NZ196837A - Rium for use in aromatic alkylation zeolite catalyst composition modified with strontium or ba - Google Patents

Description

New Zealand Paient Spedficaiion for Paient Number 1 96837 1 9 68 3 , , i i i i i t Priority Datsfs): .

Corsiplet© Specification Filed: c\«*&.ccnc$L't coics* co7c.u°bofi sft\o& ViUsUi. • *■•<•••«( |)» | f iHt Mil I »«***-■ «j ' * 1 ^UAW jnni . IX-V-VI i « « * k * * >8o&MI 31 MAY 191 Stf k wi'OO. • ■ ■ • f / —w _ 51 MAY 1984 Publication Date: ......... .w'Ji P.O. Journal Wo: J?5?....... f NEW ZEALAND PATENTS ACT, 1953 No.: Date: COMPLETE SPECIFICATION "SHAPE SELECTIVE REACTIONS WITH ALKALINE EARTH METAL-MODIFIED ZEOLITE CATALYSTS" kl We, MOBIL OIL CORPORATION, a corporation organised under the laws of the State of New York, United States of America, of 150 East 42nd Street, New York, State of New York, United States of America, hereby declare the invention for which &/ we pray that a patent may be granted to axe/us, and the method by which it is to be performed, to be particularly described in and by the following statement:- (followed by page la) SHAPE SELECTIVE REACTIONS WITH ALKALINE EARTH METAL-MODIFIED ZEOLITE CATALYSTS BACKGROUND OF THE INVENTION Field of the Invention The invention disclosed herein relates to the production of dialkylbenzene compounds utilizing a modified crystalline zeolite catalyst to yield a product mixture in which the 1 ,4-dialkylbenzene isomer is substantially in excess of its normal equilibrium concentration.

Description of the Prior Art The disproportionation of aromatic hydrocarbons in the presence of zeolite catalysts has been described by Grandio et al. in the OIL AND GAS JOURNAL, Vol. 69., Number 48(1971).

U.S. Patents Nos. 3,126,422; 3,413,374; 3,598,878; 3,598,879 and 3,607,961 show vapor-phase disproportionation of toluene over various catalysts.

In these prior art processes, the dimethylbenzene product produced has the equilibrium composition of approximately 24 percent of 1,4-, 54 percent of 1,3- and 22 percent of 1,2-isomer. Of the dimethyl-benzene isomers, 1 ,3-diinethylbenzene is normally the' least desired product, with 1,2- and 1,4-dimethylbenzene being the more useful products. 1,4-Dimethylbenzene is of particular value, being useful in the manufacture of terephthalic acid which is an intermediate in the manufacture' of synthetic fibers such as "Dacron". Mixtures of dimethylbenzene \<=K,- isomers, either alone or in further' admixture with ethylbenzene, have previously, been separated by expensive i! superfractionation and multistage refrigeration steps. Such process, as will be realized, involves high operation costs and has a limited yield. ,i' Various modified zeolite catalysts have been developed to alkylate or disproportionate toluene with a greater or lesser degree of selectivity to 1,4-dimethyl- benzene isomer. Hence, N-.Z. Patent No. 178,543 and U.S. Patents ,034,053, / 4,128,592 and 4,137,195 disclose particular zeolite catalysts which have been treated with compounds of phosphorus and/or magnesium. Boron-containing zeolites are shown in U.S. Patent 4,067,920 a'nd antimony-containing zeolites in U.S. Patent 3,979,472. Similarly, U.S. Patents 3,965,208 and 4,117,026 disclose other modified zeolites useful for shape selective reactions.

While the above-noted prior art is considered of interest in connection with the subject matter of the present invention, the conversion process described herein, utilizing a crystalline zeolite catalyst of specified characteristics which has undergone the particular treatment disclosed, has not, insofar as is known, been previously described.

SUMMARY OF THE INVENTION In accordance with the present invention, there has now been discovered a novel process for conversion of organic compounds (e.g. hydrocarbon compounds) in the presence of a particular type of modified zeolite -catalyst.

N OFFIPP 1 - t NOV 1983 I ■ O / c ~ "7 1 ✓ u /-• An especially advantageous element of the invention comprises the selective production of the 1,4-isomer of dialkylated "benzene compounds. The process involves contacting an alkylated aromatic compound, either alone or in admixture with a suitable alkylating agent such as methanol or ethylene, with a particular type of modified crystalline zeolite catalyst and under suitable conversion conditions to effect disproportionation or transalkylation of alkylbenzene compounds or alkylation of aromatic compounds to selectively produce the 1 ,4-dialkylbenzene isomer in excess of its normal equilibrium concentration.

The particular type of crystalline zeolite catalysts utilized herein are zeolite materials having a silica to alumina ratio of at least about 12, a constraint index within the approximate range of 1 to 12 and which have been modified by initial treatment with a compound derived a proportion of from one or more of the elements comprising/the alkaline-earth metals (i.e. Sr and Ba) to yield a composite containing a minor proportion of an oxide of such element, In addition to treatment of the catalyst with the strontium or barium containing compound, the zeolite may also be treated with a phosphorus-containing compound to deposit a minor proportion of an oxide of phosphorus thereon in addition to the oxide of the alkaline-earth metal.

An embodiment of the disclosed invention is a process for the alkylation of aromatic compounds, in the presence of the herein described modified zeolite catalysts, with selective production of the 1 ,4-diaIkylbenzene isomer in preference to the 1,2- and 1,3- isomers thereof.

N.Z. PAT-TKT OFFICE - f NOV 1983 Deceived Especially preferred embodiments involve the selective production of 1,4-dimethylbenzene from toluene and methanol and 1 -ethyl-4-methylbenzene from toluene and ethylene.

Another embodiment contemplates the selective disproportionation or transalkylation of alkylbenzene and polyalkylbenzene compounds in the presence of the disclosed catalysts, thereby yielding 1,4-disubstituted benzenes in excess of their normal equilibrium concentration. For example, under appropriate conditions of temperature and pressure, toluene will disproportionate in;the presence of these catalysts to produce benzene and dimethylbenzenes rich in the desirable 1,4-isomer.

DESCRIPTION OF SPECIFIC EMBODIMENTS The crystalline zeolites utilized herein are members of a novel class of zeolitic materials which exhibit unusual properties. Although these zeolites have unusually low alumina contents, i.e. high silica to alumina mole ratios, they are very active even when the silica to alumina mole ratio exceeds 30. The activity is surprising, since catalytic activity is generally attributed to framework aluminum atoms and/or cations associated with these aluminum atoms. These zeolites retain their crystallinity for long periods in spite of the presence of steam at high temperature which induces irreversible collapse of the framework of other zeolites, e.g. of the X and A type. Furthermore, carbonaceous deposits, when formed, nay be removed by burning at higher than usual temperatures to restore activity. These zeolites, used as catalysts, generally have low coke-forming activity and therefore are conducive to long times on stream between regenerations by fj burning carbonaceous deposits with oxygen-containing gas such as air.

An important characteristic of the crystal / structure of this novel class of zeolites is that it provides a selective constrained access to and egress from the intracrystalline free space by virtue of having an' effective pore size intermediate between the small por,e Linde A and the large pore Linde X, i.e. the pore windows of the structure are of about a size such as would be provided by 10-membered rings of silicon atoms interconnected by oxygen atoms. It is to be understood, of course, that these rings are those formed by the regular disposition of the tetrahedra making up the anionic framework of the crystalline zeolite, the oxygen atoms themselves being bonded to the silicon (or aluminum, etc.) atoms at the centers of the tetrahedra.

