CN1028019C - Isoparaffin-Olefin Alkylation Process - Google Patents

Abstract

This invention relates to the alkylation of isoparaffins with olefins to provide alkylates, the reaction being carried out in the presence of zeolites as catalysts.

Description

This invention relates to a process for the alkylation of olefins with isoparaffins.

As a result of the simplification by using tetraethyllead as a modified octane additive to gasoline, not only has the number of unleaded gasolines increased but the octane number in all grades of gasoline has also increased. Isoparaffin-olefin alkylation is a key process for producing highly branched paraffin octane enhancers for blending into gasoline.

Alkylation involves the addition of alkyl groups to organic molecules. Thus, isoparaffins can react with olefins to form higher molecular weight isoparaffins. Alkylation in industry often involves the reaction of C ₂ -C ₅ olefins with isobutane in the presence of an acid catalyst. In the past, the alkylation process involved the use of hydrofluoric acid or sulfuric acid as catalysts under controlled temperature conditions. Low temperatures are used in the sulfuric acid process to minimize unwanted olefin polymerization side reactions, and the acid strength is maintained at 88-94% by continuous addition of fresh acid and continuous removal of spent acid. The hydrofluoric acid method is less sensitive to temperature and the acid is easily recovered and purified. However, hydrofluoric acid and sulfuric acid alkylation methods have unique disadvantages, including environmental concerns, acid consumption, and handling of corrosive substances. As octane demand increases and environmental concerns increase, it is desirable to develop an alkylation process based on a solid catalyst system.

Crystalline metallosilicates or zeolites have been extensively studied for use in catalytic processes for the alkylation of isoparaffins. For example, U.S. Patent No. 3,251,902 describes the use of a fixed bed of ion-exchanged crystalline aluminosilicates for _C4 - _C20 branched alkanes and _C2 - _C12 alkenes in the liquid phase Reduce the number of effective acid sites during the alkylation reaction. The invention further discloses that the _C4 - _C20 branched alkanes should be allowed to substantially saturate the crystalline aluminosilicate prior to feeding the olefin into the alkylation reactor.

U.S. Patent No. 3,549,557 discloses the alkylation of isobutane with _C2 - _C3 olefins using specific crystalline aluminosilicate zeolite catalysts in fixed-bed, moving-bed or fluidized-bed systems , preferably injecting the olefins at different points in the reactor.

U.S. Patent No. 3,644,565 discloses the alkylation of paraffins and olefins in the presence of a catalyst comprising the presence of a Group VIII noble metal on a crystalline aluminosilicate zeolite pretreated with hydrogen to enhance selectivity. deal with.

U.S. Patent No. 3,655,813 discloses a process for the alkylation of C ₄ -C ₅ isoparaffins with C ₃ -C ₇ olefins using crystalline aluminosilicate zeolite catalysts, wherein in an alkylation reactor Halide ingredients. Isoparaffins and olefins are fed into the alkylation reactor at a certain concentration, and the catalyst is continuously regenerated outside the alkylation reactor.

U.S. Patent No. 3,893,942 discloses an isoparaffin alkylation process using a Group VIII metal zeolite as a catalyst. When the catalyst is partially deactivated, it is necessary to periodically hydrogenate the catalyst with hydrogen in the gas phase to activate the catalyst .

U.S. Patent No. 3,236,671 discloses the use of crystalline aluminosilicate zeolites having a molar ratio of silicon to aluminum of about 3 in an alkylation reaction. This patent also discloses the use of various exchanged metals and/or impregnated in this in zeolites.

U.S. Patent No. 3,624,173 discloses the use of gadolinium-containing zeolite catalysts in isoparaffin alkylation reactions.

U.S. Patent No. 3,738,977 discloses the alkylation of paraffins with ethylene over a zeolite catalyst having a Group VIII metal component which has been pretreated with hydrogen.

U.S. Patent No. 3,865,894 discloses the use of substantially anhydrous acidic zeolites such as acidic zeolite Y (zeolite HY) and halide excipients to combine C ₄ -C ₆ isoparaffins with C ₃ -C ₉ monoalkenes. Basicization.

U.S. Patent No. 3,917,738 discloses the alkylation of isoparaffins with olefins using solid particulate catalysts capable of adsorbing olefins. The isoparaffin is mixed with the olefin to form a reactant stream, which contacts the catalyst particles at the inlet end of the adsorption zone, and the reactant is passed co-currently with the catalyst so that a controlled amount of the reactant and catalyst mixture is introduced into the alkylation zone. Olefins can be adsorbed on the catalyst. This controlled amount of olefin adsorption is said to prevent polymerization of olefins during alkylation.

U.S. Patent No. 4,377,721 discloses isoparaffin-olefin alkylation using a catalyst of ZSM-20, preferably HZSM-20 or rare earth cation exchange ZSM-20.

U.S. Patent No. 4,384,161 discloses a method for producing alkylate by alkylation of isoparaffins and olefins, which adopts a large-pore zeolite capable of adsorbing 2,2,4-trimethylpentane, such as ZSM-4 , ZSM-20, ZSM-3, ZSM-18, zeolite Beta, faujasite, mordenite, zeolite Y and their rare earth metal-containing forms, and Lewis acid as catalyst. According to the report of this patent, the use of large pore zeolites in combination with Lewis acids can greatly increase the activity and selectivity of zeolites to allow efficient alkylation reactions with high olefin space velocities and low isoparaffin/olefin ratios.

The present invention provides a process for the alkylation of isoparaffins with olefins, which comprises reacting isoparaffins with olefins in the presence of a catalyst which is a synthetic porous crystalline zeolite having values including values substantially as shown in Table 1 X-ray diffraction pattern.

