CA1061769A - Phosphorus-containing catalyst-its preparation and use - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE
A novel phosphorus containing zeolite catalyst is desribed, as well as its preparation and use in conversion of a large variety of organic compounds. The novel catalyst comprises a crystalline aluminosilicate zeolite which has a silica to alumina ratio of at least 12 and a constraint index in the range 1 to 12, and which has been treated so as to include at least 0.5 weight percent of phosphorus (by weight of the zeolite) in intimate association therewith.

Description

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~-848r+ PHOSPHORUS-CONTAINING CATALYST
ITS PREPARATION AND USE

This invention relates to a phosphorus containing catalyst to its preparation and to its use in conversion of a large variety of organic compounds. More particularly it relates to catalysts which comprise one of a defined class of zeolite in which phosphorus is incorporated and to certain conversions, both of hydrocarbons and non-hydrocarbons, which proceed in a uniquely advantageous manner under the in~luence of such catalysts.

Significant commercial use of zeolite catalyst com~enced in the early nineteen sixties, when they were introduced (in base-exchanged form, in a matrix, as described in U.S. Patent 3,140,249) as cracking catalysts. In a surprisingly short time these catalysts virtually entirely displaced the amorphous catalysts which had previously been used. The zeolite employed has been a synthetic fauJasite, originally zeolite X (silica/alumina ratio about 2.5), later zeolite Y (silica/
alumina ratio about 5.0).

During this period the technical literature has abounded with reports of new synthetic zeolites and of proposals for the use of zeolites, both new and old, as catalysts capable of improving performance of almost every commercially interesting organic conversion. The oil industry has been a particularly prolific source of such proposals, ~` many of which therefore concern conversions basic to that industry such as iscmerisation, alkylation and aromatisation. -_J_ .

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The earlier proposals for use of zeolites as catalysts ~ere, on the whole, relatively unspecific insofar as selection of particular zeolites for a particular purpose was concerned: by and large they contemplated use of any zeolite the pores of which were large enough to pass the reagent and products. More recently, however, there has been observable a tendency toward more restrictive definition of zeolites employed to catalyse, and toward morè specific identification of reactions catalysed. This tendency has developed with the appearance of what might be termed a new breed of synthetic zeolites, of which members continue to appear and of which more later: and it has yielded some outstanding advances in conversions of particular interest to the chemical as well as to the petroleum refining industry. The conversion ~ of oxygen-containing aliphatics to aromatics described in OLS 2,438,252 .~ is a good example of the trend.

We have now discovered a catalyst which advances the art still further. According to the present invention a catalyst for the conversion of organic compounds comprises a crystalline aluminosilicate zeolite which has a silica to alumina ratio of at least 12 and a constraint index in the range 1 to 12, is at least partly in the hydrogen form, and which includes at least 0.5 weight percent of phosphorus (by weight of the zeolite) in intimate association therewith.
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i The catalyst may include 0.5 to 25 weight percent of phosphorus, `~ mDre usuall~ 2 to 15 ~eight percent; however, we have ~ound that for certain applications 0.78 to 4.5, preferably o.78 to 2.5% wt. suffices.
qhe zeolite preferably has a silica to alumina ratio of at least 30 .~ .

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!~ members of the ZSM-5 family, preferably zeolite ZSM-5 itself, bein~

particularly useful. Nevertheless many other zeolites have high utility in the invention, zeolites ZSM-12 and SZM-21 being two such.
The zeolite, whichever it might be, is desirably composited with a catalytically relatively inert matrix, as in the weight proportion of 35 parts of zeolite to 65 of matrix.

In certain applications catalysts according to the invention have impregnated on the zeolite at least 0.1 percent of its weight of zinc, a preferred quantity of such zinc being 1 to 4 weight percent: and generally we prefer to employ zeolites having a silica to alumina ratio in the range 60 to 300 and which have a crystal density, in~the dry hydrogen form, of not less than 1.6 g/cc.

The invention further comprehends a method of preparing the afore-said catalyst which method comprises contacting said zeolite with a phosphorus-containing compound and heating the product of the contact.
e phosphorus-containing compound may in this method be in the vapour or liquid phase, and in the latter instance may be in solution. A
preferred phosphorus-containing compound is orthophosphoric acid or one ; of its esters, but a very extensive range of such compound may be successfully employed, such as phosphorus trichloride, diphenyl phosphine chloride, diphenyl phosphinous acid, trimethyl phosphite, or the product of reactlon of P205 with an alcohol. The ester or alcohol is preferably methyl. A suitable temperature range ~or the heating is 150 to 500C, desirably effected in an atmosphere in which oxygen is present. It ~s often of advantage to expose the zeolite to the action of water vapour 1(~6176~
between the contacting and the heating.

When a zinc-containing catalyst is employed, the zinc is impregnated upon the zeolite by contact of the zeolite with a liquid medium contain-ing zinc, followed by drying, so as to impregnate at least 0.1% wt. zinc upon the zeolite. me liquid medium containing zinc is usually a solution of a zinc salt such as the nitrate.

From the conversion aspect the invention comprehends a process for converting an organic compound comprising contacting the same, under conversion conditions, with a catalyst described or prepared in the manner set forth hereinabove.Hydrocarbons which can be converted to highly desirable products include paraffins such as n-hexan~ or even light naphtha, and olefins such as ethylene, propylene and butenes.
Such conversion is best carried out at a temperature of 300 to 700C, preferably 500 to 700C.

The invention, however, extends to more co~,plicated conversions.
AIkylation of an olefin with an alkylating agent simultaneously in contact with the catalyst-is very effectively accomplished, particularly when the alkylating agent contains a methyl group as in methanol, dimethyl ether or methyl chloride. Such aIkylation is typically carried out at a temperature o~ 250 to 400C, preferably at a temperature of at ` least 300C, a weight hourly space velocity in the range 0.5 to l9,and with the catalyst in the form of a fixed bed, the reactants in the vapour phase.

In a further embodiment an aromatic hydrocarbon is alkylated with an olerinic hydrocarbon, preferably one containing 2 to 20 carbon atoms: a , . : ,- , . . - ~

` 1()~17~i9 favoured case of this embodiment is that in which the olefinic hydro-carbon is ethylene and the aromatic hydrocarbon is benzene. Suitable reaction conditions for this embodiment comprise a temperature of 575 to 900F, preferably between 600 and 850F, a pressure of 0 to 3,000 p.s.i.g., preferably between 25 and 450 p.s.i.g., a mole ratio of aromatic to olefinic of 1:1 to 30:1 and a weight hourly space velocity o~ 2 to 2000.

A particularly advantageous embodiment of the invention is the catalysis of the methylation of toluene, employingas preferred methylating agents methanol, methyl chloride, methyl bromide, dimethyl ether or dimethylsulphate. The methylation is carried out at a temperature of 250 to 750C, preferably. 500 to 700~, a pressure of 0 to 1,000 p.s.l.g., at spheric being preferred, a weight hourly space velocity of 1 to 2000 preferably 5 to 1500 and a mole ratio of methylating agent to toluene of 0.05 to 5, preferably 0.1 to 2.

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Catalysts to be employed in this particular reaction may with advantage be sub~ected, before contacting the reagents, to an activation ; treatment comprising exposure to mixture of methanol and water for at least 1 hour (preferably 5 to 30 hours) at a temperature of 400 to 650C, preferably above 500C. The water/methanol volume ratio in the mixture is preferably in the range 2:1 to 1:2.

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Crystalline aluminosilicate zeolites having a silica to alumina ratio of at least about 12 and a constraint index of about 1 to 12 has recently been discovered to have some very unusual catalytic properties.
They induce profound transformations of aliphatic hydrocarbons to aromatic hydrocarbons in commercially desirable yields.
Further, although they have unusually low alumina contents, i.e., high silica to alumina ratios, they are active even when the silica to alumina ratio exceeds 30. This activity l~ is considered to be surprising since the alumina in the zeolite framework is believed responsible for catalytic activity. They retain their crystallinity for long periods in spite of the presence of steam at high temperature which lnduces irreversible collapse of the framework of other zeolites~
e.g., of the X and A type. Furthermore, carbonaceous deposits, when formed, may be removed by burning at higher than usual temp-eratures to restore activity.
An important characteristic of the crystal structure of these zeolites is that it provides constrained access to, and egress from, the intracrystalline free space by virtue of having a pore dimension greater than about 5 Angstroms and pore windows of about a size such as would be provided by ten-membered rings of oxygen atoms. It is to be understood, ` of course, that these rings are those formed by the regular disposltion of the tetrahedra making up the anionic framework o~ the crystalline aluminosilicate, the oxygen atoms themselves , .. ~ .. . ....
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~ being bonded to the silicon or alumlnum atoms at the center of the tetrahedra. Briefly, the zeolites useful for preparing the phosphorus-containing zeolite employed as catalyst in this invention, hereinafter termed "the phosphorus-containing zeolite", possess, in combination, a silica to alumina ratio of at least about 12 and a structure providing constrained access to the crystalline free space defined in terms of a constraint index of about 1 to 12. Further reference will be made hereinafter to the constraint index.
The silica to alumina 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 form within the channels.
Although zeolites with a silica to alumina ratio of at least about 12 are useful to prepare the phosphorus-containing zeollte employed as catalyst in this invention, it is preferred to use zeolites having higher ratios of at least about 30.
Such zeolites, after activation, acquire an intracrystalline sorption capacity ~or normal hexane which is greater than that ~or water, i.e., they exhibit "hydrophobic" properties.
It is believed that this hydrophobic character is advantageous. -The zeolites useful ~or preparation of the phosphorus-containing zeolite employed as catalyst in this invention freely sorb normal hexane and have a pore dimension greater than about ` 5 Angstroms. In addition, the structure must provide con--~ strained access to larger molecules. It iæ sometimes possible , '.
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to judge from a known crystal structure whether such constrained access exists. For example, if the only pore windows in a crystal are ~ormed by eight-membered rings of oxygen atoms, then access to molecules of larger cross-section than normal hexane is excluded and the zeolite is not of the ~esired type. Windows of ten-membered rings are preferred, although excessive puckering or pore blockage may render these zeolites ineffective. Twelve-membered rings do not ~enerally appear to offer sufficient constraint, although structures can be conceived, due to pore blockage or other cause, that may be operative.
Rather than attempt to ~udge from crystal structure whether or not a zeolite possesses the necessary constrained access, a simple determination of the "constraint index"
may be made by passing continuously a mixture of equal weight of normal hexane and 3-methylpentane over a small sample, approximately 1 gram or less, 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 ls treated with a stream of air at 1000F for at least 1~ minutes. The zeolite is then flushed with helium and the temperature ad~usted between 550F and ~50F to give an overall conver-sion between 10 percent and 60 percent. The mixture of hydrocarbons is passed at 1 liquid hourly space velocity ti.e-, 1 volume of hydrocarbon per volume of zeolite per hour) 617~

over the zeolite with a helium dilution ~o giv_ 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 hydro-carbons.

The "constraint index" is calculated as follows:

Constraint Index= lo~ 10 (fraction_of n-hexane remaining) log 10 ~fraction of 3-methylpentane rema n ng) The constraint index approximates the ratio~of the cracking ratio constants for the two hydrocarbons. Zeolites suitable for use are those having a constraint index, as mentioned, from about 1 to 12. Preferably, the constraint index is from about 2 to 7.

The zeolites defined herein are exemplified, to the extent that they have a silica to alumina ratio of at least about 12 and a constraint index of about 1 to 12, by zeolites ZSM-5, (described in U. S. Patent No.3,702,886), ZSM-ll ; (described in U.S. Patent No.3,709,979), ZSM-12 (described in West German OLS 2,213,109) and ZSM- 21 (described in French Speciflcatlon 74-12078).

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1061~;;9 The zeolites, when prepared in the presence of organic cations, are catalytically rather inactive, possibly because the intracrystalline free space is occupied by organic cations from the forming solution.
They may be activated by heating in an inert atmosphere at 500C for one hour, for example, followed by base exchange with ammonium salts followed by calcination at 500 C in air. The presence of organic cations in the forming solution may not be absolutely essential to the formation of the zeolite; however, the presence of these cations does appear to favor the formati~n of these special zeolites. More generally, it is desirable to activate the zeolite catalyst by base exchange with ammonium salts followed by calcination in air at about 500 C for from about 15 minutes to about 24 hours.

Natural zeo~-ites may sometimes be converted to zeolites suitable for preparing the catalysts for use in the present invention by various activation procedures and other treatments such as base exchange, steaming alumina extract.ion and calcination, in combinations.

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17tj5 ~atural minerals which may be so treated include ferrierite, brewsterite, stilbite, dachiardite, epistilbite, heulandite, and clinoptilolite. The preferred zeolites are ZSM-5, ZSM-ll, ZSM-12, ZsM-21, and TEA mordenite, with ZSM-5 parti-cularly preferred.
In a preferred aspect, the zeolites for preparation of the phosphorus-containing zeolite employed as catalyst in this invention are those having a crystal density, in the dry hydrogen form, of not substantially below about 1.6 grams per cubic centimeter. It has been found that zeolites which satisfy all three of these criteria are most desired. There- -fore, the preferred phosphorus-containing zeolites are pre-pared from zeolites having a constraint index as defined above of about 1 to 12, a silica to alumina 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 may be calculated from the number of silicon plus aluminum atoms per 1000 cubic Angstroms, as given, e.g. on page 11 of the article on Zeolite Structure by W.M. Meier.

2~ This paper, is included in "Proceedings of the Conference on Molecular Sieves, London, April 1967", published by the Society of Chemical Industry, London, 1968. When the crystal - s~ructure is unknown, the crystal framework density may be -determined by classical pyknometer 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. This density of not substantially below about .~ .

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1.6 grams per cubic centimeter of course must 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 ~s the locus of catalytic activity.
The zeolites whether having phosphorus incorporated therewith or not are capable of having at least a portion of the original cations associated therewith replaced by a wide variety of other cations according to technlques well known in the art. Replacing cations include ammonium and metal cations, including mistures of the same. The phosphorus-containing zeolite employed as catalyst in this invention - is prepared from zeolites wherein at least a portion of the original cations associated therewith have been replaced by hydrogen.
The crystalline aluminosilicate zeolites can be converted to the hydrogen form, i.e., having at least a portion of the original cations associated therewith replaced by hydrogen, generally by two methods. The first involves direct ion exchange employing an acid. Suitable acids include both inorganic acids and organic acids. Typical inorganic acids which can be employed include hydrochloric acid, hypochlorous acid, suIfuric acid, sulfurous acid, hydrosulfuric acid, nitric acid, nitrous acid, hyponitrous acid, phosphoric acid, and carbonic acid. Typical organic acids which can be employed are the monocarboxylic and polycarbo~ylic acids which can be aliphatic, aromatic, ' .

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or cycloaliphatic in nature. Representative suitable acids include acetic, trichloroacetic, bromoacetic, citric, maleic, fumaric, itaconic, phenylacetic, benzene sulfonic and methane sulfonic acids. The second method for preparing the hydrogen form, which is preferred, involves first preparing an ammonium or other hydrogen ion precursor form by base e~change and then calcining to cuase evolution of the ammonia leaving a hydrogen lon remalning on the zeolite.
Calcining is carried out in air at 500C ~or about 15 minutes to about 24 hours. Suitable compounds for preparing the hydrogen ion precursor form include ammonium compounds such as the chloride, bromide, iodide, bicarbonate, sulfate, cltrate, borate, and palmltate. Still other ammonium compounds which can be employed include quaternary ammonium compounds such as tetramethylammonium hydroxide and trimethylammonium chloride.
The phosphorus-containlng zeolite employed in the process of the present invention is prepared by reacting a zeollte as de~ined herein wlth a phosphorus-containing compound.

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A phosphorus-containing compound having a covalent or ionic constituent capable of reacting with -hydrogen ion may be employed. Suitable phosphorus-containing compounds include derivatives of groups represented by PX3, RPX2, R2PX. R3P, R3P=O, RP02, RP(O)(OX)2, R2P(O)OX, RP(OX) ROP(OX)2 and (RO)2POP(OR)2, where R is an alkyl or phenyl radical and X is hydrogen, R, or halide. These compounds include primary, RPH2, secondary, R2PH, and tertiary, R3P, phosphines such as butyl phosphine; the tertiary phosphine oxides, R3PO, such as tributylphosphine oxide; the primary, RP(o)(OX)2, and secondary, R2P(o)OX, phosphonic acids such as benzene phosphonlc acid; the esters of the ph~sphonic acids such as diethyl phosphonate, tRO)2P(O)H, dialkyl alkyl phosphonates, (RO)2P(O)R, and alkyl dialkylphosphinates, (RO)P(O)R2; phosphinous acids, R2POX, such as diethylphos-phinous acid, primary, (RO)P(OX)2, secondary, (RO)2POX, and tertiary, (RO)3P, phosphites; and esters thereof such as the monopropyl ester, alkyl dialkylphosphinites, (RO)PR2, and dialkyl alkylphosphonite, (RO)2PR esters. Examples of phosphite esters include trimethylphosphite, triethylphosphite, diisopropylphosphite, butylphosphite; and pyrophosphites. ~ ;
Furthermore, particularly good results are obtained by the use of orthophosphorlc acld, H3PO~, and of lts e~ter~.

