WO1993002026A1

WO1993002026A1 - Aromatics alkylation process

Info

Publication number: WO1993002026A1
Application number: PCT/US1992/005971
Authority: WO
Inventors: Quang Ngoc Le
Original assignee: Mobil Oil Corporation
Priority date: 1991-07-18
Filing date: 1992-07-16
Publication date: 1993-02-04

Abstract

A process for preparing an alkyl-substituted aromatic compound comprises reacting the aromatic compound with an alkylating agent in the presence of a catalyst comprising an inorganic, porous, non-layered crystalline phase material exhibiting, after calcination, an X-ray diffraction pattern with at least one peak at a d-spacing greater than about 18 Angstrom Units and having a benzene adsorption capacity greater than 15 grams of benzene per 100 grams of said material at 6.7 kPa (50 torr) and 25 °C.

Description

AROMATICS ALKYLATION PROCESS

This invention relates to a process for alkylating aromatic compounds.

Aromatics alkylation is used to produce a variety of valuable commercial products. For example, ethylbenzene is a commodity chemical which is used on a large scale industrially to produce styrene monomer. Ethylbenzene is typically produced by the alkylation of benzene with ethylene in the presence of a solod acidic zeolite catalyst, such as ZSM-5.

In addition, onoalkylated naphthalenes have excellent thermal and oxidative stability, low vapor pressure and flash point, good fluidity and high heat transfer capacity and other properties which render them suitable for use as thermal medium oils. The use of a mixture of monoalkylated and polyalkylated naphthalenes as a base for synthetic functional fluids is described in U.S. Patent no. 4,604,491 (Dressier). Alkylated naphthalenes are usually produced by the alkylation of naphthalene or a substituted naphthalene in the presence of an acidic alkylation catalyst such as a Friedel-Krafts catalyst, for example, an acidic clay as described in Yoshida U.S. 4,714,794 or Dressier U.S. 4,604,491 or a Lewis acid such as aluminum trichloride as described in Pellegrini U.S. 4,211,665 and 4,238,343.

It has now been found that certain mesoporous crystalline catalytic materials having a unique and novel crystalline structure are extremely effective catalysts for the production of alkylated aromatic compounds, including ethylbenzene and alkylated naphthalenes.

Accordingly the present invention resides in a process for preparing an alkyl-substituted aromatic compound by reacting the aromatic compound with an alkylating agent in the presence of a catalyst comprising an inorganic, porous, non-layered crystalline phase material exhibiting, after calcination, an X-ray diffraction pattern with at least one peak at a d-spacing greater than about 18 Angstrom Units and having a benzene adsorption capacity of greater than 15 grams of benzene per 100 grams of said material at 6.7 kPa (50 torr) and 25"C.

Preferably, the crystalline phase material has a hexagonal arrangement of uniformly-sized pores having diameters of at least about 13 Angstrom Units and, after calcination, exhibits a hexagonal electron diffraction pattern that can be indexed with a de¬ value greater than about 18 Angstrom Units. This material is referred to herein as MCM-41. Alkylation Catalyst

The catalyst employed in the process of the invention comprises an inorganic, porous, non-layered crystalline phase material exhibiting, in its calcined form, an X-ray diffraction pattern with at least one peak at a position greater than about 18 Angstrom Units d-spacing (4.909 degrees two-theta for Cu K-alpha radiation) with a relative intensity of 100. More particularly, the calcined crystalline non-layered material of the invention may be characterized by an X-ray diffraction pattern with at least two peaks at positions greater than about 10 Angstrom Units d-spacing (8.842 degrees two-theta for Cu K-alpha radiation) , at least one of which is at a position greater than about 18 Angstrom Units d-spacing, and no peaks at positions less than about 10 Angstrom units d-spacing with relative intensity greater than about 20% of the strongest peak. Still more particularly, the X-ray diffraction pattern of the calcined material of this invention will have no peaks at positions less than about 10 Angstrom units d-spacing with relative intensity greater than about 10% of the strongest peak. X-ray diffraction data were collected on a Scintag PAD X automated diffraction system employing theta-theta geometry, Cu K-alpha radiation, and an energy dispersive X-ray detector. Use of the energy dispersive X-ray detector eliminated the need for incident or diffracted beam monochromators. Both the incident and diffracted X-ray beams were collimated by double slit incident and diffracted collimation systems. The slit sizes used, starting from the X-ray tube source, were 0.5, 1.0, 0.3 and 0.2 mm, respectively. Different slit systems may produce differing intensities for the peaks. The materials of the present invention that have the largest pore sizes may require more highly collimated incident X-ray beams in order to resolve the low angle peak from the transmitted incident X-ray beam.

The diffraction data were recorded by step-scanning at 0.04 degrees of two-theta, where theta is the Bragg angle, and a counting time of 10 seconds for each step. The interplanar spacings, d's, were calculated in Angstrom units (A) , and the relative intensities of the lines, I/Io, where lo is one-hundredth of the intensity of the strongest line, above background, were derived with the use of a profile fitting routine. The intensities were uncorrected for Lorentz and polarization effects. The relative intensities are given in terms of the symbols vs = very strong (75-100) , s = strong (50-74) , m = medium (25-49) and w = weak (0-24) . It should be understood that diffraction data listed as single lines may consist of multiple overlapping lines which under certain conditions, such as very high experimental resolution or crystallographic changes, may appear as resolved or partially resolved lines. Typically, crystallographic changes can include minor changes in unit cell parameters and/or a change in crystal symmetry, without a substantial change in structure. These minor effects, including changes in relative intensities, can also occur as a result of differences in cation content, framework composition, nature and degree of pore filling, thermal and/or hydrothermal history, and peak width/shape variations due to particle size/shape effects, structural disorder or other factors known to those skilled in the art of X-ray diffraction.