The silica to alumina mole ratio referred to may be determined by conventional analysis. This ratio is meant to represent, as closely as possible, the ratio in the rigid anionic framework of the zeolite crystal and to exclude aluminum in the binder or in cationic or other form within the channels. Although zeolites with a silica to alumina mole ratio.of at least 12 are useful, it is preferred in some instances to use zeolites having substantially higher silica/alumina ratios, e.g. 1600 and above. In addition, zeolites as otherwise characterized herein but which are substantially free of aluminum, that is zeolites having silica to alumina mole ratios of up to infinity, are found to be useful and even preferable in some instances. Such "high silica" or "highly siliceous" zeolites are intended to be included within this description. Also to be included within this definition are substantially pure silica analogs of the useful zeolites described herein, that is to say those zeolites having no measurable amount of aluminum (silica to alumina mole ratio of infinity) but which-otherwise embody the characteristics disclosed.

The novel class of zeolites, after activation, acquire an intracrystalline sorption capacity for normal hexane which is greater than that for water, i.e. they exhibit "hydrophobic" properties. This hydrophobic character can be used to advantage in some applications.

The novel class of zeolites useful herein have an effective pore size such as to freely sorb normal hexane. In addition, the structure must provide constrained access to larger molecules. It is sometimes possible to judge from a known crystal structure whether such constrained access exists. For example, if the only pore windows in a crystal are formed by 8-membered rings of silicon and aluminum atoms, then access by molecules of larger cross-section than normal hexane is excluded and the zeolite is not of the desired type. Windows of 10-membered rings are preferred, although in some instances excessive puckering of the rings or pore blockage may render these zeolites ineffective.

Although 12-membered rings in theory would'not offer sufficient constraint to produce advantageous conversions, it is noted that the puckered 12-ring structure of TMA offretite does show some constrained access. Other 12-ring structures may exist which may be operative for other reasons and, therefore, it is not the present intention to entirely judge the usefulness of a particular zeolite solely from theoretical structural considerations.

Rather than attempt to judge from crystal structure whether or not a zeolite possesses the necessary constrained access to molecules of larger cross-section than normal paraffins, a simple determination of the "Constraint Index" as herein defined may be made by passing continuously a mixture of an equal weight of normal hexane and 3-methylpentane over a sample of zeolite at atmospheric pressure according to the following procedure. A sample of the zeolite, in the form of pellets or extrudate, is crushed to a particle size about that of coarse sand and mounted in a glass tube. Prior to testing, the zeolite is treated with a stream of air at 540°C for at least 15 minutes. The zeolite is then flushed with helium and the temperature is adjusted between 290°C and 510°C to give an overall conversion of between 107. and 607.. The mixture of hydrocarbons is passed at 1 liquid hourly space velocity -(i.e., 1 volume of liquid hydrocarbon per volume of zeolite per hour)•over the zeolite with a helium dilution to give a helium to (total) hydrocarbon mole ratio of 4:1. After 20 minutes on stream, a sample of the effluent is taken and analyzed, most conveniently by gas chromatography, to determine the fraction remaining unchanged for each of the two hydrocarbons. 9y vr: While the above experimental procedure will enable one to achieve the desired overall conversion of 10 to 607. for most zeolite samples and represents preferred conditions, it may occasionally be necessary to use somewhat more severe conditions for samples of very low-activity, such as those having an exceptionally.high silica to alumina mole ratio. In those instances, a temperature of up to about 540°C and a liquid hourly space velocity of less than one, such as 0.1 or less, can be employed in order to achieve a minimum total conversion of about 1-07..

The "Constraint Index" is calculated as follows: Constraint Index « Iqri n (fraction of hexane remaining) logio (fraction of 3-methyIpentane remaining) The Constraint Index approximates the ratio of the cracking rate constants for the two hydrocarbons. Zeolites suitable for the present invention are those having a Constraint Index of 1 to 12. Constraint Index (CI) values for some typical materials are: C.I.

ZSM-4 0.5 ZSM-5 8.3 ZSM-11 8.7 ZSM-12 2 ZSM-23 9.1 ZSM-35 4.5 ZSM-38 2 ZSM-48 '3.4 TMA Offretite 3.7 Clinoptilolite 3.4 Beta 0.6 H-Zeolon (mordenite) 0.4 REY 0.4 Amorphous Silica-Alumina 0.6 Erionite 38 The above-described Constraint Index is an important and even critical definition of those zeolites which are useful in the instant invention. The very nature of this parameter and the recited technique by which it is determined, however, admit of the possibility that a given zeolite can be tested under somewhat different conditions and thereby exhibit different Constraint Indices.

Constraint Index seems to vary somewhat with severity of operation (conversion) and the presence or absence of binders. Likewise, other variables such as crystal size of the zeolite, the presence of occluded contaminants, etc., may affect the constraint index. Therefore, it will be appreciated that it may be possible to so select test conditions as to establish more than one value in the range of 1 to 12 for the Constraint Index of a particular zeolite. Such a zeolite exhibits the constrained access as herein defined and is to be regarded as having a Constraint Index in the range of 1 to 12. Also contemplated herein as having a Constraint Index in the range of 1 to 12 and therefore within the scope of the defined novel class of highly siliceous zeolites are those zeolites which, when tested under two or more sets of conditions within the above-specified ranges of temperature and conversion, produce a value of the Constraint Index slightly less than 1, e.g. 0.9, or somewhat greater than 12, e.g. 14 or 15, with at least one other value within the range of 1 to 12. Thus, it should be understood that the Constraint Index value as used herein is an inclusive rather than an exclusive value. That is, a crystalline zeolite when I /' uC J- ■/ identified by any combination of conditions within the testing definition set forth herein as having a Constraint Index in the range of 1 to 12 is intended to be included in the instant novel zeoliti definition whether or not the saae identical zeolite, when tested under other of the defined conditions, nay give a Constraint Index value outside of the range of 1 to 12.

The novel class of zeolites defined herein is exemplified by ZSM-5, ZSM-11, ZSM-12, ZSM-23, ZSM-35, ZSM-38, ZSM-48 and other similar materials.

ZSM-5 is described in greater detail inN.z.

Patent No. 152,150. The entire descriptions contained within those patents, particularly the X-ray diffraction pattern of therein disclosed ZSM-5, are incorporated herein by reference.

ZSM-11 is described in U.S. Patent No. 3,709,979. That description, and in particular the X-ray diffraction pattern of said ZSM-11, is incorporated herein by reference.

. ZSM-12 is described in U.S. Patent No.. 3,832,449. That description, and in particular the X-ray diffraction pattern disclosed therein, is incorporated herein by reference.

ZSM-23 is described in U.S. Patent No. 4,076,842. The entire content thereof, particularly•the specification of the X-ray diffraction pattern of the disclosed zeolite, is incorporated herein by reference.

N.Z. PATENT OFFICE 1 9 60 7 ZSM-35 is described in U.S. Patent No. 4,016,245. The description of that zeolite, and particularly the X-ray diffraction pattern thereof, is incorporated herein by reference.

ZSK-38 is more particularly described in U.S. Patent No. 4,046,859. The description of that zeolite, and particularly the specified X-ray diffraction pattern thereof, is incorporated herein by reference.