One measure of the selectivity of an alkylation catalyst is the G ⁺ ₉ yield. This component is often due to the oligomerization of olefins in the feed, resulting in a decrease in the yield of alkylation, reducing the quality of the alkylate and possibly forming an acidic syrupy component. The use of zeolite alkylation catalysts in the process of the present invention reduces the G ⁺ ₉ yield. Such known zeolite alkylation catalysts are, for example, HY disclosed in the aforementioned U.S. Patent No. 3,865,894.

The alkylate produced by the process of the present invention is of high quality on a research octane and motor octane basis and is particularly suitable for blending into gasoline pools.

The synthesized porous crystalline zeolites used in the alkylation process of the present invention have, in their calcined form, an X-ray diffraction pattern comprising the lines listed in Table I below:

Table I

d-planar distance (A) relative intensity, I/I ₀ ×100

12.36±0.4 W-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

Table II below lists more specific spectral lines

Table II

d-planar distance (A) relative intensity, I/I ₀ ×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

Table III below also lists more specific spectral lines

Table III

d-plane distance (A) relative strength, I/Io×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±0.08W

4.41±0.08 W-M

4.25±0.08W

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±0.05W

2.68±0.05W

2.59±0.05W

More specifically, the calcined crystalline material including the X-ray diffraction pattern of the spectral lines is listed in Table IV below.

Table IV

d-planar distance (A) relative intensity, I/I ₀ ×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 W-VS

6.00±0.10 W-M

5.54±0.10 W-M

4.92±0.09 W

4.64±0.08W

4.41±0.08 W-M

4.25±0.08W

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±0.05W

2.68±0.05W

2.59±0.05W

These values are determined using standard techniques. The radiation is copper K-alpha doublet and a diffractometer equipped with a scintillation counter and a computer is used. An algorithm on a computer coupled to the diffractometer was used to determine peak height, 1, and position as a function of 20, where 0 is the Bragg angle. From this one can determine the relative intensity 100I/ _I0 , where _I0 is the intensity of the most intense line or peak corresponding to the recorded line, and the d-plane spacing in angstroms (A). In Tables I-IV the relative strength is represented by symbols W-weak, M-medium, S-strong, VS-very strong. Regarding strength, it is often defined as follows:

W=0-20

M=20-40

S=40-60

VS=60-100

It should be understood that these X-ray diffraction patterns are characteristic of all classes of zeolites. The sodium form and other cationic forms are essentially the same spectrum with a slight shift in interplanar spacing and a change in relative intensity. according to Some other minor variations of Y to X, such as the molar ratio of silicon to aluminum and the degree of heat treatment, may occur.

Zeolites useful in the present invention typically have compositions comprising the following molar relationships:

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 is at least 10, usually from 10-150, preferably 10-60, most preferably 20-40. In the synthesized form, the zeolite has the following structure on an anhydrous basis and in terms of moles of oxide per mole of _YO2 :

(0.005-0.1) Na ₂ O : (1-4) R : X ₂ O ₃ : nYO ₂

where R is an organic component. Due to the presence of Na and R components during crystallization, which are related to zeolite, they can be easily removed by post-crystallization methods, which will be specifically described below.

The zeolites used here are thermally stable and have a large surface area (greater than 400 ^m² /gs by BET [Bruenaner, Emmet and Teller] test). In addition, the equilibrium adsorption value of zeolite is generally greater than 4.5% (weight), usually greater than 7% (weight) for cyclohexane vapor, greater than 10% (weight) for n-hexane vapor, and preferably greater than 10% (weight) for water vapor , preferably greater than 10% (by weight) for water vapor. As shown in the above formula, the zeolite synthesized in this way therefore has almost no Na cations and thus has acidic catalytic activity. It can therefore be used here as an alkylation catalyst without first undergoing a conversion step. However, by extension, the original sodium cations of such synthetic materials can be replaced, at least in part, by ion exchange with other cations according to prior art known techniques. Preferred substituting cations include metal ions, hydrogen ions, hydrogen precursors, eg, ammonium ions, hydrogen ions, hydrogen precursors, eg, ammonium ions, and mixtures thereof. The preferred cations among these are those that confer catalytic activity in alkylation. These include hydrogen, rare earth metals, and metals of Groups IIA, IIIA, IVA, IB, IIB, IIIB, IVB, and VIII of the Periodic Table of Elements.

Before 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 catalysts used here can also be used in close combination with hydrogenation components such as tungsten, vanadium, molybdenum, rhenium, nickel cobalt, chromium, manganese or noble metals such as platinum or palladium, which can hydrogenate - Dehydrogenation. Such components may be chemically and/or physically bound to the zeolite and/or the matrix which optionally forms the zeolite. Thus, for example, the hydrogenation component can be introduced into the catalyst composition by co-crystallization, switching the composition in structure to a Group IIIA element, such as aluminum, by impregnating it or by intimate physical admixture. Such components may be impregnated in or on the zeolite, for example, in the case of platinum, by treating the zeolite with a solution containing platinum metal ions. Thus, suitable platinum compounds for this purpose include chloroplatinates, platinous chlorides, and various compounds containing platinum amine complexes.

The zeolite should be at least partially dehydrated prior to use as an alkylation catalyst in the inventive process. This can be accomplished by heating the crystallization at 200°C to 595°C for 30 minutes to 48 hours in an atmosphere such as air, nitrogen, etc., and at atmospheric, subatmospheric or superatmospheric pressure. Dehydration can also be carried out at room temperature, and it is only necessary to place the crystal material in vacuum for a long time to achieve the appropriate degree of dehydration.

