CA1270809A - Phosphorus modified magnesium silicate - Google Patents

Abstract

ABSTRACT

Porous crystalline magnesium silicates modi-fied by addition of phosphorus in an amount from about 0.25 percent to about 30 percent by weight are dis-closed. The new silicates are useful in alkylating aromatic hydrocarbons.

Description

~F~ ! 7~ q~

PHOSPHORUS MODIFIED MAGNESIUM SILICATE

The present invention concerns to novel phos-phorus modi*ied, porous magnesium silicates. More par-ticularly the present invention concerns such phosphorus modified porous magnesium silicates having ca'alytic properties that are usefully employed in the alkylation of aromatic compounds.

Porous aluminosilicates, i.e., zeolites, especially highly siliceous forms thereof, such as ZSM-5, silicalite, ZSM-35, and others, are well-known in the art. Typically such compounds are porous crystalline frameworks based on an extended three-dimensional net-work of SiO4 and greater or lesser amounts of A104 tetrahedra linked to each other by shared oxygens. u. s.
Patent 4,049,573 discloses that zeolites such as ZSM-5, ZSM-11, ZSM-12, ZSM-35, ZSM-38, and others, could be beneficially treated by impregnation with modifying sub-stances including phosphorus compounds thereby preparing zeolitic catalysts having deposited or occluded modifying 31,372A-F -1-~7~ qt species. These modifiers are believed to affect the acid sites of the zeolites and were found tc be useful catalysts in hydrocarbon converslon processes.

U.S. Patent 4,002,698 describes phosphorws modified aluminosilicates that are particularly suited for the alkylation of toluene. Preferred compounds possessed a silica/alumina ratio of at least about 12 and were modified by the addition thereto o~ at least 0.5 percent by weight phosphorus Numerous additional references teach -that alumino~ilicate zeolites may op-tionally further contain modifying substances including phosphorus. The phos~
phorus may be added by contacting the zeolite with an organic phosphorus compound or an inorganic phosphorus compound such as quaternary ammonium phosphate salts.
Illustrative of such references are U.S. Patents 4,140,726; 4,276,437; 4,276,438; 4,275,256; 4,278,827;
4,259,537; 4,230,894; 4,250,345; 3,962,364 and 4,270,017.

In 1972, U.S. Patent 3,702,886 issued directed to a synthetic zeolite termed ZSM-5 and method for making it. This patent discloses a zeolite having a SiO2/A12O3 molar ratio from about 5 to 100. The main claim characterized ZSM~5 by reference to a table of X-ray diffraction lines (see Table I following) and the following composltion in terms of mole ratios of oxides 0.9~0.2 M2~nO:Al2o3:ysio2 2H2 31,372A-F -2-~ ~'7~

wherein M ls at leas-t one ca-tion having a valance n, Y, is a-t least 5 and z is between 0 and 40.

TABLE I
ZSM-5, Interplanar Spacing d(A) .
11.1~0.2 6.30~0.1 5.01~0.1 3.71~0.05 lO.o~Q.2 6.04~0.1 . 4.60~0.08 3.04~0.03 7.4~0.15 5. 97IO . 1 4.25iO.08 2.99~0.02 7.1~0.15 5.56~0.1 3.~5~0.07 2.94~0.02 According to Mobil scientists, the ZSM-5 aluminosilicate is prepared by including nitrogenous organic molecules such as tetrapropyl ammonium bromide in the reaction mixtures. For very high SiO2/Al2O3 preparations, no aluminum need be deliberately added since it is present as an impurity in the reactants.
The organic molecules are incorporated into the frame-work structure as it forms and-these as-synthesized materials are termed "nitrogenous zeolltesi'. Appli-cation of high temperatures will free high SiO2/Al203 materials of these organic components without altering the basic framework structure, D. M. Olson et al., "Chemical and Physical Properties of the ZSM-5 Sub-stitutional Series", J. Catal., 61, 390 396 at 391 (1980).

According to the present invention, there are provided novel porous, crystalline magnesium sili-cates modified by the addition thereto of phosphorus in the amount from about 0.25 percent by weight to about 30 percent by weight.

