CS277225B6 - Aromatic compound alkylation process - Google Patents

Abstract

Alkylation of aromatic cpds. is effected by reaction with an alkylating agent in the presence of a catalyst comprising an anonymous zeolite (I) with an X-ray diffraction pattern having lines corresp. to d-spacings (in Angstroms) of 12.36 +- 0.4 (m-vs), 11.03 +- 0.2 (m-s), 8.83 +- 0.14 (m-vs), 6.18 +- 0.12 (m-vs), 6.00 +- 0.10 (w-m), 4.06 +- 0.07 (w-s), 3.91 +- 0.07 (m-vs) and 3.42 +- 0.06 (vs). (I) has a YO2:X2O3 molar ratio of at least 10, where X is a trivalent element (esp. Al) and Y is a tetravalent element (esp. Si). The alkylating agent (II) is an olefin. The aromatic cpd. (III) is benzene, cumene or a phenol. The reaction is effected at 0-500 (esp. 10-350) deg.C and 0.2-250 (esp. 1-25) atmos. with a WHSV of 0.1-500 (esp. 0.5-100) and a (III):(II) molar ratio of 0.1-50:1 (esp. 0.5-10:1).

Description

The invention relates to a process for the production of alkylated aromatic compounds which utilizes porous crystalline zeolites as alkylation catalysts.

Zeolites, both natural and synthetic, have been shown in the past to have catalytic properties for various types of hydrocarbon conversions. Certain zeolite materials are ordered, porous crystalline aluminosilicates having a certain crystalline structure defined by X-ray diffraction in which there are a large number of smaller cavities that can be interconnected by a number of smaller channels or pores. These cavities and pores are of uniform size in specific zeolite materials. Since the dimensions of these pores are suitable for adsorbing molecules of certain sizes and not accepting larger size materials, these materials are known as molecular sieves and are utilized in a number of ways where these properties are desirable. Such molecular sieves, both natural and synthetic, include a wide range of positive ionic crystalline silicates. These silicates can be described as solid three-dimensional structures of SiO ₄ and a Group IIIA element of the Periodic Table of Elements, eg A10 ₄ , in which tetrahedra are crosslinked by oxygen atom sharing, the ratio of total Group IIIA elements, eg aluminum and silicon atoms to oxygen atoms 1: 2. The electrovalence of a tetrahedra containing a Group IIIA element, eg aluminum, is counterbalanced by the inclusion of cations in the crystal, for example, an alkali metal or alkaline earth metal cation. This can be expressed by the ratio of the Group IIIA element, eg aluminum, to the number of different cations such as Ca / 2, Sr / 2, Na, K or Li, which is equal to the unit. One type of cation may be exchanged for another either wholly or partially by various conventional ion exchange techniques.

These techniques have led to the formation of a considerable amount of synthetic zeolites. Many of these zeolites have been marked with a letter or other conventional symbols such as zeolite Z (US Patent No. 2882243), zeolite X (US Patent No. 2882244), zeolite Y (US Patent No. 3130007), zeolite ZK-5 (US patent 3247195), ZK-4 zeolite (US Patent No. 3314752), ZSM zeolite (US Patent No. 3702886), ZSM-11 zeolite (US Patent No. 3709979), ZSM-12 zeolite (US Patent No. 3832449) , zeolite ZSM-20 (US Patent No. 3972983), zeolite ZSM-35 (US Patent No. 4016245) and zeolite ZSM-23 (US Patent No. 4076842).

The SiO ₂ / Al ₂ O ₃ ratio in said zeolites often changes. For example, zeolite X can be synthesized with SiO ₂ / Al ₂ O ₃ ratios of from 3 to 3; zeolite Y from 3 to 6. In these zeolites, the upper limit of the SiO ₂ / Al ₂ O ₃ ratio is not limited. ZSM-5 is one such example where the SiO ₂ / Al ₂ O ₃ ratio is at least 5 up to the limits of current analytical measurement techniques. US Patent No. 3941871 (Re. 29948) discloses a porous crystalline silicate made from a reaction mixture not containing specifically alumina in the formulation and showing an X-ray diffraction pattern characteristic of ZSM-5. US Patent Nos. 4061724, 4073865 and 4104294 disclose crystalline silicates with varying alumina and metal contents.

Alkylation is one of the most important and used hydrocarbon reactions. Lewis and Bronstedt acids, including a large number of natural and synthetic zeolites, can be used as catalysts. It is known in the art to alkylate aromatic hydrocarbon compounds using certain crystalline zeolite catalysts. For example, US Patent No. 3251897 describes liquid-phase alkylation in the presence of crystalline aluminosilicates such as faujasite, heulandite, clinoptilolite, mordenite, dachiardite, zeolite X and zeolite Y.

U.S. Pat. Nos. 3651120 and 3641177 disclose a process for the liquid phase alkylation of aromatic hydrocarbons by olefins in the presence of certain zeolites.

U.S. Pat. Nos. 3,751,504 and 3,751,506 disclose vapor-phase aromatic hydrocarbon olefins in the presence of a specific zeolite catalyst.

US Patent Nos. 3,755,483 and 4,393,362 disclose a gas-phase reaction of propylene with benzene in the presence of zeolite ZSM-12 to form isopropylbenzene.

US Patent No. 4469908 describes the alkylation of aromatic hydrocarbons with a relatively short chain alkylating agent having from 1 to 5 carbon atoms using the ZSM-12 alkylation catalyst.

US Patent No. 4283573 discloses a process for preparing relatively long chain alkylphenols by alkylating phenol with a relatively long chain alkylating agent containing one or more suitable alkyl groups of at least 5 carbon atoms using a zeolite such as cancrinite, gmelinite, mordenite, offretit as catalyst or ZSM-12.

The invention consists in a process for alkylating an aromatic compound with at least one alkylating agent in the presence of an alkylating catalyst, which is a synthetic porous crystalline zeolite having an X-ray diffraction pattern having the values substantially given in Table I of this description.

The term aromatic refers to alkylatable compounds which, in accordance with the known art, include substituted and unsubstituted mono- and polynuclear compounds. Aromatic compounds containing a heteroatom are also suitable, as long as they do not act as catalyst poison under the selected reaction conditions.

Substituted aromatic compounds which may be alkylated must contain at least one hydrogen atom directly bonded to the aromatic core. Aromatic rings may be substituted with one or more alkyl, aryl, alkoxy, aryloxy, hydroxyl, cycloalkyl, halogen and / or other groups that do not interfere with the alkylation reaction. In a preferred embodiment, the aromatic compound is a phenolic compound.

Suitable aromatic hydrocarbons include benzene, toluene, xylene, naphthalene, anthracene, naphthacene, perylene, coronene and phenanthrene.