The zeolites used in the present invention can also be prepared from reaction mixtures containing an alkali metal or alkaline earth metal (M), for example, sodium or potassium, their cations, for example aluminum oxides of trivalent elements X, for example silicon Oxides of tetravalent elements (Y), organic (R) directing agents, hexamethyleneimine, and water, in terms of oxide molar ratios. The components of the reaction mixture are within the following ranges:

Reagents Useful Preferred

YO ₂ /X ₂ O ₃ 10-60 10-40

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 synthesis method, the YO ₂ reagent contains a substantial amount of solid YO ₂ , for example containing at least 30% by weight solid YO ₂ , wherein YO ₂ is silica, and using a solid YO 2 containing at least 30% by weight Silica raw materials for silicon, for example, Ultrasil (a precipitate, spray-dried silica containing 90% by weight silica) or Hisil (87% by weight silica, 6% by weight ), free H ₂ O and 4.5% by weight hydrated H ₂ O bound precipitated hydrated SiO ₂ with a particle size of 0.02 microns) are the preferred crystal structures in the above mixture. If another silica raw material is used, for example, Q-Brand (sodium silicate comprising 28.8% by weight SiO ₂ , 8.9% by weight Na ₂ O and 62.3% by weight water), crystallization is almost impossible. To the desired zeolites as well as other crystal structure impure phases such as ZSM-12 can be produced. Thus, it is preferred that the _YO₂ , such as silica, be used as a starting material containing at least 30% by weight solid _YO₂ such as _SiO₂ , and most preferably at least 40% by weight solid _YO₂ such as silica.

Crystallization of the desired zeolite is carried out under static or stirred conditions in a suitable reaction vessel such as a polypropylene bottle or an autoclave lined with Teflon or stainless steel. Crystallization is usually carried out at 80-225°C for 25 hours to 60 days. Thereafter, the crystals are separated from the liquid and recovered.

Crystallization is promoted by the presence of at least 0.01%, preferably 0.1%, most preferably 1% seed crystals, calculated on the total weight of crystals produced.

Prior to use in the process of the invention, the zeolite is preferably combined with other materials, namely a binder, which can withstand the temperatures and other conditions employed in the isoparaffin alkylation process of the invention. Suitable binder materials include active and inactive materials as well as synthetic or naturally occurring zeolites and inorganic materials such as clays, silica and/or metal oxides such as alumina. The latter can be naturally occurring or gelatinous precipitates or mixtures comprising silica and metal oxides. The conversion and/or selectivity of the catalyst can be altered by using a binder material in combination with the zeolite, ie, the binder is incorporated at the time of synthesis, while the binder itself is catalytically active. Suitable inactive materials may be used as diluents to control the amount of conversion so that isoparaffin alkylation products can be obtained economically and to control product formation without other means of controlling the reaction rate. These materials can be incorporated into natural clays such as bentonite and kaolin to improve the crush strength of the zeolite under commercial isoparaffin alkylation operating conditions. Since good crushing strength prevents or delays the catalyst from becoming a powdery substance, it makes an excellent contribution to commercial application.

Naturally occurring clays with which the zeolite can be combined include the montmorillonite and kaolinite families which include subbentonites, kaolinites known as Dixie, McNamee, Georgia and Florida clays or whose major inorganic components are halloysite, kaolin, Other substances such as diokite, nacrite, and creeping soil. These clays can be used in their raw state, or first after being roasted, acid-treated or chemically modified. Useful binders in combination with zeolites also include inorganic oxides, notably alumina.

In addition to the aforementioned binder materials, the zeolite can also be combined with materials such as silica thorium monoxide, silica-beryllia, silica-titania and silica-alumina-thoria, silica- The inorganic oxides of the ternary compositions of alumina-zirconia, silica-alumina-magnesia and silica-magnesia-zirconia are substantially bonded. It is advantageous that at least part of the aforementioned matrix material is in gel form to facilitate extrusion of the bound catalyst component.

The relative properties of the zeolite and the inorganic oxide matrix can vary considerably with the zeolite content ranging from 1 to 9.5% by weight, and more commonly, when the composition is prepared in bead form, the zeolite content ranges from 2-80% (by weight).

The stability of the alkylation catalyst of the present invention is increased by steam, contacting the zeolite with, for example, 5-100% steam at a temperature of at least 300° C. (e.g., 300-650° C.) at a pressure of 101-2,500 KPa for at least one hour (e.g., 1 -200 hours) can easily carry out the process. In a more specific example, the catalyst can be prepared by steaming 75-100% steam at 315-500°C for 2-25 hours at atmospheric pressure.

The alkylation catalyst used in the process of the present invention may include a Lewis acid promoter in addition to the zeolites described above. A Lewis acid is generally considered to be a molecule that binds to another molecule or ion by forming a covalent chemical bond that carries two electrons from the second molecule or ion, that is, a Lewis acid is an electron acceptor. Examples of Lewis acids include boron trifluoride (BF ₃ ), antimony pentafluoride (SbF ₅ ), and aluminum trichloride (AlCl ₃ ). Other Lewis acids contemplated for use in the present invention include those disclosed in "Friedel-Crafts and Related Reagents," Interscien Publishers, Chapters III and IV (1963). A preferred Lewis acid for use in the alkylation process of this invention is _BF3 . In the case of _BF3 , the promoter is preferably present in the alkylation zone in an amount required to saturate the zeolite catalyst component, taking into account not only the zeolite itself but also other materials such as viscose which may be incorporated into the zeolite. Mixture or base material.