ZSM-48 can be identified, in terms of moles of anhydrous oxides per 100 moles of silica, as follows: (0-15)RH : (0-1.5)M2/nO : (0-2)Al203 : (100)Si02 " wherein: M is at least one cation having a valence n; and RN is a C1-C20 organic compound having at least one amine functional group of pKaX7.

It is recognized that, particularly when the composition contains tetrahedral, framework aluminum, a fraction of the amine functional groups may be protonated. The doubly protonated form, in conventional notation, would be (RNH)20 and is equivalent in stoichiometry to 2RN + H2O.

The characteristic X-ray diffraction pattern of .the synthetic zeolite ZSM-48 has the following significant lines: v • O 0T7 1 ✓ u c J / Characteristic Lines of ZSM-48 d(A) Relative Intensity tf-.VS' ■ U 1 1 .9 .2 7.2 W 4.2 VSs 3.9 VS 3.6 W 2.85 W These values were determined by standard techniques. The radiation was the K-alpha doublet of copper, and a scintillation counter spectrometer with a strip chart pen recorder was used. The peak heights, I, and the positions as a function of 2 times theta, where theta is the Bragg angle, were read from the spectrometer chart.

From these, the relative intensities, 100 I/Ic, where IQ is the intensity of the strongest line or peak, and d (obs.), the interplanar spacing in A, corresponding to the recorded lines, were .calculated. In the foregoing table the relative intensities are given in terms of the symbols W = weak, VS •* very strong and W-VS = weak-tcwl^trong. Ion exchange of the sodium with cations reveals 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 aluminum ratio of the particular sample, as well as if it has been subjected to thermal treatment.

N.Z. PATENT office " -f NOV 1983 The ZSM-48 can be prepared from a reaction mixture containing a source of silica, water, RN, an alkali metal oxide (e.g. sodium) and optionally alumina. The reaction, mixture should have a composition, in terms of mole ratios of oxides, falling within the following ranges: REACTANTS BROAD PREFERRED Al203/Si02 a 0 to 0.02 0 to 0.01 Na/Si02 = 0 to 2 0 • ft O • O RN/Si02 - 0.01 to 2.0 0.05 to 1.0 0H"/Si02 - 0 to 0.25 0 to 0.1 H20/Si02 - to 100 to 70 H+(added)/ Si02 S3 0 to 0.2 0 to 0.05 wherein RN is a *-1-^20 organic compound having amine functional group of pKa>7. The mixture is maintained at 80-250°C until crystals of the material are formed.

H+(added) is moles acid added in excess of the moles of hydroxide added. In calculating H+(added) and OH values, the term acid (H+) includes both hvdronium ion, whether free or coordinated, and aluminum. Thus aluminum sulfate, for example, would be considered a mixture of aluminum oxide, sulfuric acid, and water. An amine hydrochloride would be a mixture of amine and HCl. In preparing the highly siliceous « form of ZSM-48 no alumina is added. Thus, the only aluminum present occurs as an impurity in the reactants.

Preferably, crystallization is carried out under pressure in an autoclave or static bomb reactor, at 80°C to 250°C. 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, RN, sodium hydroxide, sodium chloride, aluminum sulfate, sodium aluminate, aluminum oxide, or aluminum itself. RN is a C1-C20 organic compound containing at least one amine functional group of pka>7, as defined above, and includes such compounds as 03-0*13 primary, secondary, and tertiary amines, cyclic amine (such as piperidine, pyrrolidine and piperazine), and polyaiaines • such as NH2-CnH2n-NH2 wherein n is 4-12.

The original cations can be subsequently replaced, at least in part, by calcination and/or ion exchange with another cation. Thus, the original cations are exchanged into a hydrogen or hydrogen ion precursor form or a form in which the original cation has been replaced by a metal of Groups II through VIII of the Periodic Table. Thus, for example, it is contemplated to exchange the original cations with ammonium ions or with hydronium ions. Catalytically active forms of these would_include, in particular, hydrogen, rare earth metals, aluminum, manganese and other metals of Groups II and VIII of the Periodic Table.

It is to be understood that by incorporating by reference the foregoing patents to describe examples of * specific members of the novel class with greater particularity, it is intended that identification of the therein disclosed crystalline zeolites be resolved on the basis of their respective X-ray diffraction patterns". As discussed above, the present invention contemplates utilization of such catalysts wherein the mole ratio of -14 silica to alumina is essentially unbounded. The incorporation of the identified patents should therefore not i be construed as- limiting the disclosed crystalline zeolites to those having the specific silica-alumina mole ratios discussed therein, it now being known that such zeolites may be substantially aluminum-free and yet, having the same' crystal structure as the disclosed materials, nay be useful or even preferred in some applications. It is the crystal structure, as identified by the X-ray diffraction "fingerprint", which establishes the identity of the specific crystalline zeolite material.

The specific zeolites described, when prepared in the presence of organic cations, are substantially, catalytically inactive, possibly because the intra-crystalline free space is occupied by organic cations from the forming solution. They may be activated by heating in an inert atmosphere at 540°C for one hour, for example, followed by base exchange with ammonium salts followed by calcination at 540°C in air. The presence of organic cations in the forming solution may not be absolutely essential to the formation of this type zeolite; however, the presence of these cations does appear to favor the formation of this special class of zeolite. More generally, it is desirable to activate this type catialyst by base exchange with ammonium salts followed by calcination in air at about 540°C for from about 15 minutes to about 24 hours.

Natural zeolites may sometimes be converted to zeolite structures of the class herein identified by various activation procedures and other treatments such as base -15 exchange, steaming, alumina extraction and calcination, alone or in combinations. Natural minerals which may be so treated include ferrierite, brewsterite,■ stilbite, dachiardite, epistilbite, heulandite, and clinoptilolite.

The preferred crystalline zeolites for utilization herein include ZSM-5, ZSM-11, ZSM-12, ZSM-23, ZSM-35, ZSM-38 ■and ZSM-48, with ZSM-5 being particularly preferred.

In a preferred aspect of this invention, the zeolites hereof are selected as those providing among other, things a crystal framework density, in the dry hydrogen form, of not less than about 1.6 grams per cubic centimeter. It has been found that zeolites which satisfy all three of the discussed criteria are most desired for several reasons. When hydrocarbon products or by-products are catalytically formed, for example, such zeolites tend to maximize the production of gasoline boiling range hydrocarbon products. Therefore, the preferred zeolites useful with respect to this invention are those having a Constraint Index as defined above of about 1 to about 12, a silica to alumina mole ratio of at least about 12 and a dried crystal density of not less than about 1.6 grams per cubic centimeter. The dry density for known .structures nay be calculated from the number of silicon plus aluminum atoms per 1000 cubic Angstroms, as given, e.g., on Page 19 of the article ZEOLITE STRUCTURE by W. M. Meier. This paper, the entire contents of which are incorporated herein by reference, is included in PROCEEDINGS OF THE CONFERENCE ON MOLECULAR SIEVES', (London, April 1967) published by the Society of Chemical Industry, London, 1968. 19683? When the crystal structure is unknown, the crystal framework density may be determined by classical pycnoaeter ■ techniques. For example, it may be determined by immersing the dry hydrogen form of the zeolite in an organic solvent which is not sorbed by the crystal. Or, the crystal density may be determined by mercury porosimetry, since mercury will fill the interstices between crystals but will not penetrate the intracrystalline free space.

It is possible that the unusual sustained activity and stability of this special class of zeolites is associated with its high crystal anionic framework density of not less than about 1.6 grams per cubic centimeter. This high density must necessarily be associated with a relatively small amount of free space within the crystal, which might be expected to result in more stable structures. This free space, however, is important as the locus of catalytic activity.