In general, they contain alkyl groups which may be present as substituents on the aromatic compound from one to twenty-two carbon atoms, and preferably from one to eight carbon atoms, and most preferably from one to four carbon atoms.

Suitable alkyl-substituted aromatic compounds include toluene, xylene, isopropylbenzene, normal propylbenzene, alphamethylnaphthalene, ethylbenzene, cumene, mesitylene, duene, p-cymene, butylbenzene, pseudocumen, o-diethylbenzene, m-diethylbenzene, p-diethylbenzene, isoamylbenzene, isoamylbenzene, isoamylbenzene, isoamylbenzene, , pentamethylbenzene, 1,2,3,4-tetraethylbenzene, 1,2,3,5-tetramethylbenzene, 1,2,4-triethylbenzene, 1,2,3-trimethylbenzene, m-butyltoluene, p-butyltoluene, 3,5 -diethyltoluene, o-ethyltoluene, m-propyltoluene, 4-ethyl-m-xylene, dimethylnaphthalenes, ethylnaphthalene,

2,3-dimethylantracene, 9-ethylantracene, 2-methylantracene, o-methylantracene, 9,10-dimethylphenanthrene and 3-methyl-phenanthene. Higher molecular weight alkyl-aromatic hydrocarbons may also be used as starting material and include aromatic hydrocarbons obtained by alkylation of aromatic hydrocarbons with olefin oligomers. Such products are often referred to in the art as alkylates and include hexylbenzene, nonylbenzene, dodecylbenzene, pentadecylbenzene, hexyltoluene, nonyltoluene, dodecyltoluene and pentadecyltoluene. Very often the alkylate is obtained as a high-boiling fraction in which the alkyl groups attached to the aromatic ring vary from C ₆ to C ₁₂ .

A reformer comprising substantially benzene, toluene and / or xylene is a particularly suitable starting material for the alkylation process of the invention.

Suitable alkylable phenol compounds include methylphenols (cresols), dimethylphenols (xylenols), ethyl, propyl and butylphenols, halophenols (eg chlorine and bromine), alkyl halophenols, alkoxyphenols, dihydroxybenzenes (eg hydroquinone, catechol, resorcinol) and hydroxylated fused ring systems, e.g., naphthols, anthranols and phenantranols.

In an embodiment of the invention, the alkylating agent is an organic compound having at least one accessible alkylating group capable of reaction and an alkylable aromatic compound and containing from 1 to 5 carbon atoms. Examples of suitable alkylating agents are C ₂ -C ₅ olefins, such as ethylene, propylene, butenes and pentenes, alcohols (including monohydric alcohols, dihydric, trialcohols etc.) such as methanol, ethanol, propanols, butanols and pentanols, aldehydes such as formaldehyde, acetaldehyde , propionaldehyde, butyraldehyde and n-valeraldehyde, alkyl halides such as methyl chloride, ethyl chloride, propyl chlorides, butyl chlorides and pentyl chlorides.

Light olefin mixtures are particularly suitable alkylating agents in one embodiment of the invention. Accordingly, particularly suitable alkylating agents are mixtures of ethylene, propylene, butenes and / or pentenes, which are the main constituents of various refinery streams, eg fuel gas, ethylene, propylene-containing gas off-gas, etc. olefins and refinery PCC propane / propylene stream. For example, a typical light olefin PCC stream exhibits the following composition:

mass% _mol. %

ethane 3.3 5.1 ethylene 0.7 1,2 propane 14.5 15.3 propylene 42.5 46.8 isobutane 12.9 10.3 n-butane 3.3 2.6 butenes 22.1 18.32 pentanes 0.7 0.4

In one embodiment of the present invention, suitable products that can be obtained by the process of the present invention include ethylbenzene and cumene (alkylation of benzene with ethylene and optionally propylene) and alkylated reformate (alkylation of reformate with a heating gas or other light hydrocarbon source). In the case of alkylation of benzene to form ethylbenzene or cumene, it has been found that the process of the invention results in the formation of less than 500 ppm xylene by-product.

In another embodiment of the present invention, the alkylating agent is an aliphatic or aromatic organic compound with one or more useful alkylating aliphatic groups having at least 6 carbon atoms, preferably at least 8 and particularly preferably at least 12 carbon atoms. Examples of suitable alkylating agents are olefins such as hexene (s), heptenes, octenes, nonenes, decenes, undecenes and dodecenes; alcohols such as hexanols, heptanols, octanols, nonanols, decanols, undecanols and dodecanols; and alkyl halides such as hexyl chlorides, octyl chlorides and dodecyl chlorides. Branched alkylating agents, in particular oligomerized olefins such as trimers, tetramers and pentamers of light olefins such as ethylene, propylene and butelynes are also useful. Typical products of this further embodiment, particularly where the starting material is benzene, toluene, xylene and / or naphthalene, are low freezing point and cloud point aromatic lubricants, high viscosity, and good thermal and oxidative stability. If the starting material is phenol, long chain alkylphenols useful in the manufacture of synthetic detergents can be obtained.

In calcined form, the porous crystalline zeolite used as catalyst in the alkylation process of the invention has an X-ray diffraction pattern comprising the lines shown in Table I below:

Table I

Interplanar d-distances (A) Relative intensity, T / Ix100

12.36 ± 0.4 M-VS 11.03 + 0.2 M-S 8.83 + 0.14 M-VS 6.18 + 0.12 M-VS 6.00 + 0.10 W-M 4.06 ± 0.07 W-S 3.91 + 0.07 M-VS 3.42 + 0.06 VS

more specifically, the lines listed in Table II below:

Table II

Interplanar d-distances (A) Relative intensity, I / Io x 100

30.0 ± 2.2 W-M 22.1 ± 1.3 W 12.36 + 0.4 M-VS 11.03 + 0.2 M-S 8.83 + 0.14 M-VS 6.18 + 0.12 M-VS 6.00 + 0.10 W-M 4.06 + 0.07. W-S 3.91 + 0.07 M-VS 3.42 ± 0.06 VS

and more specifically the lines in Table III below:

Table III

Interplanar d-distance (A) Relative intensity, I / Io x 100

12.36 ± 0.4 M-VS 11.03 ± 0.2 M-S 8.83 ± 0.14 M-VS 6.86 ± 0.14 W-M 6.18 ± 0.12 M-VS 6.00 ± 0.10 W-M 5.54 ± 0.10 W-M 4.92 ± 0.09 W 4.64 ± 0.08 W 4.41 ± 0.08 W-M 4.25 ± 0.08 W 4.10 ± 0.07 W-S 4.06 ± 0.07 W-S 3.91 ± 0.07 M-VS 3.75 ± 0.06 W-M 3.56 ± 0.06 W-M 3.42 ± 0.06 VS 3.30 ± 0.05 W-M 3.20 ± 0.05 W-M 3.14 ± 0.05 W-M 3.07 ± 0.05 W 2.99 ± 0.05 W 2.82 ± 0.05 W 2.78 ± 0.05 W 2.68 ± 0.05 W 2.59 ± 0.05 W

