SK277832B6 - Alkylation method of isoparafin by olefin - Google Patents

Abstract

Alkylation isoparafin by olefin by origin alkylate, is realised with present of catalyst-zeolite having next lines of diffraction diagram of rontgene rays: interplanar d-distance (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 ------------------------------------------------------------- where relative intensities are marked as follows: W = 0 to 20, M = 20 to 40, S = 40 to 60, VS = 60 to 100.

Description

Technical field

The present invention relates to a process for alkylating isoparaffins with olefins.

BACKGROUND OF THE INVENTION

As a result of the reduction in the use of tetraethyl lead as an additive improving the octane rating of gasoline, not only increased the production of unleaded gasoline but also the octane rating of all gasoline types. Alkylation of olefins with isoparaffins is a key process for the production of highly branched octane number-increasing paraffinic substances that are added to gasoline.

Alkylation is the addition of an alkyl group to an organic molecule. Thus, isoparaffin can react with ocfin to produce isoparaffin of higher molecular weight. In industry, alkylation often involves the reaction of C 2 -C 5 olefins with isobutane in the presence of an acid catalyst. Previously, the alkylation processes involved the use of hydrofluoric acid or sulfuric acid as a catalyst under controlled temperature conditions. In the sulfuric acid process, low temperatures are used to minimize unwanted olefin polymerization side reactions and the acid concentration is generally maintained at 88-94% by continuous addition of fresh acid and continuous removal of spent acid. The hydrofluoric acid process is less temperature sensitive and the acid is easier to remove and clean. However, alkylation processes using hydrofluoric acid and sulfuric acid have considerable disadvantages, including environmental pollution, acid consumption and the use of corrosive materials. With increasing requirements for octane number and increasing environmental requirements, it is desirable to develop an alkylation process based on a solid catalyst system.

Crystalline metallosilicates or zeolites are widespread in the catalysis of isoparaffin alkylation. For example, U.S. Pat. No. 3251902 discloses the use of a fixed bed of crystalline aluminosilicates that have been treated by ion exchange having a reduced number of available acid sites for alkylation of C4-C20 branched paraffins with C1-C12 olefins in the liquid phase. The patent further discloses that C4-C20 branched paraffins could substantially saturate the crystalline aluminosilicate prior to introducing the olefin into the alkylation reactor.

U.S. Pat. No. 3549557 describes the alkylation of isobutane with C2-C3 olefins using certain crystalline aluminosilicate zeolite catalysts in a fixed, moving or fluidized bed system, the olefin is preferably injected at various locations into the reactor.

U.S. Pat. No. 3644565 describes the alkylation of paraffin with an olefin in the presence of a catalyst comprising noble metal of Group VI 'on crystalline aluminosilicate zeolite, the catalyst being pretreated with hydrogen to improve selectivity.

U.S. Pat. No. 3655813 describes a process for alkylating C4-C5 isoparaffins with C3-C9 olefins using a crystalline aluminosilicate zeolite catalyst wherein a halide additive is introduced into the alkylation reactor. Isoparaffin and olefin are fed to the alkylation reactor at specific concentrations and the catalyst is continuously recovered outside the alkylation reactor.

U.S. Pat. No. 3893942 discloses an isoparaffin alkylation process using a zeolite containing a VHI group metal catalyst that is periodically hydrogenated with hydrogen in the gas phase to reactivate the catalyst while partially deactivating it.

U.S. Pat. 3236671 discloses the use, in alkylation, of a crystalline aluminosilicate zeolite having a silica to alumina molar ratios above 3 and also describes the use of various such zeolites which are treated by ion exchange with different metals and / or impregnated therewith.

U.S. Pat. 362173 discloses the use, in alkylation with isoparaffins of olefins, of a gadolinium containing zeolite catalyst.

U.S. Pat. No. 3738977 describes the alkylation of paraffins with ethylene using a zeolite catalyst which contains a Group VIH metal component, the catalyst being pretreated with hydrogen.

U.S. Pat. No. 3865894 discloses alkylation of C ₄ -C 6 isoparaffins with a C 3 -C 9 monoolefin using a substantially anhydrous acidic zeolite, for example an acidic zeolite Y (zeolite HY) and a halide additive.

U.S. Pat. No. 3,917,738 discloses a process for alkylating isoparaffin with an olefin using a solid, particulate catalyst that is capable of olefin absorption. Isoparaffin and olefin are mixed into the reaction stream in contact with the catalyst particles at the upstream end of the adsorption zone, then the reactants are passed in parallel with the catalyst such that a controlled amount of olefin is adsorbed onto the catalyst prior to the reactant combination and introduced into the alkylation zone. Controlled olefin adsorption is performed to prevent olefin polymerization during alkylation.

U.S. Pat. No. 4377721 discloses an isoparaffin / olefin alkylation process using ZSM20, preferably HZSM-20 or ZSM-20, a rare earth metal cation exchange catalyst as catalyst.

U.S. Pat. No. 4,384,161 describes a process for alkylating isoparaffins with olefins to form an alkylate which utilizes large pore zeolite as a catalyst capable of absorbing 2,2,4-trimethylpentane, e.g. ZSM-4, ZSM-20, ZSM-3, ZSM-18, beta zeolite, faujasite, mordenite, zeolite Y and their forms containing rare earth metals and Lewis acid such as boron trifluoride, antimony fluoride or aluminum chloride. The use of large pore zeolite in combination with the Lewis acid of this patent greatly increases the activity and selectivity of the zeolite by performing alkylation with a high olefin space velocity and a low isoparaffin / olefin ratio.