The alkylation process herein operates at temperatures within a wide range, for example -40 to 400°C, with lower temperatures being used when Lewis acid promoters are present. The temperature of the Lewis acid accelerator thus used is usually -40-250°C, preferably -20-100°C. When no Lewis acid accelerator is used, the temperature is usually from -25 to 400°C, preferably from 75 to 200°C. A practical upper operating temperature is often set at a temperature at which undesired side reactions are avoided.

The pressure used in the process can vary widely, for example, from subatmospheric to 34580 KPa (5000 psig), preferably from 100-7000 KPa (1 atm to 1000 psig).

The amount of zeolite used in the present alkylation process varies with the corresponding bulk limit. Generally speaking, the amount of zeolite used to measure the olefin weight hourly space velocity may be in the range of 0.01-100, preferably in the range of 0.1-20.

The isoparaffin reactants used in the present alkylation process often have up to 20 carbon atoms, preferably 4-8 carbon atoms, such as isobutane, 3-methylhexane, 2-methylbutane alkanes, 2,3-dimethylbutane and 2,4-dimethylhexane.

The olefinic reactants used herein usually contain 2 to 12 carbon atoms. Representative examples are ethylene, propylene, butene-1, butene-2, isobutene-pentene, hexene, heptene and octene. Most preferred are _C3 and _C4 olefins and mixtures thereof.

Generally speaking, the ratio of total isoparaffins to total olefin alkylated groups in the mixed hydrocarbon feed may be from 0.5:1 to 500:1, preferably from 3:1 to 50:1. The isoparaffin and/or olefin reagents may be in the gaseous or liquid phase and may be pure, i.e. free from an intentionally mixed mixture upon dilution with other substances, or after the reagents have been allowed to dissolve with the aid of a carrier gas or diluent such as nitrogen. in contact with the catalyst composition.

The reactants may be introduced into the alkylation reaction zone along with one or more other materials which enhance the overall conversion operation. Thus, for example, relatively small amounts of hydrogen and or hydrogen acceptors may be present in the reaction zone to inhibit catalyst aging. Water and/or materials capable of providing water under the alkylation conditions, such as alcohols, can also be introduced into the reaction zone for this purpose. Oxygen and/or materials that tend to inhibit olefin oligomerization can also be present.

When water is introduced into the alkylation reactor, it is conveniently refed at 0.1 ppmw to 1% by weight, preferably 0.1 ppmw to 500 ppmw, based on the total hydrocarbon feed rate. Alternatively, water can be introduced into the zeolite catalyst first, and the suitable amount is 0.5-25% by weight of the catalyst, preferably 1-10%.

The alkylation process of the present invention can be carried out in a batchwise, semi-continuous or continuous manner using a fixed or moving bed of the zeolite catalyst component. A preferred example is the use of a catalyst zone in which the hydrocarbon feed is passed cocurrently or countercurrently through a moving bed of zeolite catalyst. After use, the latter is directed to a regeneration zone where the coke is debranched, e.g. by combustion at high temperature in an oxygen-containing atmosphere (e.g. air) or extracted with a solvent, after which the regenerated catalyst is recycled Enter the conversion zone for further contact with organic reactants.

The invention will be described more particularly with reference to the accompanying drawings and examples, in which:

Figures 1-5 are the X-ray diffraction patterns produced by the calcined crystalline material of Examples 1, 3, 4, 5, and 7, in succession.

In the examples, in order to compare the adsorption data established for the adsorption capacity of water, cyclohexane and/or n-hexane, the measured equilibrium adsorption values are as follows:

Put the melted adsorbent in contact with the adsorbate vapor with the required purity in the adsorption chamber, pump the gas to less than 1mmHg, and then mix it with 1.6Kpa (12Forr) water vapor or 5.3Kpa (40Torr) n-hexane vapor or 5.3Kpa ( 40 Torr) cyclohexane vapor contact, the pressure should be lower than the gas-liquid equilibrium pressure of each adsorbate at 90 °C. The pressure is kept constant (within about ± 0.5 mm Hg) by adding adsorbate vapor and controlled with a pressure regulator during the adsorption period, which does not exceed about 8 hours. As the adsorbate is adsorbed by the crystalline zeolite, the pressure drop causes the valve of the pressurizer to open, thus allowing more adsorbate vapor to enter the chamber for storage to the above controlled pressure. Adsorption is complete when the change in pressure is insufficient to activate the pressurizer. Calculate the increased weight as the adsorption capacity of roasted adsorbate g/100g sample. The equilibrium adsorption value of the zeolite used here is always greater than 10% (weight) for water vapor, generally greater than 4.5% (weight) for cyclohexane vapor, usually greater than 7% (weight), and greater than 10% (weight) for n-hexane vapor ).

When examining the alpha value, it has been noted that the alpha value is an approximate indicator of the catalytic cracking activity of the catalyst compared to a standard catalyst, and the alpha value gives the relative rate constant (n-hexane conversion rate per unit volume of catalyst per unit time). It is based on the activity of a highly active silica-alumina cracking catalyst with an alpha value of 1 (rate constant -0.016 sec ^-1 ). The alpha test used here is described in J. Calalysis, 61, pp. 390-396 (1980). It has been noted that the characteristic rate constants associated with many acid-catalyzed reactions are proportional to the value of α for a particular crystalline silicate catalyst, even the rates of toluene disproportionation, xylene isomerization, olefin conversion, and methanol conversion (see "The Active Side of Acidie Aluminesilicate Cala lysts" Nature Vol. 309, No. 5969, Nos. 589-591 June 14, 1984).

Example 1

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% NaOH solution and 103.13 parts of H ₂ O. 4.50 parts of hexamethyleneimine were added thereto. 8.55 parts of Ultrasil were added to the resulting solution. Ultrasil is a precipitated, spray-dried silica (approximately 90% SiO ₂ ).