Most specifically, the calcined zeolite has an X-ray diffraction pattern comprising the lines shown in Table IV below:

Table IV

Interplanar d-distance (A) Relative intensity, I / Io

30.00 ± 2.2 W-M

22.1 ± 1.3 W

X 100

Table IV / continued / 12.36 + 0.4 M-VS 11.03 + 0.2 M-S 8.83 + 0.14 M-VS 6.86 + 0.14 W-M 6.18 + 0.12 M-VS 6.00 + 0.10 W-M 5.54 + 0.10 W-M 4.92 + 0.09 W 4.64 + 0.08 W 4.41 + 0.08 W-M 4.25 + 0.08 W 4.10 + 0.07 W-S 4.06 + 0.07 W-S 3.91 + 0.07 M-VS 3.75 ± 0.06 W-M 3.56 + 0.06 W-M 3.42 + 0.06 VS 3.30 ± 0.05 W-M 3.20 + 0.05 W-M 3.14 + 0.05 W-M 3.07 + 0.05 W 2.99 + 0.05 W 2.82 + 0.05 W 2.78 ± 0.05 W 2.68 ± 0.05 W 2.59 and 0.05 W

These values were determined by standard techniques. The radiation was K-alpha doublet of copper and a diffractometer equipped with a scintillation counter with a connected computer was used. Peak heights, I, and position as a function of 2 theta, where theta is the Bragg angle, were determined using a computer algorithm coupled to a diffractometer. From this, relative intensities were determined, 100 I / Io, where lo is the intensity of the strongest line or peak and d (pos) the interplanar distance in Angstrom units (A), corresponding to the recorded lines. In Tables I-IV, relative intensities are indicated by W = weak, M = medium, S = strong, and VS = very strong. Intensities can be labeled as follows:

W = 0 to 20 May M = 20 to 40 S = 40 to 60 VS = 60 to 100 ALIGN!

X-ray diffraction diagrams are characteristic of all kinds of zeolites. The sodium form as well as the other cationic forms show essentially the same diagrams with some small variations in interplanar distances and changes in relative intensity. Other small variations may occur depending on moles of the Y to X ratio, eg silicon to aluminum, in the individual samples as well as the degree of their heat treatment.

Synthetic porous crystalline zeolites used as catalysts in the alkylation process of the present invention generally have a composition which corresponds to the following formula:

X ₂ O ₃ : / n / YO ₂ , wherein X is a trivalent element such as aluminum, boron, iron and / or gallium, preferably aluminum, Y is a tetravalent element such as silicon and / or germanium, preferably silicon and n has a value of at least 10, preferably from 10 to 150, particularly preferably from 10 to 60 and even more preferably from 20 to 40. In the as-synthetic form, the zeolite has the formula as anhydrous and expressed in moles of oxides per n mol of YO ₂ :

(0.005 - 0.1) Na ₂ O: (1-4) R: X ₂₀ O ₃ : nYO ₂ , where R is an organic component. The Na and R components are associated with the zeolite as a result of their presence during crystallization and are readily removable by post-crystallization procedures, which are described in more detail below.

The zeolite used in the invention is thermally stable and has a high surface area (greater than 400 m ² / gm as measured by BET / Brunauer, Emmet and Teller / test) and an extremely high sorption capacity compared to similar crystalline structures. In particular, the zeolite has an equilibrium sorption capacity of greater than 4.5 wt. %, usually greater than 7 wt. % for cyclohexane vapor and greater than 10 wt. % for n-hexane vapor and normally greater than 10 wt. % for water vapor. As can be seen from the above formula, the zeolite present is synthesized almost free of Na cations. It can therefore be used as an alkylation catalyst with acid activity without a step exchange. If desired, the original sodium cations in the as-synthesized material may be replaced by techniques known in the art, at least in part, by exchanging ions for other cations. Preferred exchanged cations include ions, metals, hydrogen ions, hydrogen precursors such as ammonium ions and mixtures thereof. Particularly preferred cations are those which alter the efficiency of the alkylation catalyst as desired. These include hydrogen, rare earth metals and metals of Groups IIA, IIIA, IVA, IB, IIB, IIIB, IVB and VIII of the Periodic Table of the Elements.

Prior to use as an alkylation catalyst, the zeolite should be heat treated to remove some or all of the organic components present therein.

The zeolite alkylation catalyst used herein can also be used in close combination with a hydrogenation component such as tungsten, vanadium, molybdenum, rhenium, nickel, cobalt, chromium, manganese, or noble metals such as platinum or palladium in which the hydrogenation function is fulfilled. -dehydrogenace. Such a component may be introduced into the catalyst composition by co-crystallization, exchanged in the composition to the content of a Group IIIA element, eg, aluminum, in the structure, impregnated therein or physically blended into it. Such a component may be impregnated at 0 or onto a zeolite, such as in the case of platinum, by treating the zeolite with a solution containing a platinum metal ion. Suitable platinum compounds include chloroplatinic acid, platinum (II) chloride, and various compounds containing a platinamine complex.

Prior to use in the alkylation process of the present invention, the zeolite crystals should be dehydrated, at least partially. This can be done by heating the zeolite to a temperature in the range of 200 ° C to 595 ° C in an atmosphere such as air, nitrogen, etc. and at atmospheric pressure, higher or lower than atmospheric pressure, for between 30 minutes and 48 hours. Dehydration can also be performed at room temperature only by placing the crystalline material under vacuum, but a longer time is required to achieve sufficient dehydration.

The zeolite used in the present process can be prepared from a reaction mixture comprising alkali metal and alkaline earth metal (zdroje) sources, such as sodium or potassium, in the form of cations, an oxide of a trivalent element X, such as aluminum, a tetravalent element oxide Y, such as silicon. , organic (R) control agent, hexamethyleneimine and water. Said reaction mixture has the composition given in molar ratios of oxides, in the following ranges:

The reactants suitably

YO ₂ / X ₂ O ₃ 10-60 10-40 y

H ₂ O / YO ₂ 5 - 100 10 - 50 oh ~ / yo ₂ 0.01-1.0 0.1-0.5

M / YO ₂ 0.01 - 2.0 0.1 - 1.0

R / YO ₂ 0.05-1.0 0.1-0.5

In a preferred synthetic method, the YO ₂ reactant comprises a substantial amount of solid YO ₂ , eg at least about 30 wt. % solid Y0 ₂ . If Y ₂ is silica, use of a silica source containing at least 30 wt. solid silica, eg Ultrasil (precipitated, spray-dried silica, containing 90% by weight silica (or HiSil), precipitated hydrated SiO ₂ , containing 87% by weight silica, 6% by weight free H ₂ O and 4.5 % by weight bound H ₂ O by hydration and having a particle size

0.02 µm) promotes crystal formation from the above mixture. If another silicon oxide source is used, eg Q-Brand (sodium silicate containing 28% SiO ₂ , 8.9% Na ₂ QO and 62.3% H ₂ O), crystallization may lead to less the amount of zeolite required and impurities formed by other crystalline structures, e.g. ZSM-12 Therefore, preferably, the source of Y ₂ comprises eg silica, at least 30 wt. % of a solid Y ₂ O, eg silica and more preferably at least 40 wt. solid YO ₂ , eg silica.