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such as tetraethylpyrophosphite. The alkyl groups in the mentioned compounds contain one to four carbon atoms.
Other suitable phosphorus-containing compounds include the phosphorus halides such as phosphorus trichloride, bromide, and iodide, alkyl phosphorodichloridites, (RO)PC12, dialkyl phosphorochloridites, (RO)2PX, dialkylphosphino-chloridites, R2PCl, alkyl alkylphosphonochloridates, (RO)(R)P(O)Cl, and dialkyl phosphinochloridates, R2P(O)Cl.
Preferred phosphorus-containing compounds include trimethylphosphite and phosphorus trichloride. In the trimethylphosphite, the covalent ionic constituent capable of reacting with hydrogen ion is [CH3-0-]. In the phosphorus trichloride, the covalent or ionic constituent capable of reacting with hydrogen ion is [-Cl].
` 15 While we do not wish to be limited by the conse-quences of a theory, it is believed that the constituent of the phosphorus-containing compound capable of reacting with hydrogen ion reacts with the hydrogen of the original zeolite. Thus, with trimethylphosphite, it is believed that ; ~o the hydrogen on the zeolite reacts with one of the [CH3-0-]
ions of the trimethylphosphite to from CH30H and is believed thereby to chemically bond the remainder of the trimethyl-phosphite molecule, namely, the rH3- ~ ~ + , to the

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crystal structure of the zeolite possibly through a silanol group. In a similar manner, a phosphonate may undergo ~
prototropic change in the manner. ~-.
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P~ ~ H (zeolite) --3 [ ~ P~' ~ (zeolite) (-H2O) RO ~ ~ +
~ RO / (zeolite) With phosphorus trichloride, it is believed that the hydrogen on the zeolite reacts with one Or the [-Cl] ions of the phosphorus trichloride to form HCl and is believed thereby to chemically bond the remainder of the pnosphorus trichloride molecule namely, the [-PC12] , to the crystal structure of the zeolite possibly through a silanol group. These phosphorus-~` containing moieties, after the heating, in the presence Or free oxygen, could be present as [P02] or various phosphorus anhydride or hydroxyl forms. In any case, it is believed that the phosphorus is chemically bonded to the crystal structure of the zeolite since the phosphorus-containing zeolite can be used for extended periods of time at high temperatures without loss Or phosphorus. Further reference will be made to this hereinafter. Further, the phosphorus is not likely present as a crystalline framework constituent, i.e., it has not been substituted for silicon or aluminum atoms, since the unit cell di~ensions Or the zeolite are unchanged on incorporation Or phosphorus atoms with the ;;~
zeolite. Further reference to this point will also be made hereinafter.
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Incorporation of the phosphorus with the zeolite provides a composition having unique properties as a catalytic agent. For example, while the zeolites as defined herein are excellent aromatization catalysts, the phosphorus-containing zeolite does not possess such aromatizing activity.
The ability of the zeolite to catalyze the transformation of aliphatic hydrocarbons to aromatic hydrocarbons in com-merclally desirable yields is not present with the phosphorus-containing zeolite. The zeolites possess strong acid sites and, while again we do not wish to be limited to the consequences of a theory, it is believed that the strong acid sites of the zeolites are responsible for their aromatizing activity. On the other hand, the phosphorus-containing zeolite does not possess these strong acid sites.
Rather, the phosphorus-containing zeolite possesses a greater number of acid sites than the parent zeolite but these sites appear to have a lesser acid strength than those found in the parent zeolite. It is believed that the apparent replacement of the strong acid sites with a greater number of relatively weak acid sites may be responsible for the unique catalytic properties of the phosphorus-containing zeolite. ~ ~
Reaction of the zeolite with the phosphorus- ;
containing compound is effected by contacting the zeolite with the phosphorus-containing compound. Where the phosphorus-containing compound is a liquid, the phosphorus-containing compound can be in solution in a solvent at the ,.

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time contact with the zeolite is effected. Any solvent relatively inert with respect to the phosphorus-containing compound and the zeolite may be employed. Suitable solvents include aliphatic, aromatic or alc~holic liquids. Where the phosphorus-containing compound is trimethylphosphite or llquid phosphorus trichloride, a hydrocarbon solvent such as n-octane may be employed. The phosphorus-containing compound may be used without a solvent, i.e., may be used as a neat liquid. Where the phosphorus-containing compound is in the gaseous phase, such as where gaseous phosphorus trlchloride is employed, the phosphorus-containing compound can be used by itsel~ or can be used in admixture with a gaseous diluent relatively inert to the phosphorus-containing compound and the zeolite such as air or nitrogen.
Preferably, prior to reacting the zeolite with the phosphorus-containing compound, the zeolite is dried.
` Drying can be e~fected in the prèsence of air. Elevated i temperatures may be employed. However, the temperature should not be such~ as mentioned hereina~ter, that the crystal structure o~ the zeolite is destroyed.

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Heating of the phosphorus-containing catalyst subsequent to preparation and prior to use is also preferred.
The heating can be carried out in the presence of oxygen, for example air. Heating can be at a temperature of about 150 C.
However, higher temperature, i.e., up to about 500 C, are preferred. Heating can be carried out for 3-5 hours. It has been found that heating increases catalyst efficiency of the phosphorus-containing zeolite probably due to an increase in the number of acid sites rather than an increase in the strength of the existing acid sites. Increasing the heating temperature increases the catalyst efficiency.
However, while heating temperature above about 500 C can be employed, they are not necessary. At temperatures of about 1000 C, the crystal structure of the zeolite is destroyed.
The amount of phosphorus incorporated with the -~
crystal structure of the phosphorus-containing zeolite should be at least about 0.5 percent by weight. With this amount of phosphorus, replacement of a sufficient proportion of the strong acid sites of the zeolite with an increased number of weak acid sites is e~ected. However, it is preferred in order to increase the replacement of the strong acid sites s with an increased number of these weaker acid sites that the amount of phosphorus in the phosphorus-containing catalyst be at least about o.78 percent by weight. The amount of t phosphorus can range up to 2.5 to 4.5 percent by weight.
The amount of phosphorus may be higher than about 1~;17~;~

4.5 percent, for instance up to 15 or even 25 percent by weight, although with these higher amounts a decline in catalytic activity can on occasion occur. By "percent by weight" we mean the unit weight of phosphorus per 100 unit weights of the zeolite. Amounts of phosphorus from about o.78 to 4.5 percent by weight correspond to about 0.25 to 1.45 mllliequivalents of phosphorus per gram of zeolite.
It was mentioned previously that the phosphorus is not likely present as a crystalline framework constituent of the phosphorus-containing zeolite. Evidence for this has been obtained by X-ray diffraction analysis of the zeolite before and after it has been modified by incorporation of phosphorus with the crystal structure to form the phosphorus-containing zeolite. The interplanar spacings are substantially identical for the zeolite before and after phosphorus incorporation. On the other hand, the relative intensities of the 11.10 and 9.95 A d-spacings o~ the phosphorus-containing zeolite are phosphorus dependent, ~`
the relative intensities decreasing with phosphorus concentration in the phosphorus-containing zeolite. The relative intensities of the remaining d-spacings are unaffected `~
by the presence of the phosphorus in the phosphorus-containing zeolite. Characterization of the phosphorus-containing zeolite with respect to the zeolite can, in fact, be made on the basis f the decrease in the 11.10 and the 9.95 A d-spacings as a result of the incorporation of the phosphorus with the zeoli~e.
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The amount of phosphorus incorporated with the zeolite by reaction with the phosphorus-containing compound will depend upon several factors. One of these is the reaction time, i.e., the time that the zeolite and the phosphorus-containing compound are maintained in contact with each other. With greater reaction times, all other factors being equal, a greater amount of phosphorus is incorporated with the zeolite. Another factor is the ratio of the phosphorus-containing compound to the zeolite in the reaction mixture employed to effect incorporation of the phosphorus with the zeolite. With greater ratios of phosphorus-containing compound to zeolite, again all other factors being equal, a greater amount of phosphorus is incorporated with the zeolite. Other factors upon which the amount of phosphorus incorporated with the zeolite is dependent include reaction temperature, concentration of the phosphorus-containing compound in the reaction mixture, the degree to which the zeolite has been dried prior to reaction with the phosphorus-containing compound and the conditions of drying of the phosphorus-containing zeolite after reaction of the zeolite with the phosphorus-containing compound.
It has been found that the concentration of phosphorus-induced weak acid sites, and thus the catalytic actlvity, of the phosphorus-containing zeolite is altered upon contact with water vapor. Thus, upon contact with :~ water vapor the number of weak acid sites appears to be increased.

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This increase may occur after the phosphorus-containing zeolite is put into use as a catalyst as a result of contact with water vapor contained in the feed to the catalyst or formed during the reaction of the feed with the catalyst.
Preferably, however, in order to obtain the benefits of an lnitial increased catalytic activity of the phosphorus-containing zeolite, the phosphorus-c~ntaining zeolite is contacted with water vapor prior to its use as a catalyst.
Further, it is preferred that this contact with water vapor be carried out subsequent to contact with the phosphorus-containing compount but prior to heating. Contact of the phosphorus-containing zeolite with the water vapor may be carried out in any suitable manner. For example, sorption of water vapor on the phosphorus-containing zeolite can be effected in a vaccum desiccator at ambient condltions for one hour. Water vapor can also be sorbed by passing an inert gas such as helium through a water bubbler and passing -~
; the entrained water-vapor through the phosphorus-containing ` zeolite in a reaction tube.
The phosphorus-containing zeolite may be modified by impregnating with zinc. Impregnation of the phosphorus-containing zeolite wlth zinc significantly increases the activity of the phosphorus-containing zeolite as a catalyst--~or the conversion of methanol and/or dimethyl ether, and of ` certain hydrocarbons. -In general, however, the product spectrum obtained with the phosphorus-containing zeolite impregnated with the zinc is similar to that obtained with the phosphorus-containing zeolite.

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The phosphorus-containing zeolite may be impregnated with the zinc by contacting the zeollte with a solution of a zinc salt. For example, the phosphorus-containing zeolite may be contacted with a sufficient amount of a solution of a zinc salt to fill the pore volume of the phosphorus-containing zeolite, the concentration of the zinc salt in the solution being such that the phosphorus-containing zeolite, when its pore volume is filled with the solution, will be impregnated with the desired amount of zinc. If the zinc salt is not sufficiently soluble in the solvent such that the desired amount of zinc will be impregnated in the phosphorus-containing zeolite, the process may be repeated one or more times after removal of the solvent by drying following each contact with the solution. The solvent for the zinc salt is preferably water. However, any relatively inert solvent may be employed.
The zinc salt may be an organic salt or an inorganic salt. Organic salts of zinc that may be employed include the acetate, benzoate, butyrate, formate, lactate, and others. Inorganic salts of zinc that may be employed lnclude the bromide, chlorate, chloride, iodide, nitrate, sulfate, and others.
Following impregnation with the zinc salt, the phosphorus-containing zeolite is heated as described hereinabove. In this connection, where the phosphorus-containing zeolite is to be impregnated with zinc, the heating after impregnation with the zinc can substitute ~or the heating described hereinabove.

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~0617tj9 The amount of zinc impregnated into the phosphorus-containing zeolite may be as desired. Any finite amou~t will be effective. However, the amount should be at least about 0.1 percent by weight. On the other hand, amounts in excess of about 4 percent by weight will not ordinarily be necessary. These amounts are intended to mean the amount of zinc and do not include the anion of the salt.

With respect to the anion of the salt, heating of the phosphorus-containing zeolite following impregnation with the zinc salt or during use thereof as a catalyst may remove or destroy the anion leaving the zinc as the material impregnating the phosphorus-contvaining zeolite.
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_24-.. .

-10617t;~t The phosphorus-containing zeolites of this invention are effective catalysts for the conversion of aliphatic hydrocarbons. The hydrocarbons may be olefinic or paraffinic. The use of the zeolite without incorporation of phosphorus for the conversion of aliphatic hydrocarbons results in the formation of appreciable quantities of aromatic compounds, as indicated previously. On the other hand, the use of the phosphorus-containing zeolite for the conversion of aliphatic hydrocarbons under substantially the same operating conditions results in the formation of only ; minor amounts of aromatics. With olefins, the products are mainly higher aliphatic compounds, the reaction product having high olefin to paraffin ratios. With paraffins, the products are mainly olefins and other paraffins.

15Conversion of aliphatic hydrocarbons employing the ` phosphorus-containing zeolite as a catalyst can be carried out under a variety of reaction conditions. The temperature employed may be about 250 C to 700 C. With the more reactive aliphatic hydrocarbons, particularly olefins, temperatures in the lower portion of this range may be employed while with less reactive aliphatic hydrocarbons higher temperatures are employed. For example, effective conversion of propylene can be obtained with a temperature of about 300 C, whereas effective conversion of ethylene requires a temperature of at least about 500 C. Weight per hour space velocities may be about 1.5 to 13.5 although much higher :

.. .. . - . .. . . ~ .. . ~ , .

space velocitles may also be employed depending upon the activity of the aliphatic hydrocarbon reactant and the molecular weight and configuration of the product desired.
Pressures may be as desired.

.

, .
' :

' 1'7ti9 For catalytic applications the phosphorus-contaln-lng zeolites employed herein may be composited with a porous matriz material, such as silica-alumina, silica-magnesia, silica-zirconia, silica-thoria, silica-berylia, 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 finely divided modified zeolite and inorganic oxide gel matrix may vary widely with the zeolite content ranging from between about 1 to about 99 per-` cent by weight and more usually in the range of about 5 to about 80 percent by weight of the composite.
~,.
Exemplary of the aromatic hydrocarbons which may bealkylated by the process of this invention are compounds such as benzenes, naphthalines, anthracenes, and the like and substituted derivatives thereof; and alkyl substituted aromatics, e.g. toluene, xylene and homologs thereof. The alkylating agents empl~yed are olefinic hydrocarbons having from 2 to 20 carbon atoms such as ethylene, propylene, and dodecylene operating conditions employed are critical and will be dependent,at least in part,on the specific alkylation reaction being effected. Such conditions as temperature, pressure, space velocity and molar ratio of the reactants and the presence ` of inert diluents will have important affects on the process.
Accordingly, the manner in which these conditions affect not ' ` -27-10~17tj~

~only the conversion and distribution of the resulting alkylated products but also the rate of deactivation of the catalyst will be described below.
Aromatic alkylation is conducted such that alkylation of an aromatic hydrocarbon compound, exemplified by benzene, with an al~ylating agent, i.e. an olefinic hydrocarbon exemplified by ethylene, is carried out in the vapor phase by contact in a reaction zone, such as, for example, a fixed bed of catalyst, under alkylation e~fective conditions, said catalyst being characterized as above-described and preferably hydrogen exchanged such that a predominate portion of its exchangeable cations are hydro-` gen ions. In general, it is contemplated that more than 50 percent and preferably more than 75 percent of the cationic sites of the crystalline aluminosilicate zeolite, above-described, will be occupied by hydrogen ions. The alkylatable aromatic compound and olefinic hydrocarbon are desirably fed to a first stage at an appropriate mole ratio of one to the other. The feed to such first stage is heated. After some reaction takes place, such as, for example, when about 80~
of the olefinic hydrocarbon is consumed, the effluent of the first stage is cooled to remove heat of reaction and more olefinic hydrocarbon is added (second stage) to maintain the mole ratio of aromatic compound to olefinic hydrocarbon wlthin ~r 25 the range established for the first stage. A plurality of reaction stages are possible for the process of this invention.
It is generally desirable to provide cooling between reactor ~ stages. `
'~ Considering vapor-phase alkylation of benzene with ethylene, the first stage mole ratio of benzene to ethylene ~j .

.

~ay be in the range of about 1:1 to about 30:1. The first stage feed is heated to a reactor lnlet temperature within the range of about 575F. to about 900F. at a pressure within the range o~ about atmospheric to about 300 psig.
Preferred inlet temperatures fall within the range of about 600~. to about 850F. and preferred pressures fall within the range of about 25 psig to about 450 psig. The repeating of reaction staging is carried out while maintaining an overall aromatic hydrocarbon, e.g. benzene, to alkylating agent, e.g. ethylene, mole ratio of about 1:1 to about 30:1, with a preferred range of about 2.5:1 to about 25:1. As the reaction proceeds through the stages, the aromatic:alkylating agent mole ratio increases.
It is noted that extremely high total feed space velocities are possible in the process of this invention, l.e. up to 2000 lb. total feed/hr.-lb. crystalline alumino-silicate. An important factor in the present process is, however, the welght hourly space velocity (WHSV) of the -~
alkylating agent, e.g. ethylene. The alkylating agent WHSV to each of any alkylation reactor stages is maintained -between about 1 and about 10 lb. alkylating agent/hr.-lb.
crystalllne aluminosilicate. The most desirable ethylene, i.e. alkylating agent, WHSV is within the range o~ about 2 to about 8 lb. ethylene/hr.-lb. crystalline aluminosilicate.
When the ethylene WHSV is maintained within the above limits, an economical cycle between regeneration of catalyst exists.
This alkylation`may be carried oùt as a batch-type, semi-continuous or continuous operation utilizing a ~ixed or moving bed catalyst system. A pre~erred .'~
~ -29-, . . ., ., . ~ .. .

1()6~ i't;~

embodiment entails use of a fluidized catalyst zone wherein the reactants, e.g. benzene and ethylene, are passed con-currently or countercurrently through a moving fluidized bed of the catalyst. The fluidized catalyst after use i8 conducted to a regeneration zone wherein coke is burned from the catalyst in an oxygen-con~aining atmosphere,e.g. air, at an elevated temperature, after which the regenerated catalyst is recycled to the conversion zone for further contact with the benzene and ethylene reactants.

Reactivation of the phosphorus mod~fied zeolite catalyst can be effected by passing a vaporized phosphorus compound through the catalyst bed after the catalyst has been ~` used for the desired alkylation. Thus, for example, after a period of continued use of the catalyst, it can be revivified by passage therethrough of a vaporized mixture, e.g. an equal volume mixture, of toluene and diphenyl phosphine chloride at an elevated temperature, i.e. about 250C. over a 1/2 hour period of time. This treatment is then suitably followed by heating in air at 150 cc/minute at about 550C. for approximately 1/2 hour.

. . . , ~ , .

1(~61~

A particular case of aromatic alkylation which benefits enormously from the use of catalysts according to the invention is the methylation of toluene, since under their influence selectivity to p-xylene is outstandingly high.

Methylation of toluene in the presence of the above-described catalyst is e~fected by contact of the toluene with a methylating agent, preferably methanol, at a temperature between about 250C. and about 750C. and preferably between about 500C. and about 700C. At the higher temperatures, the zeolites of high silica/alumina ratio are preferred.
For example, ZSM-5 of 300 SiO2/A1203 ratio and upwards is very stable at high temperatures. The reaction generally takes place at atmospheric pressure, but the pressure may be within the approximate range of 1 atmosphere to 1000 psig. The molar ratio of methylating agent to toluene is generally between about .05 and about 5. When methanol is employed as the methylating agent a suitable molar ratio of methanol to toluene has been found to be approximately 0.1-2 moles of methanol per mole o~ toluene. With the use of other methylating agents, such as methylchloride, methylbromide, dimethylether, methyl carbonate, light olefins or dimethylsulfide, the molar ratio of methylating agent to toluene may vary within the a~orenoted range. Reaction is suitably accomplished utilizing a weight hourly space velocity of between about 1 and about 2000 and preferably between about 5 and about 1500. The reaction product consisting predominantly of para-xylene or a mixture o~
para- and ortho-xylene together with comparatively smaller 1(J617ti5~

amounts of meta-xylene may be separated by any suitable means, such as by passing the same through a water condenser and subsequently passing the organic phase through a column in which chromatographic separation of the xylene isomers is accompllshed.