31,372A-F -3-The porous crystal:line magnesium silicate may be further described as follows. The amount of magnesium present 1n this silica-te may vary. However, for all com-positions of the present invention, it is essential that some magnesium which is not ion-exchangeable by conven-tional techniques be presen-t i~ the silica-te. Conven-tional techniqlles of ion-exchange are presented in Breck, Zeolite Molecular Sieves, John Wiley & Sons (1~74). Other elemen-ts may be present in porous magnesium silicates as impurities such as aluminum, germanium, or gallium or chemlcals may be delib~rately added either to modify or improve the properties of the magnesium silicate or for other advantageous reasons, for example, to ameliorate process parameters. Suitable additional chemicals include primarily chromium, iron, copper, barium and boron.

These porous magnesium silicates have a com-position which may be expressed according to the follow ing formula in terms of the molar ratios of oxides on a dry basis:

(M2~n)p(Mg3)X(R23 )y(si~)2 )Z

wherein M is at least one ion-exchangeable cation having a valence of n; R is at least one element (with valence 3 ) which is not ion-exchangeable by conventional means;
x/z>0; y/z~0; p/n~y; and p, x, z are positive numbers and y is a positive number or zero. By dry basis is meant material which has been heated in air at about 500C for a period of one hour or more. The invention is not limited to use only of such dried material or said oxide forms, 31,372A-F -4-_ ) _ ra-ther the composi-tion of the porous magnesium silicates employed herein may be presented in terms of oxides and on a dry basis (as in the above formula) in order -to pro-vide a means for identifying such compositions.

The porous magnesium silicates modlfied by addition of phosphorus accorclin~ to the present inven-tion are prepared by hydro~hermal me-thods from a variety of silicate and magnesium sources leading to produc~s, all of which incorporate magnesium into the struc-ture of the resul-ting porous crystalline magnesium silicate.

Incorporation of phosphorus may be performed by any suitable technique. Advantageously, the previously prepared porous magnesium silicate is physically contac-ted with a suitable phosphorus compound optionally in a solvent.
Removal of the solvent as, for example, by evaporation, results in isolation of the phosphorus modified porous magnesium silicate. Once prepared, the phosphorus modi-fied porous crystalline magnesium silicates may be han-dled like previously known alkylation catalysts. The composition may be mixed with binders such as clays and compressed into pellets, pulverized or otherwise machined prior -to use and calcined. The phosphorus modified por-ous crystalline magnesium silicates of the invention are useful catalysts in the alkylation of aromatic compounds such as benzene, toluene, etc., with a variety of alkyl-ating agents including olefins, primary alcohols, and others.

The term crystalline when used herein refers to materials which are recognized by those skilled in the art as having a highly ordered structure.

31,372A~F -5-f9[)~ 3 --6~

Three dimensional periodicity is characteristic of a highly ordered structure. The skilled artisan recognizes that evidence of such periodicity may be presented by cata-lytic reactivity, infrared spectroscopy or other means of analysis as well as by the commonplace X-ray diffraction analysis. Porous magnesium silicates employed in the present 1nvention are "crystalline" as that term is char-acterized above even if said silicates appear amorphous to X-ray diffraction analysis if a skilled artisan recog-nizes a highly ordered structure by other evidence. Ar~cent article by P. A . Jacobs et al., "Evidence of X-ray Amorphous Zeolites", ~ s~ C~:c~ ro~ , 591, 1981, is useful on this point.

By the term "porous" are meant those sili-cates having a framework structure con-taining cavities capable of allowing the entrance or absorbance of mole-cules such as water, nitrogen or toluene.

Due to the differences in ionic radii of Si (0.41 A) and Al (0.50 A) replacement of Si by Al in TO4 sites will cause a unit cell volume expansion in most zeolites. The degree of unit cell volume expan-sion will depend on the amount of Al substitution for Si in the TO~ sites. If -the substitution is low, as in some ZSM-5 and silicalite zeolites, high resolution, calibrated X-ray diffraction techniques must be utili7ed to detect the expansion.