The material employed in the process of the invention is further characterised by an equilibrium benzene adsorption capacity of greater than about 15 grams benzene/100 grams crystal at 6.7 kPa (50 torr) and 25°C. The equilibrium benzene adsorption capacity characteristic of this material is measured on the basis of no pore blockage by incidental contaminants. For instance, the sorption test will be conducted on the crystalline material phase having any pore blockage contaminants and water removed by ordinary methods. Water may be removed by dehydration techniques, e.g. thermal treatment. Pore blocking inorganic amorphous materials, e.g. silica, and organics may be removed by contact with acid or base or other chemical agents such that the detrital material will be removed without detrimental effect on the crystal of the invention. The equilibrium benzene adsorption capacity is determined by contacting the material of the invention, after dehydration or calcination at, for example, 450 to 700"C, typically 540°C, for at least one hour and other treatment, if necessary, in an attempt to remove any pore blocking contaminants, at 25"C and 50 torr benzene until equilibrium is reached. The weight of benzene sorbed is then determined as more particularly described hereinafter.

The materials used in the process of the invention are generally mesoporous, by which is meant they have uniform pores within the size range of 13 to 200 Angstroms, more usually 15 to 100 Angstroms. In a preferred embodiment, the material appears to have a hexagonal arrangement of large channels with open internal diameters from 13 to 200 Angstroms. This structure can be revealed by transmission electron microscopy and electron diffraction. Thus, electron micrographs of properly oriented specimens of the material show a hexagonal arrangement of large channels and the corresponding electron diffraction patterns give an approximately hexagonal arrangement of diffraction maxima. The dlOO spacing of the electron diffraction patterns is the distance between adjacent spots on the hkO projection of the hexagonal lattice and is related to the repeat distance aO between channels observed in the electron micrographs through the formula dlOO = a0 3/2. This ... spacing observed in the electron diffraction pattern corresponds to the d-spacing of the low angle peak (>18 Angstrom d-spacing) in the X-ray diffraction pattern. The most highly ordered preparations of the material obtained so far have 20-40 distinct spots observable in the electron diffraction patterns. These patterns can be indexed with the hexagonal hkO subset of unique reflections of 100, 110, 200, 210, etc., and their symmetry-related reflections.

The inorganic, non-layered mesoporous crystalline material used in this invention typically has the following composition:

Mn/q(Wa Xb Yc Zd Oh) wherein W is a divalent element, such as a divalent first row transition metal, e.g. manganese, cobalt and iron, and/or magnesium, preferably cobalt; 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; Z is a pentavalent element, such as phosphorus; M is one or more ions, such as, for example, ammonium, Group IA, IIA and VIIB ions, usually hydrogen, sodium and/or fluoride ions; n is the charge of the composition excluding M expressed as oxides; q is the weighted molar average valence of M; n/q is the number of moles or mole fraction of M; a, b, c and d are mole fractions of W, X, Y and Z, respectively; h is a number of from 1 to 2.5; and (a+b+c+d) = 1.

A preferred embodiment of the above crystalline material is when (a+b+c) is greater than d, and h ■= 2. A further embodiment is when a and d = 0, and h = 2.

In the as-synthesized form, the material employed in this invention typically has a composition, on an anhydrous basis, expressed empirically as follows: rRMn/q(Wa Xb Yc Zd Oh) wherein R is the total organic material not included in M as an ion, and r is the coefficient for R, i.e. the number of moles or mole fraction of R. The M and R components are associated with the material as a result of their presence during crystallization, and are easily removed or, in the case of M, replaced by conventional post-crystallization methods.

Preferably, the crystalline material is a metallosilicate which is synthesized with Bronsted acid active sites by incorporating a tetrahedrally coordinated trivalent element, such as Al, Ga, B, or Fe, within the silicate framework. Aluminosilicate materials of this type are thermally and chemically stable, properties favored for acid catalysis; however, the advantages of mesoporous structures may be utilized by employing highly siliceous materials or crystalline metallosilicate having one or more tetrahedral species having varying degrees of acidity. In addition to the preferred aluminosilicates, the gallosilicate, ferrosilicate and borosilicate materials may be employed. Although matrices may be formed with the germanium analog of silicon, these are expensive and generally no better than the metallosilicates. Most preferably, the crystalline material is an aluminosilicate.

Synthesis of the crystalline material employed in the process of the invention is described in detail in our International Patent Publication No. WO 91/11390. In particular, materials having the composition defined by the above formula can be prepared from a reaction mixture having a composition in terms of mole ratios of oxides, within the following ranges: Reactants X₂O₃/YO₂

X₂°₃/(Y0₂+Z₂0₅)

^X2°3/^(Y02^{+ O+Z}2°5> Solvent/

wherein e and f are the weighted average valences of M and R, respectively, wherein the solvent is a C to C_β alcohol or diol, or, more preferably, water and wherein R comprises an organic directing agent having the formula R_;,R₂R_{3 4}Q⁺ wherein Q is nitrogen or phosphorus and wherein at least one of R., R₂, R₃ and is aryl or alkyl group having 6 to 36 carbon atoms, e.g.

^•C6^H13 -^C10^H21 ' ^"C16^H33 ^{and "C}18^H37' ^{and βaCh} °^{f thβ} remainder of R_, ₂, R₃ and R₄ is selected from hydrogen and an alkyl group having 1 to 5 carbon atoms. The compound from which the above ammonium or phosphonium ion is derived may be, for example, the hydroxide, halide, silicate or mixtures thereof. The particular effectiveness of the above directing agent, when compared with other such agents known to direct synthesis of one or more other crystal structures, is believed due to its ability to function as a template in the nucleation and growth of the desired ultra-large pore materials. Non-limiting examples of these directing agents include cetyltri ethylammonium, cetyltrimethylphosphonium, octadecyltrimethylphosphonium, benzyltrimethylammonium, cetylpyridinium, myristyltrimethylammonium, decyltrimethylammonium, dodecyltrimethylammonium and dimethyldidodecylammonium compounds.