The process of this invention may be carried out as a batch-type, semi-continuous or continuous operation utillzing a fixed or moving bed catalyst system. A preferred embodiment entails use of a fluldized catalyst zone wherein the reactants, i.e. toluene and methylating agent, are passed concurrently or countercurrently through a moving fluidized bed of the catalyst. The fluidized catalyst after use 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 toluene and methylating agent reactants.

~' Reactivation of the phosphorus-containing zeolite catalyst can be effected by passing a vaporized phosphorus compound through the catalyst bed after the catalyst has been ` used ~or the deslred methylation of toluene to para-xylene.
` Thus, for example, after a period of continued use of the catalyst, it can be revivified by passage therethrough of a vaporized mixture, e.g. an equal volume mixture, of toluene 25` and diphenyl phosphine chloride at an elevated temperature,i.e.
about 250C. over a 1/2 hour period of time. This treatment is then suitably followed by heating in air at 150 cc/minute at about 550C. for approximately 1/2 hour.

11~617ti~
We have discovered that activation of phospho~Js-mod~ied crystalline aluminosilicate catalyst for methylation of toluene may be accomplished by vapor phase treatment with a mixture of methanol and water at a temperature between about 400C and about 650C for at least about 1 hour. The preferred temperature of treatment is between about 500C and about 600C. Preferred treating times are generally between about

5 and about 30 hours and particularly between about 10 and about 20 hours. The mixture of methanol and water employed may vary from a methanol/water volume ratio of 2/1 to 1/2 with an approximately equal volume ratio being particularly preferred. The weight hourly space velocity~at which the toluene/water mixture is passed over the described catalyst is preferably between about 5 and about 15. Activation o~ the phosphorus-modified catalyst, as above described, may be effected after the catalyst has been employed in methylation of toluene or alternati~ely the catalyst may be activated prior to its use.

.. .. . , . ~ . : . - .: .
: . . .. :. . . .

17t;~

In yet a further embodiment of the invention, non-hydrocarbons such as methanol or dimethyl ether are sub~ected to the action, at a temperature of at least about 300C, of a catalyst as hereinabove set forth.

Methanol or dimethyl ether is contacted with the catalyst at a temperature of about 300C to 700C. Preferably, the temperature is at least about 350C. As t~e temperature is lncreased above about 300C, the conversion of the methanol or dimethyl ether is increased. By "conversion" we mean the weight percent of the methanol or dimethyl ether that reacts in the presence of the catalyst and forms other compounds.
However, as the temperature approaches about 700C, the selectivity to olefins decreases. By "selectivity" we mean the weight percent of the converted methanol or dimethyl ether that is olefins. Temperatures greater than about 750C should not be employed because of deleterious effect on the catalyst, the olefin products, o~both.

Methanol alone or dimethyl ether alone may be contacted with the catalyst. However, a mixed feed of methanol and dimethyl ether may also be employed. It is believed that, where methanol is employed as the reactant, either alone or ln a mixed feed with dimethyl ether, the methanol reacts in the presence o~ the catalyst to form first dimethyl ether and the products formed thereafter are those resulting from reaction of the dimethyl ether in the presence of the catalyst. Further, the products obtained result solely from reaction of the methanol or the dimethyl ether each with itself and the presence 1(~617tj~

of a co-reactant with the methanol or (~imethyl ether i~ nGt required.

The reaction of the methanol or the dimethyl ether is preferably carried out in the vapor phase.

Fixed bed or movable bed operation may be employed.
Preferably, a fixed bed operation is employed. The methanol or dimethyl ether may be passed over a bed of the catalyst at rates of about 1.5 to 14.5 unit weights of reactant per hour space velocities (WHSV) of about 1.5 to 14.5. Lower weight per hour space velocities can, of course, be employed.
With any temperature of conversion, a greater degree of con-version is obtained with lower space velocities.

-lU6176~
The following Examples are presented bv way of illustration of the many aspects of the present invent$on.
Of these Examples:

Example 1 to 7 illustrate the preparation and characteristics of catalytic compositions in accordance with the present invention;

Examples 8 to 15 illustrate the use of these compositions as catalysts for the conversion of paraffins and olefins to a highly olefinic product;

Examples 16 to 23 illustrate the use of these compositions as catalysts for the alkylation of an olefin to yield an olefin of molecular weight higher than that of the feed olefin;

Examples 24 to 40 illustrate the use of these compositions as catalysts for alkylation of aromatic hydro-carbons, specifically c~o~nversion of benzene to ethylbenzene;

Examples 41 to 151 illustrate the use of these compositions as catalysts for methylation of toluene to yield an enhanced proportion of para-xylene;

Examples 152 to 162 illustrate the activation of ~^ these compositions for toluene methylation by pre-treatment with a mixture of methanol and water; and .
Examples 163 to 168 illustrate the use of the compositions as catalysts for the conversion of non-hydrocarbons, particularly methanol and dimethyl ether, to an olefin-rich product.

Exampl.e 1 1 This example will illustrate the preparation of !¦ phosphorus-containing zeolites.
`~1 Several preparations of crystalline aluminosilica~e zeolites were combined to form a composite. Each of these aluminosilicate zeolites was ZSM-5 containing sodium as the cation associated therewith and had been prepared by S conventional techniques employing tetrapropylammonium hydroxide~ The composite had a silica to alumina ratio o 70 and the individual zeolite catalysts had components falling in ~he ranges~ 1.4% Na, 4.22-7.31% C, 0~3~-0~63~/o N, 2.25-2.45% A12O3, and 91.3-95.0% SiO2. The C/N atomic ratio was 12.5-13.5 and the Na/Al ratio ~7as approximately 1.2.
The composite, in powder form,~was brought to a temperature of 540 C under a stream of nitrogen (the heati.ng rate was about 2.5 C per minute) and held for 16 hours to remove residue of the tetrapropylammonium hydroxide. It was then pressed into wafers, crushed, and screened to 8-12 mesh, followed by ion exchange with 0.5 N NH4NO3, the NH4+
replacing the Na+. -The resulting pellets were air-dried and calcined in air at 500 C for 3-16 hours whereby H+ replaced :~ `,''. ' . .

106~7~3 ,the NH4+. The sample at this point can be referred to as the "activated acid form of the zeolite".
A ten-gram sample of the zeolite was added to 3.94 cubic centimeters of trimethylphosphite dissolved in 50 cubic centimeters of n-octane in a flask.
Under a slow stream of nitrogen the mixture was heated to reflux temperature (about 120 C) for 72 hours. A ten-inch vigreaux column was added to the flask for distillation and 21 grams of liquid were collected at 90-113 C for subsequent analysis. The solids were filtered and washed with 100 cubic centimeters each of pentane, methylene chloride, and pentane.
They were then air-dried followed by drying in a vacuum oven overnight at 110 C. They were next pressed into wafers, broken and screened to 8-12 mesh slze and heated in air at 500 C for 3 hours. The resulting product was the phosphorus-c~ntaining zeolite.
The above procedure was repeated with ten other samples with variations in the ratio of trimethylphosphite to zeolite and reaction time, i.e., time of contact of the trimethylphosphite with the zeolite. One of the samples was heated at 300 C rather than at 500 C. Another one of the samples was treated with a large excess of neat trimethylphosphite, i.e, without any n-hexane solvent.
A portion of each of the phosphorus-containing zeolites was analyzed by X-ray. The results are listed in Table I in weight percent and are calculated on a dry weight basis after a heating of about 0.5 hour at r ., " .." ... ...

l.U~17~

_ 1000-1100~ C. This heating was only or analytical purposes of assuring dryness and whereas the phosphorus was retained the crystalline structure was probably destroyed. For comparison purposes, there is included an analysis of the zeolite, identified in the table as Sample 1, prior to ` ` conversion to a phosphorus-containing zeolite. Sample 6 was the sample heated at 300 C. Sample 11 was the sample treated with a large excess of neat trimethylphosphite. The weight loss is the thermsl gravimetric weight loss and was determined at 900 C by standard techniques using a basic DuPont Model instrument. Most of the weight loss Indicated in the table was found to be due to water a~though traces of organic material (rv0.5-2%) were also noted in effluent gases.

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--i Example 2 This example will further illustrate the prepara~ion of a phosphorus-containing zeolite.
Six grams of activated acid form of ZSM-5 zeoli-~e ~ere placed in a flask fitted with a thermometer, a nitro~e~
purge, a reflux condenser, a dropping funnel, and a calcium chloride trap on the nitrogen exit line leading ~rom the top of the flask. The zeolite was heated to 230-240 C for ab~ut 2 hours while nitrogen was passed through the flask to remave moisture. After allowing the zeolite to cool, 50 cubic centimeters of phosphorus trichloride from the dropping funnel were added to the æeolite. The surface of~the zeolite turned a light yellow-orange color immediately. The slurry o - zeolite and phosphorus trichloride was carefully refluxed ~or 20 hours.
After cooling, the phosphorus-containing zeolite was filtered off, washed with 150 cubic centimeters o~
chloroform, and dried n a vacuum oven a~ 110 C. It was then placed in a quartz tube with a thermowell in the center and heated to 130-140 C. Nitrogen saturated with water at 30-50 C was passed through the tube for 20 hours.
Hydrogen chloride was evolved in the process.
The phosphorus-containing æeolite ~as then heated ~ at 150 C.in dry nitrogen. Analysis of this zeolite t~ ~5 indicated that it contained 2.95 perc~nt by weight of phosphorus.

i .

~ _41;_ 106~7~'~
Example 3 This example will still further illustrate the preparation of a phosphorus-containing zeolite.
Seven grams of activated acid form of ZSM 5 zeolite were placed in a quartz tube fitted with a thermowell in the center. The zeolite was heated in dry nitrogen at 500 C for 1.5 hours to remove moisture. After cooling to 300 C, 44 grams of phosphorus trichloride vapor were passed through the zeolite over a period of 3 hours. Nitrogen was used as a carrying gas. The system was carefully protected from moisture.
After this treatment, air was substituted for the nitrogen and was passed over the zeolite at a rate of 100 cubic centimeters per minute for 16 hours and at a temperature of 400 C. Analysis of the resulting phosphorus-containing zeolite indicated that it contained 1.38 percent by weight of phosphorus.
Example 4 This example will illustrate still another method of preparing a phosphorus-c~ntaining zeolite.
In an apparatus similar to that described in Example 2~ 15.0 grams of dry actlvated acid form of ZSM-5 ` zeolite were refluxed with 100 cubic centimeters of neat ` trimethylp~osphite for 20 hours. After cooling, the zeolite was filtered off, washed with methylene chloride followed by pentane, pumped down in a vaccum oven, and heated in air at 500 C for 22 hours. The total dry weight after heating ,: ~

~ ' ;17t;~t - was 15.8 grams. Analysis of the phosphorus-containing zeolite indicated that it contained 2.68 percent by weig~t of phosphorus.
Example 5 This example will illustrate another method of preparing a phosphorus-containing zeolite.
In a manner similar to that described in Example 3, 8.8 grams of activated acid form of ZSM-ll zeolite were treated with 74 grams o~ an equivolume solution of phosphorus trichloride and cyclohexane at 300-450 C over a period of 3.3 hours.
Example 6 ` This example will illustrate the stability of the phosphorus-containing zeolite under conditions of use as a catalyst.
The phosphorus-containing zeolit~sidentified in Example 1 as Samples 4, 5, and 7 ~ere each used as ca,aly~ts for conversion reactio~ns. The conversion in which Sample 7 was employed was carried out in the presence of water vapor.
In the reaction in which Sample 4 was employed~ the phosphorus-containing zeolite was regenerated two times during ~he reaction by calcining in air at 500 C. In the reactions in which Samples 5 and 7 were employed, the phosphorus-containing zeolite~
were simi,Iarly regenerated one time and four times, respectively.
Analyses ~ the phosphorus-containing zeolites were made by X-ray prior and subsequ~nt to being used as the catalysts and the results are given in Table II.

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, '7~9 : It ~ill be observed from Table II that the compositions of the phosphorus-containing zeolites were substantially unaltered, particularly as to phosphorus content, by use as a catalyst and by regeneration. The absence of loss of phosphorus indica~es a strong bonding of the phosphorus with the zeolite.
Example 7 This example will demonstrate the lack o~ ef~ect of the incorporation of the phosphorus with the æeolite on ; 10 the unit cell dimPnsions of the zeolite and the decrease in the relative intensities of the 11.10 and 9.95 A d-spacings by the incorpora~ion of the phosphorus wit~ the zeolite.
One ZSM-5 zeolite without phosphorus and four phosphorus-containing ZSM-5 zeolites, each of the phosphorus-containing zeolites containing a different amount of phosphorus, were subjected to X-ray analysis to determine ~heir definitive X-ray diffraction patterns. The pat~erns were measured automatlcally by a proportional counter diffractometer using CuK c~ (doublet) radiatîon. Peak height, I, and band position as a function o 2~ were used to calculate relative intensities (100 I/I), where I i5 the strongest line intensity and (dobs) the interplanar spacings in angstroms. Table III compares the relative in~ensitiës of the seven major d-spacings as a ~unction ~f phosphorus concentration.
It will be observed from Table III that the d-spacings are essentially identical ~or the zeolite without -45_ : . . . :. , 10~765 phosphorus and the phosphorus-containing zeolite. It wi.ll also be observed that there was a decrease in the relatlve intensities of the in~erplanar spacings at d=ll.lOA and d-9,95A of the phosphorus-containing zeolite and the decrease was in a linear manner proportional to the amount of the phosphorus. The d-spacings of the zeolite without ; phosphorus and the phosphorus-containing zeolite being essentially identicalare indicative that the phosphorus is not present as a constituent of the crystalline framework of the phosphorus-containing zeolite. It will be further observed that~ with an amount of phosphorus of 0.78 percent by weightj the decrease in the 11.10 and 9.95~ d-spacings was at least 15 percent.
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~1~6~7~;9 This example will illustrate the catalytic effect of the phosphorus-containing zeolite on the conversion of an olefin, namely, ethylene.
The catalyst employed was the phosphorus-containing zeolite identified as Sample 3 in Example 1. The ethylene was passed over the catalyst at 500 C and at a weight per hour space velocity (WHSV) of 1.45. The products were collected over a one hour period and the products analyzed.
For comparison purposes, ethylene was also passed at 500 C
and a WHSV of 1.5 over the zeolite without phosphorus identified as Sample 1 in Example 1. ~
; ` The results are given in Tables IV and V.
Tab~e IV gives the results in terms of weight percent product selectivity and Table V gives tbe results in terms of weight percent product analysis.
It will be observed from Table IV that arom~tics selectivity was 4.04 ~ercent with the phosphorus-containing zeolite as compared to 37.37 percent with the zeolite without ; 20 phosphorus. It will also be observed that the olefin-paraffin ratio ~as 38.7/1 wi~h the phosphorus~containing zeolite as compared to 0.2/1 with the zcolite without phosphorus. It ~11 further be observed from th~ table that, wi~h the phosphorus-containing zeolite, the eth~lene was converted into propylene (42~13~/o selectivity) and Cs's (33.83% selectivity) as the major products.

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Example 9 This example will illustrate the catalytic effect o~
the phosphorus-containing zeolite on the conversion of another olefin, namely, propylene.
Propylene was passed over the phosphorus-containing zeolite identified as Sample 3 in Example 1 at 300 C and 400 C. The rate of passage of the propylene was 82 cubic centimeters per minute and the amount of the phosphorus-containing zeolite was 4.75 grams. The weight per hour space velocity was 1.8. The products were collected over a one hour period at each temperature and analyzed. For comparison purposes, propylene was similar~y passed over the zeolite without phosphorus identified as Sample 1 in Example 1.
The results are given in Tables VI and VII.
Table VI gives the results in terms of weight percent product selec-ivity and Table VII gives the results in terms - of weight percent product analysis.
It will be observed from the tab~es that the use of the phosphorus-containing zeolite as catalyst resul~ed ~ in the suppression of the formation of aromatics and the `~ production of high olefin-paraffin ratios as compared to the use of ~he zeolite without phosphorus. The major reaction;of the propylene over the phosphorus-containing ~5 zeolite ~s a dimerization to C6 aliphatics which are ~ believed to be predominantly olefins. It ~ill he observed `~ from Table VI that, at 400 C, with the phosphorus-containing ., ~ -51-:

... . . ...
.. .. . .. ...

~ 7 ~

;~`'.~'5 æeolite, selectivity to the C6 fraction was 58 weight percent compared with about 3 weight percent using the zeolite wit~.out phosphorus. Aromatics selectivity was 3 weight percent wi~h the phosphorus-containing zeolite with about 38 weight percent using the zeolite without phosphorus. The next major (oleinic) product fraction was C5 and the combined yield based on products (selectivity) of Cs and C6 aliphatics from propylene was 80.9 weight percent. Associated with the very low aro.r~tic yield was the absence of ethane and butane, and low (~ 1~) propane yield. Somewhat lower C6 selectivity (39.5%) was obtained at 300 C. At this temperature, 300 C, compared to 400 C, the Cs yield was reduced and ~ increased to 21.6 weight percent. The combined C5, C6, and C7~ fractions totaled 74.9 weight percent.

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.; TABLE VII
Phosphorus-Containing Zeolite CATALYST Zeolite Without Phosphorus TE~IP., C 400 300 400 300 Products, Wt. %

CH4 0 0 0.03 0 C2H6 0.69 0.06 C2H4 0.11 0.09 2.14 0.11 C3Hg 0.06 0 26.79 8.27 C3H~ Feed Feed Feed Feed i-C4H10 0 0.02 12.5Q 7.86 n-C4H10 o 0.03 5-37 2.46 C4H8 1.38 1.28 0.15 1.52 C4H6 0 0 `1.75 2.27 ; 15 Cs 3.60 1.38 6.92 27.26 C6 ` 9.18 3.g6 3.37 18.4~
C7~ 1 00 2.16 1.90 6.07 Benzene 0.08 0.11 2.07 0.80 ; ~.oluene O.Q7 0.17 10.89 5~36 ~0 Xylenes 0.31 0.48 12.38 8.93 Cg+ Aromatic~ 0 0.33 12.43 9.13 Conversion, Wt. % 15.81 10.04 99.37 98.58 Material Balance~ 9g.6 97.0 10~.50 100.11 Wt. 7. .' .