SUMMARY OF THE INVENTION

The present invention relates to a process for alkylating isoparaffin with an olefin, comprising reacting isoparaffin and olefin in the presence of a synthetic porous crystalline zeolite having an X-ray diffraction pattern comprising the values substantially listed in Table I as a catalyst.

One measure of the selectivity of the alkylation catalyst is C9 + yield. This fraction usually results from the oligomerization of the olefin feedstock, resulting in lower alkylate yield, reduced alkylate quality and allows the formation of acid sludge. The zeolite alkylation catalyst used in the process of the present invention reduces C9 + compared to known zeolite alkylation catalysts such as HY zeolite, e.g. disclosed in U.S. Pat. 3865894, cited above.

The alkylate obtained by the process of the present invention is of high quality according to the octane numbers determined by both the research and engine methods and is particularly suitable for admixing with gasoline.

The synthetic porous crystalline zeolite used in the alkylation process of the present invention has, in its calcined form, an X-ray diffraction pattern comprising the lines shown in Table I:

Table I

Interplanar d-distance (A) relative intensity

Xο x 100

30.0 +2.2 22.1 +1.3 12.36 + 0.4 11.03 ± 0.2 8.83 + 0.14 6.18 + 0.12 6.00 + 0.10 4.06 + 0.07 3.91 +0.07 3.42 + 0.06 W-M W M - VS M - S M-VS M-VS W-M W-S M-VS VS more specific lines in table Π: Table Π Interplanar d-distance (A) relative intensity 100οx 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 below in the table ΙΠ: Table ΙΠ Interplanar d-distance (A) relative intensity Xο 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 + 0.07 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

Table ΙΠ (continued) Interplanned d-distance (A) relative intensity 100οx 100 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, it has a calcined crystalline X-ray diffraction pattern, which includes the lines shown in Table 1V: Table IV Interplanar d-distance (A) relative intensity Xο 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 6.86 + 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

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 theta, where theta is the Bragg angle, were determined using computer algorithms coupled to a diffractometer. From this, relative intensities were determined, 100 ΙΛο, where the tallow intensity of the strongest line or peak and d (pos.) Interplanar distance in Angstrom units (A), corresponding to the recorded lines. In Tables I and Π, the relative intensities indicated by the symbols W = = weak, M = medium, S = strong and VS = very strong. Intensities can be labeled as follows:

W = 0-20, M = 20-40; S = 40-60; VS = 60-100.

X-ray diffraction patterns are characteristic of all kinds of zeolites present. The sodium form, as well as other cationic forms, show essentially the same diagrams with some small variations in interplanar distances and variations in relative intensity. Other small variations can

SK 277832 Β6 depending on the molar ratio Y to X, e.g. silicon to aluminum, in the individual formulas, as well as at the degree of their heat treatment.

The zeolite used according to the present invention usually has a composition corresponding to the following molar relationship

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

(0.005-0.1) Na ₂ O: (M) R ₁ O ₂ O ₂ O ₂ O ₁ O where R is an organic component. The Na and R components are associated with the zeolite due to their presence during crystallization and are readily removable by post-crystallization methods, which are described in more detail below.

The zeolite used in the process of the invention is thermally stable and has a large specific surface area (greater than about 400 m ² / g as measured by BET (Brunauer, Emmet and Teller) test). In addition, zeolite typically exhibits equilibrium adsorption values greater than 4.5% by weight, usually greater than 7% by weight. % for cyclohexane steam, greater than 10 wt. % for n-hexane vapor and preferably greater than 10 wt. for water vapor. As can be seen from the above formula, the zeolite is synthesized as substantially free of sodium cations and thus exhibits the activity of the acid catalyst as synthesized. It can therefore be used as an alkylation catalyst in the process according to the invention without being exchanged in the first step. If desired, the original sodium cations of the as-synthesized material may be replaced by techniques well known in the art, at least in part, by ion exchange with other cations. Preferred exchanged cations include metal ions, hydrogen ions, hydrogen precursor ions, e.g. ammonium and mixtures thereof. Preferred cations are those which affect the activity of the catalyst in alkylation. These include hydrogen, rare earth metals and metals of the ΠΑ, ΠΙΑ, IVA, IB, ΠΒ, ΙΠΒ, 1VB and VHI metals of the Periodic Table of the Elements.

Before being used as an alkylation catalyst, the zeolite should be heat treated to remove some or all of the organic components present.

The zeolite used herein may also be used in close association with a hydrogenation component such as tungsten, vanadium, molybdenum, rhenium, nickel, cobalt, chromium, manganese, or noble metals such as platinum or palladium, where hydrogenation is guaranteed. -dehydrogenation function. Such a component may be associated chemically and / or physically with the zeolite and / or matrix with which the zeolite may optionally be present. For example, the hydrogenation component, fed to the catalyst composition by co-crystallization, may be exchanged in the composition to the content of the ΠΙΑ group element, for example, aluminum, in the structure, impregnated thereon or physically mixed therewith. Such a component may be impregnated into 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 for this purpose include chloroplatinic acid, platinum (II) chloride and various compounds containing a platinum amine complex.