Preferably, the total organic, R, present in the reaction mixture comprises an additional organic directing agent in the form of an ammonium or phosphonium ion of the above directing agent formula but wherein each R_, R_, R₃ and R. is selected from hydrogen and an alkyl group of 1 to 5 carbon atoms (2 of the alkyl groups can be interconnected to form a cyclic compound) . Examples of the additional organic directing agent include tetramethylammonium, tetraethylammonium, tetrapropylammonium, tetrabutylammonium and pyrrolidinium compounds. The molar ratio of the first-mentioned organic directing agent to the additional organic directing agent can be in the range 100/1 to 0.01/1. Where the additional organic directing agent is present, the molar ratio R_?/fO/(YO.+WO+Z 0₅+X.O ) in the reaction mixture is preferably 0.1 to 2.0, most preferably 0.12 to 1.0.

In addition, to vary the pore size of the final crystalline phase material, the total organic, R, in the reaction mixture can include an auxiliary organic in addition to the organic directing agent(s) described above. This auxiliary organic is selected from (1) aromatic hydrocarbons and amines having 5-20 carbon atoms and halogen- and C.-C.. alkyl-substituted derivatives thereof, (2) cyclic and polycyclic aliphatic hydrocarbons and amines of 5 to 20 carbon atoms and halogen- and ^C ₁~C₁₄ alkyl-substituted derivatives thereof and (3) straight and branched chain aliphatic hydrocarbons and amines having 3-16 carbon atoms and halogen-substituted derivatives thereof. In the above auxiliary organics, the halogen substituent is preferably bromine. The C.-C.. alkyl substituent may be a linear or branched aliphatic chain, such as, for example, methyl, ethyl, propyl, isopropyl, butyl, pentyl and combinations thereof. Examples of these auxiliary organics include, for example, p-xylene, trimethylbenzene, triethylbenzene and triisopropylbenzene.

With the inclusion of the auxiliary organic in the reaction mixture, the mole ratio of auxiliary organic/YO will be from 0.05 to 20, preferably from 0.1 to 10, and the mole ratio of auxiliary organic/organic directing agent(s) will be from 0.02 to 100, preferably from 0.05 to 35.

When a source of silicon is used in the synthesis method, it is preferred to use at least in part an organic silicate, such as, for example, a quaternary ammonium silicate. Non-limiting examples of such a silicate include tetramethylammonium silicate and tetraethylorthosilicate.

Non-limiting examples of various combinations of W, X, Y and Z contemplated for the above reaction mixture include:

X z

Si

P

Si P

P

Si P

Si including the combinations of W being Mg, or an element selected from the divalent first row transition metals, e.g; Mn, Co and Fe; X being B, Ga or Fe; and Y being Ge.

To produce the crystalline material of the invention, the reaction mixture described above is maintained at a temperature of 25 to 250°C, preferably 50 to 175°C, and preferably a pH of 9 to 14 for a period of time until the required crystals form, typically 5 minutes to 14 days, more preferably 1 to 300 hours.

When the crystalline material of the invention is an aluminosilicate, the synthesis method conveniently involves the following steps:

(1) Mix the organic (R) directing agent with the solvent or solvent mixture such that the mole ratio of solvent/R__/fO is within the range of 50 to 800, preferably from 50 to 500. This mixture constitutes the "primary template" for the synthesis method.

(2) To the primary template mixture of step (1) add the silica and alumina such that the ratio of

R _/fO/(SiO +A1_0₃) is within the range 0.01 to 2.0.

(3) Agitate the mixture resulting from step (2) at a temperature of 20 to 40°C, preferably for 5 minutes to 3 hours.

(4) Allow the mixture to stand with or without agitation, preferably at 20 to 50°C, and preferably for 10 minutes to 24 hours.

(5) Crystallize the product from step (4) at a temperature of 50 to 150°C, preferably for 1 to 72 hours.

The crystals of the mesoporous support material will normally be composited with a matrix material which is resistant to the temperatures and other conditions employed in the alkylation process to form the finished catalyst. Such materials include active and inactive materials and synthetic or naturally occurring zeolites as well as inorganic materials such as clays and/or oxides such as alumina, silica or silica-alumina. The latter may be either naturally occurring or in the form of gelatinous precipitates or gels including mixtures of silica and metal oxides. Use of a material in conjunction with the zeolite, i.e., combined therewith or present during its synthesis, which itself is catalytically active may change the conversion and/or selectivity of the catalyst. Inactive materials suitably serve as diluents to control the amount of conversion so that alkylation products can be obtained economically and orderly without employing other means for controlling the rate of reaction. These materials may be incorporated into naturally occurring clays, e.g., bentonite and kaolin, to improve the crush strength of the catalyst under commercial alkylation operating conditions and function as binders or matrices for the catalyst. The mesoporous material is usually composited with the matrix in amounts from 80:20 to 20:80 by weight, typically from 80:20 to 50:50 mesoporous material:matrix. Compositing may be done by conventional means including mulling the materials together followed by extrusion of pelletizing into the desired finished catalyst particles. Aromatic Compound

The starting materials for the production of the alkylaromatic products include various aromatic compounds such as benzene and the low and high molecular weight alkylbenzenes, including low molecular weight alkylbenzenes such as toluene and the isomeric xylenes and mixtures of such materials. Higher molecular weight alkylbenzenes may be alkylated in this way as well as other aromatics including anthracene, phenanthrene and aromatics with other fused ring systems. One particularly preferred starting material is naphthalene as well as substituted naphthalenes containing one or more short chain alkyl groups containing up to eight carbon atoms, such as methyl. ethyl or propyl. Suitable alkyl-substituted naphthalenes include alpha-methylnaphthalene, dimethylnaphthalene and ethylnaphthalene. Naphthalene itself is preferred since the resulting mono-alkylated products have better thermal and oxidative stability than the more highly alkylated materials. Alkylating Agents

The alkylating agents which are used to alkylate the aromatic compound include any aliphatic or aromatic organic compound having one or more available alkylating aliphatic groups.

