36~+_ 0.4 M-VS 11.03 + 0.2 M-S 8.83 + 0.14 M-VS 6.18 + 0.12 M-VS 6.00 + 0.10 W-M 4.06 +_ 0.07 W-S 3.91 *_ 0.07 M-VS 3.42 + 0.06 VS

and yet more specifically the lines listed in Table III below:

cont.

Most specifically,-the calcined zeolite has an X-ray diffraction pattern which includes the lines listed in Table IV below:

TABLE IV

Interplanar d-Spacing (A) Relative Intensity, I/Io x 100

W-M

W

M-VS

M-S

M-VS

W-M

M-VS

W-M

W-M

W

W

W-M

W

W-S

W-S

M-VS

W-M

W-M

VS

W-M

W-M

W-M

W

W

W

W

W 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 diffractometer. From these, the relative intensities, 100 I/I _Q , where I _Q is the intensity of the strongest line or peak, and d (obs.) the interplanar spacing in Angstroms Units (A), corresponding to the recorded lines, were determined. In Tables I-IV, the relative intensities are given in terms of the symbols W=weak, M^medium,

S=strong and VS=very strong. In terms of intensities, these may be generally designated as follows:

W = 0 - 20 M = 20 - 40

S = 40 - 60 VS = 60 - 100

It should be understood that these X-ray diffraction patterns are characteristic of all species of the zeolite. The sodium form as well as other cationic forms of this zeolite 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 Y to X, e.g., silicon to aluminum, mole ratio of the particular sample, as well as its degree of thermal treatment. The zeolite defined in Tables I - IV generally has a composition involving the molar relationship:

X ₂ 0 ₃ :(n)Y0 ₂ , 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 at least 10, usually from 10 to 150, more usually from 10 to 60, and even more usually from 20 to 40. In the as-synthesized form, the zeolite has a formula, on an anhydrous basis and in terms of moles of oxides per n moles of Y0 ₂ , as follows: (0.005-0.l)Na ₂ 0:(1-4)R:X ₂ 0 ₃ :nY0 ₂

wherein R is an organic component. The Na and R components are associated with the zeolite as a result of their presence during crystallization, and are easily removed by post-crystallization methods hereinafter more particularly described.

The above zeolite is thermally stable and exhibits high surface area (greater than 400 m /gm as measured by the BET (Bruenauer, Emmet and Tellerl test). In addition, the zeolite normally exhibits equilibrium adsorption capacities greater than 4.5 wt.% for cyclohexane vapor, greater than 10 wt.% for n-hexane vapor and preferablly greater than 10 wt.% for water vapor. As is evident from the above formula, the zeolite is synthesized nearly free of Na cations. It can therefore be used as a catalyst with acid activity without an exchange step. To the extent desired, however, the original sodium cations of the as-synthesized zeolite and the other zeolites useful in the present process 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 transalkylation/disproportionation. These include hydrogen, rare earth metals and metals of Groups IIA, IIIA, IVA, IB, IIB, IIIB, IVB and VIII of the Periodic Table of the Elements.

The zeolite defined in Tables I - IV 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, an organic (R) directing agent in the form of hexamethyleneimine and water, said reaction mixture having a composition, in terms of mole ratios of oxides, within the following ranges:

Reactants Useful Preferred

In a preferred synthesis method the Y0 ₂ reactant contains a substantial amount of solid Y0 ₂ , e.g., at least about 30 wt.% solid Y0 ₂ . Where Y0 ₂ is silica, the use of a silica source containing at least about 30 wt.% solid silica, e.g., Ultrasil (a precipitated, spray dried silica containing about 90 wt.% silica) or HiSil (a precipitated hydrated Si0 ₂ containing about 87 wt.% silica, about 6 wt.% free H.,0 and about 4.5 wt.% bound H ₂ 0 of hydration and having a particle size of about 0.02 micron) favors crystal formation from the above mixture. If another source of oxide of silicon, e.g., Q-Brand (a sodium silicate comprised of about 28.8 wt.% of Si0 ₂ , 8.9 wt.% Na ₂ 0 and 62.3 wt.% H ₂ 0) is used, crystallization may yield little if any of the desired crystalline material and impurity phases of other crystal structures may be produced. Preferably, therefore, the Y0 ₂ , e.g., silica, source contains at least about 30 wt.% solid Y0 ₂ , e.g., silica, and more preferably at least about 40 wt.% solid Y0 ₂ , e.g., silica.