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Example 10 This example will illustrate the catalytic effect of the phosphorus-containing zeolite at higher space ~ velocities on the conversion of propylenes.
Propylene was passed at three different temperatures ever phosphorus-containon~ zeolite prepared from an activated acid form of ZSM-5 zeolite at a weight per hour space velocity of 13.5. The products were collected and analyzed. Table VIII
gives the temperatures of reaction, the degree of conversion, and the product selectivities.

TABLE VIII
Temperature, C300 350 400 Converslon, ~t. % 29.2 45.3 54.8 Products, Wt. %
Ethylene 0.1 0 0.1 ` Butenes 25.4 30.2 37.9 c5 38.2 37.8 29.3 C6 14.8 13.9 17.2 `~
C7 17.3 15.9 15.0 Aromatics 4.2 2.2 0.5 Total 100.0 100.0100.0 It will be seen from the table that the ma~or products were C4-C7 aliphatic compounds which are rich in olefins. It will also be seen from the table tnat the amount of butenes was relatively high. It will further be seen from the table that the C5-C7 aliphatic fraction consisted largely of mixtures Or olefinic compounds.

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-- Example 11 This example ~ill illustrate the catalytic activity of the phosphorus-containing zeolite on the conversion o~ a paraffin, namely, n-hexane.
N-hexane was passed over the phosphorus-containing zeolite identified as Sample 3 in Example l at 600 C and 700 C. The weight per hour space velocity was 1.96 and 1.95, respectively. The products were analyzed and the resuLts in terms of product selectivities are set forth in Table IX. For comparison purposes, there is included in the table the results obtained by passing n-hexane over three different zeolites without phosphorus at 600 C and 700 C
and at a weight per hour space velocity of 2Ø The zeolite identified in the table as A was the same as the zeolite identified as Sample l in Example 1. The zeolites identified in the table as B and C were similar but were smaller and larger crystallites than the æeolite identified as A. Further, in the con~ersion reaction employing the æeolite identified as C, air was co-fed with the n-hexane and the products ~0 included 14.8 percent by weignt of carbon monoxide and carbon dio~ide~
It will be observed from the table that the use of the phosphorus-containing zeolite resulted in a lower yleld of aro~atics as ~ompared to the zeolite without phosphorus.
~5 It will also be observed that, in addition~ the use of the phosphorus-containing zeolite resulted in a greater yield of olefins than the zeolite without phosphorus.

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~~ ` E~ample 12 This example will illustrate the catalytic effect of the phosphorus-containing zeolite on the conversion of a paraffin, namely, n-he~ane, in the presence of a diluent, namely, water or nitrogen.
N-hexane was passed at 600 C over phosphorus-containing zeolite containing 4.38 weight percent of phosphorus prepared from an activated acid form of ZSM-5 zeolite. In Run No. l, the n-hexane was diluted with nitrogen and in Run No. 2 the n-hexane was diluted with water. The products were collected and analyzed. The results are given in Table X in terms of weight~percent product selectivities. The table also gives the weight per hour space velocitles of the n-hexane and of the nitrogen and water. The weight percent conversion in Run No. 1 ~as 16 and in Run No. 2 was 3.9.

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Run No. 1 2 WHSV N-hexane 2.7 N-hexane 2.7 Nitrogen 1.7 Water 1.2 Total 4.4 Total 3.9 Products Wt. %
Methane 13.3 11.5 Ethane 9.2 7.4 Propane 0.6 0.7 Butanes 0 0 Total, Cl-C4 22.9 19.6 parafflns Ethylene 29.0 26.2 Propylene 22.5 25.6 Butenes 14.5 19 9 ~` 15 Total, C2-C4 66.0 71.7 olefins C5 10.9 8.7 Total ~- 100.0 100.0 It will be noted rrom the .a~le that no aromatics were detected and that the major products were C2-C4 oleins.

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Example 13 This example will illustrate the cataly~ic activity of phosphorus-containing zeolite impregnated with zinc on the conversion of a paraffin, namely, n-hexane.
A phosphorus-containing zeolite containing 4.45 percent by weight of phosphorus prepared from activated ac d form of ZSM-5 zeolite was immersed in an amount of aqueous solution of zinc nitrate sufficient to fill its pore volum2.
Thereafter, the phosphorus-containing zeolite containing the zinc nitrate solution was heated at 500 C for one hour in a stream of air a~ 100 cubic centimeters per minute. The resulting zinc-impregnated, phosphorus-containing zeolite contained 1 percent by weight o zinc.
N-hexane was passed over the zinc-impregnated, ` 15 phosphorus-containing zeolite at four different temperatures.The products were collected and analyzed. Table XI gives ~ the temperstures, the weight per hour space velocities, `~ the conversion, and the results obtained in terms of product ~ selectivities.
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Run No. 1 2 3 4 Temp., C 500 550 600 650 WHSV 3.1 3.0 3.0 3.0 Conversion, Wt. /~3.4 13.0 42.0 78.4 `` Products W~. %
Hydrogen 0 0.3 0.1 0.8 Methane 0 7.1 12.1 14.1 Ethane 0 10.8 13.8 12.1 Propane ~ 23.3 11.2 5.7 3.9 Butanes 0 0.6 0.8 0.4 Total H~+Cl-C4 23,3 30.0~32.5 31.3 paraf~ins Ethylene 0 14.3 23.0 24.6 Propylene 22.4 29.0 26.7 23.9 Butenes 0 5.1 5.8 3.5 Total C2-C4 22.4 48.4 55.5 52.0 olef7ns Cs - 38.6 21.6 9.~ 8.5 C7~ 15.7 0 1.1 0.
Arom.~tics 0 0 1.5 7.3 Tota lO0,0 lO0.0lO0.0 lO0.0 , ~. .

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Example 14 This example will illustrate the catalytic activity of the phosphorus-containing zeolite on the conversion of another olefin, namely, butene-2 (a mixture of cis and trans S isomers).
Butene-2 was passed at four di~ferent temperatures over phosphorus-containing zeolite prepared from an activated acid form of ZSM-5 zeolite. In the first three runs, the phosphorus-containing zeolite contained 4.~8 weight percent of phosphorus and the butene-2 was mixed with nitrogen. In the fourth run, the phosphorus-containing zeolite contai~ed 3.67 weight percent of phosphorus and nitro~en was not mixed with the butene-2. The products were coLlected and analyzed.
~ Table XIIgives the temperatures, the weight per hour space `; 15 velocities ol the butene-2 and, where used~ of -,'ne nitrogen, the conversion in weight percent and the product selectivities in weight percent.

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Run No. 1 2 3 4 Temp., C 275 300 325 350 Conversion Wt. % 24.746.o 52.8 87.3 WHSV
Butene-2 2.7 2.7 2.7 2.4 Nitrogen 1.6 1.6 1.6 0 Total 4.3 4.3 4.3 2.4 Products, Wt. %
Ethane 0.1 0 0 0 Propane 0 0 0.1 1.3 Butanes 1.4 1.1 1.1 3.0 Total C2-C4 1.5 1.1 1.2 4.3 paraffins Ethylene 0.7 1.9 0.3 0.4 Propylene 7.813.1 18.4 1.5 C4H6 - - _ 3 5 Total C2-C4 8.515.0 18.7 5.4 Qlefins ~ C5 30.828.9 39.2 40.7 ; C6 11.115.8 15.5 28.7 c7+ 40.032.5 24.1 10.8 Aromatlcs 8.1 6.7 1.3 10.1 Total 100.0100.0 100.0 100.0 It will be observed from the table that the major `~ products were C5+ compounds. These compounds are highly~ -olefinlc in nature and are mixtures of isemers. The amounts of aromatic compounds are relatively small.
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Example 15 This example will illustrate the catalytic a tivi~
of the phosphorus-containing zeolite on the conversion of a predominantly paraffinic feed, namely, a light naphtha An Arabian light naphtha (C5-290 F, densi~y=0 6g84 was fed at ~50 C over a phosphorus-containing zeolite prepared rom an activated acid orm of ZSM-5. The naph;ha had a composition in weight percent as follows: C5-19.51, C6-47.80, C7~-24.06, benzene-0.57, toluene-2.90, xylene-5.07, Cg~ aromatics~0, and total aromatics-8.54. The phosphorus-containing zeolite contained 4.42 weight percent o~ phosphorus and was calcined in air at 500 C prior to making three two-hour runs at WHSV's of 2.41, 2.38, and 2.44, respecti~ely.
The products were collected and analyzed. Table XIII gi.ves the conversion and the products in weight percen~. In the table, the figures in parentheses are the prod~ct selectivities in weight percent.
It will be observed from the table that the resuLts are ro~ghly comparable to those obta;ned with the n-hexane ir ~Y2mple 11. The C2-C4 olefins were formed in 51 weight percent selectivity (average of the three runs) at 650 C
compared with 56 weight percent selectivity from n-he~ane at 600 C and 700 C. Aromatics were slightly higher than `~ with n-hexane, averaging 7.9 percent new aromatics formed~The feed naphtha, as indicated, contained 8.54 weight percent of aromatics.

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TABLE XIII
Run No. 1 2 3 Products, Wt. %
H2 1.01 (1.5) 0.74 (1.1)0.54 to-8) CH411.64 (17.0) 11.06 (16.2)10.56 (16.1) C2H68.52 (12.4) 7.82 (11.4)8.14 (12.4) C2H413.18 (19.2) 13.23 (19.4)12.84 (19.5) C3H82.23 (3.3) 1.93 (2.8)2.00 (3.0) C3H615.75 (23.0) 17.18 (25.2)17.81 (27.1) C4H10 o.89 (1.3)1.03(1.5) 1.00 (1.4) C4H8 2.81 (4.1)4.00(5.8) 3.39 (5.2) 4H6 1.37 (2.0)2.17(3.2) 1.57 (2.4) C5 11.00 - 11.28 - 12.24 -

6 10.10 - 10.56 - 11.69 ~` 15 C7 3.00 - 2.86 - 3.41 ` Benzene 5-41 (7.1)4.63(5.9) 3.93 (5.1)

7` Toluene 7.12 (6.2)6.41(5.1) 5.86 (4.5) Xylenes3.90 (-1.2) 3.44 (-1.6)3.34 (-1.7) Cg+ Aromatics 2.00 (3.0) 0.99 (1.4)1.69 (2.6) ~otal Aromatics18.43 (14.9) 15.47 (10.8)13.82 (10.5) ~` ` Conversion, Wt.% 68.51 68.30 65.75 . ~ .
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Example 16 This example will illustrate the alkylation reaction Or the process of the invention employing ethylene as the olefin to be alkylated and dimethyl ether as the alkylating agent.
The catalyst employed in this example was prepared by the following described procedure. Several preparations crystalline aluminosilicates were combined to form a composite. Each o~ these aluminosilicates was ZSM-5 containin~ sodium as the cation associated therewith and had been prepared employlng tetrapropylammonium hydroxide. The composite had a silica to alumina ratio of 70 and the individual zeolite catalysts ha~ components falling in the ranges: 1.1-1.4% Na, 4.22-7.31% C, 0.39-0.63% N, 2.25-2.45% A1203, and 91.3-95.0% Si~2. The C/N atomic ratio " was 12.5-13.5 and the Na/Al ratio was approximately 1.2.
The composite, in powder form, was brought to a temperature of 540 C under a stream o~ nitrogen (the heating rate was about 2.5 C per minute) and held for 16 hours to remove residue o~ the tetrapropylan~onium hydroxide. It was then pressed into warers, crushed, and screened to

8-12 mesh, rollowed by ion exchange with 0.5 N NH4N03, the NH4~ replacing the Na+. The resulting pellets were air-dried ~?~ and calcined in air at 500~C for 3-16 hours whereby H+
25 ` replaced the NH4+ to rorm the zeolite catalyst.
A ten-gram sample of the zeolite was added to 3.94 cubic centimeters of trimethylphosphite dissolved in -66_ s ':';, ~` ,.
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10~17~3 50 cubic centimeters of n-octane in a flask. Under a slo~,J
stream of nitrogen the mixture was heated to re1ux temperature (about 120 C) for 72 hours. A ten-inch vigreaux column was added to the flask for distiLlation and 21 grams of liquid were collected at 90-113 C or subsequent analysis, The solids were filtered and ~Jashed with 100 cubic centimeters each of pentane, methylene chloride, and pentane. They were then air-dried followed by drying in à vacuum oven overnight at 110 C. They were next pressed into wafers, broken and screened to 8-12 mesh size and heated in nitr~gen for 3~ minutes at the temperature of reaction before use. The resulting phosphorus-containing zeolite catalyst contained about 3.5 percent by weight of phosphorus.
An approximately equimolar mixture of e.hylene and dimethyl ether was passed over a ixed bed of the catalyst at a temperature of 300 C. The products were collected and analyzed. For comparison purposes, ethylene `
` alone and dimethyl ether alone were similarly passed over a `~ 20 fixed bed of the catalyst and the products collected and analyzed.
` Table i4~as well as the tables set forth in Examplesl7-23following~ identifies the respective reactants, identiies reaction products, gives the selectivities of the reaction ~roducts in terms of weight percent, giV2S the weight per hour space velocity of the respective reactants, the degreè of conversion in ~eight percent of the respective `~ reactants, and the matèrial balance.

.
; 7 - - . It will be observed ~rom Tablel4 that, in the alkylation reaction, the selectivity to propylene, which i.s the desired alkylation reaction product, was 85%. On the other hand, the selectivity to propylene was zero with ethylene alone and only 50% with dimethyl ether alone.
Concerning the negative degree of conversion of ethylene in the alkylation reaction, this was the result of more ethylene being produced from the dimethyl ether than was consumed by allcylation to produce propylene and other products.

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T~LE 14 Run No. 1 2 3 Temp, C 300 300 ~00 Feed C2H4 ~ C2H4 - MeO~e ~eO~le I~HSV C2~4 1.~ _ 1.4 MeOMe - 2.4 2 8 Conversion, W~.%
C2H4 0 _ -5.8 MeO~le - 0.22 23.4 ~Iaterial Balance,99 98.6 98.1 Wt. %
Selectivity to Products, Wt. ~/O
C2H4 Feed 40.9 Feed C3~6 50.0 85.2 Cl-C3, All Other 0 0 1.1 C4H8 9.1 9.3 C4, All Other 0 0 1.5 C5~ 0 0 2.9 C6~^ 0 0 0 : ~7 0 o o * A mi~ture of olefins and paraffins; predominantLy uns-turated compounds 69_ - ~
.. . . : . . ~ . ~ . .:

Example 17 This example will illustrate the al~ylation o propylene ~ith dimethyl ether by the process o~ the inve~tion.
An approximately equimolar mixture of propylene and dimethyl ether was passed over a fixed bed of the same kind of catalyst as employed in Example 16. Various temperatures and `- weight per hour space velocities were employed. The products were collected and analyzed For comparison purposes, at each of the temperatures employed, propylene alone and dimethyl ether alone were similarly passed over a fixed bed o~ the catalyst and the products collected and analyzed. At the temperature of 300 C, two comparison runs were made but the second comparison run was made at a higher wetght per hour space velocity than the first. The reaction conditions and the results are given in Tables 15, i6, and ~7.
; It will be observed from the tables that decrease in the selectivity to butenes (n-C4H8), the desired alkylation ~` product, occurred when going from temperatures of 300 C to 350 C (compa~e Tables~ ~ and 16 ). In the runs showr. in `~ ~0 Table IV, it can be seen that the selectivity to butenes ~7as highest at 300 C but was significantly ~ower at 350~ C
and ~00 C~ At the higher temperatures, apparently, side ~reactions or other reaction paths became more prominent.
It wili also be noted from the tables tha~ the degree of ¦~ ~5 conversion o~ the dimethyl ether increased with ` temperature~

~' .

` 70 The negative degree o conversion of propylen~
in Run 3 was the result of more propylene being produced from the dimethyl ether than was consumed by alkylation to produce butenes and other products.

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! __ TABLE15_-Run No. 1 2 3 Temp., C 300 300 300 Feed C3H6 - C3H6 - MeO~e MeOMe I~HSV 1,7 2.4 4.5 Conversion~ Wt.%
C3H6 7.3 _ -8.2 ~IeO~Ie - 0.22 13.1 ~Iaterial Balance, 97 98.6 103 ~t. %
Selectivity to Products, ~t. %
C2H~ 1.0 40.9 .9 C3H6 Feed 50.0 Feed Cl-C3, All Other 1.0 0 1.9 n-C4H8 12.8 9.1 82.1 C~, All Other .6 0 0 C;' 13.8 0 15.2 ~ C6'` 39.5 Q 0 `` C7 33.3 o o * A mixture or olefins and paraffins; predominantly ~nsaturated compounds ~, .

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;' ~~ TABLE 16~
Run No. 4 5 _ 6 Temp., C 400 400 400 Feed C3H6 ~ C3H6 - MeO~e MeO~Ie ~SV 1.9 2.4 4.5 Conversion, Wt.%
C3H4 15.8 - 44.2 MeOMe - 56.7 99.5 Material Balance,100 101.7 99.2 Wt.%
Selectivity to Products, Wt.%
C2H4 .7 4.4 .5, C3H6 Feed 27.1 Feed Cl-C3, All Other .4 1.5 1.9 n-C4H8 8.8 11.4 22.4 C4, All Other . O 3.5 3.0 ~ C5* 22.8 13.2 27.6 `~ . C6* 58.1 23.2 30.3 C7t* 9.2 15.7 14.3 * A mixture of olefins and paraffins; predominantly unsaturated compounds ~ `
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-~V~lt7 Example 18 This example will illustrate the alkylation o~
propylene with dimethyl ether by the process o the in~entlon employing a catalyst having a lower phosphoxus content.
The catalyst employed was o~ ~he same type and prepared in a manner similar to the cataly~t employed in Example I~except that its phosphorus content was 1.45% by weight. An approximately equimolar mixture of propylene and dimethyl ether was passed over a fixed bed of th2 catalyst at a temperature of 250 C. The products were collected and analyzed. For comparison purposes, propylene alone and dimethyl ether alone were similarly passed over a fixed bed of the catalyst and the products collected and analyzed.
The results are given in Table 18.
The negative degree of conversion in Run 3 was for the same reason 85 in Run 3 in the previous ex-mple.