In one preferred embodiment, in which the aromatic compound to be alkylated is benzene, the alkylating agent is ethylene.

In another preferred embodiment, in which the aromatic compound is naphthalene or a substituted naphthalene, the alkylating group of the alkylating agent has at least 6 carbon atoms, preferably at least 8, and still more preferably at least 12 carbon atoms. For the production of functional fluids and additives, the alkyl groups on the alkyl-naphthalene preferably have from 12 to 30 carbon atoms, preferably 14 to 18 carbon atoms. A preferred class of alkylating agents is the olefins with the requisite number of carbon atoms, for example, hexenes, heptenes, octenes, nonenes, decenes, undecenes, dodecenes. Mixtures of the olefins, e.g. mixtures of ^C ₁₂~ 2₀ ^{or C}14~^C1₈ olefins, are useful. Branched alkylating agents, especially oligomerized olefins such as the trimers, tetramers, pentamers, etc., of light olefins such as ethylene, propylene, the butylenes, etc., are also useful. Other useful alkylating agents include alcohols (inclusive of monoalcohols, dialcohols, trialcohols, etc.) such as hexanols, heptanols, octanols, nonanols, decanols, undecanols and dodecanols; and alkyl halides such as hexyl chlorides, octyl chlorides, dodecyl chlorides; and higher homologs. A particularly useful class of alkylating agents are the poly-alpha-olefins produced by the oligomerization of alpha-olefins. Commercial products of this kind are widely available and are usually produced by the oligomerization of 1-olefins such as 1-decene over a Friedel-Crafts catalyst such as aluminum trichloride, boron trifluoride or its complexes e.g. with alcohols or esters. These materials are usually liquids ranging in viscosity from mobile (5cS or lower) up to viscous semi-liquids. Products of this type may be used as alkylating agents in the present process because the pore structure of the mesoporous alkylation catalysts used in the process is able to accommodate these species even when they have high molecular weight and bulky molecular dimensions, enabling the alkylation reaction to occur and facilitating the production of alkylated products with a wide range of varying properties.

A particularly favored class of PAO alkylating agents are the HVI-PAO products. These olefin oligomers are produced by the oligomerization of alpha-olefins such as 1-decene over a reduced Group VI metal catalyst, especially reduced chromium catalysts. The HVI-PAO olefin oligomers are characterized by a low branch ratio of less than 0.19 as well as by other properties such as low pour point. HVI-PAO materials are described in U.S. Patents Nos. 4,827,064 and 4,827,073. Alkylation Conditions

The alkylation is conducted such that the organic reactants, i.e., the alkylatable aromatic compound and the alkylating agent, are brought into contact with the catalyst in the liquid or vapor phase in a suitable reaction zone such as, for example, in a batch type reactor or flow reactor containing a fixed bed of the catalyst composition, under effective a.lkylation conditions. Such conditions generally include a temperature of 90°C to 500°C, a pressure of 100 to 25000 kPa, a feed weight hourly space velocity (WHSV) of 0.1 to 10 hr and an alkylatable aromatic compound to alkylating agent mole ratio of 0.1:1 to 50:1.

Where the aromatic compound being alkylated is naphthalene or a substituted naphthalene, the process is preferably conducted at a temperature of 200" to 600°F (90° to 315°C), more preferably 300° to 400°F (150° to 205°C), a pressure of 50 to 1000 psig (450 to 7000 kPa) , a WHSV of 0.1 to 5.0, more preferably 0.5 to 5.0 and an alkylatable aromatic compound to alkylating agent mole ratio of 0.5:1 to 5:1. The alkylation process can be carried out as a batch-type reaction typically employing a closed, pressurized, stirred reactor with an inert gas blanketing system or in a semi-continuous or continuous operation utilizing a fixed or moving bed catalyst system.

Where the alkylation reaction is the ethylation of benzene, the reaction is preferably conducted in the vapor phase at a temperature of 600° to 800°F (315 to 430°C) and a pressure of 200 to 500 psig (1480 to 3550 kPa) . Alternatively, the reaction can be conducted in the liquid phase at a temperature of 300° to 600"F (150 to 315°C) and a pressure of 400 to 800 psig (2860 to 5620 kPa) . The reaction is carried out in the absence of hydrogen, at a space velocity of 1 to 10, typically 1 to 6, WHSV based on the ethylene and with the weight ratio of benzene to ethylene being 15:1 to 25:1, normally about 20:1. The alkylation process can be carried out as a batch-type, semi-continuous or continuous operation utilizing a fixed, fluidized or moving bed catalyst system. The process is, however, preferably operated in the general manner described in U.S. Patent No. 3,751,504 (Keown) but using the present alkylation catalysts. Examples

Examples 1 to 19 below illustrate the preparation of the mesoporous crystalline materials used to prepare the catalysts. In these examples, the sorption data for water, cyclohexane, benzene and/or n-hexane, they are Equilibrium Adsorption values determined as follows:

A weighed sample of the adsorbent, after calcination at about 540°C for at least about 1 hour and other treatment, if necessary, to remove any pore blocking contaminants, is contacted with the desired pure adsorbate vapor in an adsorption chamber. The increase in weight of the adsorbent is calculated as the adsorption capacity of the sample in terms of grams/100 grams adsorbent based on adsorbent weight after calcination at about 540°C. The present composition exhibits an equilibrium benzene adsorption capacity at 50 Torr and 25°C of greater than about 15 grams/100 grams, particularly greater than about 17.5 g/100 g/ and more particularly greater than about 20 g/100 g.