Crystallization can be carried out at either static or stirred conditions in a suitable reactor vessel such as, e.g., polypropylene jars or teflon-lined or stainless steel autoclaves.

Suitable crystallization conditions include a temperature of 80°C to 225°C for a time of 25 hours to 60 days. Thereafter, the crystals are separated from the liquid and recovered.

Synthesis is facilitated by the presence of at least about 0.01 percent, preferably about 0.10 percent and still more preferably about 1 percent, seed crystals (based on total weight) of the required crystalline product.

The zeolite catalyst used in the process of the invention is conveniently employed 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 introduced in the catalyst composition by way of co-crystallization, 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, the zeolite such as, for example, by, in the case of platinum, treating the zeolite with a solution containing a platinum metal-containing ion. Thus, suitable platinum compounds for this purpose include chloroplatinic acid, platinous chloride and various compounds containing the platinum amine complex.

Prior to the use in the process of the invention, the selected zeolite catalyst is preferably combined with another material which is resistant to the temperatures and other conditions employed in the process. 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. Use of a material in conjunction with the catalyst zeolite, i.e., combined therewith or present during its synthesis, which itself is catalytically active may change the conversion and/or selectivity of the catalyst. Inactive materials suitably serve as diluents to control the amount of conversion so that transalkylated/ disproportionated 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 alkylation 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 zeolite catalyst herein 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 zeolite also include inorganic oxides, notably alumina. In addition to the foregoing materials, the zeolite catalyst 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. It may also be advantageous to provide at least a part of the foregoing matrix materials in colloidal form so as to facilitate extrusion of the bound catalyst component(s) .

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 stability of the zeolite catalyst may be increased by steaming , with suitable steam stabilization conditions include contacting the catalyst with, e.g. , 5-100% steam at a temperature of at least 300°C (e.g. , 300-650°C) for at least one hour (e.g. , 1-200 hours) at a pressure of 100-2, 500 kPa. In a more particular embodiment, the catalyst can be made to undergo steaming with 75 -100% steam at 315 -500°C and atmospheric pressure for 2-25 hours.

The feedstock employed in the conversion process of the invention comprises one or more methylnaphthalenes, preferably 2-methylnaphthalene. Where mixtures of methylnaphthalenes are employed, it is preferred that they contain substantial quantities of 2-methylnaphthalene, e.g., in amount of at least 20 weight percent, and preferably at least 50 weight percent, of the total weight of methylnaphthalenes present in the feed. Using such a feed, the catalyst disproportionation process of this invention can provide all 10 isomers of dimethylnaphthalene, but is selective for the production of 2,6-dimethylnaphthalene which is the precursor of 2,6-naphthalenedicarboxylic acid, a valuable monomer for the production of polyesters. Most importantly, the process affords the production of dimethylnaphthalenes without significant production of the more highly substituted and commercially less valuable methylnaphthalenes such as trimethylnaphthalenes and tetramethylnaphthalenes.

In effecting the disproportionation process of the invention, the conditions preferably include a temperature of 300 to 675°C, more preferably from 375 to 575°C, a pressure of 100 to 14000 kPa (atmospheric to 2000 psig), more preferably 240 to 7000 kPa (20 to 1000 psig) and a feed weight hourly space velocity (WHSV) of 0.1 to 500, more preferably from 0.5 to 100.

The invention will now be more fully described with reference to the following Examples and the accompanying drawings in which:

Figures 1-5 are X-ray diffraction patterns of the calcined crystalline material products of Examples 1, 3, 4, 5 and 7, respectively.

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 adsorbent was contacted with the desired pure adsorbate vapor in an adsorption chamber,

evacuated to less than 1 mm Hg and contacted with 1.6 kPa (12 Torr) of water vapor or 5.3 kPa (40 Torr) of n-hexane or 5.3 kPa (40 Torr) of cyclohexane vapor, pressures less than the vapor-liquid equilibrium pressure of the respective adsorbate at 90°C. The pressure was kept constant (within about + 0.5 in Hg) by addition of adsorbate vapor controlled by a manostat during the adsorption period, which did not exceed 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 g/100 g of calcined adsorbent.