Similarly, in the present invention, it is believed -that nonion-exchangeable Mg is contained in the magnesium silicate lattice. Replacement of Si I~ o 30 (0.41 A) by Mg (0.65 A) in T04 sites will also cause 31,372A~F -6-~ ~ . 7 { ~ 3 a un:it cell expansion. Once again, the amount of Mg - subs-titution for Si, will influence the degree of cell volume expansion.

Evidencing element loca-tion in a framework lattice struc-ture by de-termining cell volume expansion ~con-traction) has been done by others skilled in making silicates. See, e.g., M. Taramasso, G. Perego and B. Notari, "Molecular Sieve Borosilicates", Proceedings of the Fifth International Conference on Zeolites, 40-48 10 at 44 (Heyden ~ Sons Ltd.) (1980).

High resolution X-ray powder diffraction data were obtained from Huber-Guinier powder diffraction cam-eras equipped with Ge and quartz monochromators for pro~
viding-CuK~l and FeK~1 radiation, respectively. The films were calibrated, with well-known internal stan~ards such as NBS Si (NBS Circular 539 Vol._9, p. 3~ or As2O3, scanned with a densitometer and the re~ulting data profile fit by techniques described in: J. W. Edmonds and W. WO
Henslee, Adv. in X-ray Anal., 22, 143 (1978) and J. W.
Edmonds, "Precision Guinier X-ray Powder Diffraction Data", NBS Special Publication 567, Proceedin~s of Symposium on Accuracy in Powder Diffraction Held at NBS, Gaithersburg, MD, June 11-15, 1979 (Issued February 1980~. The cali-brated data were least-squares refined and fitted to -obtain accurate cell dimensions and volumes.

Using data from the method described above and using single crystal X-ray crystallographic data from the literature, the cell volume for porous magnesium sili-cates employed in the present invention where Mg I is believed to replace SiIV, can be compared to the cell 31,372A-F -7-volume of silicalite which has SiIV in all the T04 sites.
Typical data are shown in Table II, for ei-ther anhydxous zeoli-tes or calcined zeolites. (Minimum calcination of 50GC for 1 hour.) TABLE II
Cell Volumes Compound Volume (A3) Reference Silicali-te 5306 Silicalite 5305 2 10 Magnesium Silicate 5347 2 Magnesium Silicate 5349 2 Cell volumes were obtained from the lattice param-eters given in an article by E. M. Flanigen, J. M.
Bennett, R. W. Grose, J. P. Cohen, R. L~ Patton, 15 R. M. Kirchner and J. V. Smith, Nature, 271, 512 (1978~.
2Cell volumes were calculated using the National Bureau of Standards - Geological Survey Lattice Parameter Refinement Program written by Dan Appleman (available through NTIS~ on XRD data obtained on samples made either according to the process explained herein or according to the sili-calite patent.

The above values are typical examples of cell volumes of porous magnesium silicates employed in -the invention and a highly siliceous zeolite such as silica~
lite. The difference between these volumes shows a cell volume expansion. The exact amount of expansion will be composition dependent. The porous magnesium silicate compounds employed in -the present invention will exhibi-t 31,372A~F -8-unit cell volume expansion when compared to silicalite, but expansion is not limited to that derived from the data shown ln Table II. I-t is believed -that the above-mentioned uni-t cell expansion evidences the placemen-t of maynesium as a part of the lattice framework struc-ture. It is believed that altering the SiO2~MgO ratio varies the pore size and volume, framework density and refractive inde~ of the resulting magnesium silicates.
If small ranges of the SiO2/MgO ratios are utilized, the ability to detect volume, pore size and density differences will be dependent on the resolution capa-bilities of the analytical technigue used.

Samples of compositions of the present inven-tion whose crystallite size is appropriate to produce a distinct X-ray powder diffrac-tion trace, have a pattern which includes at least the interplanar d spacings listed in Table III.