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-~- T~BLE 18 Run No. 1 2 3 Feed/~SV MeOMe - 2.3 2.3 3H6 2-3 _ 2.3 2.3 2.3 4.6 Conversion, Wt.%
MeO~le - 8.8 8.7 .
C3H6 22.5 - -6.0 ~Iaterial Balance,102.1 99.1 101.5 Wt. %
Selectivity to Products, Wt.%
2H4 0 8.6 3.2 ~ Cl-C3, All Other 3.8 2.4 36.9 `~ C3 ~ Feed 20.7 Feed .` C4Hlo . 3.1 0 Ç4H8 8.2 14.9 26.3 C5* 13.5 5.6 27.0 C6'` 28.8 5.0 3.2 ~' C7~ 4~.8 39.7 3.5 .

* A mixture of olefins and paraffins; predominantly :~ unsaLuratad co~pounds . , ', . ; ~
~ _76,_ i ~ '7~ ~

-- Example I9 This example will further illustrate the alkylation of propylene with dimethyl ether by the process of the invention.
In this example, an approximately equimolar mixture of propylene and dimethyl ether was passed over a fixed bed of the same kind of catalyst employed in Examplelç at various temperatures and space velocities. The catalyst, however, - prior to use~ was heated in air at 500 C for one hour and contained 3.77 weight percent of phosphorus. The product~
were collected and analyzed. Tables l9 ~0 , and 21_ give the reaction conditions and the results~
It will be observed from the tables that the selectivity to the desired alkylation product, i.e., the C4 olefin, was significantly increased with increases in the weight per hour space velocity but was not greatly affected by temperature. However~ the degree ~f convPrsion of reactants increased with temperature.

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~V~1'7 Example2D
This example will illustrate the alkylati~n of butene-2 with dimethyl ether by the process of the invention.
An approximately equimolar mixture of butene-2 and dimethyl ether was. passed over a fixed bed of the same kind of catalyst employed in Example 19 at various temperatures The products were collected and analyzed.
For comparison purposes, at each temperature, an equimolar mixture of butene-2 and nitrogen and an equimolar mixture of dimethyl ether and nitrogen were simiIarly passed over a ~ixed bed of the catalyst and the products similarly collected and analyzed. Dilution with nitrogen of the two individual components, olefin and ether, was intended to permit a comparison of the results with that of the mixture of olefin and ether at similar space velocities and other conditions within the catalyst bed. The reaction conditions and results are set forth in Table 22 .
~- I It will be noted from the table that the selectivity to the C5 olefin, the desired alkylation reaction product, increased when the temperature was ` increased from ~75 C to 300 C but decreased when the te~peratur- was increased to 325 C.

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, .: ' 7~3 Example 2l This example will illustrate the alkylation of isobutene with dimethyl ether by the process of t~e invention.
An approximately equimolar mixture of isobuteno.
and dimethyl ether was passed at 300 C over a fixed bed of the same kind of catalyst employed in Examplel9..but h~ving a diffe~ent phosphorus content. The products were co~leced and analyzed, For purposes of comparison, isobutene alon~
was similarly passed over a fixed bed of the catalyst.
Also for purposes of comparison, an approximately equimolar mixture of nitrogen and dimethyl ether was passed over a ~ixed bed of a similar kind of catalyst but having a different phosphorus content. In each case, the products were collected and analyzed. The results, as well as the phosphorus contents of the catalysts, are given in Table 2 . ~ .

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TA~LE 23 Run No. 1 2 3 Wt. % P 3.72 4.38 3.72 Temp, C 300 300 30 Feed/WHSV i-C4H8 3-1 N2 1.6 i~4~8 3 1 MeOMe 2.4 MeOMe 2.2 3.1 4.0 5.3 Conversion, Wt.%
i-C4H8 61.6 - 38.7 ~IeOMe - 1.55.1 Material Balance,96.0 93102.1 Wt. %
Selectivi~y to Products, Wt./o C2H4 26.7 .7 3H6 5.0 5.53.2 , l~ Cl-C3, All Other.3 54.1 0 `'~ C4H10 2.8 9.110.8 C4H~ Feed 4.5Feed 4~6 2.2 0 .2 ~- C~ 18.4 0 34.6 C~* 37.6 0 11.0 " C ~ 33.7 0 39.5 * ~ mixture of olefins and paraffins; predominantly unsaturated compounds " ~ ~
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1U~j17 ~9 ~` Example22 In this example, the results obtained by ~he alkylation of isobutene employing dimethyl ether as tke alkylating agent are compared with those employing methanol as the alkylating agent.
Approximately equimolar mixtures of isobutene and dimethyl ether and isobutene and methanol were passed at three different temperatures over tha same kind of catalyst employed in Example-16. The products in each run were collected ~nd analyzed. The results are given in Table 24.~
It will be observed from the table that the selec~ivities to the C5 olefins, the desired reaction products~ were higher with dimethyl ethe~ than with methsnol.

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106~769 ~3 This example will illustrate the all~ylation of propylene with methyl chloride by the process of the invention .
An approximately equimolar mixture of propylene and methyl chloride was passed at two different temperatur~s over a fixed bed of catalyst, the catalyst having been prepared as described in Examplelg but containing a different amount of phosphorus. For purposes of comparison, at one temperat~re, an appro~imately eq~imolar mixture o~
nitrogen and propylene was passed over a bed of the same kind of catalyst employed for the mixture o~ propylene and methyl chloride. Also for purposes of~comparison, at the other temperature, propylene alone was passed o~er `~ 15 a fixed bed of the catalyst, the catalyst having been prepared as described in Examplel9 but containing a slightly greater amount of phosphorus. The products were collected and a~alyzed. Table 25 gives the amoun~s o the phosphorus .
`; in the catalyst, the Xeaction conditions, and the results 2~ obtained in terms of product selectivity.
It will be observed from the table that, at 300 C, the methyl chloride was inert. However, it will also ~e observed that, at 350 C, the methyl chloride entered into the alkylation reaction and the selectivity to the C4 olefins,,the desired allcylation reaction product, was 45.1 percent.

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Example 24 Three (3) grams of an HZSM-5 extrudate containing 65 weight percent HZSM-5 and 35 weight percent of alumina binder were refluxed with 45 ml. toluene for one hour. The mixture was then cooled and 1.15 grams of trimethylphosphate were added. Reflux was continued for an additional 16 hours and then the solvent was evaporated to yield the phosphorus modified catalyst. The theoretical weight percent phosphorus in the catalyst was 7.1 whereas the actual amount of phosphorus in the catalyst used was 4.7 weight percent.

A feed consisting of a mixture of benzene and ethylene in which the molar ratio of benzene to ethylene was 1.41 was passed over the above catalyst at a weight hourly space velocity of 7.51 and a temperature of 842F.

A catalyst of 65 weight percent of HZSM-5 and 35 weight percent of alumi~a which had not undergone modificatlon with phosphorus was likewise used under comparable experimental conditions.

The phosphorus-treated catalyst was found to produce a considerably purer ethylbenzene product with higher selectivity to ethylbenzene than the untreated catalyst as will be evident from the comparable data set forth in Table 26.

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A further breakdown of impurities relatlve to - ethylbenzene is shown in Table 27 below.

Catalyst of Example 1 -Phosphorus-Unmodified Modified Extrudate Extrudate of of HZSM-5 HZSM-5 (65%) (65%) and and Alumina Catalyst Alumina (35%) (35%) .
` Impurities/
Ethylbenzene ~ ppm \ 15 Ortho-xylene 11,000 1,350 `~ Cumene 38,500 10,000 n-propylbenzene 70,000 19,500 ` Toluene 140?000 8,100 259,500 38,950 It will be evident from the above data that the phosphorus-modified catalyst afforded an ethylbenzene produ-ct with considerably less impurities and in higher selectivity and yield.
;`~

Forty-five (45) grams of an HZSM-5 extrudate con-talning 65 welght percent HZSM-5 and 35 weight percent o~
alumina binder were refluxed with 675 ml. toluene for 1 hour~ The mixture was then cooled and 20.70 grams of 3 trimethylphosphate were added. Reflux was con1inued for an~additional 16 hours and then the solvent was evaporated ?
~` to yield the phosphorous-modified catalyst having a ~-' .

. ., , . . . , . - : .

17~

theoretical phosphorous content of 8.26 weight percent.
The catalyst was calcined at 500C for 3 hours before testing.
The actual amount of phosphorous on the catalyst after use was 4.7 weight percent.
A feed consisting of a mixture of benzene and ethylene in which the molar ratio of benzene to ethylene was 5.5 was passed over the catalyst at a weight hourly space veloclty of 9.4 hour~l and a temperature of 752F.
A catalyst of 65 weight percent of HZSM-5 and 35 weight percent of alumina which had not undergone modification with phosphorus was li~ewise used under comparable experimental conditlons.
The phosphorus-treated catalyst was again found to produce a considerably purer ethylbenzene product than the .
untreated catalyst as will be evident from the comparable data set ~orth ln Table 28.

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Catalys,t of Example 1-Phosphorus-Unmodified Modified Extrudate Extrudate of of ~iZSM-5 HZSM-5 (65~) (65%) and and Alumina Catalyst Alumina (35%) (35%) __ % P 0 4.7 Ben~ene/Ethylene (Mole) 5.6 5.5 WHSV 9.6 9.4 Temp~, F 752 752 Impurity/Ethyl-benzene, ppm Toluene 10035 4170 Para-xylene 1845 450 Meta-xylene 3690 900 Ortho-xylene 1845 450 Cumene 2820 700 ` n-Propylbenzene~
Styrene 6660 2000 p-Ethyltoluene 500 155 m-Ethyltoluene 1095 475 o-Ethyltoluene/
sec. Butylbenzene 940 230 C10 780 small .~
~ 30210 9530 ~, .
~ 30 EXAMPLE 26 . _ Utilizing the catalyst of Example 1, a feed ~ consisting of a mixture of benzene and ethylene in which `~ the molar ratio of benzene to ethylene was 1.4 was passed `~ over the catalyst at a weight hourly space velocity of 7.5 and a temperature of 570F. The temperature was periodically raised to 750F. and the catalyst performance was evaluated at this temperature.
:~
~ ~ A catalyst Or 63 weight percent of HZSM-5 and 35 I wei~ht percent Or alumina which had not undergone modification ~ :
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with phosphorus was likewise used under comparable experimental conditlons. The effect of aging on ethylene conversion is shown in the attached single figure of the drawing wherein ethylene conversion is plotted against hours on stream. Referring to this figure it will be seen that the phosphorus-modified catalyst showed a slower aging rate that the unmodified catalyst. This unexpected result is highly advantageous since it affords means for increasing the cycle length between the catalyst regeneration thereby providing a definite economic advantage for the phosphorus-modified catalyst over the unmodified catalyst.

Forty-five (45) grams of an HZSM-5 extrudate con-taining 65 weight percent HZSM-5 and 35 weight percent of alumina binder were refluxed with 675 ml. toluene for 1 hour.
The mixture was then cooled and 17.25 grams of trimethylphos-phate were added. Reflux was continued for an additional 16 hours and then the solvent was evaporated to yield the phos-phorus-modified catalyst having a theoretical phosphorus content of 7.11 weight percent. The catalyst was calcined one hour at 500C and 13.5 hours at 450C before testing.
The actual amount of phosphorus on the catalyst after use was 4.9 weight percent.
~` EXAMPLE 28 Ten (10) grams of an HZSM-5 extrudate containing 65 weight percent HZSM-5 and 35 weight percent of alumina binder were contacted with 14.0 grams of an anueous solution o~ phosphoric acid containing 24.3 weight percent H3PO4.

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~Impregnation of the catalyst was accomplished by sub~ecting the mixture to vacuum and releasing three times to fill the catalyst pores. The mixture was then evaporated to dryness under reduced pressure and calcined at 500C. for 14 hours.
The theoretical weight percent of phosphorus in the catalyst was 8.6. The actual amount of phosphorus on the catalyst after use was 7.3 weight percent.

Ten (10) grams of HZSM-5 extrudate containing 65 weight percent HZSM-5 and 35 weight percent of alumina binder were soaked in an aqueous solution of phosphoric acid con-taining 30 grams of 85% H3P04 diluted to 100 milliliters for 15 minutes. Excess solution was decanted and the catalyst was dried at 110C. for 2 hours and calcined at 500C. for about 14 hours before testing. The theoretical weight per-cent phosphorus in the catalyst was 6.8. The actual amount of phosphorus on the catalyst after use was 7.3 weight percent.
EXAMPLE_30-32 The catalysts of examples 4, 5 and 6 were used for alkylating benzene with ethylene employing a feed con-sisting of a mixture of benzene and ethylene in which the molar ratio of benzene to ethylene was 5.5. Reaction con-`~t ditions included a temperature of 752F., a pressure of zero psig and a weight hourly space velocity of 9.4 hour 1.
The results obtained were compared with those obtained under identical conditions utilizing a catalyst of -t' 65 weight percent of HZSM-5 and 35 weight percent of alumina which has not undergone modification with phosphorus. The ` results are set forth in TABLE 29.

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, 1()~17~ô'3 Ten (10) grams of an HZSM-5 extrudate contàining 65 weight percent HZSM-5 and 35 weight percent of alumina binder were contacted with a solution of 4.79 grams tri-methylphosphate and 10.0 grams water. Impregnation of the catalyst was accomplished by sub~ecting the mixture to a vacuum and releasing three times to fill the catalyst pores.
The mixture was then evaporated to dryness under reduced pressure and calcined at 500C. for 14 hours. The theoretical welght percent of phosphorus in the catalyst was 8.5.

Ten (10) grams of an HZSM-5 extrudate containing 65 weight percent HZSM-5 and 35 weight percent o~ alumina binder were contacted with a solution of 6.8 grams trimethyl-phosphate diluted to 20 cc. with water. After the mixture, ; was maintained for 15 minutes the liquid was decanted and ~ the catalyst was dried at 110C. for 1 hour and calcined at `' 500C. for 14 hours. The actual amount of phosphorus on the ` catalyst after use was 3.1 weight percent.
. : :

A catalyst was prepared as described in Example 11 except that 5.8 grams methyl acid phosphate in 20 cc. of aqueous solution was substituted for aqueous trimethylphos-`~ phate. Methyl acid phosphate is a reaction product o~ -methanol and phosphorus pentoxide which in this instance contained 26 weight percent phosphorous. The actual amount of phosphorus on the catalyst after use was 6.4 weight percent.

. . .

. . . . .

i17~

The catalysts of Examples 33-35 were used for alkylating benzene with ethylene employing a feed consisting of a mixture of benzene and ethylene in which the molar ratio of benzene to ethylene was 5.5. Reaction conditions included a temperature of 752F., a pressure of zero psig and a weight hourly space velocity of 9.4.
The reaction results were compared with those obtained under identi~al conditions utilizing a catalyst ~- 10 of 65 weight percent of HZSM-5 and 35 weight percent of - alumina which had not undergone modification with phosphorus.
The results are set forth in Table 30 below.

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Ten (10) grams of an HZSM-5 extrudate containing 65 weight percent HZSM-5 and 35 weight percent alumina binder were contacted with water. The catalyst pores were filled by sub~ecting the mixture to~vacuum and releasing three times. The excess water was decanted and the catalyst was calcined ~or 1/2 hour at 500C. The entire impregnation-calcination procedure was repeated a total of five times.
The catalyst was used for alkylating benzene with ethylene employing a feed consisting of a mixture of benzene and ethylene in which the molar ratio of benzene to ethylene was 5.5. Reaction conditions included a temperature of 752F., a pressure of zero psig and a weight hourly space velocity of 9.4 hour 1.
The results obtained were compared with those obtained under identical conditions utilizing an untreated catalyst of 65 weight percent HZSM-5 and 35 weight percent -~ of alumina. The results set forth in Table 31 below show that phosphorus is a necessary ingredient in the catalyst treatment.

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~XAMPLE 40 The catalyst of Example 27 was compared with an unmo~ified catalyst utilizing conditions of superatmospheric pressure. The conditions and results are set forth in Table 32 below.
The results illustrate that a lower impurity level is exhibited by the phosphorus-modified catalyst under commer-cially attractive conditions.

' '7~'~

" TABLE 32 Unmodified Catalyst of Catal~st ExamPle 4 PPM PPM
Relative Relative To Ethyl- To Ethyl-Component benzene benzene . .
Toluene 8300 3510 P-xylene 3060 840 M-xylene 6110 1690 0-xylene/Cumene5000 1950 n-Propylbenzene~
Styrene 6110 2730 p-Ethyltoluene 110 130 m-Ethyltoluene 560 260 o-Ethyltoluene/
sec-Butylbenzene 1110 650 Clo 940 o .

Time on Stream, Hr. 6.5-72 30-95 " ~IHSVl(Ethylene), Hr. 4.26 4.05 Benzene/Ethylene (Mole Ratio) 8.o4 8.72 Temp., Inlet 800F. 800F.
Temp., Max. 857F. 839F.
Pressure, PSIG 300 300 ~ ': .

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, Exam~e 41 Employing the catalyst of Example 1 (Sample 5), toluene and dimethylether were reacted utilizing a feed wherein the molar ratio o~ toluene to dimethyl ether was 1.4. This feed was passed over 5 grams of the catalyst at a weight hourly space velocity of 5. at a temperature of 450c. ~or a period of 350 minutes. Conversion of toluene was 61 percent. Xylene production amounted to 32.7 percent with the para:meta:ortho weight ratio being 30.2:45.7:24.1.

Examples 42 - 48 These examples were carried out in a manner similar to that for Example 41 but at di~ering temperatures and for di~erent reaction times. Results are shown in the table below.
Example 42 43 44 45 46 47 48 Temp. C. 250 275 300 300 350 400 400 Time On-Stream860 920 60 440 320 135 290 ~ (Min.) ; % Conversion 3.6 7. o 2.2 14.2 34.8 40.5 54 1 Of Toluene Xylene 1.4 4.8 1.3 9.8 20.6 23.6 30.1 ~rQd~c~lon, %
Xylene Isomers ~5 Para 30.3 30.8 33.4 31.4 32.3 32.5 31.9 Meta 20.3 21.4 21.3 23.3 24.3 27.9 35.1 Ortho 49.4 47.8 45.3 45.3 43.3 39.6 33.0 ' '"; ' ";~'''".

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10~:i17~9 It will be noted from the above data that the catalyst underwent activation with time on-stream. Thus, at 300 C, conversion increased from 2.2% to 14.2% and at 400 C from 40.5% to 54.1%.

Examples 49 -77 ~ Jsing a catalyst similar to those o~ Example 1 and containing 3.5 weight percent phosphorus, toluene and methanol were reacted under differing conditions as shown in the following Table 33.