A preferred way to measure adsorption is to contact the desired pure adsorbate vapor in an adsorption chamber evacuated to less than 1 mm at conditions of 12 Torr (1.6 kPa) of water vapor, 40 Torr (5.3 kPa) of n-hexane or cyclohexane vapor, or 50 Torr (6.7 kPa) of benzene vapor, at 25^βC. The pressure is kept constant (within about + 0.5 mm) by addition of adsorbate vapor controlled by a manostat during the adsorption period. As adsorbate is adsorbed by the new crystal, the decrease in pressure causes the manostat to open a valve which admits more adsorbate vapor to the chamber to restore the above control pressures. Sorption is complete when the pressure change is not sufficient to activate the manostat.

Another way of measuring benzene adsorption is on a suitable thermogravimetric analysis system, such as a co puter-controlled 990/951 duPont TGA system. The adsorbent sample is dehydrated (physically sorbed water removed) by heating at, for example, about 350"C or 500°C to constant weight in flowing helium. If the sample is in as-synthesized form, e.g. containing organic directing agents, it is calcined at about 540°C in air and held to constant weight instead of the previously described 350°C or 500°C treatment. Benzene adsorption isotherms are measured at 25°C by blending a benzene saturated helium gas stream with a pure helium gas stream in the proper proportions to obtain the desired benzene partial pressure. The value of the adsorption at 50 Torr (6.7 kPa) of benzene is taken from a plot of the adsorption isotherm.

In the examples, percentages are by weight unless otherwise indicated.

Example 1 One hundred grams of cetyltrimethylammonium (CTMA) hydroxide solution, prepared by contacting a 29 wt.% N,N,N- trimethyl-1-hexadecanaminium chloride solution with a hydroxide-for-halide exchange resin, was combined with 100 grams of an aqueous solution of tetra ethylammonium (TMA) silicate (10% silica) with stirring. Twenty-five grams of HiSil, a precipitated hydrated silica containing about 6 wt.% free water and about 4.5 wt.% bound water of hydration and having an ultimate particle size of about 0.02 micron, was added. The resulting mixture was placed in a polypropylene bottle, which was placed in a steam box at 95^βC overnight. The mixture had a composition in terms of moles per mole A1_?0 :

The resulting solid product was recovered by filtration and dried in air at ambient temperature. The product was then calcined at 540°C for l hour in nitrogen, followed by 6 hours in air.

The calcined product proved to have a surface area of 475 2/g and the following equilibrium adsorption capacities in grams/100 grams:

H₂0 8.3

Cyclohexane 22.9 n-Hexane 18.2

Benzene 21.5

The product of this example may be characterized by X-ray diffractiion as including a very strong relative intensity line at 37.8 + 2.0 A d-spacing, and weak lines at 21.6 ± 1.0 and 19.2 ± 1.0 A. Transmission electron microscopy (TEM) produced images of a hexagonal arrangement of uniform pores and hexagonal electron diffraction pattern with a d._Q0 value of about 39 A.

Example 2 One hundred grams of cetyltrimethylammonium (CTMA) hydroxide solution prepared as in Example 1 was combined with 100 grams of an aqueous solution of tetramethylammonium (TMA) hydroxide (25%) with stirring. Twenty-five grams of HiSil, a precipitated hydrated silica containing about 6 wt.% free water and about 4.5 wt.% bound water of hydration and having an ultimate particle size of about 0.02 micron, was added. The resulting mixture was placed in a static autoclave at 150°C overnight. The mixture had a composition in terms of moles per mole A1₂0 :

The resulting solid product was recovered by filtration and dried in air at ambient temperature. The product was then calcined at 540°C for 1 hour in nitrogen, followed by 6 hours in air.

The calcined product proved to have a surface area of 993 m 2/g and the followi.ng equi.li.bri.um adsorption capacities in grams/100 grams:

H₂0 7.1

Cyclohexane 47.2 n-Hexane 36.2

Benzene 49.5

The X-ray diffraction pattern of the calcined product may be characterized as including a very strong relative intensity line at 39.3 + 2.0 A d-spacing, and weak lines at 22.2 + 1.0 and 19.4 + 1.0 A. TEM indicated that the product contained the ultra-large pore material.

A portion of the above product was then contacted with 100% steam at 1450°F for two hours. The surface area of the steamed material was measured to be 440 m 2/g, indicating that about 45% was retai.ned followi.ng severe steaming.

Another portion of the calcined product of this example was contacted with 100% steam at 1250"F for two hours. The surface area of this material was measured to be 718 m 2/g, indicating that 72% was retained after steaming at these conditions.

Example 3

Water, cetyltrimethylammonium hydroxide solution prepared as in Example 1, aluminum sulfate, HiSil and an aqueous solution of tetrapropylammonium (TPA) bromide (35%) were combined to produce a mixture having a composition in terms of moles per mole 1₂0₃: 0.65 moles Na,0 65 moles Si0₂

8.8 moles (CTMA)₂0

1.22 moles (TPA)₂0 1336 moles H₂0 The resulting mixture was placed in a poly¬ propylene bottle, which was kept in a steam box at 95°C for 192 hours. The sample was then cooled to room temperature and combined with CTMA hydroxide solution prepared as in Example 1 and TMA hydroxide (25% by weight) in the weight ratio of 3 parts mixture, 1 part CTMA hydroxide and 2 parts TMA hydroxide. The combined mixture was then placed in a polypropylene bottle and kept in a steam box at 95°C overnight. The combined mixture had a composition in terms of moles per mole

The calcined product proved to have a surface area of 1085 m 2/g and the followi.ng equi.li.bri.um adsorption capacities in grams/100 grams:

The X-ray diffraction pattern of the calcined product of this example may be characterized as including a very strong relative intensity line at 38.2 + 2.0 A d-spacing, and weak lines at 22.2 + 1.0 and 19.4 + 1.0 A. TEM indicated the product contained the ultra-large pore material.