31,372A-F -9-'t~ 3 TABLE III

Ma~nesium silicate, interplanar spacings d(A) 11.2 +0.2 10.1 ~0.2 10.0 ~0.2 9.8 ~0.2 6.0 ~0.2 5.8 +0.2 5.6 +0.2 4.26*0.1 3.85_0.05 3.81+0.05 3.74+0.03 3.72+0.03 3.64+0.03 The range cited is due to unit cell volume expansion with decreasing SiO2/MgO ratio. Magnesium silicates with low Mg content in the TO4 sites will be near the low d spacing limit and those with high Mg content in TO4 sites will be near the high d spacing limit.

The magnesi.um silicates employed in the pre-sent invention are further characterized by a minimum of two reflections at 10.1+0.3 A and a minimum of four reflections between 3.72 and 3.gO A.

31,372A-F -10-t These values were obtained by Huber-Guinier techniques (preferred method) mentioned previously or by a Philips Electronics X-ray powder diffraction unit equipped with scintillation-counter detector, yraphite monochromator, and a strip char-t recorder. The recorded reflections were identified by their two thçta locations, after these locations were calibrated with an internal standard. The-standar~ used wa~ either Nss Si (Nss Cir-cular 539, Vol. 9, p. 3) or As2O3. The maynesium sili-cate diffraction peaks at approximately 10.0 and 3.81 Acan often be obscured in poorly crystalline samples or ln low~resolution X-ray diffraction data.

X-ray analyses of magnesium silicates employed in the present invention reveal distinct differ-ences in the diffraction patterns as a result of specifictreatments given to these magnesium silicates. Intensity changes are observed and lines may appear, disappear or merge depending on the exact calcination procedure uti-lized. Ion-exchange of these silicates may also cause changes in certain cases. Several authors have made similar observations on related materials like zeolite ZSM-5. See H. Nakamoto and H. Tarahashi, Chem. Lett., 1013-1016 (1981). Regardless of the causes of the above--mentioned changes, they are expected by those people skilled in the art of analyzing porous crystalline sili-cates.

The magnesium silicates employed in this invention are characterized also by infrared analysis.
The use of infrared analysis is recognized as a standard method in the characterization of inorganic and organic materials and has been used in the study of both natural and synthetic zeolites. See for example, E M. Flanigen 31,372A-F -11-1~7(~3~t et al., Adv._Chem. Series, Vol. 101, p. 201-229, 1971.
See also P. A. Jacobs, supra. For examples from the patent literature pertaining to the use of inf'rared analysis in zeolite characterization, see U.S. Patent 4,257,885.
Poro~s magnesium silicates employed in the present invention exhibit unique features in the 1300-400 cm~1 region. Many compositions employed in this invention exhibit at least two distinct bands in the 1200-980 cm~1 region. Preferred compositions employed in the present invention exhibit these two distinct ~ands and al~o characteristic infrared bands at 1225+10 cm~1, 800+20 cm~1 ~20+10 cm~1, 550+20 cm~1 and 450+20 cm~1.

It should be recognized that bands located between 1200-980 cm~1 may be due to asymmetric stretch of T04 units in zeolites and silicates, see, e.g., 20 Flanigen et al., "Molecular Sieve Zeolites-1," Adv. !
Chem. Series, 101, 201 A.C.S. (1971). It is believed - that the band found nearest to 980 cm~1 in the magnesium silicates employed in the present invention is due to silanol groups of the form -Si(OH)3, >Si(OH)2, >SiOH, or to their corresponding silicate forms.
Differential thermal analysis (DTA) is one of the thermal methods used in the literature as an aid in zeolite characterization. See D. W. Breck, Zeolites Molecular Sieves, John Wiley, 1974.

31,372A-F -12-Compcsitlons employed in the present invention may be analyzed by DTA methods. When using a Dupont~ 990 thermal analysis unit e~uipped with a 1200C furnace, a 10-mg sample is tested against alumina as a reference mate-rial (both contained in platinum crucibles). The heatingrate for the system is 20C per minute in air with an air flow rate of S0 cm3 per minute. Under these conditions, one obser-~es a distinGt exotherm at 870+30~C. X-ray dif-Eraction (XRD) analysis of the sample both before and after the exotherm yields at least the interplanar d spacings listed in Table III, suPra.