Crystallization of the desired zeolite can be carried out either under static conditions or with stirring in a suitable reaction vessel such as a polypropylene vessel or a Teflon lined or stainless steel autoclave. Crystallization is generally performed at a temperature of from 80 ° C to 225 ° C for 25 hours to 60 days. The crystals are then separated from the liquid and isolated.

The crystallization is carried out in the presence of at least 0.01 percent, preferably 0.10 percent and even more preferably 1 percent of seed crystals, based on the total weight of the crystalline product.

Prior to use in the process of the invention, the resulting zeolite is preferably combined with another material that is resistant to temperature and other conditions used in the alkylation process of the invention. Such materials include active and inactive materials and synthetic or natural zeolites as well as inorganic materials such as clays, silica and / or metal oxides such as alumina. These may be either of natural origin or in the form of gelled precipitates or gels containing mixtures of silica and metal oxides. The use of the material in combination with the instant zeolite, i.e., the association with it or the presence during its synthesis, which itself is catalytically active, may alter the conversion and / or selectivity of the catalyst. Preferably, the inactive materials serve as conversion control diluents such that the alkylation products can be obtained economically and properly without the use of other reaction rate control devices. These materials can be incorporated into natural clays, such as bentonite and kaolin, to improve the crush strength of the catalyst under the conditions of conventional alkylation operations. These materials, ie clays, oxides, etc., act as binders for the catalyst. It is desirable to provide a catalyst having good resistance to crushing, since in commercial use it is desirable to protect the catalyst from disintegration into a pulverulent material. These clay binders are commonly used only to improve the grinding resistance of the catalyst.

Natural clays that may be used as instant substance composites include the montmorillonite and kaolin types of clays, these include subbentonites and kaolins commercially referred to as Dixie, McNamee, Georgia and Florida clays or others in which the main mineral component is halloysite, kaolinite, dickite, nacrit, or anauxite. These clays may be used in the raw state as extracted or processed by calcination, acid treatment or chemically modified. Binders suitable for use with the zeolite also include inorganic oxides, especially alumina.

As an additive to the above materials, the present zeolite may comprise a porous matrix material such as silica-alumina, silica-magnesium oxide, zirconia, silica-thorium oxide, beryllium, silica-titanium dioxide as a composition such as oxide silica-alumina-silica-alumina-zirconia, silica-silica-silica-ternary, silica-alumina-magnesium-oxide and silica-magnesium-zirconia. It may also be advantageous to provide at least a portion of said matrix material in a kaloid form to facilitate extrusion of the bonded catalyst component (s).

The ratio of zeolite to inorganic oxide matrix is highly variable, with a zeolite content ranging from 1 to 90% by weight and preferably, especially when the composite is prepared in the form of spheres, ranging from 2 to 80% by weight of the composite.

The stability of the alkylation catalyst of the present invention can be increased by steaming, which is conveniently done by contacting the zeolite with 5 to 100% steam at a temperature of at least 300 ° C (preferably

300 to 650 ° C) for at least one hour (preferably 1 to 200 hours) at a pressure of 101 to 2500 kPa. In a particularly preferred embodiment, the catalyst is prepared by steaming with 75 to 100% steam at 315 to 540 ° C and atmospheric pressure for 1 to 25 hours.

The alkylation process according to the invention is generally carried out at temperatures between 0 ° C and 500 ° C, preferably at 50 ^e C to 400 ° C, most preferably 100-350 ° C, pressure of 20 to 25350 kPa, preferably 100 to 2550 kPa, a molar a ratio of the alkylated aromatic compound to the alkylating agent of from 0.1: 1 to 50: 1, preferably 0.5: 1 to 10: 1 and a mass hourly feed rate (WHSV) of from 0.1 to 500, preferably from 0.5 to 100 WHSV is based on the total weight of the active catalyst (and binder, if present).

The alkylation process of the present invention may be carried out in a batch, semi-continuous, or continuous operation using a solid, fluidized, or moving bed catalyst.

The present invention is further elucidated in the examples and the accompanying drawings in which:

Giant. 1 to 5 are X-ray diffraction diagrams in the calcined crystalline materials produced in Examples 1, 3, 4, 5 and 7, and FIGS. 6 to 10 are graphical representations of the data of the example.

15 Dec

In the examples, whenever sorption data is given to compare the sorption capacities of water, cyclohexane and / or n-hexane, the equilibrium adsorption values were determined as follows:

The weighed sample of calcined adsorbents was contacted with the desired clean steam in the absorption chamber, evacuated to less than 1 mm Hg and contacted with 1.6 kPa of water vapor or 5.3 kPa of n-hexane or 5.3 kPa of cyclohexane vapor, pressures are less than the vapor-liquid equilibrium pressure of the respective adsorbate at 90 ° C. The pressure was kept constant (and about ± 0.5 mm Hg) by the addition of adsorbate vapor by a controlled manostat during the adsorption period, which did not exceed 8 hours. As the adsorbate is adsorbed by the zeolite, a pressure relief valve opens to allow a larger amount of adsorbate vapor to enter the chamber to maintain the above pressures. The sorption is terminated when the pressure change is not sufficient to activate the manostat. The weight gain is calculated as the adsorption capacity of the sample in g / 100 g of calcined adsorbant. The gelatin used in the process of the invention has equilibrium adsorption values greater than 4.5% by weight, usually greater than 7% by weight. % for cyclohexane steam and greater than 10% w / w; % for n-hexane steam and normally greater than 10 wt. for water vapor.

When the alpha value is tested, it should be noted that the alpha value is an approximate indication of the catalytic cracking activity of the catalyst as compared to the standard catalyst and indicates the relative rate constant (rate of conversion of normal hexane to catalyst volume per unit time). It is based on the activity of the highly active silica-alumina cracking catalyst, evaluated as alpha 1 (rate constant = 0.016 s ^-1 ). The alpha assay that was used is described in J. Catalysis, 61, pp. 300-306 (1980).