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

The zeolite used in the process of the invention may be prepared from a reaction mixture comprising alkali or alkaline earth (M) sources, for example sodium or potassium, in the form of a cation, a trivalent element X, for example aluminum, a tetravalent element oxide Y, for example silicon, organic (R) diluent, hexamethyleneimine and water. Said reaction mixture has a composition expressed in molar ratios of oxides in the following range:

Suitable preferred reactants

Yo / XoO 10-60 10-40

H ₂ O / YO ₂ 5-100 10-50

OlT / YCh 0.01-1.0 0.1-0.5

M / YCl 0.01-2.0 0.1-1.0

R / YCl 0.05 -1.0 0.1-0.5

In a preferred synthetic method, the Y Ch reactant contains a substantial amount of solid YCh, for example at least 30 wt. If YO _{2 is} silica, for example, 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 0 and 4.5 wt% H ₂ O bound by hydration, having a particle size of 0.02 microns (promotes crystal formation from the above mixture. IF another silicon oxide source is used, for example QBrand (sodium silicate containing 28.8% lunotine) SiO ₂ , 8.9 wt% Na ₂ O and 62.3 wt% H ₂ O), crystallization can provide a small amount of the desired zeolite and impurities having a different crystalline structure such as ZSM-12 can be produced. the YO ₂ source, for example silica, comprises at least 30% by weight of solid YO ₂ , for example silica, and more preferably at least 40% by weight of solid SiO ₂ , for example silica.

Crystallization can be carried out either under static conditions or with stirring in a suitable reactor, such as a polypropylene vessel or autoclaves, lined with Teflon or stainless steel. Generally, the crystallization is carried out at a temperature of 80 ° C to 225 ° C, 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%, preferably 0.10% and particularly preferably 1% of seed crystals in the reaction mixture, based on the total weight of the crystalline product formed.

Prior to use in the method of the invention, the zeolite is preferably combined with another material, i. a binder that is resistant to the temperatures and other conditions used in the isoparaffin alkylation process of the present invention. Suitable binder 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 aluminum. These may be either of natural origin or in the form of gel-like precipitates or gels comprising mixtures of silica and metal oxides. Use of a binder material in conjunction with a zeolite, i. in conjunction with them, or its presence during its synthesis, which is itself catalytically active, may alter the conversion and / or selectivity of the catalyst. The inactive materials preferably serve as diluents to control the amount of conversion, so that the isoparaffin alkylation products can be obtained economically and in a controlled manner without the use of additional reaction rate control devices. These materials can be incorporated into natural clays, such as bentonite and kaolin, to improve the crushing resistance of the zeolite under conventional isoparailin alkylation conditions. Good crush resistance is an advantageous property for commercial use, since it is desirable to protect the catalyst from disintegration into a pulverulent material.

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

Before or during the addition of the above binder materials, the present zeolite may be coupled to an inorganic oxide matrix such as silica-toric oxide, silica-barium oxide, silica-titanium dioxide, as well as themed compositions such as silica-alumina toric oxide, silica alumina-zirconia, silica-alumina-magnesium oxide and silica-magnesium-zirconia. It may also be advantageously provided at least a portion of the above matrix materials in colloidal form to facilitate extrusion of the coupled catalyst component (s).

The ratios of zeolite and inorganic oxide matrix material vary widely, with a zeolite content ranging from 1 to 90% by weight. % and particularly preferably, especially when the composite is prepared in the form of spheres, in the range of from 2 to 8 wt. composite.

The stability of the alkylation catalyst of the invention can be increased by steaming, which is conveniently accomplished by contacting the zeolite with, for example, 5 to 100% steam at a temperature of at least 300 ° C (e.g. 300 to 650 ° C) for at least one hour (e.g. 1 to 200 hours). at 101 to 2500 kPa. In a particularly preferred embodiment, the catalyst may be steamed with 75-100% steam at 315-500 ° C and atmospheric pressure at 2-25 hours.

The alkylation catalyst used in the process of the invention may further comprise a Lewis acid promoter as an additive to the zeolite described above. Lewis acid is generally required to be able to combine with another molecule or ion to form a covalent chemical bond with the two electrons of the other molecule or ion, thus the Lewis acid is an electron acceptor. Examples of Lewis acids include boron trifluoride, antimony fluoride, and aluminum chloride. The present invention contemplates the use of these or other Lewis acids, including those listed in Friedel-Crafls and Related Reactions, Interscience Publishers, Chapters, and IV (1963). BF3 is the preferred Lewis acid for use in the alkylation process of the present invention. In the case of BF 1, the promoter is preferably present in the alkylation zone in an amount that exceeds the amount required to saturate the zeolite catalyst containing not only the zeolite itself, but also other material, such as a binder or matrix material, which may be associated therewith.

The operating temperature of the alkylation process can be varied over a wide range, e.g. from -40 to 400 ° C, lower temperatures are used when the Lewis acid promoter is present. With the Lewis acid promoter, the temperature can generally be from -40 to 250 ° C and preferably from -20 to 100 ° C. If the Lewis acid promoter is not used, the temperature is generally from -25 to 400 ° C and preferably from 75 to 200 ° C. The actual upper working temperature can often be due to the need to suppress unwanted side reactions.

The pressures used in the present process may vary over a wide range, for example from subatmospheric to 34580 kPa, preferably from 100 to 7000 kPa.