Crystal framework densities of some typical zeolites, including some which are not within the purview of this invention, are: I Void Framework Volume Density Ferrierite 0.28 cc/cc 1 .76 g/cc Mordenite .28 1 .7 ZSM-5, -11 .29 1 .79 ZSM-12 - 1.8 ZSM-23 - 2.0 Dachiardite .32 1.72 L .32 1.61 Clinoptilolite .34 1 .71 Lauinontite .34 1 .77 ZSM-4 (Omega) .38 1.65 Heulandite ' .39 1.69 P .41 1.57 Offretite .40 1.55 Levynite .40 1 .54 Erionite .35 1.51 Gmelinite .44 1.46 Chabazite .47 1.45 A .5 1.3 Y .48 1.27 When synthesized in the alkali metal form, the zeolite is conveniently converted to the hydrogen form, generally by intermediate formation of the ammonium form as a result of ammonium ion exchange and calcination of the ammonium form to yield the hydrogen form. In addition to the hydrogen form, other forms of the zeolite wherein the original alkali metal has been reduced to less than about 1.5 percent by weight may be used. Thus, the original alkali metal of the zeolite nay be replaced by ion exchange with other suitable metal cations of Groups I through VIII of the Periodic Table, including, by way of example, nickel, copper, zinc, palladium, calcium or rare -earth metals.

In practicing a particularly desired chemical conversion process, it may be useful to incorporate the above-described crystalline zeolite with a matrix comprising another material resistant to the temperature and other conditions employed in the process. Such matrix material is useful as a binder and imparts greater resistance to the Catalyst for the severe temperature, pressure and reactant • feed stream velocity conditions encountered in many cracking processes.

Useful matrix materials include both synthetic and naturally occurring substances, as well as inorganic materials such as clay, 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. Naturally occurring clays which can be composited with the zeolite include those of the montmorillonite and kaolin families, which families include the sub-bentonites 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.

In addition to the foregoing materials, the zeolites employed herein may be composited with a porous matrix material, such as alumina, silica-alumina^ silica-magnesia, silica-zirconia, silica-thoria, silica-beryllia, and silica-titania, as well as ternary compositions, such as silica-alumina-thoria, silica-alumina-zirconia, silica-alumina-magnesia and silica-magnesia-zirconia. The matrix may be in the form of a cogel. The relative proportions of zeolite component and inorganic oxide gel matrix, on" an anhydrous basis, may vary widely with the zeolite content ranging from between about 1 to about 99 percent by weight _ ( '• o o ~ ~7 i/uuj/ and more usually in the range of about 5 to about 80 percent by weight of the dry composite.

The above crystalline zeolites employed are, in accordance with the present invention, contacted with a solution of one or more compounds of the elements comprising a proportion of the alkaline-earth metals, such elements being strontium (Sr) and barium (Ba). Solutions of such compounds may be in any suitable solvent which is inert with respect to the metal-containing compound and the zeolite. Non-limiting examples of some suitable solvents include water, aromatic and aliphatic hydrocarbons, alcohols, organic acids (such as acetic acid, formic acid, propionic acid and so forth), and inorganic acids (such as hydrochloric acid, sulfuric acid and nitric acid). Other commonly available solvents such as halogenated hydrocarbons, ketones, ethers, etc., may also be useful to dissolve some metal compounds or complexes. Generally, the most useful solvent will be found to be water. However, the solvent of choice for any particular compound will, of course, be determined by the nature of that compound and for that reason the foregoing list should not be considered exhaustive of all of the suitable possibilities.

Oxides of strontium are effective modifying components for imparting the desirable shape selective activity to the particular^type of zeolites disclosed. Examples of representative strontium-containing compounds suitable for deposition of that metal on the zeolite include strontium acetate, strontium bromide, strontium carbonate, strontium chloride, strontium fluoride, strontium iodide, strontium formate, strontium chlorate, strontium lactate, strontium nitrate, strontium nitrite, strontium oxide, strontium hyponitrite, strontium salicylate, strontium sulfide, and strontium dithionate. This listing is not to be taken as n.z. patent gl '-icii received encompassing all of the utilizable strontium containing compounds. It is merely intended to be illustrative of some of the representative metal compounds which those in the art will find useful in practicing the disclosed invention. The knowledgeable reader will^ readily appreciate that there are numerous other known strontium salts and complexes which would .prove useful herein to provide solutions containing strontium suitable for combination with the zeolite in the manner hereinafter described. _ Reaction of the zeolite with the . treating strontium compound is effected by contacting the- zeolite with such compound. Where the treating compound is a liquid, such compound can be in solution in a solvent at the time contact with the zeolite is effected. Any solvent relatively inert with respect Co the treating strontium compound and the zeolite may be employed. Suitable solvents include water and aliphatic, aromatic or alcoholic liquid. The treating compound may also be used without a solvent, i.e. nay be used as a neat liquid. Where the treating conpound is in the gaseous phase, it can be used by itself or in admixture with a gaseous diluent relatively inert to the treating compound and the zeolite (such as helium or nitrogen) or with an organic solvent such as octane or toluene. Heating of the strontium compound impregnated catalyst subsequent to preparation and prior to use is preferred, and such heating can be carried out in the presence of oxygen - for example, in air. Although heating may be carried out at a temperature of about 150°C, higher temperatures, e.g. up to about 500°C, are preferred. Heating..J.s„,generally carried t 96831 out for 1-5 hours but may be extended to 24 hours or longer. While heating temperatures above about 500*0may be employed, they are generally not necessary, and at tanperatures of about 1000°C the crystal structure of the zeolite tends to deteriorate. After heating in air at elevated temperatures, and without being limited by any theoretical considerations, it is contemplated that the strontium is ., actually present in the zeolite in an oxidized state, such as SrO.

The amount of strontium oxide incorporated in the zeolite catalyst composition should be at least about 0.25 percent by weight, calculated on the basis of elemental strontium. However, it is preferred that the amount be at least about 1 percent by weight, calculated on the basis of elemental strontium, particularly when the zeolite is contained with a binder, e.g. 35 weight percent of alumina. The amount of strontium oxide can be as high as about 40 percent by weight or more, calculated on the basis of elemental strontium, depending on the amount and type of binder present. Preferably, the amount of strontium oxide added to the zeolite composite will be between about 1 and about 30 percent by weight, calculated on the basis of elemental strontium.

The amount of strontium incorporated with the zeolite by reaction with elemental strontium or strontium-containing ccnpound will depend upon several factors. One of these is the reaction time, i.e., the time that the zeolite and the strontium-containing source are maintained in contact with each other. With greater reaction times, all other factors being equal, a greater amount of metal is incorporated with the zeolite. Other factors upon which the amount of strontium incorporated with the zeolite is dependent include reaction tenperature, concentration of the treating N.Z, PATENT OFFICE 3 0 JAN 1984 compound in the reaction mixture, the degree to which the zeolite has been dried prior to reaction with the metal-containing compound, the conditions of drying of the zeolite after reaction with the treating compound, and the amount and type of binder incorporated with the zeolite.