Example 1 part of sodium aluminate (43.5% Al ₂ O ₃ , 32.2% Na ₂ O, 25.6% H ₂ O) was dissolved in a solution containing 1 part of 50% sodium hydroxide solution and 103.13 parts of water. To this mixture is added hexamethyleneimine. The resulting solution was added to 8.55 parts of Ultrasil, precipitated, spray dried silica (about 90% SiO ₂ ).

The reaction mixture has the following composition, in mol. ratios:

sieve ₂ / ai ₂ o ₃ = 30.0 oh / sieve ₂ = 0.18 h ₂ o / s ₂ = 44.9 Na / SiO ₂ = 0.18 r / sieve ₂ . = 0.35

wherein R is hexamethylenimine.

The mixture was allowed to crystallize in a stainless steel reactor with stirring at 150 ° C for 7 days. The crystalline product is filtered off, washed with water and dried at 120 ° C. After 20 hours of calcination at 538 ° C, the X-ray diffraction pattern contains the main lines shown in Table V. FIG. 1 is a X-ray diffraction pattern of a calcined product. The sorption capacities of the calcined material were determined as follows:

h ₂ o cyclohexane 15.2 wt. 14.6 % wt. n-hexane 16.7 % wt.

The calcined surface area measured 494 m ² / g.

the crystalline material was

The chemical composition of the uncalcinated material was determined as follows:

% wt.

SiO ₂ 66.9

A1 ₂ O ₃ 5.40

On

N ash

SiO ₂ / Al ₂ O ₃ , mol

0.03

2.27

76.3

21.1

Table Degrees 2-theta IN interplanar d-distances (A) i / i _o 2.80 31.55 25 4.02 21.98 10 7.10 12.45 96 7.95 11.12 47 10.00 8.85 51 12.90 6.86 11 14.34 6.18 42 14.72 6.02 15 Dec 15.90 5,57 20 May 17.81 4.98 5 20.20 4.40 20 May 20.91 4.25 5 21.59 4.12 20 May 21.92 4.06 13 22.67 3.92 30 23.70 3.75 13 24.97 3.57 15 Dec 25.01 3.56 20 May 26,00 3.43 100 ALIGN! 26.69 3.31 14 27.75 3.21 15 Dec 28.52 3.13 10 29.01 3.08 5 29.71 3.01 5 31.61 2,830 5 32.21 2,779 5 33.35 2,687 5 34.61 2,592 5 Example 2 Part calcined crystalline pro tested in the alpha-test and was found to live

of Example 1 was

Examples 3 to 5

Three separate synthesis reaction mixtures, the composition of which is shown in Table VI, were prepared. Mixtures were prepared from sodium aluminate, sodium hydroxide, Ultrasil, hexamethylenimine (R) and water. The mixtures were maintained at 150 ° C, 143 ° C, and 150 ° C for 7.8 and 6 days in stainless steel autoclaves at autogenous pressure. The solid was separated from the unreacted components by filtration and then washed with water, followed by drying at 120 ° C. The obtained crystals were subjected to X-ray diffraction, sorption, surface area determination and chemical analyzes. The results of the sorption analysis, surface area determination and chemical analysis are shown in Table VI and the X-ray diffraction diagrams are shown in Figures 2,3 and 4. Sorption and surface area were measured for the calcined product.

Table VI

Example 3 4 5 synthesis mixture, mol. ratios S1O2 / A12O2 30.0 30.0 30.0 oh '/ sieve ₂ 0.18 0.18 0.18 h ₂ o / s ₂ 19.4 19.4 44.9 Na / SiO ₂ 0.18 0.18 0.18 r / sieve ₂ 0.35 0.35 0.35 Product composition,% by weight SiO ₂ 64.3 68.5 74.5 ^Α1 2θ3 4.85 5.58 4.87 On 0.08 0.05 0.01 N 2.40 2.33 2.12 ash 77.1 77.3 78.2 SiO ₂ / Al ₂ O ₃ , mol. ratio 22.5 20.9 26.0 adsorption,% by weight h ₂ ° 14.9 13.6 14.6 cyclohexane 12.5 12.2 13.6 n-hexane 14.6 16.2 19.0 specific surface area, m ² / g 481 492 487 Example 6 Calcined samples (538 ’C Mon. 3 hours) crystalline Liqueur products from examples 3,4 and 5 have been tested

in the alpha-test and the alpha-values 227, 180 and 187 were found.

Example 7

To demonstrate further zeolite preparation, 4.49 parts of hexamethylenimine was added to a solution containing 1 part sodium aluminate, 1 part 50% sodium hydroxide solution and 44.19 parts water. To this solution was added 8.54 parts of Ultrasil silica. The mixture was crystallized with stirring at 145 ° C for 59 hours and the resulting product was washed with water and dried at 120 ° C.

The X-ray diffraction pattern of the dried crystals of the product is shown in Figure 5 and demonstrates that the product is a crystalline material of the present invention. The chemical composition of the product, the specific surface area and the adsorption analyzes are given in Table VII:

Table VII Composition of product

N

At ^A1 2 ° 3

SiO ₂

SiO ₂ / Al ₂ 0 ₃ , mol.

(uncalcinated)

12.1 wt.

1.98 wt. 640 ppm 5.0 wt.

74.9 wt. 25.4 adsorption ratio, wt.

cyclohexane 9.1 n-hexane 14.9

H ₂ O 16.8 specific surface area, m ² / g 479 Example 8 g of the solid crystalline product of Example 7 was calcined in a stream of nitrogen at 538 ° C for 5 hours, then purged with 5% oxygen gas (N ₂ equilibrium) 16 hours at 538 ° C.

Individual 3 gram samples of calcined material were ion exchanged with 100 ml of 0.1N TEABr, TPABr, and LaCl ₃ solution. Each exchange was performed at ambient temperature for 24 hours and repeated three times. The exchanged samples were collected by filtration, washed with water to remove halides, and dried. The composition of the exchanged samples is tabulated below for various ions.

La

nx crystalline exchange capacity Silicate Ions exchanged Ion content,% by weight TEA TPA On 0,095 0,089 N 0.30 0.38 C 2.89 3.63 La - -

0,063

0.03

1.04

Example 9

The La-replaced sample of Example 8 was calcined in air at 538 ° C until the material had an alpha value of 173.

The 14 to 25 mesh was 3 hours. Calcined

Example 10

The calcined sample of La-exchanged material of Example 9 was steamed under harsh conditions at 649 ° C in 100% steam for 2 hours. The steamed sample has an alpha value of 22, indicating that the zeolite has very good stability under harsh hydrothermal treatment.

Example 11

This example illustrates the preparation of a zeolite wherein X in the above formula is boron. 2.59 parts boric acid was added to a solution containing 1 part 45% potassium hydroxide solution and 42.96 parts water. To this solution is added 8.56 parts of Ultrasil silica and the mixture is carefully homogenized. 3.88 parts of hexamethyleneimine are added to the mixture.