The amount of zeolite used in the alkylation process of the present invention can vary widely. In general, the amount of zeolite, measured as the mass hourly space velocity (WHSV) of the olefin, may range from 0.01 to 100, preferably from 0.1 to 20.

The isoparaffin reactant used in the alkylation process of the invention typically contains up to 20 carbon atoms and preferably 4 to 8 carbon atoms such as isobutane, 3-methylhexane, 2-methylbutane, 2,3-dimethylbutane and 2,4-dimethylhexane.

The olefin reactant, as used herein, typically contains from 2 to 12 carbon atoms. Representative examples are ethylene, propylene, 1-butene, 2-butene, isobutylene, pentenes, hexenes, heptenes and octenes. Preferred are C 3 and C 4 olefins and mixtures thereof

In general, the mole ratio of total isoparaffin to total olefinic alkylating agent in the combined hydrocarbon feedstock may be from 0.5: 1 to 500: 1, preferably from 3: 1 to 50: 1. The isoparaffin and olefin reactants may be either vapor phase or liquid. phase and may be undiluted, i without deliberate admixture or dilution with other material, or the reactants may be contacted with the catalyst composition using a carrier gas or diluent, such as nitrogen.

The reactants may be fed to the alkylation reaction zone together with one or more other materials to improve the reaction conditions. For example, relatively small amounts of hydrogen and / or hydrogen donors may be present in the reaction zone to suppress the aging of the catalyst. For this purpose, water and / or materials such as alcohols which provide water under the alkylation reaction conditions can also be fed to the reaction zone. Oxygen and / or other materials that inhibit oligomerization of the olefin feedstock may also be present.

If water is fed to the alkylation reactor, it is preferably simultaneously fed with the feedstock at a rate of 0.1 ppmhm. % to 1 wt.%, preferably 0.1 ppm. up to 500 ppmhm., based on the total hydrocarbon feed rate. Alternatively, it may be zeolite

Pre-introduced water, preferably in an amount of 0.5 to 25%, more preferably 1-10% by weight of the catalyst.

The alkylation processes of the present invention can be carried out as batch, semi-continuous or continuous operations using a fixed or movable catalyst bed. A preferred embodiment involves the use of a catalyst zone wherein the hydrocarbon component passes through a supercurrent or countercurrent moving bed of the zeolite catalyst. The countercurrent is introduced into the recovery zone to remove coke, for example, by burning in an oxygen-containing atmosphere (such as air) at elevated temperature or solvent extraction, then the recovered catalyst is recycled to the conversion zone for further contact with organic reactants.

The invention will now be described in more detail by the following examples and the accompanying drawings.

BRIEF DESCRIPTION OF THE DRAWINGS

In FIG. 1-5 are X-ray diffraction diagrams of the calcined products of Examples 1, 3, 4, 5 and 7.

DETAILED DESCRIPTION OF THE INVENTION

Whenever sorption data for water, cyclohexane and / or n-hexane are compared in the examples, the equilibrium adsorption values were determined as follows:

A weighed sample of calcined adsorbent was contacted with the desired clean adsorbate vapor in the adsorption chamber, evacuated to less than 1 mm Hg and contacted with 1.6 kPa water vapor or 5.3 kPa n-hexane vapor or 5.3 kPa vapor cyclohexane, these pressures being less than the equilibrium para-liquid pressure of the respective adsorbate at 90 ° C. The pressure was kept constant (with about + 0.5 mm Hg) by the addition of adsorbate vapor by a controlled manostat during an adsorption period not exceeding about 8 hours, when adsorbate is adsorbed by crystalline zeolite, a pressure relief valve opens to reduce vapor adsorbate into the chamber for maintaining the above pressures. Sorption is complete 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 adsorbent. The zeolite of the present invention always has equilibrium adsorption values greater than 4.5% by weight, usually greater than 7% by weight. % for cyclohexane vapor and greater than 10 wt. % for n-hexane vapor and typically 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 cracking catalyst, aluminum oxide, classified as alpha 1 (velocity constant = 0.016 m ¹ ). The alpha assay to be used is described in J. Catalysis, 61, p. 300-306 (1980). It should be noted that the true rate constants of many acid catalysed reactions are proportional to the alpha value for a single crystalline silicate catalyst, i.

rates for toluene disproportionation, xylene isomerization, alkene conversion and methanol conversion (see The Active Side of Acidic Aluminosilicate Catalysts, Nature, Vol. 309, No. 5969, pp. 589-591, June 14, 1964).

Example 1 part of sodium aluminate (43.5% Al2O3, 32.2% NajO, 25.6% H2O) is dissolved in a solution containing 1 part of 50% sodium hydroxide solution and 103.13 parts of water. To this solution was added 4.50 parts of hexamethyleneimine. To the resulting solution was added 8.55 parts of Ultrasil, precipitated, spray-dried silica (about 90% SiO 2).

The reaction mixture has the following composition in molar ratios

SiO2 / Al2O3 = 30.0

OJT / SiCl = 0.18

H2O / SiO2 = 44.9

Na / SiO? = 0.18

R / S1O2 = 0.35 where R is hexamethylenimine.