The reaction mixture had the composition in the following molar ratios.

SiO ₂ /Al ₂ O ₃ -30.0

OH ^- /SiO ₂ -0.18

H ₂ O/SiO ₂ -44.9

Na/SiO ₂ -0.18

R/SiO ₂ -0.35

wherein R is hexamethyleneimine.

The mixture was crystallized in a stainless steel reactor at 150° C. for 7 days with stirring. The crystalline product was filtered. Wash with water and dry at 120°C. Calcined at 538°C for 20 hours, the X-ray diffraction pattern contained the major lines listed in Table V. Figure 1 shows the X-ray diffraction pattern of the calcined product. The measured sorption capacity of the calcined material is:

_H2O 15.2% (weight)

Cyclohexane 14.6% (weight)

n-Hexane 16.7% (weight)

The measured surface area of the zeolite was 494 m ² /g.

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

Component wt.%

SiO ₂ 66.9

Al ₂ O ₃ 5.40

Na 0.03

N 2.27

Ash 76.3

SiO ₂ /Al ₂ O ₃ , molar ratio 21.1

(See Table V at the end of the text)

Example 2

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

Example 3-5

Three separate synthesis reaction mixtures were prepared using the compositions listed in Table VI. A mixture was prepared with sodium aluminate, sodium hydroxide, Ultrasil, hexamethyleneimine (R) and water. The mixture was successively incubated in a stainless steel autoclave at 150°C, 143°C and 150°C under autogenous pressure for 7 days, 8 days and 6 days, respectively. Unreacted components were separated from the solid by filtration, washed with water, and dried at 120°C. The product crystals were subjected to X-ray diffraction analysis, sorption analysis, surface area analysis, and chemical analysis. The results of sorption, surface area and chemical analysis are listed in Table VI, and the X-ray diffraction patterns are shown in Figures 2, 3 and 4, respectively. The sorption and surface area of the calcined products were measured.

Example 6

Quantitative quantities of the calcined (538C for 3 hours), crystalline silicon ester salt products of Examples 3, 4 and 5 were tested for alpha and had alpha values of 227, 180 and 187, respectively.

Example 7

In order to confirm the mass preparation of the desired zeolite, 1200 g of hexamethyleneimine was added to a solution of 268 g of sodium aluminate, 267 g of 50% (NaOH solution and 11,800 g of _H2O . To the combined solution 2.280 grams of Ultrasil silica was added. The mixture was stirred in a 5 gallon reactor at 145°C (about 200 rpm to crystallize, the crystallization time was 59 hours. The product was washed with water and dried at 120°C.

Fig. 5 shows the X-ray diffraction pattern of the crystals of the dried product, which confirms that the product is the crystalline material of the present invention. Table VII lists the results of product chemical composition, surface area and adsorption analysis;

Table VII

Product composition (unroasted)

C 12.1 (weight)%

N 1.98 (weight)%

Na 640ppm

Al ₂ O ₃ 5.0 (weight)%

SiO ₂ 74.9 (weight)%

SiO ₂ /Al ₂ O ₃ , molar ratio 25.4

Adsorption, % (weight)

Cyclohexane 9.1

n-Hexane 14.9

H ₂ O 16.8

Surface area, m ² /g 479

Example 8

25 g of the solid crystalline product obtained in Example 7 were calcined at 538°C for 5 hours in a flowing nitrogen atmosphere and then purged with 5% oxygen (balance _N₂ ) at 538°C for 16 hours.

Each 3 gram sample of the calcined material was ion exchanged separately with 100 mL of 0.1 NTEABr, TPABr and _LaCl3 solutions. Each exchange was performed at room temperature for 24 hours and repeated three times. Exchanged samples were collected by filtration, washed with water free of halides and dried. The composition of the exchanged samples is tabulated below, which shows the exchange capacity of the crystalline silicate for different ions.

ion exchange

Ionic composition % (weight) TEA TPA La

Na 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 from Example 8 was 14-25 mesh in size and calcined in air at 538°C for 3 hours. The calcined material had a value of 173.

Example 10

A calcined sample of La-exchange material from Example 9 was steamed vigorously at 649°C in 100% steam for 2 hours. The alpha value of the steamed sample was 22, which indicates the excellent stability of the zeolite under severe hydrothermal treatment.

Example 11

This example illustrates the preparation of zeolites wherein X in the above general formula is boron. 2.59 parts of boric acid were added to a solution containing 1 part of 45% KOH solution and 42.96 parts of _H2O . Add 8.56 parts of Ultrasil silica and mix the mixture well. To the mixture was added 3.88 parts by weight of hexamethyleneimine.

The reaction mixture had the following composition in molar ratio.

SiO ₂ /B ₂ O ₃ -6.1

OH ^- /SiO ₂ -0.06

H ₂ O/SiO ₂ -19.0

K/SiO ₂ -0.06

R/SiO ₂ -0.30

wherein R is hexamethyleneimine.

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

_H2O 11.7% (weight)

Cyclohexane 7.5% (weight)

n-Hexane 11.4% (weight)

The surface area (BET) of the calcined crystalline material was determined to be 405 ^m² /g.

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

N 1.94% (weight)

Na 175ppm

K 0.60% (weight)

Boron 1.04% (weight)

Al ₂ O ₃ 920ppm

SiO ₂ 75.9% (weight)

Ash 74.11% (weight)

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. The final crystalline product was subjected to an alpha test and found to have an alpha value of 1.