Oxides of barium may also be employed as a modifying component. The barium oxide is contemplated as being present as BaO alone or in combination with other compounds of barium in an oxidized state. In all instances, regardless of the particular state of oxidation of the barium, its content with respect to the zeolite is computed as if it were present as BaO. Generally, the amount of BaO in the composite catalyst will be between about 0.25 and about 4 0 weight percent, and preferably between about 1 and about 35 weight percent, based on the weight of the composite, and calculated on the basis of elemental barium. Reaction of the zeolite with the barium-containing compound is carried out as described above with respect to the treatment with compounds of the element strontium. Examples of barium compounds which may be utilized include barium acetate, barium bromide, barium carbonate, barium chloride, barium fluoride, barium iodide, barium butyrate, barium chlorate, barium perchlorate, barium cyanide, barium di-thionate, barium formate, barium nitrate, barium nitrite, barium oxide, barium propionate and barium 196831 sulfide. Again, chis listing is not intended to be exhaustive, but rather suggestive to those of skill in the . art as to the kinds of metal-containing compounds useful for treating the zeolites as herein described.

In some instances, it may be desirable to modify the crystalline zeolites by combining therewith two or more of the specified metal oxides. Thus, the zeolite may be modified by prior combination therewith of oxides of, strontium, oxides of barium, oxides- of strontium and barium, or even oxides of both elements.

When such modification technique is employed, the respective oxides may be deposited on the zeolite either sequentially or from a solution containing suitable compounds of the elements, the oxides of which are to be combined with the zeolite. The amounts of oxides present in such instance are in the same range as specified above for the individual oxides, with the overall added oxide content being between about 1 and about 35 weight percent of the composite, calculated on the basis of the elonental metal which forms the oxide.

A further embodiment of this invention includes additional modification of the above metal oxide - zeolite composites with phosphorus, whereby from about 0.25 weight percent to about 30 weight percent of an oxide of phosphorus, calculated as elemental phosphorus, is combined with the zeolite composite. The preferred amount of phosphorus oxide will be between about 1.0 weight percent and about 25 weight percent, based on the weight of the treated zeolite composite, and calculated.on the basis of elemental phosphorus. The phosphorus treatment of the zeolite catalyst will preferably be carried out before the previously described modification with the alkaline-earth metals. Reaction of the zeolite - 2.4 - N.Z. PATENT OFFiCE 3 0 JAN 1984 196831 compound with the phosphorus-containing compound is carried oiit essentially as described above with respect to the metal-containing compounds and it is preferred that the total amount of oxides combined with the zeolite, i.e. the phosphorus oxides plus the metal oxides, fall within the approximate range of 2 percent to 40 percent by weight, b.ased on the weight of the treated zeolite composite, ,and 4 saleulated on the basis of elemental phosphorus.

Representative phosphorus-containing compounds which may be used include derivatives of groups represented by PX3, RPX2, R2PX, R3P, X3PO, (X0)3P0, (X0)3P, R3P=0, R3P=S, RP02, RPS2, RP(0)(OX)2, RP(S)(SX)2 » R2P(°)°X, " R2P(S)SX, RP(SX)2, ROP(OX)2, RSP(SX)2, (RS)2PSP(SR)2, and (R0)2POP(OR)2, where R is an alkyl or aryl, such as a phenyl radical and X is hydrogen, R, or halide. These compounds include primaryRPH2, secondary, R2PH and tertiary, R3P, phosphines such as butyl phosphine; the tertiary phosphine oxides R3?0, such as tributylphosphine oxide, the tertiary phosphine sulfides, R3PS, the primary, Rp(0)(0x)2» and secondary, R2P(0)0X, phosphonic acids such as benzene phosphonic acid; the corresponding sulfur derivatives such as RP(S)(SX)2 and R2P(S)SX, the esters of the phosphonic .acids such as diethyl phosphonate, (R0)2?(0)H, dialkyl alkyl phosphonates, (R0)2P(0)R, and alkyl dialkylphospninates, (R0)P(0)R2; phosphinous acids, R2P0X, such as diethyl-phosphinous acid, primary, (R0)P(0X)2, secondary, (R0)2P0X, and tertiary, (R0)3P, phosphites; and esters thereof such as the rnonopropyl ester, alkyl dialkylphosphinites, (RQ)PR2, and dialkyl alkylphosphinite, (R0)2PR esters. Corresponding sulfur derivatives may also be employed including n.z. PATENT OFF ICE (RS)2P(S)H, (RS)2P(S)R, (RS)P(S)R2, R2PSX, (RS)P(SX)2, (RS)2PSX, (RS)3P, (RS)PR2 and <RS)2PR. Examples of phosphite esters include trimethylphosphite, triethyl-phosphite, diisopropylphosphite, butylphosphite; and pyro-phosphites such as tetraethylpyrophosphite. The alkyl groups in the mentioned compounds contain from one to four carbon atoms.

Other suitable phosphorus-containing compounds include the phosphorus halides such as phosphorus trichloride, bromide, and iodide, alkyl phosphorodichloridites, (R0)PC12, dialkyl phosphorochloridites, (R0)2PC1, di-. alkylphosphinochloridites, R2PC1, alkyl alkylphosphono-chloridates, (RO)(R)P(0)C1, dialkyl phosphinochloridates, R2P(0)C1 and RP(0)C12. Applicable corresponding sulfur derivatives include (RS)PC12, (RS)2PC1, (RS)(R)P(S)C1 and R2P(S)C1.

Preferred phosphorus-containing compounds include diphenyl phosphine chloride, trimethylphosphite and phosphorus trichloride, phosphoric acid, phenyl phosphine oxychloride, trimethylphosphate, diphenyl phosphinous acid, diphenyl phosphinic acid, diethylchlorothiophosphate, methyl acid phosphate and other alcohol-P205 reaction products.

Particularly preferred are ammonium phosphates, including ammoniua hydrogen phosphate, (NH4)2HP04,- and ammonium dihydrogen phosphate, NH4H2P04.

Still another, modifying treatment entails steaming of the zeolite by contact with an atmosphere containing from about 5 to about 100 percent steam at a temperature of from about -250° to about 1000°C for a period of between about —xC," V •15 minutes and about 100 hours and under pressures ranging 'from sub-atmospheric to several hundred atmospheres. Preferably, steam treatment is effected at a temperature of between about 400°C and about 700°C for a period of between about 1 and about 24 hours.

Another modifying treatment involves precoking of the catalyst to deposit a coating of between about 2 and about 75, and preferably between about 15 and about 75, weight, percent of coke thereon. Precoking can be accomplished by contacting the catalyst with .a hydrocarbon charge, e.g. toluene, under high severity conditions or" alternatively at a reduced hydrogen to hydrocarbon concentration, i.e. 0 to 1 mole ratio of hydrogen to hydrocarbon, for a sufficient time to deposit the desired amount of coke thereon.

It is also contemplated that a combination of steaming and precoking of the catalyst under the above conditions may be employed to suitably modify the crystalline zeolite catalyst.

Alkylation of aromatic compounds in the presence of the above-described catalyst is effected by contact of .the aromatic with an alkylating agent. A particularly preferred embodiment involves the alkylation of toluene wherein the alkylating agents employed comprise methanol or other well known methylating agents or ethylene. The reaction is carried out at a temperature of between about 250°C and about 750°C, preferably between about 300°C and 650°C. At higher temperatures, the zeolites of high silica/alumina ratio are preferred. For example, ZSM-5 - 2.7-^€T- !968 J7 having a Si02/Al203 ratio of 300 and upwards is exceptionally stable at high temperatures. The reaction generally takes place at atmospheric pressure, but pressures within the approximate range of 10^ N/m^ to 10? N/m^ (1-100 atmospheres) cay be employed.