The magnesium silicate materials employed in this invention have ion-exchange properties. The ion--exchange capacity of traditional zeolites is associated with their aluminum content. The ion-exchange properties of the magnesium silicates employed in this invention are not necessarily dependent upon any one of its particular components. Indeed it is believed, without wishing to be bound to this belief, that the ion-exchange capacity of the present invention is due to a combination of factors.
Among them are: the magnesium content, the trivalent metal ion content and also to the presence of internal silanol moieties within the silicate framework which under appropriate conditions can participate in the ion-exchange process.
.
Even though a relationship among the compo-sition and the ion-exchange capacity of these solids is recognized, the magnesium silicates employed in the present invention is not restricted by the traditional "linear relationship" between composition and ion-ex-change capacity, characteristic of traditional zeolites.

31,372A-F -13-~.~'7(3~

The exchangeable cations in zeolite composi-tions often play a critical role in their synthesis by hydrothermal methods. In certain cases, a particular cation is required to obtain a given zeolite, for exam-ple, sodium is said to be re~uired to produce zeolite Xfrom aluminosilicate gels. Apparently the cation plays a template role in the formation of certain structures and/or acts as a crystallization promoter. The magne-sium silicates employed in this invention do not appear to require a particular alkali metal cation for their formation. Magnesium silicates employed in the present invention may be obtained from magnesium silicate gels in the presence of several alkaline metal salts includ-ing sodium or potassium salts. The presence of sodium or potassium ions during and/or after the synthesis may affect certain properties o the final product in appli-cations which are susceptible to drastic changes by sub-tle differences such as catalysis and adsorption. Salts other than sodium and potassium may have similar effects.

In the synthesis of traditional zeolites the source of silica may be a critical factor in the prepa-ration of certain zeolites. In the case of the present invention, the source of silica appears to have an effect in the morphology of the crystalline product. There are many examples in the literature relating morphology to a variety of useful properties of porous crystalline sili-cates like, for example, catalytic applications, ion--exchange, and adsorption.

Typically, the porous magnesium silicates employed in the present invention are made by hydro-thermal methods using one of many sources of silicon 31,372A-F -14-~, 7~3(~'3 such as one of the commercially available soluble sili-cates or water glass solutions, amorphous silica, colloidal silica, silica gels. fumed silica or an organosilicate like ~Eto)4Si. Advantageously employed are two commercially available sources: a colloidal silica sold by the du-Pont de Nemours C~mpany under the trademark Ludox SM~ and a sodium silicate sold by the Philadelphia Quartz Company under the trademark Phila-delphia Quartz Sodium Silicate N~.

The source of magnesium usually is one of its water-soluble salts, magnesium chloride, acetate, sulfate, ~itrate, or others, or a complex ion like Mg(NH3)62 or Mg(EDTA)2 , or a slightly soluble compound like Mg(OH)2 or MgF2. A magnesium chloride salt is a preferred source of mag~lesium.

Besides these components the reaction mixture will contain a solvent such as water, along with alkali metal ion salts such as, chlorides, sulfates or hydrox-ides of sodium, potassium, rubidium or cesium. The solvent may be added separately to the reaction mixture or may already be present with one of the reactants such as the silica source. Water is the preferred solvent.

- A material which is believed to act as a crystallization promoter and is hereinafter termed a "crystallization promoter" is utilized in the process of making the porous crystalline magnesium silicates employed in the present invention. Typically, this crystallization promoter is (or is formed from) an organic nitrogen compound such as quaternary ammonium ion salts, or hexamethylene diamine, but may also be 31,372~-F -15-~'s'~ 3 other compounds such as seed crystals typically of compositions similar to those cxystals sought from the process. In particular, tetrapropyl ammonium ion salts are often used with tetrapropyl ammonlum brcmide and tetrapropyl ammonium hydroxide being preferred.
.
In a typical method of making these magnesium silicates, a magnesium source, a crystallization promoter, an alkali metal ion salt and a solvent are combined.
The pH of this combination of chemicals is usually adjusted and the combination is further combined with a mixture of a silica source and a solvent to gi~e a reaction mixture typically having a pH of about 11.
The pH may advantageously be adjusted either above or below a pH o~ 11 to modify certain crystallization or process parameters such as the solubility of magnesium in the mixture, formation of precipitates, rates of crystallization, etc. The pH is adjusted as desired using acids or bases such as H2SO4 or NaOH and may be adjusted before, after and/or during t~e mixing step of the reactants.