Example 13

This example illustrates an alternative preparation of zeolites in which X is boron in the general formula above. 2.23 parts of boric acid were added to a solution of 1 part of 50% NaOH solution and 73.89 parts of _H2O . To this solution was added 15.29 parts of Hi Sil silica. Then 6.69 parts of hexamethyleneimine were added. The reaction mixture had the following composition in molar ratio.

SiO 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/SiO ₂ -0.30

wherein R is hexamethyleneimine.

The mixture was placed in a stainless steel reactor at 300°C and stirred for 9 days for crystallization. The crystalline product was filtered, washed with water and dried at 120°C. The sorption capacity of the calcined material (calcined at 540°C for 6 hours) was measured.

H ₂ O 14.4% (weight)

Cyclohexane 4.6% (weight)

n-Hexane 14.0% (weight)

The surface area of the calcined crystalline material was measured to be 438 m ² /g.

The chemical composition of the unfired material was determined to be as follows:

Component Weight %

N 2.48

Na 0.06

Boron 0.83

Al ₂ O ₃ 0.50

SiO ₂ 73.4

SiO ₂ /Al ₂ O ₃ , molar ratio 249

SiO ₂ /(Al+B) ₂ O ₃ , molar ratio 28.2

Example 14

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

Example 15

This example compares the catalytic performance of the zeolite according to the invention with that of zeolite HY for use in the alkylation of isobutane with 2-butene.

A. Preparation of Zeolites of the Invention.

The zeolites of this invention were produced by adding 4.50 parts of hexamethyleneimine to a mixture containing 1.01 parts of sodium aluminate, 1.00 parts of 50% (NaOH, 8.56 parts of Ultrasil, _VN3 and 44.29 parts of deionized _H2O . The reaction mixture was heated to 143°C (290°F) and stirred in the autoclave at this temperature for crystallization. After all crystallization had occurred, most of the hexamethyleneimine was removed from the autoclave by controlled distillation and the zeolite was removed by filtration. The crystals were separated from the raffinate, washed with deionized water, ion-exchanged with ammonium and dried. A portion of the zeolite was then exchanged with aqueous ammonium nitrate. The material was then dried overnight at 120°C (250°F) and at 480°C (900°F) and 3v/v/minN ₂ for 3 hours, then use 50% (volume) air/50% (volume) N ₂ at 3v/v/min) at 480°C (900°F) under treatment for 1 hour. The temperature was raised at a rate of 3°C (5F)/minute to 540°C (1000°F) to complete the firing, and finally switched to 100% air (3 v/v/min) and maintained at this temperature for 6 hours. The resulting zeolite had an alpha activity of 323. It has a surface area of 455 m ² /g and contains 28 ppm sodium.

B. Preparation of Zeolite HY

_The HY catalyst was prepared by exchanging 60 g of NaY with _1NNH4NO4 at room temperature for 1 h. The catalyst is filtered, washed, and the exchange process repeated. The ammonium salt-exchanged Y zeolite was calcined at 540°C (1000°F) in air for 3 hours. The final material had an alpha activity of 61, a surface area of 721 ^m² /g, and contained 3.0% by weight sodium.

C. Alkylation of isobutane with 2-butene

In order to evaluate the boiling characteristics of the above-mentioned zeolites, the alkylation reaction was carried out separately in large batches in an autoclave. The initial steps involved adding 10 grams of catalyst to the reactor and then sealing the vessel. About 350 grams of isobutane/2-butene were then introduced into the autoclave and the slurry was stirred during the continuous nitrogen pressure test. To initiate the reaction, the nitrogen pressure was kept below 1135 kPa (150 psig) and the system was heated at a rate of 3°C (5°F) per minute. The final reaction conditions in each reaction were 120°C (250°F), an autogenous pressure of 3410 KPa or (480 psig), and a stirring rate of 500 rpm.

Table VIII below sets forth the results of the alkylation reaction. (See Table VIII at the end of the article)

As shown by these data, the use of the alkylation catalyst of the present invention actually yields more trimethylpropane alkylate than the use of the zeolite HY catalyst under the same conversion conditions, and the less than G ⁺ ₉ product is significantly lower. few.

Example 16

This example compares the alkylation performance of a _BF3 -promoted zeolite alkylation catalyst composition of the present invention with a _BF3 -promoted silica alkylation catalyst composition. The catalyst of this invention was prepared by adding 4.49 parts by weight of hexamethyleneimine to a mixture containing 1.00 parts of sodium aluminate, 1.00 parts of 50% NaOH, 8.54 parts of Utrasil VN ₃ and 44.19 parts of deionized water. The reaction mixture was heated to 143°C (290°F) and stirred at this temperature in the autoclave for crystallization. After complete crystallization was achieved, most of the hexamethyleneimine was removed from the autoclave by controlled distillation and removed from the autoclave by filtration. Zeolite crystals were separated from the raffinate, washed with deionized water and dried. The zeolite was activated by calcination at 1000° _FN2 for 6 hours, followed by exchange with aqueous ammonium nitrate solution and calcination at 1000°F in air for 6 hours.