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 a highly active silica-alumina cracking catalyst taken as an Alpha of 1 (Rate Constant = 0.016 sec ) . The Alpha Test which was used herein is described in J. Catalysis, 61 , pp. 390-396 (1980) . It is noted that intrinsic rate constants for many acid-catalyzed reactions are proportional to the Alpha Value for a particular zeolite catalyst , i.e. , the rates for toluene disproportionation, xylene isomerization, alkene conversion and methanol conversion (see "The Active Side of Acidic Aluminosilicate Catalysts, " Nature, Vol. 309, No. 5969, pp. 589-591, 14 June 1984 ).

EXA»PLE 1 1 part of sodium alumina te (43.5% Al ₂ 0 _j , 32.2% Na ₂ 0, 25.6% H ₂ 0) was dissolved in a solution containing 1 part of 50%

NaOH solution and 103 .13 parts ILO. To this was added 4.50 parts hexamethyleneimine. The resulting solution was added to 8.55 parts of Ultrasil , a precipitated, spray-dried silica (about 90% SiO- ) .

The reaction mixture had the following composition, in mole ratios:

R/Si0 ₂ = 0.35 where R is hexamethyleneimine.

The mixture was crystallized in a stainless steel reactor, with stirring, at 150°C for 7 days. The crystalline product was filtered, washed with water and dried at 120°C. After a 20 hour calcination at 538°C, the X-ray diffraction pattern contained the major lines listed in Table V. Figure 1 shows the X-ray diffraction pattern of the calcined product. The sorption capacities of the calcined material were measured to be: H ₂ 0 15.2 wt.%

Cyclohexane 14.6 wt.% n-Hexane 16.7 wt.%

The surface area of the calcined crystalline material was measured to be 494 m /g. The chemical composition of the uncalcined material was determined to be as follows:

Com onent wt.%

TABLE V

A portion of the calcined crystalline product of Example 1 was tested in the Alpha Test and was found to have an Alpha Value of 224.

EXAMPLES 3-5 Three separate synthesis reaction mixtures were prepared with compositions indicated in Table VI. The mixtures were prepared with sodium aluminate, sodium hydroxide, Ultrasil, hexamethyleneimine (R) and water. The mixtures were maintained at 150°C, 143°C and 150°C, respectively, for 7, 8 and 6 days respectively in stainless steel autoclaves at autogenous pressure.

Solids were separated from any unreacted components by filtration and then water washed, followed by drying at 120°C. The product crystals were analyzed by X-ray diffraction, sorption, surface area and chemical analyses. The results of the sorption, surface area and chemical analyses are presented in Table VI and the X-ray diffraction patterns are presented in Figures 2, 3 and 4, respectively. The sorption and surface area measurements were of the calcined product.

TABLE VI

FXAMPLF 6 Quantities of the calcined (53 °C for 3 hours) crystalline silicate products of Examples 3, 4 and 5 were tested in the Alpha Test and found to have Alpha Values of 227, 180 and 187, respectively.

EXAMPLE 7 To demonstrate a further preparation of the present zeolite, 4.49 parts of hexamethyleneimine was added to a solution containing 1 part of sodium aluminate, 1 part of 50% NaOH solution and 44.19 parts of H ₂ 0. To the combined solution were added 8.54 parts of Ultrasil silica. The mixture was crystallized with agitation at 145°C for 59 hours and the resultant product was water washed and dried at 120°C.

The X-ray diffraction pattern of the dried product crystals is presented in Figure 5. Product chemical composition, surface area and adsorption analyses results were as set forth in Table VII:

TABLE VII Product Composition (uncalcined)

C 12.1 wt.% N 1.98 wt.%

Na 6^0 ppm

A1 ₂ 0 ₃ 5.0 wt.%

Si0 ₂ 74.9 wt.%

Si0 ₂ /Al ₂ 0 ₃ , mole ratio 25.4

Adsorption, wt.%

Cyclohexane 9.1

N-Hexane 14.9

H ₂ 0 16.8

2 Surface Area, /g 479

EXAMPLE 8

25g grams of solid crystal product from Example 7 were calcined in a flowing nitrogen atmospheres at 538°C for 5 hours, followed by purging with 5% oxygen gas (balance N ₂ ) for another 16 hours at 538°C.