~ 7 ~ 9 Feed Te~p Toluene/ ml,/ Toluene Xylenes Ex. C ~Iethanol I~, HSV Conv, P ~
49 300 2:1- 8,o 1,632.0 30 22 48 ; 50 300 2:1 15,2 3,020,6 35 21 44 51 300 2:1 30,4 6,o8,2 31.8 19,0 49,2 52 350 2:1 8.o 1.647.7 28 29 43 53 350 Z:l 14.8 2.942.9 33 25 42 `0 54 350 2:1 30.4 5.925.4 31 25 44 400 2:1 8.o 1.650.0 29 40 31 56 400 2:1 15.4 3.048.2 31 31 38 57 400 2:1 30.0 5.846.1 32~ 27 41 58 300 1:1 8.o 1.6 14.4 31 21 ~8 '5 59 300 1:1 15.6 3.06.2 32 18 50 300 1:1 22.0 4,44,5 32 18,5 99.5 61 300 1:1 28.4 5.63.8 31 23 46 62 350 1:1 8.o 1.629,4 30 25 45 63 350 1:1 16.0 3.019,4 31,5 24 44.5 ,~ 64 350 1:1 29.7 6.210,6 32 25 43 400 1:1 8.o 1.631,8 34 32 34 ` 66 400 1:1 15.6 3.031.5 33 27 40 ~7 400 1:1 30.4 5.823.4 35 26 39 68 300 1:2 8.o 1.612.8 32 20 48 , 69 300 1:2 17.2 3.06.5 27 14 5g 7 300 1:2 30.0 5,81.8 33 17 50 71 350 1:2 8.o 1.630.0 32 22 46 `72 350 1:2 15.6 3,018.5 33 23 44 73 350 1:2 30.4 5.89.5 31 18 50 ~, 74 400 1:2 8.o 1,642.5 36 30 34 75 400 1:2 15,2 3,036,8 37 26 37 `~ 7~ 400 1;2 30,0 5,824,1 38 2~ 37 '~ 77 35 2:1 8.o 1.640 31 27 42 ~ - ~06-- . - .. ~ ~

1~17~;9 From the above results, it will be seen that the amounts o~ both para- and ortho-xylenes were enhanced and the amount of meta-xylene was diminished compared to the normal equilibrium mixture of 22 percent ortho-xylene, 24 percent para-xylene and 54 percent meta-xylene.

Example 78 A 3 gram sample of HZSM-5, 1.5 grams of phenyl phosphine oxychloride and 30 milliliters of ~oluene were refluxed overnight. Toluene was removed by distillation under vacuum to dryness and the residue was heated in a vacuum oven overnight at a pressure of 21 millimeters of mercury at 140C. The weight of catalyst was 4.1 grams.

A 2 gram samp~le of the resulting phosphorus-modified ZSM-5 catalyst was loaded in a reactor and a mixture of toluene and methanol (1 to 1 molar ratio) was contacted with the catalyst at 600C at a weight hourly space velocity of 11~8. The conversion of toluene was 27 percent and the ratlo of para~meta/ortho xylenes was 84/11/5.

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Ex~mple 7~-A mixture of three grams o~ large crystal XZSM-5 in 45 milliliters of toluene was refluxed for 1 hour. After cooling, 1.52 grams o~ trimethylphosphate were added and the mixture re~luxed overnight. Toluene was distilled off and the catalyst was calcined 1 hour at 550rC.
A 1/1 molar mixture ol toluene and methanol was passe`d over the catalyst at 550C. at a weight hourly space velocity o~ 9.9. The product contained 92 wei~ht percent para-xylene in the x~lene fraction and 89 weight percent x~lenes in the aromatic ~raction (excluding toluene). The toluene was 17 percent converted.
.` . . . .
ExamPles 80-81 Three grams of HZSM-5 and 45 ml. of toluene were refluxed ~or 1 hour, cooled and then 1.14 grams o~ tri~ethyl-phosphate were added. The resulting mixture was refluxed overnight, evaporated to dryness and therea~ter calcined for 1 hour at 500C. The catalyst so prepared contained 4.o6 weight percent phosphorus.
Toluene and methanol in a molar ratio of l were contacted with 2 grams o~ the above catalyst. The reaction conditions and results are shown below in Table 31 .

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~06~769 . - . : .. ~ ... . ... . .

Examples 82-84 Three grams of HZSM-5 and 45 ml. of toluene were re~luxed for l hour, cooled and then 1.14 grams of trimethyl-` phosphate were added. The resulting composite was evaporated to dryness and thereafter calcined ~or l hour at 500~C. The ` catalyst so prepared contained 2.39 weight percent phosphorus.
Toluene and methanol in a molar ratio of 1 were contacted with 2 grams of the above catalyst. The reaction conditions and results are shown below in Table 35.

-110~
:.

, . . . .

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o~ o ~
o o ~ c~ ~
o o o ~

~:
~:
c~
o co ~ ~

~ 3 w ~ ~ o 'o ~ ~ ~
g ~D ~

~ o co ~ "
P~
o tl w : ~ :
p~ ~
co co co ~
i (D
:
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' :
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o ~:
~`

s ~ co ~o ~
to ~t ~ o~

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~161769 ::

.

0 ~ 9 Exa~ple 8~

A mixture of 3 grams of HZSM-5 extrudate (containing 65 weight percent HZSM-5 and 35 weight percent A1203 binder) and 45 ml. of toluene was refluxed for 1 hour. After cooling, 2.7 grams o~ trimethylphosphate were added and the resulting mixture refluxed overnight. The composite obtained was evaporated to dryness and thereafter calcined for 1 hour at 500C.
Toluene and methanol in a 1:1 molar ratio were passed over the catalyst above prepared at a temperature of 500C. at a weight hourly space velocity of 9.3. The weight percent xylenes in the aromatic product was ~1. The para/
;~ meta/ortho xylene weight ratio was 95~1/4 at 21 percent toluene conversion. The used catalyst was found to contain 12 weight ` ` 15 percent phosphorus. The higher phosphorus content in this catalyst in comparison to the catalyst of Example80-84 is attributable to the presence of the al~lmina binder.
From the abov~ results shown in Tables 34 and 3~ , and in Example 85, it will be evident that the ZSM-5 c~talyst modified by the addition thereto of trimethylphosphate was highly effective in the selective production of para-xylene.
j Higher para-xylene selectivitie~s were observed at 600C. than at 550C. Catalyst activity was inversely related and para-xylene selectivity directly related to the phosphorus content o~ the catalyst.

_112 _ Exam~les 86 -, 93 Sixty seven (67) grams of dried HZSM-5 were com-bined with 26.5 grams of trimethylphosphite, (CH30)3 P and 235 ml. of octane in a flask. The mixture was gently re-fluxed for 18 hours. A dry nitrogen purge was used. After cooling, the catalyst was filtered and washed with 500 ml.
of methylene chloride followed by 500 ml. of pentane. m e catalyst was then calcined in air at 150 ml./min. for 16 hours at a temperature of 500aC. Analysis indicated a phosphorus content of 3.45 percent by weight.
Toluene was alkylated with methanol under various conditions of reaction with this catalyst. Ihe conditions employed and resulting conversions are shown in Table 36 below.

, ' _113, _ :, . - ~ .. - . :
..

7f~3 a ~ ~ ~ ~ O O ~ x o ~ ~
. O

~ o CO ~ U~ U~ o ~

o ~n co ~I

O ~ CO
,~ ,p, ~ O CO

~ ~ ~ ~ ~ ~ O 0 00 ~n ~ o o~ ~
I ~ ~ Ul I-- O O ~ W
O O
: :
l-- O ~
U~ O ,11 .

-- ~ ~D ;
O ~

1-- ~ O ~D
a) cx~ o .

- 114 ~

`:
~ .

It will be evident from the above results that the trimethylphosphite-modified catalyst was effective for the production of para-xylene and that selectivity for this isomer increased significantly at higher temperature and space velocity.

Exam~les 94-102 Four (4) grams of HZSM-5, 0.75 gram of 85% phos-ph~rlc acid (H3PO4) and 150 ml. of methanol were combined and refluxed gently for 16 hours with a nitrogen purge.
The solvent was removed by distillation and the remaining catalyst heated to 250C.in air. The catalyst was then placed in a furnace at 500C. in air for 1 hour. Elemental analysis showed a phosphorus content of 4.45 weight percent.
Toluene was alkylated with methanol under various conditions of reaction with this catalyst. The conditions used and the resulting conversions are shown in Table 37 below.
,,~ ,. . .

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'`

.
.

, .. , , ,.. ~ . ..... .

17t;~
O

~" ~ C -- Q~
~ ~
o ~I w ~ 0 o ~I ~ ~n ~1-- o ~n ` O a~ o o ~ ~ ~ 1--o o a~ :

~ ~ o o ~o `~ OO ~D
O ~ O CO

1--0 0 ~D
W ~n ': .

~ o O O O ~ ~

~1 CO / 10 Ul ~1 ~ o o W ,~ O

~, O 0 1~ ~O O
O ~

.
,. - . ~, . .
' ` ~

From the above results, it will be seen that the phosphoric acid-modified catalyst was ef~ective for the production of para-xylene and that selectivity for this isomer increased significantly at higher te~perature and space velocity. In addition, from a co.~parison of the re-sults of Examples 94 and 97 there would appear to be a conditioning effect with time on stream which resulted in an increase in yield of para-xylene.

Examples 103-105 Four grams of HZSM-5~ 2.50 gram of 85~ phosphoric acid (H3P04) and 150 ml. of methanol were combined-and re-fluxed gently for 17'hours with a nitrogen purge. m e solvent was removed by distillation and the remaining cata-lyst heated to 150~C. in air. The catalyst was then placed in a furnace at 500~C. in air for 1 hour, Elemental analysis showed a phosphorus content of 13.4 weight percent.
Toluene was alkylated with methanol under various conditions of reaction with this catalyst. The conditions ~-~ used and the resulting conversions are sho~n in Table 38 below.

~ ~ .

`

:
' .

7~;~

U~ o ~CO~O~ o U~ o ~ 0 ~ 0 o C- ~ , U~ ~ 0~ ,, ~ o ~D 0 O~ 0~ ~ O

, CO
`

"" ~ cr~ O U~ O
,1 ~ O ~ D ~ ~ O

O O ~ ~ a) Q) 8 ~3o o ~ h O
O ~ ~ X ~ ~ ~ o h E; ~ ' g ~? S, P~ ~ a) h ` ~

- , - . ` . .. . ...

From the above results, it will be evident that the phosphoric acid-modified catalyst containing 13.4 wt.
percent phosphorus was effective for para-xylene production.
It will also be apparent that high selectivity to para-xylene, e;g. 90 percent at lo~ toluene conversion, e g. 12 percent was realized.

Examples 106-131 Five (5) grams of HZS~1-5 pellets ana 75 ml. of toluene were placed in a flask and heated to reflux. There was no ~tirring, so as to avoid shattering the pellets and a slow stream of nitrogen was bubbled through the solution ~o minimive bumping. After 45 minutes, the mixture was cooled to room temperature and 4 grams of diphenyl phosphine chloride were added. Reflux was then re-established and allowed to continue for about 16 hours. The solvent was then removed by distilling to dryness. The residual solid was thereafter calcined in air at 500~C. for 1 hour.
Alkylation of toluene using the above modified HZS~I-5 as catalyst was carried out by contact of toluene and methanol in a reactor zone fitted with a thermocouple and containing 0.5-3 grams of the catalyst. The conditions of reaction and the results obtained are shown below in ~able 39 - .
.~

_ 119_ .
.

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~ .~ r~, ~J tJ

* * t~ r~ ~ r~ r~ 1--~ r-- t w w r~ r\~ r~r~ N r~) r~ r~ r--1--Y ~ r-- o o o o X
~ o ~ co~ ~ ~n ~ w r~ ~~ o ~o co ~ c~ .
,.

~ oogo$ooo'o`o'ggg8gggg~'gooooo c~

o co ~ o IJ~O ~ ~ .~--w ~ '1 ~w o ;ow~o~ c~w cow~ ~w 1 p7 ~ o o ~ o `~

Q ~

o p ~ o ~ ~ ~ ~ ~ o ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ o ~:

9~ o o ~;, ~) W C~' O W ~ l ~) ~ W W W .,- 0--1 0 1~ ~n ~w ~ w O ~
~ ~l~w~ ~o~ Jcoo~r~ow ~ w ' ~ , '. (D ~J~ . .
.
e~
O
~ ,~

a~ O~ ~O~O~D~O~O~~Cnoo~ 1~ P
~0 o~ ~ ~l' ow~ ~ ~ ~ ~ ~ ~ ~ o lJ lJ
o ~n o o o~n~ o~n~ ~r~) ~ OW

O ~ O O ~C~Col' ~ -~ CX)~O~ O I'~ o~
o ~ o ~ ~ o~
t ~D
IJ o ~
`.... -.-.--................................. C~
~nw 1~ ~ o ~o~o ~n ~ o~ n cow o cno~o~o o --/~10-.

From the above results, it ~ill be evident that higher reaction te.~perature within the range of 400 to 600C. a~forded higher selectivity to para-xylene. Like~,Jise, higher space velocity lead to increased selectivity to para-xylene. Increasing the toluene to methanol feed ratio at a given temperature and space velocity also served to increase the selectivi,ty to para-xylene, Increasing the phosphorus level in the catalyst leads to increased selectivity to para-xylene with hoT,~ever decreased conversion o~ both toluene and rnethanol and reduced ef~iciency o~ methanol utilization.

Examples 132 -135 Catalysts of varying phosphorus content prepared in a manner similar to that utilized in Exa-~pleslo6-l3l were synthesized. These catalysts were used in prornoting the re-action o~ toluene and ~ethanol, present in a molar ratio of 1.4 (toluene/methanol) at a te~perature of 550C. The condi-tions and results of such reaction are shoTm in Table 4 belo~.

1?:1 -~.(~17~

~ ,, ~ ~ a~ ~ N
a h P

C ~ ~
~a ~ o ~

N

E~

E~ , - .

~31 '' ' - ,, r1 , .

` ` ' , .

' ~q .
rl N N ~1 ~ c~ O 11 P' ~1 ` ~ N N

.
.
.

~ ~ , ~
X
t .
U~ , .

~ 7 ~9 It will be seen from the above data that the selectivity with respect to para-xylene increased as the phosphorus content of the zeolite catalyst ~ncrea~ed.

~ 6-137 Ten grams of pelletized HZSM-5 were combined with a solution of 10 grams of diethylchloro thiophosphate, (EtO)2P(S)Cl, and 150 ml of toluene. The suspension was gently refluxed for 18 hours over nitrogen. The solvent was distilled off and the temperature allowed to rise to 130-140~C. The resulting catalyst was heated in an oven, in air, at 140rC. for two hours. Weight after this treatment was 15.0 grams, The c`atalyst was then calcined in a furnace at 500C., in air, for a period of four hours. Elemental analysis revealed a phosphorus content o~ 5.98 percent by weight.
~o grams of this catalyst was loaded in a reactor and w`as contacted with a ~ixture ol toluene and methanol (1 to 1 molar ratio) under various conditions. The results are summarized in Table 41- belo~

. -1?3i -7 ~ ~

.
Example 13~ ~ 137 Temp. C 550 600 WHSV 10.0 10.0 Molar Feed Ratio (Toluene/Methanol) Conversion, %
Toluene 29.3 34.9 Methanol 94.4 93.2 ` 10 ~. Xylenes in Aroma~ic Product Wt. % 79.1 85.o Xylene Isomers, ~
Para . . 73.9 ~`81.9 Meta 15.6 11.9 Ortho lo.5 6.2 .
~, - .

., `

. ` `

.~ .
_ 124 _ t ' ' : " ` . `' '. '........ . `'- `

7 ~ ~
s138-139 7.91 grams of diphenylphosphinic acid, ~2P(O)OH
were dissolved in 175 ml of toluene by heating. To this solution was cautiously added 10.0 grams of pelletized ~ZSM-5. The white solid developed a light le~on yellow color, It was gently refluxed for 16 hours with a nitrogen sweep. The resulting solid had developed a dark brown-yellow color.
The solvent was distilled off and the temperature allowed to rise to 130~C. in nitrogen. The solid was placed in an oven at 150C. for 1 hour. The weight was 18.00 grams at this point. The solid was then placed in a furnace at 500C. in air for a périod of 6.5 hours to give 11.2 grams of a grey white solid. Analysis revealed a phosphorus content ` 15 of 4.99 percent by weight.
Two grams o~ this catalyst was placed in a reactor and contacted with a 1 to 1 molar mixture of toluene and methanol. m e results are s~marized in Table 42 below.

_125 _ - - ; ', : ., i(lt;l7~;~

Example 138 1~
Temp. C 550 600 WHSV 10,0 10,0 Feed Ratio, Molar (Toluene/~Iethanol) Conversion, %
Toluene 20.1 21.7 Methanol 93.8 87.o Xylenes in Aromatic Product Wt. % 78.6 88.1 Xylene Isomers Para 81.2 ~ 91.8 Meta 10.~ . 5.o O~tho 8.6 3.2 Selectivity to Aromatic Products Benzene .2 .2 Ethyl Benzene .4 .4 Para-Xylene 63.8 81.0 Meta-Xylene 8.0 4.4 .' Ortho-Xylene 6.8 2.8 p-Ethyl Toluene ~ 3~2 2.3 Pseudoc~mene 12.3 6,6 Cg-Clo Aromatics 5.4 2.4 _126 _ t .

Exarnples 140-147 Ten grams of HZS~-5 were placed in a vacuum des-sicator, over water, evacuated with an aspirator and allowed to stand for 16 hours. The increase in weight due to ad-sorption of water ~as 1.75 grams The resulting catalyst pellets were then added to a solution of 8.o grams of di-phenylphosphine chloride, 02PCl, in 150 ml of toluene and gently heated. At about 75C., quantities of HCl were evolved as the 02PCl was hydrolyzed to diphenylphosphinous ` acid 02P(O)H. All of the HCl was evolved when the boiling point o~ toluene was reached and the suspension was gently re~luxed for 17 hours. The net effect of this treatment was to combine HZSM-5 with 02P(O)~I, prepared in situ. The solvent was then boiled off and the catalyst heated in an oven for 2-l/2 hours, at 150 C., in air. It was then placed in a iurnace at 500C., in air, for 5 hours. Anal~sis revealed a - phosphorus content of 5.o8 percent by weight.
T~JO gra~s of this catalyst were placed in a reactor and contacted with various mixtures of toluene and methanol.
The results are su~marized in Table 4~ below.