The reaction mixture is vigorously mixed at room temperature for a sufficient time to produce an apparently homogeneous gel. Typically the rate of mix-ing is sufficiently vigorous to produce a satisfactory slurry or gel within one minute.

The mixture resulting from the above proce-dure is allowed to crystallize into compositions employed in the present invention. Preferably, crys-tal-lization takes place at temperatures above room temper-ature to increase the rate of crystal growth. Usually 31,372A-F -16-~_~a 79 ~t)~3 about 150C is used with autogeneous pressure. ~igher or lower temperatures may be advantageously employ~d depending upon the process or product parameters desired, e.g., larger crystals are generally formed with lower temperatures and the rate of crystallization increases with higher temperatures. When quaternary ammonium ion salts are used as crystallization promoters, temperatures above 200C are avoided to prevent the,ir decomposition.

Suitable time periods for the crystallization may be determined by analysis of reaction mixture samples at intervals. The crystalllzation time will vary depending upon the reactants or the particular process parameters chosen. Crystallization times of one to five days are not uncommon.

During the crystallization step, stirring may be advantageously employed to facilitate product forma-tion. The rate and type of stirring may affect crystal-lization parameters such as the rate of crystallization, uniformity of the product and crystal size. The effect of this parameter and optimum adjustment is dependent upon other parameters and is believed to be within the skill of the art to determine without undue experimen-- tation.

Following crystallization it is often desir-able to filter the 'crystallized mixture using a water wash to remove the mother li~uor and then to heat the crystals to about 110C to remove water and thereby produce a convenient free-flowing powder.

31,372A-F -17-0~3 The compositions as made by the above pro-cedure may contain organic moieties which, if desired, may be removed by known methods such as calcination in an oxygen-containing atmosphere at a temperature suffi-cient to decompose the organic moie-ties. Calcination at about 500C-600C for approximately an hour is suffi-cient -to remove commonly present organi-c moieties.

The magnesium silicates employed in the inven-tion may be beneficially modified by techniques well~known in the art which treat said silicates with acids, salts or other ions or molecules. Acid treatment is especially valued to produce a stable, catalytically active form of porous crystalline magnesium silicate.

As mentioned before, certain compositions employed in the invention may be expressed according to a formula in terms of the molar ratios of oxides on a dry basis, for example,

2/n)p~Mg)X(R203)y(sio2) wherein M is at least one ion-exchangeable cation having a valence of n; R is at least one element with valence

3+ which is not ion-exchangeable by conventional means x/z>0; y/z>0; p/n>y; and p, x, z are positive numbers - and y is a positive number or zero. The statement x/z>0 is essential to all compositions employed in the present invention since it defines a magnesium silicate. A11 compositions employed in the present invention must con-tain magnesium.

31,372A-F -18-The statement y/z~0 indicates that this is a nonessential term. Typical nonion-exchangeable elements which may advantageously be present include by way of example, aluminum, iron, chromium, boron and gallium.

Also the above-mentioned formula could be modified to include other elements optionally present which are not ion-exchangeable by conventional means having a valence other than 3+ such as 2+ or 4+. Ger-manium is an example of such an element.