The mixture is crystallized 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 20 ° C. After 20 hours of calcination at 538 ° C, the X-ray diffraction pattern contains the main lines shown in Table V. Fig. 1 shows the X-ray diffraction pattern of the calcined product. The sorption capacities of the calcined material were measured:

water 15.2 wt%; cyclohexane 14.6% by weight; n-hexane 16.7 wt.

The specific surface area of the zeolite was determined to be 494 m ² / g.

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

component % wt. SiO ₂ 66.9 AljOj 5.40 On the 0.03 N 2.27 ash 76.3 S1O2 / Al2O3, mol. ratio 21.1 Table V degrees interplanar I / Io 2-Theta d-spacing (A) 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 15.90 5.57 20 17.81 4.98 5 20.20 4.40 20 20.91 4.25 5 21.59 4.12 20 21.92 4.06 13 22.67 3.92 30 23.70 3.75 13 24.97 3.57 15 25,01 3.56 20 26.00 3.43 100

Table V (continued)

degrees 2-Theta Interplanar d-distance (A) ΙΛο 26.69 3.31 14 27.75 3.21 15 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

A portion of the calcined crystalline product of Example 1 was tested in an alpha assay and was found to have an alpha value of 224.

Examples 3-5

Three separate synthesis reaction mixtures were prepared as shown in Table VI. The 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 solids were filtered from all unreacted ingredients and then washed with water followed by drying at 120 ° C. The obtained crystals were subjected to X-ray diffraction analyzes, sorption analysis, specific surface determination and chemical analyzes. The results of the specific surface determination, sorption and chemical analyzes are shown in Table VI and the X-ray diffraction diagrams are shown in Figures 2, 3 and 4. Sorption and specific surface area were determined for the calcined product.

Table VI

Example synthesis mixture, mol. condition 3 4 5 SiO ₂ / Al ₂ O ₃ 30.0 30.0 30.0 OH / SiO 0.18 0.18 0.18 ILO / SiO 19.4 19.4 44.9 Na / SiO ₂ 0.18 0.18 0.18 R / SiO ₂ 0.35 0.35 0.35

Product composition, wt.

SiO ₂ 64.3 68.5 74.5 Al ₂ Ch 4.85 5.58 4.87 On the 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, mol. ratio 22.5 20.9 26.0 % Adsorption, wt. H ₂ O 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

attaches

Samples of calcine (538 'C, 3 hours) of the crystalline silicate products of Examples 3, 4 and 5 were tested in the alpha test and were found to have alpha values of 227, 180 and 187.

Example 7

To prepare a larger amount of the desired zeolite, 1200 g of hexamethylenimine was added to a solution containing 268 g of sodium aluminate, 267 g of 50% sodium hydroxide solution and 11,800 g of water. To this solution was added 2.280 g of Ultrasil (silica). The mixture was crystallized with stirring (about 200 rpm) at 145 ° C in a 5 gallon reactor. The crystallization time was 59 hours. The product was washed with water and dried at 120 ° C.

The X-ray diffraction pattern of the dried product crystals is shown in FIG. 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 VR:

Table VII

Product composition (uncalcined)

C 12.1 wt. N 1.98 wt. On the 640 ppm A1 ₂ O ₃ 5.0 wt. Sicbo 74.9 wt. SiO ₂ / Al ₂ O ₃ , mol. condition 25.4 % Adsorption, wt. cyclohexane 9.1 n-hexane 14.9 Water 16.8 specific surface area, m ² / g 479 Example 8 25 grams of the solid crystalline product of Example 7 is calcined for 5 hours in a stream of nitrogen at 538 ° C, followed by purification with 5% oxygen gas (N ₂ equilibration) for a further 16 hours at 538 ° C. Individual 3 g samples of calcined material are treated 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 filtered, washed with water to remove halides and dried. The compositions of the exchanged samples are tabulated below to demonstrate the exchange capacity of the present crystalline silicate for various ions. Ions exchanged Ion content, wt. TEA TPA La On the 0.095 0.089 0,063 N 0.30 0.38 0.03 C 2.89 3.63 la 1.04

Example 9

The La-exchanged sample of Example 8 was adjusted to a size of 1400-710 pm and then calcined in air 538 53C for 3 hours. The calcined material has an alpha value of 173.

Example 10

The calcined La-exchanged material of Example 9 was prepared under rough conditions at 649 ° C with 100% steam for 2 hours. The prepared sample had an alpha value of 22, indicating that the zeolite has very good stability under rough hydroprocessing conditions.

Example 11

This example illustrates the preparation of a zeolite of the present invention wherein X in the above general 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 was added 8.56 parts of Ultrasil silica and the mixture was carefully homogenized. 3.88 parts of hexamethyleneimine was added to the mixture.

The reaction mixture had the following composition in molar ratios:

SiO3 / B2O3 - 6.1

AlT / SiCb = 0.06

H 2 O / SiCl 2 = 19.0

K / SiO ₂ = 0.06

R / SiO 3 = 0.30 where R is hexamethylenimine.

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

water 11.7% by weight; cyclohexane 7.5 wt. n-hexane 11.4 wt.

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

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

N

On the

K boron

Al2O3

SiCh ash

SiCb / AhOj, mol. ratio

Si6) ₂ / (A1 + 6) 26) 3 mol. ratio

1.94 wt.

175 ppm

0.60 wt.

1.04 wt.

920 ppm

75.9 wt.