Example 4 Two hundred grams of cetyltrimethylammonium (CTMA) hydroxide solution prepared as in Example l was combined with 2 grams of Catapal alumina (alpha-alumina monohydrate, 74% alumina) and 100 grams of an aqueous solution of tetramethylammoniu (TMA) silicate (10% silica) with stirring. Twenty-five grams of HiSil, a precipitated hydrated silica containing about 6 wt.% free water and about 4.5 wt.% bound water of hydration and having an ultimate particle size of about 0.02 micron, was added. The resulting mixture was placed in a static autoclave at 150°C for 48 hours. The mixture had a composition in terms of moles per mole A1_0 : 0.23 moles Na O 33.2 moles SiO,

6.1 moles (CTMA)₂0

5.2 moles (TMA)₂0 780 moles H₂0

The calcined product proved to have a surface area of 1043 m 2/g and the followi.ng equi.li.bri.um adsorption capacities in grams/100 grams:

H₂0 6.3

Cyclohexane > 50 n-Hexane 49.1

Benzene 66.7

The X-ray diffraction pattern of the calcined product may be characterized as including a very strong relative intensity line at 40.8 + 2.0 A d-spacing, and weak lines at 23.1 ± 1.0 and 20.1 + 1.0 A. TEM indicated that the product contained the ultra-large pore material. Example 5

Two-hundred sixty grams of water was combined with 77 grams of phosphoric acid (85%) , 46 grams of Catapal alumina (74% alumina) , and 24 grams of pyrrolidine (Pyr) with stirring. This first mixture was placed in a stirred autoclave and heated to 150°C for six days. The material was filtered, washed and air-dried. Fifty grams of this product was slurried with 200 grams of water and 200 grams of cetyltrimethylammonium hydroxide solution prepared as in Example 1. Four hundred grams of an aqueous solution of tetraethylammonium silicate (10% silica) was then added to form a second mixture which was placed in a polypropylene bottle and kept in a steam box at 95°C overnight. The first mixture had a composition in terms of moles per mole Al O :

1.0 moles P„0--

0.51 moles (Pyr) O 47.2 moles H₂0 The resulting solid product was recovered by filtration and dried in air at ambient temperature. The product was then calcined at 540°C for 1 hour in nitrogen, followed by 6 hours in air.

The calcined product proved to have a surface area of 707 m 2/g and the followi.ng equi.li.bri.um adsorption capacities in grams/100 grams:

H₂0 33.2

Cyclohexane 19.7 n-Hexane 20.1

Benzene 23.3

The X-ray diffraction pattern of the calcined product may be characterized as including a very strong relative intensity line at 25.4 ± 1.5 A d-spacing. TEM indicated the product contained the present ultra-large pore material. Exa ple 6 A solution of 1.35 grams of NaA10₂ (43.5% A1₂0 , 30% Na₂0) dissolved in 45.2 grams of water was mixed with 17.3 grams of NaOH, 125.3 grams of colloidal silica (40%, Ludox HS-40) and 42.6 grams of 40% aqueous solution of tetraethylammonium (TEA) hydroxide. After stirring overnight, the mixture was heated for 7 days in a steam box (95°C) . Following filtration, 151 grams of this solution was mixed with 31 grams of cetyltrimethylammonium hydroxide solution prepared as in Example 1 and stored in the steam box at 95°C for 13 days. The mixture had the following relative molar composition:

The resulting solid product was recovered by filtration and washed with water and ethanol. The product was then calcined at 540°C for 1 hour in nitrogen, followed by 6 hours in air.

The calcined product composition included 0.14 wt.% Na, 68.5 wt.% Si0₂ and 5.1 wt.% A1₂0 , and proved to have a benzene equilibrium adsorption capacity of 58.6 grams/100 grams.

The X-ray diffraction pattern of the calcined product may be characterized as including a very strong relative intensity line at 31.4 + 1.5 A d-spacing. TEM indicated that the product contained the present ultra-large pore material.

Example 7

A mixture of 300 grams of cetyltrimethylammonium (CTMA) hydroxide solution prepared as in Example 1 and 41 grams of colloidal silica (40%, Ludox HS-40) was heated in a 600 cc autoclave at 150°C for 48 hours with stirring at 200 rpm. The mixture has a composition in terms of moles per mole Si0₂:

0.5 mole (CTMA)₂0 46.5 moles H₂0 The resulting solid product was recovered by filtration, washed with water, then calcined at 540°C for 1 hour in nitrogen, followed by 10 hours in air. The calcined product composition included less than 0.01 wt.% Na, about 98.7 wt.% Si0₂ and about 0.01 wt.% A1,0_, and proved to have a surface area of 896 m 2/g. The calcined product had the following equilibrium adsorption capacities in grams/100 grams: H₂0 8.4

Cyclohexane 49.8 n-Hexane 42.3 Benzene 55.7

The X-ray diffraction pattern of the calcined product of this example may be characterized as including a very strong relative intensity line at 40.0 + 2.0 A d-spacing and a weak line at 21.2 + 1.0 A. TEM indicated that the product of this example contained at least three separate phases, one of which was the ultra-large pore material.

Example 8 A mixture of 150 grams of cetyltrimethylammonium (CTMA) hydroxide solution prepared as in Example 1 and 21 grams of colloidal silica (40%, Ludox HS-40) with an initial pH of 12.64 was heated in a 300 cc autoclave at 150°C for 48 hours with stirring at 200 rpm. The mixture had a composition in terms of moles per mole Si0₂:

0.5 mole (CTMA)₂0 46.5 moles H₂0 The resulting solid product was recovered by filtration, washed with water, then calcined at 540°C for 6 hours in air. ^• The calcined product composition was measured to include 0.01 wt.% Na, 93.2 wt.% SiO_ and 0.016 wt.%

^Δ 2

Al₂0_, and proved to have a surface area of 992 m /g and the following equilibrium adsorption capacities in grams/100 grams:

H₂0 4.6

Cyclohexane > 50 n-Hexane > 50 Benzene 62.7

The X-ray diffraction pattern of the calcined product may be characterized as including a very strong relative intensity line at 43.6 + 2.0 A d-spacing and weak lines at 25.1 + 1.5 and 21.7 + 1.0 A. TEM indicated that the product contained the ultra-large pore material.