, ~ 1'7t;~

~_ O ~ ~ N O~ t'~
~0 O N 0 C~ oL~ ~ ri~
~1 oo~

O ~ ~ ~~ C~J C`J~O

O
~ ~~ o NO ~t a ~ O

3 0 1~

~ O,:;1 ' ' 00 ~tO O -1 0 3 tr~ ~ N
U~ O ~ N ~ ~

o~r) o C~J C~ O 00 N O
3 ~ O rl 0~O O ~
_~ "

o o ~ .

.

h V ~ H

~ o ~ O ~ O

o Lr~
l2~-Exa~ples 148~

4.00 gr~ls o~ ZSI~1-35, uncalcined, ~tere added to a solution of 1.50 grams of diphenyl phosphine chloride dis-solved in 150 ml of toluene. m e suspension, blanketed with a stream of nitrogen, was refluxed for 20 hours. The solvent was boiled down and the remaining concentrated slurry was placed in a dlsh and heated in an oven at llO'C. for 2 hours.
A uniform powder remained which was calcined in air, in a ~urnace at 500'C. for 2.25 hours. m e black solid weighed lO ~ 3.96 grams, Analysis revealed a phosphorus content o~ 3.67 percent.
Two grams o~ this catalyst were placed in a reactor and contacte~ with various mixtures o~ toluene and methanol.
The results are su~mari~ed in Table 44. It can be seen that very high selectivities were obtained to xylenes, with unusually small amounts o~ higher alkylated products. m e selectlvity to para-xylcn, eRpecially at 600~C., was excellent.

, .

_ 129 _ 7~i~

g ~ ,~ ~o ~ ~ U~ 0~1~
, ~ ~O O C~ D 0,~ Ir~ ~u~

o ~ ,, ~o ~ ~o ~ ~o CU0 o o ~ ~` ~ ~ ~0 ~ ~0 ,i a~ ~ tr) ~ ~1 ~ O O C--~ CU C~ N ~
3 ~ "~ o ~ ~o ~ ~_~) ~J:~C\~) ~ .
,` ~ U~ ~ 'I ~i ~ C-- ~~ ~~
`i ~ .

.,o Y 'P U

G) ~ ~ , O

-:

u~ O ~ O

. . ....

1(~61~7~ 3 Example 152 A 2 gram sample of HZSM-5 was impregnated with phosphorus by contact with a toluene solution of diphenyl phosphinous acid (2 weight percent concentration), refluxed for 17 hours, after which the solvent was boiled off and the remaining catalyst placed in a furnace in air at 500C.
ror 5 hours. The phosphorus content o~ the catalyst product was 5.08 percent by weight. The catalyst was evaluated by ~eeding a 2/1 molar solutlon of toluene/methanol mlxture at 550C. at a weight hourly space velocity of 10 over a 10 hour perlod. Toluene conversion during this period ranged from 12.2 to 9.9 weight percent and paraxylene content of the xylene product ranged ~rom 81 to 88 weight percent. The cataly~t was thereafter activated by treating with a 1:1 volume mixture of methanol/water at 550C. for 16 hours at a weight hourly space velocity of 10. A 2/1 molar solution of toluene/methanol-was again fed over the treated catalyst at 550~C. at a weight hourly space velocity of 10 over a 10 hour perlod. Toluene conversion during this period ranged from 26 to 20 weight percent and paraxylene content of the xylene product ranged from 75 to 86 weight percent. As a result of the actlvating treatment with the methanol/water mixture, the average toluene conversion increased from 11 to 23 percent.

Example 153 In a manner similar to that o~ Example 152, lo grams o~ HZ~M-5 were impregnated with phosphorus by contact with iO~

diphenyl phosphine chloride to yield a catalyst product containing 6.78 weight percent phosphorus.

Catalyst performance was evaluated by alkylation of toluene with methanol utilizing a 2/1 molar solution of toluene/methanol under the following conditions of time and temperature:

, . - , . ~ , , , , , , -, . , ~o ~ ~
o oo ~ o ~ ~
~ ~ o X ~ X

v o ~` o ~`
~l o ~ o ~ ~ o o r~ ~

~ . ~

E~ ~ =~! ~ ~ _ .
~ cu o~
,.~ a~ tn u o o o o o o o ` ~ ~ ~o ~ ~o ~ ~
`" :`~` ', I,t ~ Z ~ O ~ ~
~i "., ~; CU L~

.

lV~

From the above tabulated data, it will be evident that toluene conversion was increased substantially by the methanol/water treatment between runs 3 and 4.

Example 154

10 grams of HZSM-5 were treated with 4.16 g. of H3P04 in 150 ml of methanol to yield a catalyst product containing 8.51 weight percent phosphorus after heating in a furnace at 500C. in air for 4.5 hours.

Catalyst performance was evaluated~by alkylation of toluene with methanol utilizing a 1/1 molar solution of toluene/methanol under the following conditions of time and temperature:
:`

1'7ti~
`
o .
o E~

~ = a ~0 g~ ' ~ o a~ - ~1 o h p,, ~ ~ ~ ~ Lr ~O
h ~ C~
~ ~I
P~ ..

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~ ~ O ~ ~~
.. ~1 C~ O
O O
C~

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g ~

o O O O O
~ ~. L~ O O O
~ ~ Lt~ ~O~

.

O
:~; L~
~ ~I N
1~

_ 135_ ilt7~i~
It will be seen from the above t,abula,t~d da,~a ~;na',, both the toluene conversion and selectivity ~o the de.;ired p-xylene product were improved as a resu'~, of the rne~nanol/
water activation treatment.

Example 155 Utilizing the s~me catalyst as described -'~n E~ c152 and employing a toluene/methanol molar f~ed ratio of 1/1, t~.e following results were observed after treatment of the catalyst with a 1:1 volume mixture of methanol/water at 550C. for 16 hours at a weight hourly space velocity of 10: , _ oluene Conversion Para-Xylene Selec~iv~y Before After Before Alte r ~emp, C Treatment Treatment Treatment Treatmer~
... .

550 20.7 37.5 82 86 -' 600 27.6 39.8 90 90 .
As will be evident from the above data, a sîgni~icant improvement in toluene conversion was observed as a result of the catalyst activation treatment with met,hanol/water.

Example ~56 ~rams ol HZSM-5 1/16'~ extrudate containing 35~ alumina binder was treated with a 5 weight percent trimet~yl phosphite solution in toluen~, in the vapor phase at a temper~lture o~ 115 to 250C. to yield a catalyst with a phos~horus conten~
o~ 10 wel~ht percent. The catalyst was calcined ~or 16 hour at 550C. ~n a stream o~ air flowing through it.
The catalyst was evaluated for alkylation of toluene with methanol by feeding a 4/1 molar toluene/methanol mixture at a weight hourly space velocity of 10. It should be noted that,the maximum theoretical toluene conversion is 25 percent~

_ 136 _ - . , .-. - . . . .
. .

11)~17~
.~ , since methanol is the limitin~ reagent. Xhe follor,rin~ r~zult~
were obtained at the indicated times and temperatures:

_ 137 _ .

1()~17t;~
o .~ ~, ~3o bD V
~ ~ o ~ If~ h S~ ~ ~ "~ ,~ ~ ~ O
E~ ~ _ - V ~ ~
~d ~ o ~ fi u~~ o ~ v U~ V ~ O G~ ~ ~0 C) o td O
,~ C) o~ ~ ~ U~
U~ o ~ L~
a~ ~1 oa) ,~ O
~d ~ O ~ o S~ \
V ~ V ~ ~ ~ r~

~0 h CS~t ~1 ~0 U~ C\.l ~0 0~ 0 00 ~100 00 CU ~ C'~l CU
4 .... ..... ..... .....
~1 r~ ~) o~o ao o ~-1 N
P~ ~ L~ O ~00 0 ~ O~O~)~

a~ h ~ t~)C~ r-l N N ~)~ L~ ~1~)~)~:) ~)N ~:~
~C~ - - - ..... ..... .....
E~ ~ Ir-lr~lr~ lr~
V

. .

.` ~0 O
.~ 00``00 0 ' O O
4 l~ O U~ O O = = = _ IS~= = = = 1~- = = =
~U~O ~O In U~
E~

Q "
. ~ ,~ o _ 138 ` _ ~ '7 It will be evident from the above tabulated dat~
that toluene conversion increased significantly after the used catalyst was treated with the methanG1/~.Jater Mixture.

Example 157 5 grams of HZSM-5 were treated with 6.6g of a solution of 20 weight percent H3P04 in water. The trea~ed composite was dried in ar. oven at 110C. and placed in a furnace at 500C. in air for 56 hours. The catalyst contained 8.17 weight percent phosphorus. In a ~anner similar to Exam~le 5, it was tested for alkylation of toluene at 600C.
under the following conditions o~ time and ternperature:

.

- ~ : . .. .

h O
O h C~ g~
~ ~ $ .~ o ,, ~ -~ ~ ,~ o 11 ~ ~o 11 E~ c~ rl N
~ C~ 0 ;~ \0 ~
~o ~_Io ~o ,~ o o t~ h ~ O \ L~ 3 0 ~i U~ ~ ~0 000 a) ~a~ ~ ~ o~ u~o ~ ,i ,i ~) ` ~

~ xo ~ ~l o ~~
~i o ~ ~ L~
:` ~ ~
" E~ , ,~1 -. .

_4 ~ "~

_140 i~ '7~
.
It is ag in evident that the methanol/~rater act,i~
vation treatment resulted in a significant ir.crease in toluene conversion.

Exarnple 158 In a manner similar to Example 157 HZSM-5 ~ras impregnated with aaueous H3P04 to yield a catalyst which contained 7. o8 weight percent phosphorus after it was removed fro~ an 18 hour treatment in a ~urnace at 500C. in air. The catalyst was tested for its ability to alkylate`toluene at 600C. utilizing a 4~1 molar toluene/methanol ~eed ratio at a weight hourly ~pace velocity o~ 10. The maximum theoretical toluene conversion was 25 percent since methanol was the limiting reagent. The follow-ing results were obtained at the indicated times and temperature:

_141 _ ~o 1061769 '' O i o ~ V~
~:: h O ~1 a~ ~ ~ ,~
O
a~ ~: O cd ~ V ~ ~ ~¢
U~ o a) ~ \ ,~ ~a o 5~
V C~ ~ ~ Ln ~S~
COCO ~ 0~ ~ ~0 ~
l~CO C~ t~i ~ ~i C~ C`.i ~COCO CO~ C~
X

.

. I~ ~) N ~C) CO ~1 ~10 1 ~1 ~-i E-~

." '"'.
. ~ -1~1 -1 ~i C`l ~ ~I N

N ~ ~ ~CO

_ 142 -- It will be evl~dent from the abo~e result~ tn~t simple calcination in air did not completely activate the catalyst and that substantially improved activation was achi~ved as a result of treatment with the methanol/water mixture.
Examplel59 In a manner similar to Examplel5~ HZSM-5 was im-pregnated with aqueous H3P04 to yield a catalyst which con-tained 8 . o6 weight percent phosphorus after it was heated for 15.3 hours in air at 500C.
The catalyst was evaluated for alkylation of toluene at 600C. utilizing a 4/1 molar toluene/methanol feed mixture at a weight hourIy space velocity of 10. The fresh cataly~t gave a 2.1 weight percent toluene conversion. After the first 15.5 hour activation with a 1/1 volume mixture of methanol/
water, toluene conversion increased to 9.8 weight percent.
After the second and third activations, toluene conversion in-creased to 11.3 and 11.1 percent respectively. All of these - ~ activation tr~at~ents were carried out at 550C. for about 15 - hours at a ~Jei~ht hourly spac~Q- velocity of 10. A fourth ac-`` tivation was carried ou~ at 600C., whereupon toluene conversion increased to i3.~ percent Selectivity to-para-xylene was greatQr than 9C percent in each instance after activation.

~ Examplel60 ; In a manner similar to the previous example, a cata~
l~st of H2SM-5 containing 7.68 weight percent phosphorus had an initial toluene conversion of 0.5 percert. After the first, - second ~nd third activations with a 1/1 volume mixture of methanol/~ater, toluene conversions increased to 9.5 percent~
11 percent and 11.2 percent respectively. A fourth activatio~

-.

.
.: . ,, . ~ : .

17~
was carried out at 400C. In this instance, the toluene conversion was 11.7 percent, indicating the temperature was too low to increase the toluene conversion significantly.

Example 161 In a manner similar to Examples 157-160, a HZSM-5 catalyst with a phosphorus content of 7.46 percent after 61 hours in a furnace in air at 500C was obtained. In this case, however, lt was activated prior to alkylation use with a 1/1 volume mixture of methanol/water at 550C for 15.5 hours at a welght hourly space velocity of 10. The initial toluene conversion was 12.3 percent and the para-xylene selectivity was 90 percent.

; Example 162 In a manner similar to the previous example, a HZSM-5 catalyst with a phosphorus content of 6.66 percent after 41 hours in a furnace in air at 500C was obtained. It was activated immediatel-y and tested in a manner similar to Example 10. The initial toluene conversion was 16.4 percent with an 84 percent selectivity to para-xylene.

, .

.,, : , ' :
~ .

Example 163 This exàmple will illustrate the conversion of methanol by the process of the invention.

ZSM-5 zeolite, in the amount of 33.5 grams, was dried at 500 C for one hour in nitrogen and cooled. The zeolite was then placed in a gla~s flask with 167.5 milliliters of normal octane and 13.2 milliliters of trimethylphosphite. This flask was fitted with reflux condenser, a dry nitrogen purge line, and a thermometer.
The end of the reflux condenser was fitted with a calcium , . . . . ; -chloride trap to protect the contents of the flask from moisture. The contents of the flask were refluxed gent~y overnight. After cooling, the liquid p~lase în the fla~k was filtered off and the remaining solids washed on a fritted funnel with 250 milliliters of methylene chloride followed by 250 milliliters of normal pentane. The zeolite was placed in a vacuum oven for 2 hours at 110 C, cooled, and stored in a desiccator. The phosphorus content of the zeolite was 4.51 weight percent. As a final step, the zeoli~e was placed in a reactor and heated at 200-250 C
in a stream of dry nitrogen.
Methanol in the gaseous phase uas passed over the phosphorus-containing zeolite catalyst in the reactor. For . . .
each of the several runs, a different temperature was emplo~ed.
` lS Following each run, the products were collected and analyzed.
The results are given in Tables45 and 46._ In Table ~ the selectivities of the products in we~ght percent are given, normalized to provide a total of 100 percent. In Table ~46j~ the results for each run are given in terms o~ the weight percent of the products in the effluent stream rom the reactor. Tha te~peratu-e, the weight per hour space velocity, the percent conversion and the material balance for each run are also given. In Table 47~, the weight percent bf the products obtained with the phosphorus-containing zeolite in Run 2 are compared with those obtained employing, as a cat~lyst, ~he original hydrogen form of the ZSM-5 zeolite~

_146-~ .

.
, . . .

Referring to Table 46, in Run 2 at 385° C, 85 percent of the methanol was converted. This is a selectivity to hydrocarbons of approximately 13 percent, to dimethyl ether of 51 percent, and to water of 36 percent.
In Run 4 at 560° C, virtually all of the methanol and intermediate dimethyl ether was converted to hydrocarbon (approximately 45 percent) and water (approximately 54 percent). The maximum theoretical conversion to hydrocarbon is 43.8 percent and to water is 56.2 percent. Comparing the results of the use of the ZSM-5 zeolite (Table 47 ) with the use of phosporous-containing zeolite in Run 2, the C2-C4 paraffins decreased fro 39 to 5 percent and the aromatics decreased from 40 to 20 percent. On the other hand, the olefins increased from 1.57 percent to 39.4 percent. It will also be noted, still referring to Table 45 that, at a temperature of 325° C, the selectivities to the C2 and C3 olefins were high compared to the selectivities to the C2 and C3 paraffins. At temperatures above 325° C, the selectivities to the C2, C3, and C4 olefins were high compared to the selectivities to the C2, C3, and C4 paraffins.

~ TAELE4~
Run ~!o. 1 2 _ 3 4 5 Product Selectivity, l~t. %
Ethylene 10.8 7.5 4.6 13.3 1S.9 Propylene 25.8 28.039.3 37.3 36.3 Butenes 0 3.918.4 15.0 1~.6 Total Cl~C4 olefins36.6 39.462.3 65.6 67.8 Aromatics 0 20.4 8.0 12.2 ].4.3 Cs~ Aliphatics 0 35.125.4 16.4 5.1 Hydro~en 0 0 0 .3 .4 Methane 0 .1 .1 2.6 5.1 Ethane 4.1 0 .1 .3 .4.1 Propane 18.8 .7 ~.5 1.3 l.L
Butane 40.5 4.3 2.6 .9 .7 C0 ~ C02 0 0 0 ` .4 1.4 To~al 100.0 100.0100.0 lOQ.0 100.0 T~BLE 46 Run ~'o. 1 2 3 4 5 Temp., C 325 385 465 ~60 620 lr~lSV 3.4 3.8 3.9 3.2 3.
Produc,s, Wt. %
Aliphetics H2 .124 .162 CO .203 .607 CH4 .016 .035 1.175 2.189 `C2 ~ .012 .004 .026 .148 1.762 C2 ~ .031 .851 1.658 6.060 8.177 C3H8 .054 .075 ,541 .571 .493 C3H6 .074 3.159 14.277 .17.067 15. 626 i-C4H10 .057 .427 .891 .253 .120 n-C4H10 .059 , 054 . 085 .127 . 1 6Q
C4H8 .441 5.004 5.422 4.676 C~H6 .004 1.716 1.417 .712 Cs .893 3.757 4.~77 1.365 C6 . 795 3.195 1.9~8 .632 C7t 2 .278 2 .312 1. 011 . 170 d-c~,pou;l a ;;, MeO~Ie 57.68342 . 9994 . 848 . 035 . 034 MeOH 18.28514.935 5.780 .359 2.479 ' H:2 23. 74530.77552 . g47 53 .935 54.518 ~` 25 A~omatics Benzene .114 .331 .498 . 437 Toluene .089 .299 1.020 1.498 Xylenes .673 1.169 2 . 755 2 . 861 ArCg . 674 . 881 1.168 1.163 ArClo .743 .248 .126 .160 Conversion, Wt. % 81.7 85.1 94.2 99.6 97.S
~` ~2aterial Balance,Wt.% 98.0 99.6 98.8 102.0 93.9 ~ 1'7~

Phosphorus-Containing CATALYST ZSM-5 Zeolite_ _ Temp., C 370 385 WHSV 1,33 3,8 Products, Wt, /0 C2H6 .44 o C2H4 .45 7 5 C3Hg 13.58 .7 C3H6 1.09 28.0 C4, sat. 24.94 4.2 C4, unsat. .03 3.9 C5 11.07 7.9 C6 5.99 17.2 C7+ 1.21 10.2 ~romatic 40.46 20.4 Other .1 Material Balance,100.02 97.1 Wt. %

lU~

~xample 164 This example will ~urther illustrate the conversion of methanol by the process of the invention.
The phosphorus-containing zeolite employed as a catalyst in this example was prepared in a manner similar to that described for the catalyst ln Example 163. P~or to use, however, the phosphorus-containing zeolite was heated at 500 C in a stream o~ air ~lowing at the rate of 100 milliliters per mlnute ~or a period of 16 hours. Analysis of the phosphorus-containing zeolite indicated a phosphorus content of 3.48 weight percent.
Methanol was passed over the catalyst in the form of a fixed bed at several temperatures and at a weight per hour space velocity of 3.1. The products were collected and analyzed. The results are given in Tables 48 and 49.
Table 48 gives the temperature of reaction and the selectivity to the hydrocarbon product~ in weight percent, normalized to -give a total of 100 percent. The composition o~ the reactor ~ effluent stream is given in weight percent in Table 4~.
- 20 It can be seen from Table 48 that the light olefin ~defined as ethylene, propylene, and butenes) selectivities ~ ranged ~rom 43-70 percent by weight. Propylene was the `? ma~or component at temperatures of 500-700 C where high `~ conversions to hydrocarbons were obtained. The proportion of ethylene increased from 3-18 percent at these higher temperatures. Butenes production was significant and tended to fall moderately ~rom 20-14 percent at these higher .
~.