74.11% wt. 1406

25.8

Example 12

A portion of the calcined crystalline product of Example 11 was treated with NH <C1 and calcined again. The final crystalline product was tested in the alpha assay and found to have an alpha value of 1.

Example 13

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

S1O2 / B2O3 = 12.3

OH '/ SiO ₂ = 0.056

H2O / SiO2 = 18.6

K / S1O2 = 0.056

R / SiO 3 = 0.30 where R is hexamethylenimine.

The mixture was crystallized in a stainless steel reactor with stirring for 9 days at 300 ° C. The crystalline product was filtered off, washed with water and dried at room temperature

120 [deg.] C. The following sorption capacities of the calcined material (6 hours at 540 ° C) were measured: water 14.4 wt%; cyclohexane 4.6 wt%; % n-hexane 14.0 wt.

The specific surface area of the calcined crystalline material was 438 m ² / g.

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

% _______________________% wt.

N 2 ^ 48

Na0.06 boron0.83

AI2O30,50

S1O273,4

SiO2 / Al2O3, mol. pomer249

SiO ₂ / (Al + 6) 26) 3 mol. ratio 28.2

Example 14 A portion of the calcined crystalline product of Example 13 was tested in an alpha assay and was found to have an alpha value of 5.

Example 15

This example compares the performance of the zeolite of the invention with the zeolite HY in the catalytic alkylation of isobutane with 2-butene.

A. Preparation of zeolite according to the invention

The zeolite according to the invention was prepared by adding 30 4.50 parts of hexamethylenimine to a mixture containing

1.01 parts sodium aluminate, 1.00 parts 50% NaOH, 8.56 parts Ultrasil, VN3 and 44.29 parts deionized water. The reaction mixture is heated to 143 ° C and stirred in an autoclave at crystallization temperature. Upon reaching full crystallinity, the bulk of the hexamethylenimine from the autoclave was removed by controlled distillation and the zeolite crystals were separated from the remaining liquid by filtration, washed with deionized water, treated with ammonia, and treated with ammonia and dried. A portion of this zeolite was further treated with an aqueous ammonium nitrate solution by ion exchange. The material was then dried overnight at 120 ° C, calcined for 3 hours at 480 ° C in 3 v / v / min N ₂ , then treated with 50% v / v. air / 50% vol. N ₂ at 3 v / v / min, also at 480 ° C for 45 hours. The calcination is completed by increasing the temperature to 540 ° C at a rate of 3 ° C / min and finally introducing 100% air (3 v / v / min) and maintaining it at this temperature for 6 hours. The resulting zeolite has an alpha activity of 323, a specific surface area of 455 nr / g and contains 28 ppm 50 sodium.

B. Preparation of zeolite HY.

The HY catalyst was prepared by ion exchange by treating 60 g of Na Y with 1N NH 4 NO 3 for one hour at 55 room temperature. The catalyst was filtered off, washed and the exchange procedure repeated. The ammonium-treated zeolite Y was calcined in air at 540 ° C for three hours. The final material had an alpha activity of 61, a specific surface area of 721 of 60 m ² / g and contained 3.0 wt. sodium.

C. Alkylation of isobutane with 2-butene.

To compare the catalytic properties of the above zeolites, separate alkylation experiments were carried out in an autoclave batch process. The process started by placing 10 grams of catalyst in the reactor followed by closing the vessel. About 350 grams of isobutane / 2-butene was then introduced into the autoclave and the slurry was stirred during the next nitrogen pressure test. At the start of the reaction, the nitrogen pressure was less than 1135 kPa and the system was heated at a rate of 3 ° C / min. The final reaction conditions in each experiment were: temperature 120 ° C, autogenous pressure 5410 kPa and stirring speed 510 rpm.

The results of the alkylation experiments are shown in the table in m:

Table VIH Alkylation Conditions

catalyst invention invention HY HY 1C4 / 2-C4 mol. ratio 50 10 50 10 hours of experiment 76 49 28 46 Conversion (%) 95 73 99 85

VK Table (continued)

Product distribution

c ₅ 1.5 0.6 1.8 1.7 c _s 4.9 3.4 5.0 3.3 c ₇ 3.9 2.2 7.1 5.7 c ₈ 74.4 63.1 43.0 36.0 C9 + 15.4 30.8 43.2 53.3 Distribution of C ₈ products 2,2,4-trimethylolpropane 4.4 1.0 8.1 2.9 2,3,3-trimethylpropanol 43.1 31.8 18.3 8.4 2,3,4-trimethylpropanol 34.5 21.7 14.2 7.7 dimethylhexane 16.3 25.3 56.6 69.7 other product (s) 1.8 20.3 2.8 11.2 trimethylolpropane / 5.0 2.2 0.7 0.3 dimethylhexanes mol. ratio As can be seen from the above data, using an alkylation catalyst according to the invention k pod-

considerably higher trimethylpropane alkylate and significantly lower content of C9 + products compared to the use of zeolite HY catalyst under equivalent conversion conditions.

Example 16

This example compares the alkylation performance of an alkylation catalyst composition comprising the BF 1 -s promoted zeolite of the present invention and BF 1 -s promoted silica in the alkylation catalyst composition. The catalyst 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% NaOH, 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. After complete crystallinity was achieved, the bulk of the hexamethylenimine was removed from the autoclave by controlled distillation and the zeolite crystals were filtered from the remaining liquid, washed with deionized water and dried. The zeolite was activated by calcining N ₂ at 540 ° C for six hours, then treated by ion exchange with aqueous ammonium nitrate and calcined in air at 540 ° C for 6 hours.