Individual 3g samples of the calcined material were ion-exchanged with 100 ml of O.L TEABr, TPABr and LaCl ₃ solution separately. Each exchange was carried out at ambient temperature for 24 hours and repeated three times. The exchanged samples were collected by filtration, water-washed to be halide-free and dried. The compositions of the exchanged samples are tabulated below.

The La-exchanged sample from Example 8 was sized to 14 to 25 mesh and then calcined in air at 538°C for 3 hours. The calcined material had an Alpha Value of 173.

EXAMPLE 10 The calcined sample La-exchanged material from Example 9 was severely steamed at 649°C in 100% steam for 2 hours. The steamed sample had an Alpha Value of 22, demonstrating that the zeolite had very good stability under severe hydrothermal treatment.

EXAMPLE 11 This example illustrates the preparation of the present zeolite where X in the general formula, supra, is boron. Boric acid, 2.59 parts, was added to a solution containing 1 part of 45% KOH solution and 42.96 parts H ₂ 0. To this was added 8.56 parts of

Ultrasil silica, and the mixture was thoroughly homogenized. A 3.88 parts quantity of hexamethyleneimine was added to the mixture.

The reaction mixture had the following composition in mole ratios: Si0 ₂ /B ₂ 0 ₃ = 6.1

0H ^" /Si0 ₂ = 0.06 H ₂ 0/Si0 ₂ = 19.0 K/Si0 ₂ = 0.06 R/Si0 ₂ = 0.30 where R is hexamethyleneimine.

The mixture was crystallized in a stainless steel reactor, with agitation, at 150°C for 8 days. The crystalline product was filtered, washed with water and dried at 120°C. A portion of the product was calcined for 6 hours at 540°C and found to have the following sorption capacities:

H ₂ 0 11.7 wt.%

Cyclohexane 7.5 wt.% n-Hexane 11.4 wt.%

The surface area of the calcined crystalline material was treasured (BET) to be 405m ² /g.

The chemical composition of the uncalcined material was determined to be as follows:

N 1.94 wt.%

Na 175 ppm 0.60 wt.%

Boron 1.04 wt.%

A1 ₂ 0 ₃ 920 ppm

Si0 ₂ 75.9 wt.%

Ash 74.11 wt.% Si0 ₂ /Al ₂ 0 molar ratio = 1406

Si0 ₂ /(A1+B) ₂ 0 ₃ , molar ratio = 25.8

EXAMPLE 12 A portion of the calcined crystalline product of Example 11 was treated with NH^Cl and again calcined. The final crystalline

- 18 -

product was tested in the Alpha Test and found to have an Alpha Value of 1.

EXAMPLE 13 This example illustrates another preparation of the zeolite in which X of the general formula, supra, is boron. Boric acid,

2.23 parts, was added to a solution of 1 part of 50% NaOH solution and 73.89 parts H ₂ 0. To this solution was added 15.29 parts of HiSil silica followed by 6.69 parts of hexamethyleneimine. The reaction mixture had the following composition in mole ratios: Si0 ₂ /B ₂ 0 ₃ - 12.3

0H7Si0 ₂ = 0.056 H ₂ 0/Si0 ₂ = 18.6 K/Si0 ₂ = 0.056 R/Si0 ₂ = 0.30 where R is hexamethyleneimine.

The mixture was crystallized in a stainless steel reactor, with agitation, at 300°C for 9 days. The crystalline product was filtered, washed with water and dried at 120°r. The sorption capacities of the calcined material (6 hours at 540°C) were measured: H ₂ 0 14.4 wt.%

Cvclohexane 4.6 wt.% n-Hexane 14.0 wt.%

The surface area of the calcined crystalline material was measured to be 438m /g. The chemical composition of the uncalcined material was determined to be as follows:

EXAMPLE 14 A portion of the calcined crystalline product of Example 13 was tested in the Alpha Test and found to have an Alpha Value of 5.