Preferred embodiments of magnesium silicates employed in the present invention expressed in terms of the above formula are those wherein p is from about 0.1 to about 20; x is from about 0.1 to about 12; y is from about 0 to about 3 and z is from about 84 to about 96.
It is especially preferred that the term y of the above formula be from 0 to about 1Ø

Typically, the ion-exchangeable cations M (of both the magnesium silicates represented by the above for-mula and similar magnesium silicates employed in the pres-ent invention) are alkali metals, hydrogen, group VIIImetals or rare earth elements, or ammonium ions, but may be any element or moiety capable of exchange into the mag-nesium silicates of the present invention. Preferred are hydrogen, the alkali metals and the rare earth elements.
Methods of ion-exchange are well-known in the art, e.g., hydrogen may be exchanged into a silicate by simply treat-ing with acid.

31,372A-F -19-~,7~

Modification of -the porous magnesium silicate - by adding ~hosphorus thereto is accomplished by contact-ing the ma~neslum silicate with a phosphorus compound.
Sultable phosphorus compounds may be either organic or inorganic. Representative compounds include, for example, those of the formula PX3, RPX2, R2PX, X3PY, ( ) 2~ R2P(Y)X, P205 or R2PO2, wherein R is C1 6 alkyl, phenyl, Cl 6 alkoxy or phenoxy, X is halo or hydrogen and Y is oxygen or sulfur. Additional suit-able examples include salts of phosphorus acids, par-ticularly ammonium, phosphonium, or hydrogen ammonium salts of phosphorlc acid. An especially preferred phosphorus compound is ammonium hydrogen phosphate.

The phosphorus compound is employed neat or as a solution in an organic or inorganic solvent thereby simplifying contacting with the magnesium silicate and separation thereof. After contacting with the phos-phorus compound the modified porous magnesium silicates of the invention are prepared by drying and calcining thereby converting the phosphorus compound to the oxide for catalytic use. Calcining may be accomplished by heating to elevated temperatures of at least about 300C and preferably at least about 400QC in the pre-sence of oxygen for a time sufficient to convert sub-stantially all of the phosphorus to the oxide. Sui-t-able calcination times are from about 1 hour to several hours or even days.

The phosphorus modified porous magnesium sil-icates of the present invention preferably contain from about 0.5 percent to about 20 percent by weight of an oxide of phosphorus calculated as phosphorus. Preferred 31,372A-E -20-modified compounds contain from about 1 percent to about 6 percent by weight phosphorus. A unique feature of the present compounds lies in the particular alkyl-ation of toluene by reaction with ethylene, where amounts of phosphorus greater than about 6.0 percent lead -to catalyst inac~ivation, whereas amounts of phosphorus from about 2 percent to about 5.9 percent by - weight, and preferably from abQut 4.5 percent to 5.5 percent by weight are very effective in suppressing the formation of ortho- and meta-ethyl toluene during the reaction. The result (at least about 90 percent para--ethyl toluene formation) is considered surprising since phosphorus contents in phosphorus modified aluminosili-cates such as ZSM-5 are not as effective in suppressing the formation of ortho- and meta- isomers, and increasing phosphorus content in such compounds does not appear to lead to catalyst deactivation. -The above description and following examplesare given -to illustrate the invention, but these examples should not be taken as limiting the scope of the inven-tion to the particular embodiments or parameters demon-strated since obvious modifications of these teachings will be apparent to those skilled in the art.

Example 1 . .
A solution _ is made by combining 106 g of commercially available Philadelphia Quartz Sodium Sili-cate N~ type (trademark of Philadelphia Quartz Company) (8.90 weight percent Na2O, 28.7 weight percent SiO2) with 132 g of H2O. A second solution B is made by combining 180 g of H2O, 40 g of NaCl, 26 g of (C3H7)4NBr, 31,372A-F -21-~, ~'f't~

1 0 . 2 g MgC12 6H2O and 8 g of concentrated H2SO4 (96 weigh-t percent) to form a clear solution.

Solution A is transferred to a Waring~ blender and the blender is s-tarted at the lihigh" setting.
Solution B is added at once and the mixture is stirred vigorously for 1 minute. The resulting slurry is then placed inside a stainless steel autoclave, heated to about 150~C under autogenous pressure and stirred.
After 24 hours, the autoclave is cooled to room tem-perature and the solid product is isolated by filtra-tion. The filter cake is washed several times with much water and then air dried at about 110C into a free flowing powder.