In each experiment, 10 g of the catalyst and 300 ml of isobutane were introduced into the reactor. The reactor contents were cooled to the desired alkylation temperature with constant stirring at 1900 rpm, and BF3 was fed into the reactor at a flow rate of 3 wt. total hydrocarbon feedstock. The starting olefin was then fed continuously to the alkylation initiation reactor. The mole ratio of isobutane to total olefin was 10: 1, reaction temperatures were 0 or 20 ° C as shown below, and WHSV (relative to total olefin) was 1.3. The composition of the feedstock is shown in Table IX and the results of the alkylation operations on both catalyst compositions are shown in Table X below:

Table IX

Composition of paraffin-olefinic raw material

olefin propylene + butenes isobutane: olefin mol. ratio 12: 1 raw material composition % wt. propylene 3.30 isobutylene 1.24 1-butene 1.01 2-butene 2.14 isobutane 92,31 Table X BfJ-promoted with BF 3-promoted S1O2 zeolite alkylation temperature, ° C Cs + product, wt. 0 20 0 20 c ₅ 2.9 7.2 2.5 5.4 c ₆ 3.4 6.9 3.1 5.4 c ₇ 36.2 31.2 39.4 34.6 C ₈ 49.9 39.3 50.4 47.1 C9 + 7.6 15.4 4.6 7.4 TMP / DMH 2.0 1.4 2.2 1.6 Octanes, crude RON + O 93.9 90.7 95.5 91.5 MON + O 92.2 89.3 92.2 89.6

TMP = trimethylpentanes DMH = diemtylhexanes

Example 17

In principle, Example 19 is repeated, with the composition of the raw material shown in Table XI below:

Table XI: Composition of paraffin-olefinic raw material olefin propylene + butenes isobutane: olefin mol. ratio 5.7: 1 Raw material composition % wt. propylene 5.60 isobutylene 2.90 1-butene 2.00 2-butene 4.45 isobutane 84.40 n-butane 0.65 The results of the alkylation operations are shown in the following. The following table ΧΠ: Table ΧΠ: BfJ-promoted with BfJ-promoted with S1O2 zeolite alkylation temperature ° C 0 20 0 20 Cs + product, wt. c ₅ 2.5 4.0 3.0 3.7 c ₆ 2.6 3.5 3.3 3.4 C ₇ 28.6 22.9 22.5 20.4 c ₈ 56.8 56,0 64.7 63.9 C9 + 9.4 13.6 6.4 8.6 TMP / DMH 22 1.6 2.2 1.6 octanes, crude gasoline RON + O 93.2 86.8 93.5 88.4 MON + O 92.1 88.3 92.0 88.2

Example 18

Example 16 was essentially repeated, but the raw material had the composition shown in the following table ΧΠΙ:

Table ΧΙΠ

Composition of paraffinic-olefinic raw material

Olefin propylene + butenes isobutanolefin mole. 10: 1 ratio

Raw material composition% wt.

izobutylén5,73

1-butene 0.26

2-butene 2.98 isobutane 90.93 n-butane0.10

The results of the alkylation operations are shown in Table XIV below:

Table XIV

BF ₃ -promoted BF ₃ -promoted

S1O2 zeolite

alkylation temperature ’C Cs + product, wt. 0 20 0 20 c ₅ 4.9 7.0 4.3 6.4 c ₆ 4.5 4.7 3.4 4.5 C ₇ 4.1 5.3 3.4 4.9 c ₈ 77.9 71.9 83.5 77.7 C9 + 8.7 11.2 5.5 6.6 TMP / DMH 5.1 2.9 4.9 2.9 octanes, RON + O gasoline 95.5 92.8 95.9 93.1 MON + O 93.1 91.7 94.2 93.1

Example 19

In principle, Example 16 is repeated, with the raw material having the composition shown in Table XV: Table XV:

Composition of paraffin-olefinic raw material

olefin propylene + butenes isobutane: olefin mol. ratio 12.9: 1 Raw material composition % wt. propylene 3.22 isobutylene 2.74 1-butene 0.15 2-butene 1.24 isobutane 92.50 n-butane 0.15

The results of the alkylation operations are shown in Table XVI below:

Table XVI:

BF _{3 -} promoted BF _{3 -} promoted

SiOj zeolit

alkylation temperature ’C 0 20 0 20 % CI + product,% wt. C 6.5 10.1 3.3 4.9 C _ó 6.3 8.8 3.0 4.3 c ₇ 38.6 32.7 37.8 25.6 C ₈ 33.7 29.7 51.4 59.4 c '+ 14.8 18.7 4.6 5.9 TMP / DMH 4.1 2.1 5.4 3.0 octanes, RON + O gasoline 92.9 90.5 93.2 93.3 MON + O 90.7 89.5 92.8 91.7

Example 20

In principle, Example 16 is repeated, except that the raw material has the composition shown in Table XVD below:

Table XVII

Composition of paraffinic-olefinic raw material olefin butenes isobutane: olefin mol. 9.6: 1 ratio

Raw material composition% wt.