Some non-limiting examples of suitable alkylating agents would include olefins such as, for example, ethylene, propylene, butene, decene and dodecene, as well as formaldehyde, alkyl halides and alcohols, the alkyl portion thereof having from 1 to 16 carbon atoms. Numerous other aliphatic compounds having at least one reactive alkyl -radical may be utilized as alkylating agents.

Aromatic compounds which may be selectively alkylated as described herein would include any alkylatable aromatic hydrocarbon such as, for example, benzene, ethyl-benzene, toluene, dimethylbenzenes, diethylbenzenes, methylethylbenzenes, propylbenzene , isopropylbenzene , isopropylmethylbenzenes, or substantially any mono- or di-substituted benzenes which are alkylatable in. the 4-position of the aromatic ring.

The molar ratio of alkylating agent to aromatic compound is generally between about 0.05 and about 5. For instance, when methanol is employed as the methylating agent and toluene is the aromatic, a suitable Aolar ratio of methanol to toluene has been found to be approximately 1-0.1 mole of methanol per mole of toluene. Reaction is suitably accomplished utilizing a feed weight hourly space velocity (WHSV) of between about 1 and about 1000, and preferably between about 1 and about 200. The reaction product, -Jtf- 1.968 3 consisting predominantly of the 1 ,4-dialkyl isomer, e.g. I, 4-dimethylbenzene , 1 -ethyl-4-methylbenzene, etc., or a ■mixture of the '1,4- and 1,2- isomers together with comparatively smaller amounts of -1 , 3-dialkylbenzene isomer, may be separated by any suitable means. Such means may include, for example, passing the reaction product stream through a water condenser and subsequently passing the organic phase through a column in which chromatographic separation of the aromatic isomers is accomplished.

When transalkylation is to be accomplished, trans-alkylating agents are alkyl or polyalkyl aromatic hydro"-carbons wherein alkyl may be composed of from 1 to about 5 carbon atoms, such as, for example, toluene, xylene, tri-methylbenzene, triethylbenzene, dimethylethylbenzene, ethyl benzene, diethylbenzene, ethyltoluene, and so forth.

Another aspect of this invention involves the selective disproportionation of alkylated aromatic compound to produce dialkylbenzenes wherein the yield of 1,4-dialkyl isomer is in excess of the normal equilibrium concentration In this context, it should be noted that disproportionation is a special case of transalkylation in which the alkylatable hydrocarbon and the transalkylating agent are the same compound, for example when toluene serves as the donor and acceptor of a transferred methyl group to produce benzene and xylene.

The transalkylation and disproportionation reactions are carried out by contacting the reactants with the above described modified zeolite catalyst at a temperature of between about 250°C and 750°C at a pressure ^ *)68-3J of between atmospheric (10^ N/tn^) anj about 100 atmospheres (;1 0? N/ej2) . The reactant feed-WHSV will normally fall within the range.of about 0.1 to about 50. Preferred alkylated aromatic compounds suitable for utilization in the disproportionation embodiment comprise toluene, ethyl-benzene, propylbenzene or substantially any mono-substituted alkylbenzene. These aromatic compounds are selectively converted to, respectively, 1,4-dimethylbenzene, 1,4-diethylbenzene, 1,4-dipropylbenzene, or other 1,4-dialkylbenzene, as appropriate, with benzene being a primary side product in each instance. The product is _ recovered from the reactor effluent by conventional means, such as distillation, to remove the desired products of-benzene and dialkylbenzene, and any unreacted aromatic component is recycled for further reaction.

The hydrocarbon conversion processes described herein may be carried out as a batch type, seoi-continuous or continuous operation utilizing a fixed or coving bed catalyst system. The catalyst after use in a moving bed reactor is conducted to a regeneration zone wherein coke is burned from the catalyst in an oxygen-containing atmosphere, e.g. air, at an elevated temperature, after which the regenerated catalyst is recycled to the conversion zone for further contact with the charge stock. In a fixed bed reactor, regeneration is carried out in a conventional manner where an inert gas containing a small amount of oxygen (0.5-27o) is used to burn the coke in a controlled manner so as to limit the temperature to a maximum of around 500°-550°C. i Q The following examples will serve to illustrate .certain specific embodiments of the hereindisclosed invention. These examples should not, however, be construed as limiting the scope of the novel invention, as there are many variations which may be made thereon without departing from the spirit of the disclosed invention, as those of' skill in the art will recognize.

All percentages are by weight of catalyst ccnposite.

EXAMPLE 1 A [Alkylation reaction with unmodified ZSM-5] Five grams- of HZSM-5 (silica/alumina mole ratio » 70; 657. on alumina binder) were placed in a quartz flow reactor and heated to various temperatures between 350°C and 500°C. A mixture of toluene and methanol, at a 4/1 molar ratio, was passed thru the zeolite catalyst at a weight hourly space velocity (UHSV) of 10. The reactor effluent was monitored and the results obtained at the various temoeratures are shown below.

Tearnerature £C 350 400 450 500 Percent toluene conversion 47.2 58.0 68.0 87.6 Percent para-isomer in xylenes 24.8 24.4 24.3 24.2 -.MT OFFICE 2 (h ® 8.3/ EXAMPLE IB In a similar manner, toluene was alkylated with ethylene by passing toluene and ethylene, at WHSV of 7.0 and 0.5, respectively, over the unmodified zeolite. The results at various temperatures are shown below.

Percent toluene Isomer ratios of Temperature gC conversion ethyltoluene £ m o 400 76.4 29.9 58.5 11 *.6 425 76.4 29.9 57.5 12.7 450 79.0 29.6 57.1 13.4 EXAMPLE 2 [Disproportionation reaction with uncodified ZSM-5] Toluene, was passed over a 6.0g sample of HZSM-5 (Si02/Al203 mole ratio » 70; 657. on alumina binder) at a feed WHSV of 3.5-3.6 and at temperatures between 450°C and 600°C. The results are summarized below.. 7. para in Temp WHSV Tol .Cotiv. 7. Selectivity, wt xylene products £C_ Mole 7.

Benzene Xylenes 450 3.6 7.4 43.5 55.5 24.7 500 3.5 .5 44.6 53.8 24.5 550 3.5 38.8 48.0 48.8 24.2 600 3.5 49.2 54.4 41 .7 24.1 -ll- 1 96837 EXAMPLE /3 "" [Preparation of Sr-modified zeolite] A solution of 5.0g Sr(0Ac)2 in 15 ml H2O was ' prepared and heated to 80°C. Added 5.0g of HZSM-5 (Si02/-AI2O3 raole ratio = 70) and maintained the mixture at 80-90°C for 2 'hours. After filtering and drying at 90°C for 2 hours, the zeolite was calcined at 500°C to yield 5.52g of Sr-ZSM-5. The content of strontium was calculated to be 8.07. by weight of catalyst composite.

EXAMPLE 4A [Alkylation reaction with Sr-modified zeolite] Alkylation of toluene with methanol was carried out by passing a toluene/methanol mixture (molar ratio =» 4/1) over 4.0g of the Sr-ZSM-5 zeolite of Example 6 at 400°C and feed WHSV=10. Toluene conversion was 307. with 60.67» para-isomer in the xylene product. This is a two-and-a-half-fold increase in para-selectivity relative to the unmodified ZSM-5 (Example 1A).

EXAMPLE 4B In a similar manner, toluene was ethylated by passing a toluene/et'nylene feed stream (WHSV =7.0 and 0.5, respectively) over the Sr-ZSM-5 zeolite at 400°C.