In a separate reaction, 10 grams of each of the foregoing catalyst compositions and 300 milliliters of isobutane were charged to the reactor, and the reactor contents were then cooled to the desired alkylation temperature while stirring continuously at 1900 rpm, _BF3 gas was introduced into the reactor at a flow rate of 3% by weight (based on the total hydrocarbon feed). The olefin feed is then continuously introduced into the reactor to initiate the alkylation reaction. The molar ratio of isobutane to total olefins was 10:1, the reaction temperature was 0 or 20°C as indicated below, and the weight hourly space velocity (WHSV) (on a total olefin basis) was 1.3. The compositions of the feeds are listed in Table IX and the results of the alkylation reaction for the two catalyst compositions are listed in Table X:

Table IX

Composition of paraffin-olefin feed

Olefin Propylene + Butene

Isobutane: olefin molar ratio 12:1

Feed component weight%

Propylene 3.30

Isobutylene 1.24

1-butene 1.01

2-butene 2.14

Isobutylene 92.31

(See Table X at the end of the text)

Example 17

Example 16 was essentially repeated, but with the feed composition shown in Table XI below

Table Ⅺ

Composition of paraffin-olefin feed

Olefin Propylene + Butene

Isobutane: olefin molar ratio 5.7:1

Feed component weight%

Propylene 5.60

Isobutylene 2.90

1-butene 2.00

2-butene 4.45

Isobutylene 84.40

n-butene 0.65

The results of the alkylation reaction are shown in Table VII below:

(See Table VII at the end of the text)

Example 18

Example 16 was essentially repeated but with the feed composition shown in Table XIII below:

Table XIII

Feed paraffin-olefin composition

Olefin Propylene + Butene

Isobutane: olefin molar ratio 10:1

Feed component weight %

Isobutylene 5.73

1-butene 0.26

2-butene 2.98

Isobutylene 90.93

n-butene 0.10

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

Example 19

Example 16 was essentially repeated, but with the feed composition shown in Table XV below:

Table XV

Paraffin-Olefin Feed Composition

Olefin Propylene + Butene

Isobutane: olefin molar ratio 12.9:1

Feed component weight %

Propylene 3.22

Isobutylene 2.74

1-butene 0.15

2-butene 1.24

Isobutylene 92.50

n-butene 0.15

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

(See Table XVI at the end of the text)

Example 20

Example 16 was essentially repeated, but with the feed composition shown in Table XVII below:

Table XVII

Paraffin-Olefin Feed Composition

Olefin Butene

Isobutane: olefin molar ratio 9.6:1

Feed component weight%

2-butene 9.4

Isobutylene 90.60

The results of the alkylation reaction are shown in Table XVIII below:

(See Table XVIII at the end of the article)

Examples 21-24

The procedure of Example 16 (Example 21) was repeated using the _BF₃ -promoted zeolite alkylation catalyst of the present invention and the results compared with those obtained using a similar water-added catalyst. (Examples 22 and 23), and compared with the BF ₃ /H ₂ O catalyst system. The results are summarized in Table XIX.

(See Table XIX at the end of the text)

As can be seen from Table XIX, under the above process conditions, the BF ₃ /zeolite/H ₂ O system was more active than the anhydrous catalyst (100vs. 57% (olefin conversion) and produced a larger amount of alkylated products (6.2vs. .71.7% (by weight) C ¹ ₉ ). In addition, the alkylate produced by the BF ₃ /zeolite/H ₂ O catalyst is better than the product produced by the BF ₃ /H ₃ O system (the product is greater than C ₈ and lower than G ⁺ ₉ ) .

Table V

20-angle d-plane spacing (A) I/I ₀

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

14.43 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

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

Table VI

Example

Synthetic mixture, molar ratio 3 4 5

SiO ₂ /Al ₂ O ₃ 30.0 30.0 30.0

OH ^- /SiO ₂ 0.18 0.18 0.18

H ₂ O/SiO ₂ 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 % (weight)

SiO ₂ 64.3 68.5 74.5

Al ₂ O ₃ 4.85 5.58 4.87

Na 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 , molar ratio 22.5 20.9 26.0

Adsorption, % (weight)

H ₂ O 14.9 13.6 14.6

Cyclohexane 12.5 12.2 13.6

n-Hexane 14.6 16.2 19.0

Surface area m ² /g 481 492 487

Table VII

BF ₃ -promoted SiO ₂ BF ₃ -promoted zeolite

Alkylation temperature, ℃ 0 20 0 20

C ₅ + products, % (weight)

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

C ⁺ ₉ 9.4 13.6 6.4 8.6

TMP/DMH 2.2 1.6 2.2 1.6

octane, raw gasoline

RON+O 93.2 86.8 93.5 88.4

MON+O 92.1 88.3 92.0 88.2

Table Ⅷ

Alkylation conditions

Catalyst Invention Invention HY HY

iC ₄ /2-C ⁼ ₄ molar ratio 50 10 50 10

Hours of steaming 76 49 28 46

Conversion (%) 95 73 99 85

Product distribution

C ₅ 1.5 0.6 1.8 1.7

C ₆ 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

C ⁺ ₉ 15.4 30.8 43.2 53.3

C ₈ product distribution

2,2,4-Trimethylpentanol 4.4 1.0 8.1 2.9

2,3,3-Trimethylpentanol 43.1 31.8 18.3 8.4

2,3,4-Trimethylpentanol 34.5 21.7 14.2 7.7

Dimethylhexane 16.3 25.3 56.6 69.7

Other products 1.8 20.3 2.8 11.2

Trimethylpentane/dimethyl 5.0 2.2 0.7 0.3

Hexane molar ratio

Table X

BF ₃ -promoted SiO ₂ BF ₃ -promoted zeolite

Alkylation temperature, °C

C ₅ + products, % by weight 2.9 7.2 2.5 5.4

C ₅ 3.4 6.9 3.1 5.4

C ₆ 36.2 31.2 39.4 34.6

C ₇ 49.9 39.3 50.4 47.1

C ₈ 7.6 15.4 4.6 7.4

C ⁺ ₉ 2.0 1.4 2.2 1.6

TMP/DMH ^*

octane, raw gasoline

RON+O 93.9 90.7 95.5 91.5

MON+O 92.2 89.3 92.2 89.6

^* TMP = Trimethylpentane

DMH = dimethyl hexane

Table XIV

BF ₃ -promoted SiO ₂ BF ₃ -promoted zeolite

Alkylation temperature, ℃ 0 20 0 20

C ₅ + products, % (weight)