EXAMPLE 15

This Examples illustrates the use of a zeolite of Tables I-IV in the disproportionation of 2-methylnaphthalenes. The zeolite was prepared by adding adding 4.49 parts hexamethyleneimine to a mixture containing 1.00 part sodium aluminate, 1.00 part 50% NaOH, 8.54 parts Ultrasil VN3 and 44.19 parts deionized H.,0. The reaction mixture was heated to 143°C (290°F) and stirred in an autoclave at that temperature for crystallization. After full crystallinity was achieved, the majority of the hexamethyleneimine was removed from the autoclave by controlled distillation and the zeolite crystals separated from the remaining liquid by filtration, washed with deionized H ₂ 0 and dried. A portion of the zeolite crystals was then combined with A1 ₂ 0 ₃ to form a mixture of 65 parts, by weight, zeolite and 35 parts A1 ₂ 0 ₃ . Water was added to this mixture to allow the resulting catalyst to be formed into extrudates. The catalyst was activated by calcining in nitrogen at 540°C (1000°F), followed by aqueous ammoninum nitrate exchange and calcining in air at 540°C (1000°F).

The resultant catalyst was charged to a reactor and the reactor was pressurized to 4930 kPa (700 psig) with hydrogen and pre-heated to 450°C. The reactor temperature was reduced to 400°C and 2-methylnaphthalene was fed to the reactor concurrently with H _2> Process conditions were: WHSV = 2, H ₂ /2-methylnapthalene (molar) = 10, and 4930 kPa (700 psig). The reactor was allowed to equilibriate for 10 hours and after 24 hours, the reaction products were collected and analyzed. The reactor temperature was subsequently raised to 450°C and 498°C and similar analyses were made. Table VIII below summarizes the results of the product analyses.

Conversion of methylnaphthalene (MN), wt.% 6.1 15.9 26.4

Product Selectivities, wt.% DM (dimethylnaphthalene) 2,6-DMN

2,6- and 2,7-DMN

Cl3

I l/Naphthalene x 100 2,6-DMN/Total DMN x 100 2,6- + 2,7-DMN/Total DMN x 100 MN Isomerization (%) 2-NN/l-NN

*Includes small amounts of methane, ethylnaphthalenes and other compounds.

EXAMPLE 16 (COMPARATIVE)

A 65% ZSM-5/35% A1 ₂ 0 ₃ extrudate was crushed, sized to 24/40 mesh and charged to a reactor. Properties of this catalyst are set forth in Table IX as follows:

TABLE IX

Catalyst Properties

Surface Area, m ² /g 338

Density, g/cc

Packed 0.566 Particle 0.914

Real 2.629

Pore Volume, cc/g 0.714

Pore Volume, A 85

Ash, wt.% 8 1000°C 92.23 Alpha Value 246

The reactor was pressurized to 4930 kPa (700 psig) with hydrogen and pre-heated to 450°C. The reactor temperature was reduced to 400°C and 2-methylnaphthalene was fed. to the reactor concurrently with H ₂ . Process conditions were as in Example 15. The reactor was allowed to equilibriate for 10 hours and after 5 hours, the reaction products were collected and analyzed. The ZSM-5 catalyst of this example tended to age more rapidly than the catalyst of Example 15. Over the course of the next 48 hours, the reactor temperature was raised to 497°C and 548°C. Analyses of the products are set forth in Table X as follows:

TABLE X

Days-on-Stream Temperature, °C

Product Composition, wt.% Naphthalene 2-Methylnaphthalene 1 -Methylnaphthalene

Dimethylnaphthalenes 2 , 6-Dimethylnaphthalene 2 , 7 -Dimethylnaphthalene 1, 6-Dimethylnaphthalene 2 , 3-Dimethylnaphthalene

Other Dimethylnaphthalene

Tri- and tetra- methylnaphthalenes Other Compounds*

Conversion of MNs, wt.% 13.2 22.7 39.1

Product Selectivities, wt. % TMi (dimethylnaphthalene) 2,6-DMN 2 ,6- and 2 ,7-DMN

Cl3

DNN/Naphthalene x 100 2 ,6-DMN/Total DM x 100 2 ,6- + 2,7-DMN/Total DMN

MN Isomerization 2-W/l-W

*Includes small amounts of methane, ethylnaphthalenes and other compounds.

A comparison of the data in Table VIII of Example 15 and Table X of this example shows that the catalyst of the invention is more selective for the production of dimethylnaphthalenes and that the difference in DMN selectivities is accounted for in the larger amount of tri- and tetramethylnaphthalenes (C ₁₃ +) produced by

ZSM-5. From gas chromatographic analysis, it is further apparent that the catalyst of the present process is significantly more selective for the production of dimethylnaphthalenes than ZSM-5, dimethylnaphthalene losses to the tri- and tetraraethylnapahthalenes being much lower with the present catalyst.