Conversion of toluene was 47.57. and the yield of para-isomer in the ethyl toluene was 64.57o. Again, there is a very - 33 - — N.z. patent qfpirp -1 NOV 1983 1 O 0 "T 7 I y u u _• / substantial and surprising increase in para-selectivity over that attained by the unmodified zeolite (Example IB).

- EXAMPLE 5 [Disproportionation reaction with Sr-nodified zeolite] A toluene feed stream was passed over the Sr-ZSM-5 zeolite of Example 3 to study the toluene disproportionation reaction. The toluene WHSV was 3.5 and the reactor was at 550°C. Toluene conversion was 1 .57. and the para-isomer in the xylene product was 31.2%. This compares very favorably with the 24.27. selectivity of the unmodified ZSM-5 (Example 2) .

EXAMPLE 6 [Preparation of Ba-nodified zeolite] Dissolved 5.0g Ba(0Ac)2 in 7.0 ml H2O at 80°C and added 3.0g HZSM-5 (Si02/Al2C>3 mole ratio = 70). The mixture was maintained at 80-90°C for 3 hours then the zeolite was recovered by filtration and dried at about 90°C for 1.5 hours. The dried zeolite was then calcined to yield 3.57g 3a-ZSM-5. The barium content was calculated to be 14.37, by weight of catalyst composite.

EXAMPLE-7A [Alkylation reaction with Ba-modified zeolite] Alkylation of toluene with methanol in the presence of the Ba-modified zeolite catalyst was carried out by passing a feed stream of toluene and methanol (molar ratio = 4/1) over a 1.1g sample of the Ba-ZSM-5 zeolite of Example 6 at 500°C. The reactor effluent was analyzed and toluene conversion was found to be 26.07. vrith 53.67. .

N.Z. patent office -1 NOV 1983 i o Q 7 I / O KJ / •para-isomer in the xylene produced. The unmodified zeolite, under identical conditions, gave only 24.27. of the para-isomer (Example 1A).

EXAMPLE 7B In a similar manner, toluene was ethylated by. passing toluene (WHSV=7.0) and ethylene (WHSV=0.5) over the Ba-ZSM-5 zeolite of Example >6 at 400°C. Conversion of toluene was 5.57. and the yield of para-isomer in the ethyltoluene product was found to be 80.77.. The ^para-selectivity fof the unmodified ZSM-5 was only 29.97.

(Example 1 B).

EXAMPLE ,8 [Disproportionation reaction with Ba-modified zeolite] Toluene was disproportionated to xylenes by passing a feed stream of toluene over the Ba-ZSM-5 of Example 6 at WHSV of"3.5 and 550°C. Toluene conversion was 1.97. with 72.07. of the para-isotner in the xylenes produced. Once again, a very substantial improvement relative to the unmodified zeolite (Example 2) was shown.

EXAMPLE 9 [Preparation of P-modified zeolite] Two hundred grams of ammonium-ZSM-5 (657. on alumina' binder) were added to a solution of 80g of aiammonium hydrogen phosphate in 300 ml of H2O at about 90°C. After standing at about 90°C for 2 hours, the zeolite was-filtered, dried at 90°C for 2 hours and then calcined at n.z. PATENT OFFirF . - HN0VS9S3 i ✓ O b ^ '7 / 500°C for another 2 hours. The recovered P-ZSM-5 zeolite contained 3.43 wt 7. phosphorus.

EXAMPLE 10A [Alkylation reaction with P-modified zeolite] Alkylation of toluene with methanol was carried out by passing a toluene/nethanol feed stream (nolar ratio 4/1) over 5.0g of the P-ZSM-5 zeolite of Example 9,. The feed WHSV was 10 and the reactor temperature was varied between 400°C and 600°C. The results obtained are summarized below.

Percent toluene Percent para-isomer Temperature °C conversion in xylenes 400 43.6 66.6 450 54.4 57.7 500 70.4 53.7 •550 85.2 52.0 600 85.2 58.0 EXAMPLE 10B In a similar manner, ethylation of toluene was accomplished utilizing a feed stream of toluene (WHSV=7.0) and ethylene (WHSV=0.5) in the presence of the P-ZSM-5 catalyst at 400°C. Conversion of toluene was 74.87, and selectivity to the pararisomer of ethyltoluene was 55.57».

EXAMPLE 11.

[Disproportionation reaction with P-raodified zeolite] Toluene disproportionation was tested by passing a stream of toluene over the P-ZSM-5 catalyst of Example 9 at 19683 7 '' a. feed WHSV of 3.5 and at temperatures of between 475°C and 550°C. The results are summarized below.

Temperature °C Toluene Conv.

% % Selectivity Benzene , mole Xylene % Para in Xylenes 475 14 .9 52.8 47.6 39.1 500 27.1 53.3 45.4 .1 5Q0 37.4 56.1 42.2 32.1 550 44.0 60.4 37.3 .1 EXAMPLE 12 [Preparation of Sr-P-modifiqd zeolite] Six grams of the P-modified ZSM-5 zeolite from Example 9 were mixed with a solution of 5.0g SrfOAc^ in 15 ml of H20. The mixture was maintained at 80-90°C for 2.3 hours. After filtration and drying at 90°C, the zeolite was calcined at 500°C for 2 hours to yield 6.45g Sr-P-ZSM-5. Upon analysis the content of phosphorus was found to be 3.18% by weight of catalyst composite and that of strontium was 7.93% by weight of catalyst composite.

N.Z. PATL-,Vi f-;-.

= ? NOV J983 EXAMPLE 13A [Alkylation reaction ■ with Sr-P-modified zeolite] Toluene was alkylated with methanol by passing a toluene/methanol (molar ratio = 4/1) feed stream over 5.0g of the Sr-P-ZSM-5 zeolite of Example 12, Reaction temperature was 500°C and the feed rate (WHSV) was 10. Toluene conversion was found to be 56.47. with an 84.57. selectivity to' the para isomer in the xylene product, EXAMPLE 13B Toluene was reacted with ethylene to produce-ethyltoluene by passing a feed stream of toluene and ethylene (WHSV of 7.0. and 0.5, respectively) over 5.0g of the Sr-P-ZSM-5 zeolite of Example 12 at 400°C. Conversion of toluene was 70.97. with 92.37. selectivity to the para isomer' in the ethyltoluene produced.

EXAMPLE 14.

[Disproportionation reaction with Sr-P-modified zeolite] Disproportionation of toluene to xylenes was carried out.by passing a feed stream of toluene over the Sr-P-modified ZSM-5 zeolite of Example 12 at a WHSV of 3.5. The reaction was conducted at 500°C. Toluene conversion was 4.9% with 71 .27. para isomer in the xylene produced.

Examples 13 and 14 clearly demonstrate the improvement in para selectivity realized by modification of the P-ZSM-5 zeolite with strontium. n.z. patent office -f NOV 1983 I 96837 EXAMPLE 15 [Preparation of Ba-P-modified zeolite] Added 6.0g of the P-ZSM-5 zeolite prepared in Example 9 to an 80°C solution of 8.0g Ba(0Ac)2 in 15 ml of water. The mixture was maintained at 80-90°C for 2 hours then filtered and the zeolite dried at 90°C overnight.

After calcining at 500°C for 2 hours, there were 8.30g of Ba-P-ZSM-5 recovered. Analysis indicated the modified zeolite contained 2.787. phosphorus and 16.07. barium, by weight of catalyst composite.