The reaction mixture has the following composition in mol. ratios:

SiO ₂ / B ₂ O ₃ ® (s)

OH '/ SiO ₂ = 0.06

H ₂ O / SiO ₂ = 19.0

K / SiO ₂ = 0.06

R / SiO ₂ = 0.30 where R is hexamethyleneimine.

The mixture was crystallized in a stainless steel reactor with stirring at 150 ° C for 8 days. The crystalline product is filtered off, washed with water and dried at 120 ° C. Part of the product was calcined at 540 ° C for 6 hours, and the following sorption capacities were found:

H ₂ O (1.6 kPa) 11.7 wt.

cyclohexane (5.3 kPa) 7.5 wt.

n-hexane (5.3 kPa) 11.4 wt.

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

The chemical composition of the non-calcined material was determined as follows:

N 1.94% by weight

At 175 ppm

K 0.60 wt.

boron 1.04 wt.

Al ₂ O ₃ 920 ppm

SiO 75.9 wt.

ash 74.11% wt.

SiO ₂ / Al ₂ O ₃ , molar ratio = 1406 SiO ₂ // Al + B / ₂ O ₃ , molar ratio = 25.8 Example 12

A portion of the calcined crystalline product of Example 11 was treated with NH ₄ Cl and calcined again. For the final crystalline product, an alpha value of 1 was determined in the alpha test.

Example 13

This example illustrates a further preparation of a zeolite wherein X in the above general formula is boron. 2.23 parts of boric acid are added to a solution of 1 part of 50% sodium hydroxide solution and 73.89 parts of water. To this solution was added 15.29 parts of HiSil silica followed by 6.69 parts of hexamethyleneimine. The reaction mixture has the following composition in mol. ratios:

SlO ₂ / B ₂ O ₃ - 12.3

OH / SiO ₂ = 0.056

H ₂ O / SiO ₂ = 18.6

K / SiO ₂ = 0.056

R / SLO ₂ = 0.30 where R is hexamethyleneimine.

The mixture was crystallized in a stainless steel reactor with stirring at 300 ° C for 9 days. The crystalline product was filtered off, washed with water and dried at 120 ° C. The following sorption capacities of calcined material (6 hours at 540 ° C) were found:

H ₂ O (1.6 kPa) 14.4 wt% cyclohexane (5.3 kPa) 4.6 wt% n-hexane (5.3 kPa) 14.0 wt%

Specific surface area of calcined 438 m ² / g.

The chemical composition of the non-calcined crystalline material is that of the material determined

thus: Component % wt. N 2.48 On 0.06 bor 0.83 ^ · 2θ3 .0,50 Si ° ₂ 73.4 S i O ₂ / Al ₂ 0β, molar ratio sieve ₂ // ai + b / ₂ O ₃ , molar Example 14

249

28.2

A portion of the calcined crystalline product of Example 13 was tested in the alpha test and was found to have an alpha value of 5. Example 15

The zeolite of the invention and with ZSM-12 were performed comparative experiments aging of the catalyst in the alkylation of benzene with propylene under the following conditions for 17 h ^_1 benzene WHSV, 3 to 1 mole. the ratio of benzene to propylene and 2170 kPa.

AND

The zeolite of the invention was prepared by adding 4.49 parts of hexamethylenimine to a mixture containing 1.00 parts of sodium aluminate, 1.00 parts of 50% sodium hydroxide, 8.54 parts of Ultrasil VN3 and 44.19 parts of deionized water. The reaction mixture was heated to 143 ° C and stirred in an autoclave at crystallization temperature. Upon complete crystallinity, a major portion of hexamythylenimine was removed from the autoclave by controlled distillation and the zeolite crystals were separated from the remaining liquid by filtration, washed with deionized water and dried.

A portion of the zeolite crystals were combined with Al ₂ O ₃ to form a mixture of parts by weight of zeolite and 35 parts of Α1 ₂ Ο ₃ · Water was added to this mixture to allow the resulting catalyst to be extruded. The catalyst was activated by calcination in nitrogen at 540 ° C followed by exchange with aqueous ammonium nitrate and calcination in air at 540 ° C.

Giant. 6 shows the temperature required to achieve complete conversion of propylene. At 130 ° C, the zeolite of the invention does not age under isothermal reaction conditions for 270 hours.

The selectivity for isopropylbenzenes (IPBs) for the zeolite of the invention and for ZSM 12 is shown in Figures 7 and 8. Using the zeolite of the invention, the selectivity for IPBs is approximately 100% compared to 90% using ZSM-12 under full conversion conditions. propylene. This fact and chromatographic results demonstrate that propylene is oligomerized over ZSM-12, resulting in lower IPB selectivity.

The data presented in Fig. 9 show that the zeolite of the invention is more active for the formation of diisopropylbenzenes (DIPB) than ZSM-12. In the alkylation of benzene with propylene over the present zeolite, 10% of the DIPBy products are primarily meta and para isomers. Giant. 9 shows that the yield of para-DIPB is higher than the zeolite of the invention (about 5% by weight of the total hydrocarbon product) than above ZSM-12 (about 4%). DIPBs are intermediates in the preparation of dihydroxybenzenes such as hydroquinone (p-) and resorcinol (m-), both of which have significant industrial applications.

Giant. 10 shows how the ratio of n-propylbenzene to cumene in reaction products above ZSM-12 and zeolite according to the invention varies with reaction temperature. Over 270 hours of reaction with the zeolite of the invention, the ratio of n-propylbenzene to cumene remains approximately constant at 160 ppm. This corresponds to a value of 700 ppm for ZSM-12 under the same conditions of 98% propylene conversion but at a higher temperature. Example 16

This example illustrates the alkylation of cumene with propylene in the presence of the zeolite of the invention to form diisopropylbenzenes (DIPBy). The alkylation reaction conditions are 2170 kPa, 150 ° C and a 1: 1 molar ratio of cumene to propylene. In this reaction, the conversion of cumene to alkylate was 81%. The DIPBy is 84% of this alkyl product, the rest being triisopropylbenzene (TIPB). DIPBs are para (65%), meta (34%) and ortho (1%).

Example 17

This example demonstrates the alkylation of the phenol with an alpha- _C14 olefin over the zeolite of the invention to form a mixture of alkylated phenols. Alkylation was performed in a 1 liter autoclave using 400 g olefins (2.02 mol), 95 g (1.01 mol) phenol and 38 g catalyst, 65 wt% MCM-22/35 wt% Al ₂ O ₃ binder . The reaction time was six hours at 177 ° C under a pressure of 100 psig of nitrogen.