2-butene 9.4 isobutane 90.60

The results of the alkylation operation are shown in Table XVHI below:

Table ΧΠ:

BF _{3 -} promoted BF _{3 -} promoted

SiOj zeolit

alkylation temperature ’C 0 20 0 20 % Cw + product, wt. c ₅ 2.7 7.1 1.9 3.6 c ₆ 2.7 5.6 2.0 3.2 C ₇ 2.8 6.3 1.9 3.9 c ₈ 82.9 63.9 92.2 86.8 C _s + 8.9 17.2 2.0 2.6 TMP / DMH 5.9 2.8 6.7 3.4 octanes, RON + O gasoline 97.3 93.2 98.2 94.8 MON + O 94.0 91.9 95.6 93.3

Example 21-24

The procedure of Example 16 is repeated with the alkylation BF ₃ -promoted zeolite alkylation catalyst of the invention (Example 21) and the results are compared to those obtained with a similar catalyst to which water has been added (Examples 22 and 23) and BF ₃ / H 2 O catalyst. . The results are shown in Table XIX.

Table XIX Example 21 22 23 24 Catalyst BF ₃ / zeolite BFj / zeolite / BF ₃ / zeolite / l / l BF ₃

H2O H ₂ OH ₂ O (not solid) water content of fresh catalyst,

% wt. 0 10 10 temperature, ’C 10 10 20 20 pressure, kPa 1135 1135 1135 1135 BF ₃ ratio / wt. raw materials / 2.0 2.0 3.0 3.0 olefins in the raw material 2-butenes 2-butenes mixture mixture C ₃ , C ₄ C ₃ , C ₄ CI / olefins, ratio in raw material 10 10 10 10 olefin WHSV 1.35 1.35 2.24 2.24 olefin conv. (%) 57 100 100 100 yield 1.2 2.0 2.0 2.2

Total product distribution (% w / w)

c ₅ 1.4 2.5 5.4 8.2 c ₆ 2.6 2.6 5.4 7.9 c ₇ 1.4 2.8 34.6 33.1 c ₈ 22.9 85.9 47.1 41.6 CI + Total 71.7 6.2 7.4 9.1 RON + O 97.0 91.5 89.0 MON + O 93.0 89.6

It is apparent from Table XIX that under the same conditions, the BFj / zeolite / FLO system is more active than the H ₂ O-free catalyst (% olefin conversion 100 versus 57) and a higher quality alkylate is obtained (6.2 vs. 71.7 wt% C9 + ). Furthermore, the alkylate obtained on the BF 3 / zeolite / FhO catalyst was better (higher C 4 and lower C 9 +) than the product from the BF 3 / H 2 O system.

Claims (10)

A process for the alkylation of isoparaffin with an olefin to form an alkylate product comprising the reaction of an isoparail having from 4 to 8 carbon atoms and an olefin having from 2 to 12 carbon atoms, wherein the molar ratio of total isoparaffin to total olefin is from 0.5: 1 to 500: 1, at an alkylation reaction temperature of -40 to 400 ° C, in the presence of a catalyst, zeolite having an X-ray diffraction pattern comprising the following values: interplanar d-distance (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 where the intensities are indicated as follows: W = 0 to 20, M = 20 to 40, S = 40 to 60, VS = 60 to 100. Method according to claim 1, characterized The zeolite has an X-ray diffraction pattern with the following lines: Interplanar d-distance (A) relative intensity the Xο x 100 30.0 +2.2 W-M 22.1 +1.3 W 12.35 ± 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 wherein the intensities are indicated as above. The method of claim 1, characterized The zeolite has an X-ray diffraction pattern with the following lines: Interplanar d-distance (A) relative intensity the 100οχ 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 + 0.07 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 Interplanar d-distance (A) relative in- intensity to Xο x 100 2.82 + 0.05 W 2.78 + 0.05 W 2.68 + 0.05 W 2.59 + 0.05 W The method of claim 1, wherein the zeolite has the following X-ray diffraction pattern with the following lines: Interplanar d-distance (A) relative in- intensity to I / 100 100 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 6.86 + 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 5. A method according to claim 1 is characterized by zeolite other composition by interrelation voiced XjOy / n / YOJ where n is at least 10, X is a trivalent element and Y is a tetravalent element. A process according to claim 5, wherein X is aluminum and Y is silicon. 7. The process of claim 1 wherein the zeolite has an equilibrium adsorption capacity of greater than 4.5% by weight. % for cyclohexane vapor and greater than 10 wt. for n-hexane vapor. Process according to claim 1, characterized in that the isoparaffin is isobutane and the olefin is propylene and / or butanes. 9. The process of claim 1 wherein the molar ratio of total isoparaffin to total olefin is from 3: 1 to 50: 1. The process of claim 1, wherein the temperature of the alkylation reaction is from -25 to 15,400 ° C, the mass hourly space velocity of the olefin is from 0.01 to 100, and the pressure is up to 34,580 kPa. 11. The process of claim 1 wherein the zeolite is promoted with Lewis acid. 20 12. The process of claim 11 wherein the Lewis acid is BF3. The process of claim 4 wherein the temperature of the alkylation reaction is from -40 ° C to 250 ° C, the weight hourly space velocity ^{2 of the} olefin is from 0.01 to 100, and the pressure is up to 34580 kPa. 14. The process of claim 1 wherein the alkylation reaction is carried out in the presence of water.