Example 9 Sodium aluminate (4.15g) was added slowly into a solution containing 16g of myristyltrimethylammonium bromide (C-.TMABr) in lOOg of water. Tetramethyl¬ ammonium silicate (100g-10% Si0₂) , HiSil (25g) and tetramethylammonium hydroxide (14.2g-25% solution) were then added to the mixture. The mixture was crystallized in an autoclave at 120°C with stirring for 24 hours.

The product was filtered, washed and air dried. Elemental analysis showed the product contained 53.3 Wt% SiO , 3.2 Wt% A1₂0₃, 15.0 Wt% C, 1.88 wt% N, 0.11 wt% Na and 53.5 wt% ash at 1000°C. The X-ray diffraction pattern of the material after calcination at 540°C for 1 hour in N₂ and 6 hours in air includes a very strong relative intensity line at 35.3 ± 2.0 A d-spacing and weak lines at 20.4 + 1.0 and 17.7 + 1.0 A d-spacing. TEM indicated that the product contained the ultra-large pore material.

The washed product, having been exchanged with IN ammonium nitrate solution at room temperature, then

2 calcined, proved to have a surface area of 827 m /g and the- following equilibrium adsorption capacities in g/lOOg anhydrous sorbent:

Sodium aluminum (4.15g) was added slowly into a solution containing 480g of dodecyltrimethylammonium hydroxide (C.₂TMA0H, 50%) solution diluted with 12Og of water. UltraSil (50g) and an aqueous solution of tetramethylammonium silicate (200g-10% Si0₂) and tetramethylammonium hydroxide (26.38g-25% solution) were then added to the mixture. The mixture was crystallized in an autoclave at 100°C with stirring for 24 hours.

The product was filtered, washed and air dried. After calcination at 540°C for 1 hour in N_ and 6 hours in air, the X-ray diffraction pattern includes a very strong relative intensity line at 30.4 + 1.5 A d-spacing and weak lines at 17.7 + 1.0 and 15.3 + 1.0 A d-spacing. TEM indicated that the product contained the ultra-large pore material.

The washed product, having been exchanged with IN ammonium nitrate solution at room temperature, then calcined, proved to have a surface area of 1078 m 2/g and the following equilibrium adsorption capacities in g/lOOg anhydrous sorbent:

A solution of 4.9 grams of NaA10₂ (43.5 % A1₂0₃, 30% Na0_p) in 37.5 grams of water was mixed with 46.3 cc of 40% aqueous tetraethylammonium hydroxide solution and 96 grams of colloidal silica (40%, Ludox HS-40) . The gel was stirred vigorously for 0.5 hour, mixed with an equal volume (150 ml) of cetyltrimethylammonium hydroxide solution prepared as in Example 1 and reacted at 100°C for 168 hours. The mixture had the following composition in terms of moles per mole A1_0_:

The resulting solid product was recovered by filtration, washed with water then calcined at 540"C for 16 hours in air. The calcined product proved to have a surface area of 1352 m 2/g and the following equilibrium adsorption capacities in grams/100 grams:

H O 23.6

Cyclohexane >50 n-Hexane 49

Benzene 67.5

The X-ray diffraction pattern of the calcined product may be characterized as including a very strong relative intensity line at 38.5 + 2.0 A d-spacing and a weak line at 20.3 + 1.0 A. TEM indicated that the product contained the ultra-large pore material.

Example 12 Two hundred grams of cetyltrimethylammonium (CTMA) hydroxide solution prepared as in Example 1 was combined with 4.15 grams of sodium aluminate and 100 grams of aqueous tetramethylammonium (TMA) silicate solution (10% silica) with stirring. Twenty-five grams of HiSil, a precipitated hydrated silica containing about 6 wt.% free water and about 4.5 wt.% bound water of hydration and having an ultimate particle size of about 0.02 micron, was added. The resulting mixture was placed in a static autoclave at 150°C for 24 hours. The mixture had a composition in terms of moles per mole A1₂0₃:

The resulting solid product was recovered by filtration and dried in air at ambient temperature. The product was then calcined at 540°C for 1 hour in nitrogen, followed by 6 hours in air. TEM indicated that this product contained the ultra-large pore material. The X-ray diffraction pattern of the calcined product of this example can be characterized as including a very strong relative intensity line at 44.2 + 2.0 A d-spacing and weak lines at 25.2 ± 1.5 and 22.0 + 1.0 A.

The calcined product proved to have a surface area of 932 m 2/g and the followi.ng equi.li.bri.um adsorption capacities in grams/100 grams:

H₂0 39.3

Cyc1ohexane 46.6 n-Hexane 37.5

Benzene 50

Example 13 Two hundred grams of cetyltrimethylammonium (CTMA) hydroxide solution prepared as in Example 1 was combined with 4.15 grams of sodium aluminate and 100 grams of aqueous tetramethylammonium (TMA) silicate solution (10% silica) with stirring. Twenty-five grams of HiSil, a precipitated hydrated silica containing about 6 wt.% free water and about 4.5 wt.% bound water of hydration and having an ultimate particle size of about 0.02 micron, was added. The resulting mixture was placed in a steam box at 100°C for 48 hours. The mixture had a composition in terms of moles per mole A1₂0₃: 1.25 moles Na_0 27.8 moles SiO 5.1 moles (CTMA)₂0 4.4 moles (TMA) 0 650 moles H₂0 The resulting solid product was recovered by filtration and dried in air at ambient temperature. The product was then calcined at 540°C for 1 hour in nitrogen, followed by 6 hours in air. The calcined product proved to have the following equilibrium adsorption capacities in grams/100 grams: H₂0 35.2

Cyclohexane > 50 n-Hexane 40.8

Benzene 53.5

The X-ray diffraction pattern of the calcined product may be characterized as including a very strong relative intensity line at 39.1 + 2.0 A d-spacing and weak lines at 22.4 + 1.0 and 19.4 + 1.0 A. TEM indicated that this product contained the ultra-large pore material.