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

C ⁺ ₉ 8.7 11.2 5.5 6.6

TMP/DMH 5.1 2.9 4.9 2.9

octane, raw gasoline

RON+O 95.5 92.8 95.9 93.1

MON+O 93.1 91.7 94.2 93.1

Table XVI

BF ₃ -promoted SiO ₂ BF ₃ -promoted zeolite

Alkylation temperature, ℃ 0 20 0 20

C ₅ + products, % (weight)

C ₅ 6.5 10.1 3.3 4.9

C ₆ 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 ⁺ ₉ 14.8 18.7 4.6 5.9

TMP/DMH 4.1 2.1 5.4 3.0

octane, raw gasoline

RON+O 92.9 90.5 93.2 93.3

MON+O 90.7 89.5 92.8 91.7

Table XVIII

BF ₃ -promoted SiO ₂ BF ₃ -promoted zeolite

Alkylation temperature, ℃ 0 20 0 20

C ₅ + products, % (weight)

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 ⁺ ₉ 8.9 17.2 2.0 2.6

TMP/DMH 5.9 2.8 6.7 3.4

octane, raw gasoline

RON+O 97.3 93.2 98.2 94.8

MON+O 94.0 91.9 95.6 93.3

Table XIX

Example 21 22 23 24

Catalyst BF ₃ / BF ₃ / BF ₃ / I/IBF ₃ /

Zeolite Zeolite/H ₂ O Zeolite/H ₂ OH ₂ O

(no solids)

Fresh catalyst contains 0 10 10

Water volume, % (weight)

Temperature (°C) 10 10 20 20

Pressure Psig (Kpa) 150 (1135) 150 (1135) 150 (1135) 150 (1135)

BF ₃ rate (% of feed) 2.0 2.0 3.0 3.0

Feed Olefin 2-Butene 2-Butene Mixed C ₃ C ₄ Mixed C ₃ C ₄

iC olefin feed ratio 10 10 10 10

Olefin WHSV 1.35 1.35 2.24 2.24

Olefin Conversion (%) 57 100 100 100

Yield 1.2 2.0 2.0 2.2

Distribution of total product (wt%)

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

C ⁺ ₉ total 71.7 6.2 7.4 9.1

RON+O 97.0 91.5 89.0

MON+O 93.0 89.6

Claims (15)

1. A method of alkylating isoparaffins with olefins to provide alkylated products, characterized in that it comprises reacting isoparaffins with olefins under alkylation conditions in the presence of a zeolite as a catalyst, wherein The isoparaffin contains 4-8 carbon atoms, and the olefin contains 2-12 carbon atoms. The zeolite has an X-ray diffraction pattern with the following values: d-plane distance (A) Relative strength, I/Io＞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=0～20 M=20～40 S=40～60 VS=60～100 2. The method according to claim 1, wherein the zeolite has an X-ray diffraction pattern having the following values. d-plane distance (A) relative strength, I/Io×100 30.0±2.2 W-M 22.1±1.3W 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=0～20 M=20～40 S=40～60 VS=60～100 3. The method according to claim 1, wherein the zeolite has an X-ray diffraction pattern having the following values. d-plane distance (A) relative strength, I/Io×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±0.09W 4.64±0.08W 4.41±0.08 W-M 4.25±0.08W 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±0.05W 2.99±0.05W 2.82±0.05W 2.78±0.05W 2.68±0.05W 2.59±0.05W Where W=0～20 M=20～40 S=40～60 VS=60～100 4. The method according to claim 1, wherein the zeolite has an X-ray diffraction pattern with the following values: d-plane distance (A) relative strength, I/Io×100 30.0±2.2 W-M 22.1±1.3W 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±0.09W 4.64±0.08W 4.41±0.08 W-M 4.25±0.08W 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±0.05W 2.99±0.05W 2.82±0.05W 2.78±0.05W 2.68±0.05W 2.59±0.05W Where W=0～20 M=20～40 S=40～60 VS=60～100 5. The method of claim 1, wherein the zeolite has a composition comprising a molar relationship of X ₂ O ₃ : (n)YO ₂ , wherein n is at least 10 and X is a trivalent element , Y is a tetravalent element. 6. The method of claim 5, wherein X is aluminum and Y is silicon. 7. The method of claim 1, wherein the equilibrium adsorption capacity of the zeolite is greater than 4.5% by weight for cyclohexane vapor and greater than 10% by weight for n-hexane vapor. 8. A process according to claim 1, wherein the isoparaffin is isobutane and the olefin is propylene and/or butene. 9. The method of claim 1, wherein the molar ratio of total isoparaffins to total olefins is 0.5:1-500:1. 10. The process according to claim 9, wherein the molar ratio of total isoparaffins to total olefins is 3:1-50:1. 11. The process of claim 1, wherein the alkylation reaction temperature is -25°C-40°C, the weight hourly space velocity of the olefin is 0.01-100, and the pressure is up to 34,580 kPa (5,000 psig). 12. The method of claim 1 wherein the zeolite is promoted with a Lewis acid. 13. The method of claim 12 wherein the Lewis acid is _BF3 . 14. The method according to claim 12 or claim 4, wherein the alkylation reaction temperature is -40°C-250°C, the weight hourly space velocity of the olefin is 0.01-100, and the pressure can reach 34580Kpa (5000psig) . 15. The method of claim 1, wherein the alkylation reaction is carried out in the presence of water.

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