EXAMPLE 16"/ [Disproportionation reaction with Ba-P-modified zeolite] Disproportionation of toluene to xylenes was carried out at 500°C by contacting toluene (feed WHSV=3.5) with the Ba-P-ZSM-5 of Example 15. Toluene conversion was 0.37. with 657. selectivity to para-xylene in xylenes.

EXAMPLE 17: [Disproportionation reaction~with unmodified ZSM-11] A 1.0g portion of_unmodified HZSM-1 1 zeolite (silica to alumina mole ratio = 70) was placed in a quartz flow reactor and heated to temperature. Toluene was passed over the zeolite at WHSV of 3.8 and various temperatures between 400°C and 600°C. The results are summarized below.

N.z. patent office - t NOV 1983 I o ,c o ~ 7 I y ^ c J / Temperature £C Toluene Conv mole 7. 7o Selectivity, mole 3enzene Xylene 7. Para in Xylenes 400 3.0 ' 51 .7 ' 47.8 24.3 450 8.7 48.1 50.7 24.1 500 21 .7 49.0 48.9 23.7 550 39.1 53.7 42.6 23.. 7 600 49.9 58.6 36.8 23.4 EXAMPLE 18A : [Alkylation reaction with unmodified ZSM-11] A toluene/methanol feed stream, having a 4/1 molar ratio of the respective reactants, was passed over unmodified HZSM-11 zeolite (Si02/Al203 = 70) at 400-600°C and a feed WHSV of 10. The results are shown below.

Temperature Percent toluene Percent para xylene £C Conversion in Xylenes 400 67.6 23.4 500 90.4 24.0 600 157.2 22.7 EXAMPLE 18B A.toluene/ethylene feed stream was similarly brought into contact with the unmodified HZSM-11.- The feed WHSV was 7.5 and 0.55, respectively, and the temperature of reaction 400-450°C. The results are summarized below.

• Temperature 7<, toluene Isomer ratios of £C Conversion ethyltoluene £ E £ 400 80.2 27.3 58.4 14.3 450 87.9 27.2.57.9 14.9 office 196837 EXAMPLE 19 [Preparation of 3a-modified ZSM-11] Added 1.5 grams HZSM-11 zeolite'(silica to alimina mole ratio = 70) to a solution of 3. 5g. barium acetate in 5.0 ml of vater at 80°C. The mixture was maintained at 80-90°C for 2.5 hours, then filtered and the zeolite cried at 90°C • overnight. After calcining at 500°C , 2.3Cg of Ba-ZSM-11 were recovered having a calculated barium content of 31 .17,. by weight of catalyst composite.

EXAMPLE .2OA [Alkylation reaction with Ba-nodified ZSM-11] Alkylation of toluene with methanol was carried out at a feed WHSV of 10. Toluene conversion was 37.57. with 63 -97. selectivity to the para isomer in the xylene produced.

EXAMPLE 20B Toluene and ethylene were reacted over the Ba-modified ZSM-11 at A00°C. The feed WHSV for toluene was 7.0 and for ethylene was 0.5. Conversion of toluene was 5.37. and the yield of para-ethyltoluene in the ethyltoluene produced was 89 .07..

EXAMPLE 21. " [Disproportionation reaction with 3a-~odified ZSM-1 1] Disproportionation of toluene to xylenes in the presence of the Ba-ZSM-1'1 zeolite of Example 19 was carried out by passing toluene over the modified zeolite at WKSV of 3.5 and a temperature of 600°C. Toluene conversion was 6.07. with 46.37, selectivity to para-xylene.

N.Z. PATENT OFFICE I =■ U ?s]0V1983 It is to be understood that the foregoing is intended to be merely illustrative of certain specific embodiments of the disclosed invention. -As those of skill in the art will readily appreciate, there are many variations which may be made "on.these specific embodiments without departing from the spirit of my invention and such variations are clearly to be encompassed within ambit of. the following claims.

N.Z. PATENT OFFICE = 1WOV1983

Claims (14)

WHAT WE CLAIM IS:

1. A process for para-selective conversion of a substituted aromatic compound via alkylation, transalkylation or disproportionation to form a dialkylbenzene compound mixture rich in the 1,4-dialkylbenzene isomer, said process comprising contacting said aromatic compound with a crystalline zeolite catalyst composition at a temperature of between >250°C and . . ; 750°C and a pressure within the . range of 10^ N/m2 to 10^ N/m2, said catalyst comprising a zeolite characterized by a silica to alumina mole ratio of at least 12 and a constraint index within the range of 1 to 12, said catalyst having deposited thereon at least ~ - 0.25 percent by weight of an alkaline-earth metal which is barium, strontium or combinations thereof, said metal being present in said catalyst in the form of its oxide.

2. The process of claim 1 wherein said temperature is between 300°C and 650°C.

3. The process of claim 1 or claim 2 wherein said metal is strontium which comprises between 1 and 30 weight percent of the modified zeolite catalyst.

4. The process of claim 1 or claim 2 wherein said metal is barium which comprises between 1 and 35 weight percent of the modified zeolite catalyst. one

5. The process of any/of claims r to 4 wherein said catalyst also has deposited thereon at least 0.25 weight percent of phosphorus, said phosphorus, being present in said zeolite in the form of an oxide of phosphorus. -43- 2 4SWJ983 196837

6. The process of any preceding claim wherein said zeolite is admixed with a binder therefor.

7. The process of any preceding claim wherein said conversion is the alkylation of an aromatic compound by contacting said compound with an alkylating agent to produce dialkylbenzene compounds wherein the 1,4-dialkylbenzene isomer is present in excess of its normal equilibrium concentration. ope

8. The process of any/of claims 1 to 6 wherein said conversion is the transalkylation of aromatic compounds to produce dialkylbenzene compounds wherein the 1,4-dialkylbenzene isomer is present in excess of its normal equilibrium concentration. one

9. The process of any/of Claims 1 to 6 wherein said conversion is disproportionation of alkylbenzenes to produce benzene and dialkylbenzene in which the proportion of 1,4-dialkylbenzene isomer is in excess of its normal equilibrium concentration.

10. The process of any preceding claim wherein said zeolite is ZSM-5, ZSM-11, ZSM-12, ZSM-23, ZSM-35, ZSM-38 or ZSM-48.

11. A catalyst composition comprising a crystalline zeolite having a constraint index of 1 to 12 and a silica to alumina mole ratio of at least 12 and further comprising at least 0.25 weight percent of alkaline-earth metal which is strontium or barium deposited thereon, said metal being present in said catalyst in the form of its oxide.

12. The composition of claim 11 wherein said alkaline-earth metal is strontium comprising between 1 and 30 weight percent of said catalyst composition. -44- 196831

13. The composition of claim 11 wherein said alkaline-earth metal is barium comprising between 1 and 35 weight percent of said catalyst composition. in the form of an oxide of phosphorus. 15. The composition of any of claims 11 to 14 wherein said zeolite is ZSM-5, ZSM-11, ZSM-12, ZSM-23, ZSM-35, ZSM-38 or ZSM-48. one 16. The composition of any/of claims 11 to 15 wherein said zeolite is admixed with a binder therefor.

14. The composition of any one of claims 11 to 13 wherein said zeolite catalyst composition also has deposited thereon at least 0.25 weight percent of phosphorus, said phosphorus being present in said composition ©ATE© THIS OAT OF & SON AGENTS FOR THE APPLICANT! -45- ra"rn\n' office 3 ©JAN 1984 iV-7r> i