Analysis of the product revealed the presence of mono-, di- and tri-tetradecylphenols.

Example 18

This example relates to the alkylation of benzene with 1-dodecene using each of the two known alkylation catalysts, namely Lewis acid AlCl ₃ and zeolite beta, as disclosed in US Patent No. 4301316. The isomer distribution is shown in Table VIII:

Table VIII

Distribution of 1-dodecene alkylation isomers, wt. Alkylbenzene

isomer AlClo zeol 2 30 57 3 19 Dec 18 4 17 10 5 17 7 6 17 8

The composition of the dodecylbenzene mixture is to some extent dependent on the acid catalyst used. For sulfuric acid, results of 41 wt. 2-dodecylbenzene while HF yields were only about 20% .. Similar results can be demonstrated for other alkylations containing relatively large, i.e. _C6 +, alkylating agents.

Example 19

This example describes the alkylation of benzene alpha- _{C14 with an} olefin (Shell Neodene-14) over the zeolite of the invention (produced according to Example 15) and separately over the zeolite Beta. Alkylation was carried out in a 1 liter autoclave using 400 g (2.02 mol) olefin, 79 g (1.01 mol) benzene and 38 g catalyst. The reaction time was six hours at 204 ° C under a pressure of 100 psig of nitrogen. The isomer distributions are shown in Table IX below:

Table IX

Distribution of alkylation isomers,% by weight Alkylbenzene zeolite zeolite isomer according to the invention Beta 2 59.2 54.7 3 36.5 20.3 4 2.5 9.4 5 0.9 5.8 6 0.4 5.3 7 0.5 5.5

As can be seen from Examples 18 and 19, the use of the zeolite of the invention as an alkylation catalyst results in a significantly higher content of the 2- and 3-alkyl isomer type alkyl product than the use of a Lewis acid or Beta zeolite as an alkylation catalyst under the same or similar conditions.

Alkyl products containing alkyl side chains of about 8 to 16 carbon atoms are particularly useful as intermediates for the production of linear alkyl benzene sulfonate synthetic detergents.

Example 20

Two different zeolite catalysts, a zeolite according to the invention prepared according to Example 15 and a zeolite beta, were used in separate alkylation experiments, A and B, carried out under substantially the same conditions for the preparation of lubricant bases. Each catalyst composition contains 65% zeolites combined with 35% by weight. aluminum oxide.

The alkylation reaction in each experiment was performed in a 1 liter autoclave using 400 g (2.02 mol) of alpha-C-olefin (Shell).

Neodene-14), 79 g (1.01 mol) of benzene (5: 1 mole ratio of benzene to olefin) with 38 g of catalyst at 204 ° C for 6 hours under a nitrogen pressure of 2,860 kPa.

Table X below lists the lubricant yields and properties obtained by alkylation performed with each of the zeolites.

Table X

Catalyst Lubricant yield,% by weight of the lubricant property: freezing point ( ⁰ C) cloud point, (° C)

KV at 40 ° C, cSt KV at 100 ° C, cSt VI Experiment A Experiment B Example 15 of the invention Beta 77.0 37.0

-51 -51

-39 -46

12.39 '14.54

3,151 3,471

113 117

Gas Chromatography and Ionized Field Mass Spectrography (FIMS) show that the synthetic lubricant prepared with the catalyst of the present invention contains a mixture of mono- and di-alkylbenzene compounds, 67 and 33% by weight. formation of mono- and di-alkylbenzenes, but also C ₁₄ oligomerization to form C ₂ g olefins. Further, as evidence of unique alkylation selectivity, the catalyst of the invention is significantly more active and produces an alkylated benzene grease base with a very low cloud point and freezing point compared to beta zeolite.

Example 21

This example compares the activity of a catalyst of the invention with a zeolite beta in the alkylation of naphthalene alpha _{C14 with an} olefin. The reaction was carried out under conditions essentially the same as in Example 20 using a 0.5: 1 molar ratio of alpha-olefin to naphthalene. The alkylated naphthalene lubricant is obtained in a yield of about 94% by weight. and the synthetic lubricant-containing product mainly comprises a mixture of mono-, di- and tri-alkylnaphthalenes and has the following properties (Table XI):

Table XI

Catalyst zeolite according to the invention Lubricant yield, wt.% 94 Lubricant properties Pour point (° C) <-54

KV at 40 ° C, cSt 37.27

KV at 100 ^e C QST 5894

VI 100

Example 22

This example also demonstrates excellent activity and selectivity

of the zeolite catalyst of the present invention for alkylation other aromatics such as toluene (Example 22A); xylene (example 22B) alpha- _C14 olefin ve comparison with benzene (Example 22C) after same processing conditions (table XII): Table XII Example # 22A 22B 22C aromat toluene xylene benzene olefins ^C 14 ^c 14 ^C 14 molar ratios c ₁₄ / aromatics 1 1 1 lubricant yield,% wt. 86.6 73.0 92.0 lubricant properties pour point (’C) <-54 < : -54 -43 cloud point ( ⁰ C) <-54 -47 -42 HF at 40 ° C, CSt 9,408 16.13 7,651 HF at 100 ° C, cSt 2,505 3,393 2,265 VI 87 70 106

Example 23

This example illustrates an alkylation process according to the invention which uses an olefinic feedstock obtained from oligomerization

1-decene using a propanol-promoted BF ₃ catalyst.

The catalyst used was a zeolite according to the invention prepared in Example 15 containing a combination with Al ₂ O ₃ binder and converted to a hydrogen form.

1-Decene, BF ₃ and propanol were introduced into the 1-decene oligomerization reactor. The oligomerized product was first washed with sodium hydroxide and then with water before separating the light products in a vacuum distillation unit. For the alkylation of 78 g of benzene, 25 g of 1-decene oligomers containing 33 wt. % _C30 olefin, 52 wt. % C ₄₀ olefin and 15 wt. C ₅₀ olefin, using 22 g of the zeolite of the invention as a catalyst. The reaction was carried out at 28 psi of nitrogen and 204 ° C for 6 hours.

After decanting the catalyst and distilling off all unreacted benzene, the lubricant yield was 88% by weight, indicating that 12% by weight was alkylated. benzene and incorporated into the chain structure of the decene oligomers. This was further confirmed by IR analysis. The properties of oligomers before and after alkylation of benzene are shown below (Table XIII):

Table XIII

Process lubricant properties pour point, ° C cloud point, ´C

KV at 40 ’C, cSt

KV at 100 ’C, CSt VI product quality temperature stability at reduced vis.

B-10 oxidation stability viscosity increase DSC-IP minutes at 180 ° C oligomerization <-54 <-54

25.73

5,225 138

C,%

10.9%

120

5.0 alkylation <-54 <-54

33.03

6,039

131

4.6

80.6

10.5

The results show that the alkylation step produces benzene containing a synthetic lubricant base with excellent product properties such as very low pour point and turbidity and high viscosity index along with improved solubility characteristics as well as increased thermal and oxidative stability.