-151- :~ ~
~.

t;'3 Run No. 1 2 3 _ Aliphatics Wt. %
CH4 .101.347 C2H6 .090 .011.044 C2H4 .5361.416 C3H8 .013.104 C3H6 .111 .9098.633 i-C4Hlo .471.458 n C4Hlo 0 .046 C4H8 .023 .0283.634 C4H6 0 .646 c5 .1674.215 C6 .2747.345 c7+ .1502.216 O-Compounds, Wt. %
MeOMe 99.77694.25443.272 MeOH 2.601 11.077 H2O .186 13.813 Aromatics, Wt. %
Benzene .o36 .533 Toluene .013 .335 Xylenes .169 .943 ArCg .063 .636 ArC10 .018 .287 Conversion, .225.7 56.7 ; Wt. %
Mat` rià~ Balance, 98 6 98.7 101.7 ,.:

7 ~

ExamPle 166 This example ~7ill illustrate the conversion ~r dimethyl ether by the process of the invention, The phosphorus-containing zeolite employed as th~
catalyst in this example was prepared by the general method described for Example I64 The z~olite in this case contained 3.77 percent of phosphorus by weight. Dimethyl ether in the gaseous phase was passed over a fixed bed of the catalyst in a reactor at several temperatures and a weight per hour space velocity of 14.5. The products were collected and analyze~.
The results are given in Tables 52 ands3 ~ Table 5Z gives the hydrocarbon product selectivities in weight percent and Table~ ~ gives the composition in weight percent of the effluent stream from the reactor.

' .

Run No. 1 2 3 Temp., C 300 350 40 Product Selectivity, Wt. %
Ethylene 1.1 2.1 2.7 Propylene 38.7 32.3 22.6 Butenes 10.0 9.1 16.7 Total Cl-C4 ole~ins49.8 43.5 42.0 Aromatics 0 0 2.4 C5~ Aliphatics 50.1 56.3 53.8 Hydrogen 0 0 0 ~lethane 0 .2 1.8 Ethane 0 0 ~ 0 Propane .1 0 0 1~ Butane 0 0 0 :` - CO~C02 0 0 0 ~ 1 -` Total 100.0 100.0 100.0 .~ .
:`

1~4 .

.

1(J~17~3 - rA~TJE 53 Run No. 1 2 3 Temp., C 300 35f' 40C
Aliphatics, Wt. %
. _ CH4 .003 .09g C2 ~ .011 .037 .151 C3H8 . 001 0 0 C3H6 .380 .553 1.257 i-C4~10 O O
n-C4H10 O o 4H8 . .072 .115 .657 C4H6 .027 .042 .272 Cs .492 .967 ~ 2.38~
C6 0 0 .100 C7~ 0 0 .504 , O-Compounds, _~t. %
: MPOMe 98.028 96.21988.632 I~OH .927 1.885 5.007 H20 ~ .063 .17$ .802 Conversion, ~t. %2.0 3.8 11.4 Material Balance,102.0 103.6 99.7 ~` Wt. %

.. . .. .. .

~ '7 ExamPle167 This example will further illustrate the conversion of dimethyl ether by the process of the invention.
The phosphorus-containing zeolite employed as catalyst in this example was prepared by the l~ethod descr;bed in Example 104. In this case, the zeolite contained 3~48 percent by weight o~ phosphorus. Dimethyl ether was passed over a ~ixed bed of the catalyst in 2 reactor at various temperature~
and at weight per hour space velocity of 2.3. The products ~ere collected and analyzed. The results are given in Tables 54andss , Table 54 giving the hydrocarbon product selectivi~ies in weight percent and Table 55 giving the composition in weight percent of the effluent stream from the reactor.

~, ` 156 . .

.

1()f~17~
" : TABLE54 Run No. 1 2 3 4 5 6 .
Temp., C 300 350 400 500 6~iO 700 Conversion, l~t. %3.6 21.8 62.5 1.00 100 100 Product Selectivity, Wt %
_ _ Ethylene 10.7 7.2 5.2 2.6 15.1 4.~
Propylene 32.0 28,2 23.2 33.9 38.4 7.0 Butenes 11.8 15.1 18.1 21.2 19.9 .9 Total Cl-C4 olefins54.5 50.5 46.5 S7.7 73.4 12.7 Aromatics 12.9 15.6 11.9 3.6 6.6 4.6 Cs~ Aliphatics 7.3 27.1 36.5 33.3- 13.0 3.9 Hydrogen 0 0 0 0 .1 3.8 Methane 0 .4 1.7 ~ 2.6 3.5 32.4 Ethane 10.9 1.3 .5 .4 .5 .9 Propane 8.3 1.7 .6 .7 1.3 ,2 Butane 6.1 3.4 2.3 1.4 1.1 .0 CO+C02 0 0 0 .2 .5 41.5 . . ~
Total 100.0100.0 100.0 100.0100.0 100.0 1~7 --.

. . . . .. . .

1~ 1'7 TAP~LE 55 Run ,~o. 1 2 3 4 S 6 -Aliph~tics, Wt. %
~2 .00~ .065 3.08g CO .012.023 .20~ 32.~6g C2 0 .102 .126 .285 C~4 .041 .5531.5772.09325.886 C2H6 .254.134 .163.249 .331 .745 C2 ~ .248.763 1.719 1.596 9.143 3.825 C3H8 .193.184 .200 .423 .771 .136 C3H6 .7453.006 7.678 20.699 23.193 5.655 i-C4H10 .072.253 .678 .679 .375 0 n-C4H10 .069.109 .093 .211. .313 0 C4Hg .2751.438 5.018 10.864 11.039 .574 C4H6 0 .167 .959 2.081 .99~ .164 C5 .005~635 3.0~9 8.881 5.594 2.gs8 ' C6 .~10.588 3.53Q 7.799 1.411 .141 C7~ .1551.65g 5.446 3.690 .912 .030 O-Compounds~ Wt. ^/O
MeO~Ie 96.352 78.2~2 37.532 0 0 0 ,~ieOn ;.23, ,.46~ 12.$54 .139 .0'7 ~008 H20 .086 3.661 16.983 38.797 39.404 19.754 Arcmatics Wt. ~, Ben~ene .008 .108 .354 .414 .564 .334 Toluene .044 .287 .679 .256 .855 .842 Xylenes ` .095 .494 1.265 .810 1.917 1.692 ArCg .065 .405 .874 .530 .585 .665 ArC10 .088 .367 .761 .176 .085 .25Q
Conversion, Wt. %3.6 21.8 62.5 100.0 100.0 100.() 3Q ~aterial Balance,102.4 101.5 101.0 98.4 96.4 92.5 ~t. %
1~

. . . : - . - . . . .. .

EYample 16~
This example will illustrate the conver~ion of dimethyl ether by the process of the lnvention where ~he phosphorus-containing zeolite is impregnated with zir.c.
A phosphorus-containing zeolite was prepared by the general method described in Example 164. The amount or phosphorus in the zeolite was 4.5 percent by weight. An amount of zinc nitrate to give l percent by weight Qf zinc on the zeolite was dissolved in an appropriate amoun~
o~ water to fill the pore volume o the zeolite. The zeolite was placed in the aqueous solution. After application of the solution, the zeolite was heated at 500 C for l hour in a stream of air at 100 milliliters per minute. Samples of this zeolite were employed as catalysts for the conversion of dimethyl ether. The dimethyl ether was passed in the gaseous phase at a weight per hour space velocity of 2.3 over the zeolite in the form of a fixed bed. For each of the four runs a different ~emperatur2 was-e~ployed. Following each run, the products collected were analyze~.
The resul~s are given in Tables 56 and 57 In Table 56~, the selectivities of the hydrocarbon products in weight percent are given. In Table 57, the weight percent of the products in the effluent streams are given.
.

.
1~9 `

~ . . . . . . . . .

It will be observed by compari.son of Tables 56 and 57 that, at temperatures of 300 C, 350~ C, and 400 C, the conversions obtained with the zinc-impregna~ed phosphorus-containing zeolite were increased over ~hose obtained with a phosphorus-containing zeolite without impregnation with zinc from 0.22 to 4.8 percent, 5.7 to 63.3 percent, and 56.7 to 87.2 percent, respectively.

.

10~117~
TAB~
-Run No. 1_ 2 3 4_ Temp, C 300 350 400465 Product Selectivity, ~ _ _ . . .
Ethylene 13.4 9.1 5.23.1 - Propylene 43.729.1 25.631.5 Butenes 28.418.4 11.315.8 Total Cl-C4 olefins 85.5 56.642.1 50.4 Aromatics 0 7.1 9.04.8 C5~ Aliphatics 8.631.0 45.540.5 Hydrogen 0 0 0 Methane S.9 .8 .5 .5 Ethane 0 .3 1 .2 Propane 0 .6 .7 1.3 lS Butane 0 3.6 2.12.3 CO+CG2 O o O _ `' Total 100.0100.0 lO0.0100.0 .~ . .

.

.
, ` 161 ~ . .
~ , .
'. ~

Run No. 1 2 3 4 Temp., C 300/ 350 400 465 Products~ Wt. %
Aliphatics CO O O O O
CO2 0 o O O
CH4 .12 .4 .25 .32 C2H6 0 .14 .o6 .12 C2H4 .27 4.9 2.8 1.9 .~ C3H8 0 .33 .4 .8 C3H6 9 15.4 13.9 19.7 i-C4Hlo 1.9 .07 1.4 n-C4H10 o o 1.1 .05 4H8 .56 7.6 4.7 7-3 C4H6 0 2.2 1.4 2.6 C5 .17 7 9 8.3 12.2 C6 ~ 5.4 12.4 11.0 C7+ 3.2 4.0 2.2 O-Compounds NeOMe 95.2 36.7 12.8 .03 MeOH 2.8 5.8 7.5 1.2 `' 25.4 36.2 Aromatics Benzene O .09 .6 .6 Toluene 0 .29 .4 .5 Xylenes 0 1.4 1.9 1.1 ArCg 0 .9 1.1 .7 ArC10 0 1.1 .9 .2 ~62 . - .... ~ . .

- 10~
TABLE 57 (continued) Run No. 1 2 3 _ 4 Aliphatic, Wt. % 2.0 49.4 49.4 59.5 Aromatic, Wt. % 0 3.8 4.9 3.0 O-Compounds, Wt. % 98.o 42.5 20.3 1.2 H20, Wt. % 0 4.3 25.4 36.2 Conversion, Wt. % 4.8 63.3 87.2 100 Material Balance, Wt.glOO.5 100.4 102.4 97.8 , .

:

Claims (49)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A catalyst for the conversion of organic compounds comprising a crystalline aluminosilicate zeolite which has a silica to alumina ratio of at least 12 and a constraint index in the range 1 to 12, and which has been treated so as to include at least 0.5 weight percent of phosphorus (by weight of the zeolite) in intimate association therewith.

2. A catalyst according to Claim 1 wherein the zeolite includes 0.5 to 25 weight percent of phosphorus.

3. A catalyst according to Claim 2 wherein the amount of phosphorus is 0.78 to 4.5 weight percent of the zeolite.

4. A catalyst according to Claim 1 wherein the zeolite includes 2 to 15 weight percent of phosphorus.

5. A catalyst according to Claim 1, 2 or 3 wherein the zeolite has a silica to alumina ratio of at least 30.

6. A catalyst according to Claim 1, 2 or 3 wherein the zeolite is a member of the ZSM-5 family.

7. A catalyst according to Claim 1, 2 or 3 wherein the zeolite is zeolite ZSM-12 or ZSM-21.

8. A catalyst according to claim 1, 2 or 3 wherein the zeolite is composited with a catalytically relatively inert matrix.

9. A catalyst according to Claim 1 wherein there is impregnated on the zeolite at least 0.1 percent of its weight of zinc.

10. A catalyst according to Claim 9 wherein the quantity of zinc is 1 to 4 weight percent.

11. A catalyst according to Claim 1, 2 or 3 wherein the zeolite has a silica to alumina ratio in the range 60 to 300.

12. A catalyst according to Claim 1, 2 or 3 wherein the zeolite has a crystal density, in the dry hydrogen form, of not less than 1.6 g/cc.

13. A method of preparing a catalyst for the con-version of organic compounds comprising a crystalline aluminosilicate zeolite which has a silica to alumina ratio of at least 12 and a constraint index in the range 1 to 12, and which has been treated so as to include at least 0.5 weight percent of phosphorus (by weight of the zeolite) in intimate association therewith which method comprises contacting said zeolite with a phosphorus-containing compound and heating the product of the contact.

14. A method according to Claim 13 wherein said phosphorus-containing compound is in the vapour phase.

15. A method according to Claim 13 wherein said phosphorus-containing compound is in the liquid phase.

16. A method according to Claim 13 wherein said phosphorus-containing compound is in solution.

17. A method according to Claim 13 wherein the phosphorus-containing compound is orthophosphoric acid or one of its esters.

18. A method according to Claim 13 wherein the phosphorus-containing compound is phosphorus trichloride, diphenyl phosphine chloride, diphenyl phosphinous acid, trimethyl phosphite, or the product of reaction of P2O5 with an alcohol.

19. A method according to Claim 17 wherein said ester is a methyl ester.

20. A method according to claim 18 wherein said alcohol is methyl alcohol.

21. A method according to Claim 13, 14 or 15 wherein the heating is at a temperature of 150 to 500°C.

22. A method according to Claim 13, 14 or 15 wherein the heating is effected in an atmosphere in which oxygen is present.

23. A method according to Claim 13, 14 or 15 wherein the zeolite is exposed to the action of water vapour between the contacting and the heating.

24. A method according to Claim 13 wherein there is impregnated upon the zeolite at least 0.1 percent of its weight of zinc by contact with a liquid medium containing zinc followed by drying.

25. A method according to Claim 24 wherein said liquid medium containing zinc is a solution of a zinc salt.

26. A method according to Claim 25 wherein said salt is the nitrate.

27. A process for converting an organic compound comprising contacting the same, under conversion conditions, with a catalyst as claimed in Claim 1.

28. A process according to Claim 27 wherein said compound is a hydrocarbon.

29. A process according to Claim 27 wherein said organic compound is a paraffin.

30. A process according to Claim 27 wherein said organic compound is n-hexane.

31. A process according to Claim 27 wherein said organic compound is an olefin.

32. A process according to Claim 31 wherein the olefin is ethylene, propylene or a butene.

33. A process according to Claim 28 which is carried out at a temperature of 300 to 700°C.

34. A process according to Claim 31 wherein the conversion of the olefin is alkylation with an alkylating agent simultaneously in contact with the catalyst.

35. A process according to Claim 34 wherein the alkylating agent contains a methyl group.

36. A process according to Claim 34 wherein the alkylating agent is methanol, dimethyl ether or methyl chloride.

37. A process according to Claim 34 which is carried out at a temperature of 250 to 400°C.

38. A process according to Claim 34 which is carried out at a weight hourly space velocity in the range 0.5 to 19.

39. A process according to Claim 34 wherein the catalyst is in the form of a fixed bed and the reactants are in the vapour phase.

40. A process according to Claim 27 wherein said compound is toluene and its conversion is its methylation.

41. A process according to Claim 40 wherein there is employed as methylating agent methanol, methyl chloride, methyl bromide, dimethyl ether or dimethylsulphate.

42. A process according to Claim 40 which is carried out at a temperature of 250 to 750°C, a pressure of 0 to 1,000 p.s.i.g., a weight hourly space velocity of 1 to 2000 and a mole ratio of methylating agent to toluene of 0.05 to 5.

43. A process according to Claim 40, 41 or 42, wherein the temperature is 500 to 700°C, the pressure is atmospheric, the space velocity 5 to 1500 and the methylating agent: toluene mole ratio is 0.1 to 2.

44. A process according to Claim 27 wherein said compound is methanol or dimethyl ether and said contacting is effected at a temperature of at least 300°C.

45. A process according to Claim 44 wherein the contacting is effected at a temperature of 350 to 700°C.

46. A process according to Claim 44 wherein the methanol or dimethyl ether is in the vapour phase.

47. A process according to Claim 44, 45 or 46, wherein the catalyst is in the form of a fixed bed.

48. A process according to Claim 44, 45 or 46 which is carried out at a weight hourly space velocity of 1.5 to 14.5.

49. A process according to Claim 44, 45 or 46 wherein, before said contacting, said catalyst has been acti-vated by exposure for at least 1 hour to a mixture of methanol and water at a temperature of 400 to 650°C.