The above prepared porous magnesium silicate is calcined for 15 hours at 550C in air to remove the quaternary ammonium salt from the internal pores.
Next, the material is slurried with l.ON NH4NO3 solution, at a temperature of at least 80C overnight. The resulting material is filtered, washed with deionized water and dried at 110C.

Ten grams of this material is spread into a thin layer in a large petri dish and sufficient (N~4)HPO4 solution (25 weight percent concentration) is added dropwise to the powder with a syringe to provide 4.7 percent phosphorous based on dry catalyst weight. The moistened powder is then mixed well with a spatula.
The powder is first dried at room temperature and then at 110C. The dried catalyst is mixed with kaolin clay, 1/2 part clay per part catalyst, and enough water is added to form a moist cake. The cake is dried, first 31,372A-F -22-at room -temperature, then at 110C, and then calcined at 550C for 5 hours in air.

The calcined catalyst is crushed and tested in the alkylation of toluene with ethylene. Eight grams of catalyst are loaded in a 1/2-inch (1.3 cm~
diameter stainless steel reactor tube. The operating conditions of the reaction are: tem~erature 41DC, pressure 100 psi (690 mPa), toluene flow rate 104.7 g/hr, ethylene flow rate 60 cm3/min, H2 flow rate 140 cm3/min, WHSV = 13, molar ratio toluene/ethylene = 7.6, molar ratio ethylene/hydrogen = 2.3. Data are obtained during a continuous run lasting four days. At the end of two days, the temperature is increased to 440C.
The initial ethylene conversion is about 80 percent falling to a level of about 60 percent prior to increase in reaction temperature. Selectivity to para ethyl-toluene is at least 96 percent during the entire reaction period.

31,372A-E -23-

Claims (8)

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

1. A porous crystalline magnesium silicate modified by addition thereto of phosphorus in the amount of from about 0.25 percent to about 30 percent by weight, the porous crystalline magnesium silicate corresponds to the following formula in terms of molar ratios of oxide on a dry basis (M2/nO)p(MgO)x(R2O3)y(SiO2)z wherein M is at least one cation having a valence n; R
is a trivalent element or mixture thereof; x/z>0;
y/z?O, p/n>y; and p, x, z are positive numbers and y is a positive number or zero and, prior to phosphorus modification, 31,372A-F -24-the crystalline magnesium silicate is characterized by an X-ray diffraction trace having at least those inter-planer d spacings listed below:

Magnesium silicate, interplanar spacings d(A) 11.2 ?0.2 10.1 ?0.2 10.0 ?0.2 9.8 ?0.2 6.0 ?0.2 5.8 ?0.2 5.6 ?0.2 4.26?0.1 3.85?0.05 3.81?0.05 3.74?0.03 3.72?0.03 3.64?0.03

2. A phosphorus modified crystalline sili-cate of Claim 1 wherein the phosphorus is pres-ent in an amount from about 0.5 percent to about 20 per-cent by weight.

3. A phosphorus modified crystalline sili-cate of Claim 2 wherein the phosphorus is pres-ent in an amount from about 1 percent to about 6 percent by weight.

31,372A-F -25-

4. A phosphorus modified crystalline sili-cate of Claim 1 wherein p is from about 0.1 to about 20; x is from about 0.1 to about 12; y is from about 0 to about 3; and z is from about 84 to about 96.

5. A phosphorus modified porous crystalline magnesium silicate of Claim 4 wherein y is from about 0 to about 1.

6. A phosphorus modified porous crystalline magnesium silicate of Claim 1 wherein M is an alkali metal or hydrogen cation.

7. A process for alkylating aromatic hydro-carbons comprising contacting an alkylating agent with an aromatic hydrocarbon to form a reaction mixture under alkylation conditions in the presence of a cata-lytically effective amount of a phosphorus modified porous crystalline magnesium silicate of Claim 1.

8. A process of Claim 7 wherein the alkyl-ating agent is ethylene and the aromatic hydrocaron is toluene.

31,372A-E -26-