Example 24

This example illustrates the alkylation process of the invention performed with a 1-decene oligomer product obtained with a Cr / SiO ₂ catalyst.

1-Decene and Cr / SiO ₂ are fed to an oligomerization reactor from which the product is distilled off in vacuo and then fed to the alkylation reactor together with benzene.

The alkylation reaction was carried out under the same conditions as in Example 23, but using 500 g of decene oligomers and 95 g of benzene with 36 g of zeolite according to the invention as a catalyst. The properties of decene oligomers before and after benzene alkylation are shown below (Table XIV):

CS 277255 B6

Table XIV

Process oligomerization alkylation lubricant properties pour point, ° C -34 -32 cloud point, ° C <-54 -34 KV at 40 ^e C, cst 122.9 68.11 HF at 100 ’C, cSt 18.33 11.60 VI 167 166 Example 25 In the same way as in the example 23, 400 g 204-371 ° C distillate (78%), prepared by oligomerization of light olefins over ZSM-5, was alkylated with 115 g of naphthalene (12 wt%) above a catalyst according to the invention. Result: 370 ° C + lubricant was obtained but in 54 wt% yield. Table XV lists the alkylated properties naphthalene lubricant base: Table XV Process olefin conversion by alkylation to petrol and desti- lath pour point, ⁰ C <-54 -18 HF at 40 ° C, cSt 152.6 HF at 100 ° C, cSt 2.5 10.15 j edn. dest., ^e C IBP / 5% 149/191 336/359 10/20% 224/242 372/389 30/40% 253/265 401/413 50% 276 426 60/70% 289/306 441/458 80/90% 328/354 479/509 95% 385 532

Claims (11)

PATENT CLAIMS A process for alkylating an aromatic compound, comprising contacting the aromatic compound with at least one alkylating agent at a temperature of from 0 ° C to 500 ° C, a pressure of from 20 to 25350 MPa, a mass flow rate of feedstock of from 0.1 to 500 and a molar ratio alkylable aromatic compounds to an alkylating agent from 0.1: 1 to 50: 1, in the presence of a catalyst comprising a synthetic porous crystalline zeolite having the following X-ray diffraction pattern of interplanar d-distal-relative intensity, Companies (A) I / Io X 100 12.36 ± 0.4 M-VS 11.03 ± 0.2 M-S 8.83 ± 0.14 M-VS 6.18 ± 0.12 M-VS 6.00 ± 0.10 W-M 4.06 ± 0.07 W-S 3.91 ± 0.07 M-VS 3.42 ± 0.06 vs, where W means weak, S strong, M medium and VS very strong. Method according to claim 1, characterized in that the zeolite has an X-ray diffraction pattern of the following interplanar d-distance-relative intensity, company (AND) I / Io x 100 30.0 ± 2.2 W-M 22.1 ± 1.3 W 12.36 ± 0.4 M-VS 11.03 ± 0.2 M-S 8.83 ± 0.14 M-VS 6.18 ± 0.12 M-VS 6.00 ± 0.10 W-M 4.06 ± 0,07 W-S 3.91 ± 0,07 M-VS 3.42 ± 0,06 VS Way according to claim 1, characterized in that the zeolite has a diffraction · X-ray diagram containing the following values of interplanar d-distance (A) relative intensity, I / Io x 100 12.36 ± 0.4 M-VS 11.03 ± 0.2 M-S 8.83 ± 0.14 M-VS 6.86 ± 0.14 W-M 6.18 ± 0.12 M-VS 6.00 ± 0.10 W-M 5.54 ± 0.10 W-M 4.52 ± 0,09 W 4.64 ± 0,08 W 4.41 ± 0,08 W-M 4.25 ± 0,08 W 4.10 ± 0,07 W-S 4.06 ± 0,07 W-S 3.91 ± 0,07 M-VS 3.75 ± 0,06 W-M 3.56 ± 0,06 W-M 3.42 ± 0,06 VS 3.30 ± 0.05 W-M 3.20 ± 0.05 W-M 3.14 ± 0.05 W-M 3.07 ± 0.05 W 2.99 ± 0.05 W 2.82 ± 0.05 W 2.78 ± 0.05 W 2.68 ± 0.05 W 2.59 ± 0.05 w Way according to claim 1, characterized by t X-ray diffraction diagram that zeolite has interplanar d-distance (A) relative intensity, I / Io X 100 30,00 + 2.2 W-M 22.1 + 1.3 W 12.36 + 0.4 M-VS 11.03 + 0.2 M-S 8.83 + 0.14 M-VS 6.86 + 0.14 W-M 6.18 + 0.12 M-VS 6.00 + 0.10 W-M 5.54 + 0.10 W-M 4.92 + 0.09 W 4.64 + 0.08 W 4.41 + 0.08 W-M 4.25 + 0.08 W 4.10 + 0.07 W-S 4.06 + 0.07 W-S 3.91 + 0.07 M-VS 3.75 + 0.06 W-M 3.56 + 0.06 W-M 3.42 ± 0.06 VS 3.30 + 0.05 W-M 3.20 + 0.05 W-M 3.14 + 0.05 W-M 3.07 + 0.05 W 2.99 + 0.05 W 2.82 + 0.05 W 2.78 + 0.05 W 2.68 ± 0.05 W 2.59 + 0.05 1 W The method of claim 1, wherein the zeolite has a molar ratio composition X ₂ O ₃ : / n / YO ₂ , where n is at least 10, X is a trivalent element and Y is a tetravalent element. The method of claim 5, wherein X is aluminum and Y is silicon. The method of claim 1, wherein the zeolite has an equilibrium adsorption capacity of greater than 4.5 wt%. % for cyclohexane vapor and greater than 10 wt. for the n-hexane steam. The process of claim 1 wherein the alkylating agent comprises at least one unsaturated aliphatic group having 2 to 5 carbon atoms. The method of claim 8, wherein the alkylating agent is propylene and the aromatic compound is benzene and / or cumene. 10. The process of claim 8 wherein the alkylating agent is ethylene and the aromatic compound is benzene. The method of claim 1, wherein the alkylating agent comprises at least one aliphatic chain having at least 6 carbon atoms. The method of claim 1, wherein the aromatic compound is a hydrocarbon or phenol compound. The process according to claim 1, wherein the alkylation conditions comprise a temperature of 10 ° C to 350 ° C, a pressure of 100 to 2550 kPa, a mass feed rate of from 0.5 to 100 and a molar ratio of alkylated aromatic compound to alkylation. from 0.5: 1 to 10: 1.