Example 14 A mixture of 125 grams of 29% CTMA chloride aqueous solution, 200 grams of water, 3 grams of sodium aluminate (in 50 grams H₂0) , 65 grams of Ultrasil, amorphous precipitated silica available from PQ Corporation, and 21 grams NaOH (in 50 grams H₂0) was stirred thoroughly and crystallized at 150°C for 168 hours. The reaction mixture had the following relative molar composition in terms of moles per mole silica: 0.10 moles (CTMA)₂0 21.89 moles H₂0 0.036 moles NaA10₂ 0.53 moles NaOH The solid product was isolated by filtration, washed with water, dried for 16 hours at room temperature and calcined at 540°C for 10 hours in air. The' calcined product proved to have a surface area of

840 m 2/g, and the followi.ng equi.li.bri.um adsorption capacities in grams/100 grams:

H₂0 15.2

Cyclohexane 42.0 n-Hexane 26.5

Benzene 62

The X-ray diffraction pattern of the calcined product may be characterized as including a very strong relative intensity line at 40.5 ± 2.0 A d-spacing. TEM indicated that the product contained the ultra-large pore material.

Example 15

To make the primary template mixture for this example, 240 grams of water was added to a 92 gram solution of 50% dodecyltrimethylammonium hydroxide, 36% isopropyl alcohol and 14% water such that the mole ratio of Solvent/R _/f0 was 155. The mole ratio of

H₂0/R _/f0 in this mixture was 149 and the IPA/R_2/f0 mole ratio was 6. To the primary template mixture was added 4.15 grams of sodium aluminate, 25 grams of

HiSil, 100 grams of aqueous tetramethylammonium silicate solution (10% Si0₂) and 13.2 grams of 25% aqueous tetramethylammonium hydroxide solution. The mole ratio of R_2/f0/(Si0₂+Al₂0 ) was 0.28 for the mixture.

This mixture was stirred at 25°C for 1 hour. The resulting mixture was then placed in an autoclave at

100°C and stirred at 100 rpm for 24 hours. The mixture in the autoclave had the following relative molar composition in terms of moles per mole Si0₂:

0.05 mole Na₂0

0.036 mole Al₂0₃

0.18 mole (C₁₂TMA)₂0

0.12 mole (TMA)₂0

36.0 moles H₂0

1.0 mole IPA ^• The resulting solid product was recovered by filtration, washed with water and dried in air at ambient temperature. The product was then calcined at 540°C for 1 hour in nitrogen, followed by 6 hours in air.

The calcined product proved to have a surface area of 1223 m 2/g and the following equilibrium adsorption capacities in grams/100 grams:

H₂0 25.5

Cyclohexane 41.1 n-Hexane 35.1

Benzene 51

The X-ray diffraction pattern of the calcined product may be characterized as including a very strong relative intensity line at 30.8 + 1.5 A d-spacing and weak lines at 17.9 ± 1.0 and 15.5 + 1.0 A. TEM indicated this product to contain the ultra-large pore material.

Example 16

A 50.75 gram quantity of decyltrimethylammonium hydroxide (prepared by contacting a ca. 29 wt.% solution of decyltrimethylammonium bromide with a hydroxide-for-halide exchange resin) was combined with

8.75 grams of tetraethylorthosilicate. The mixture was stirred for about 1 hour and then transferred to a polypropylene jar which was then placed in a steambox for about 24 hours. The mixture had a composition in terms of moles per mole Si0₂:

0.81 mole (C_1QTMA)₂0

47.6 moles H O

The resulting solid product was filtered and washed several times with warm (60-70°C) distilled water and with acetone. The final product was calcined to 538°C in N_?/air mixture and then held in air for about 8 hours. The calcined product proved to have a surface area of 915 /g and an equilibrium benzene adsorption capacity of 35 grams/100 grams. Argon physisorption data indicated an argon uptake of 0.34 cc/gram, and a pore size of 15 A.

The X-ray diffraction pattern of the calcined product of this example may be characterized as including a very strong relative intensity line at 27.5 + 1.5 A d-spacing and weak lines at 15.8 + 1.0 and 13.7 + 1.0 A. TEM indicated that the product of this example contained the ultra-large pore material.

Example 17

To eighty grams of cetyltrimethylammonium hydroxide (CTMAOH) solution prepared as in Example 1 was added 1.65 grams of NaAlO . The mixture was stirred at room temperature until the NaAlO was dissolved. To this solution was added 40 grams of aqueous tetramethylammonium (TMA) silicate solution (10 wt.% SiO ) , 10 grams of HiSil, 200 grams of water and 70 grams of 1,3,5-trimethylbenzene (mesitylene) . The resulting mixture was stirred at room temperature for several minutes. The gel was then loaded into a 600 cc autoclave and heated at 105°C for sixty-eight hours with stirring at 150 rpm. The mixture had a composition in terms of moles per mole A1₂0₃:

The resulting product was filtered and washed several times with warm (60-70°C) distilled water and with acetone. The final product was calcined to 538°C in N_/air mixture and then held in air for about 10 hours. The calcined product proved to have an equilbrium benzene adsorption capacity of >25 grams/100 grams.

The X-ray diffraction pattern of the calcined product may be characterized as including a broad, very strong relative intensity line at about 102 A d-spacing, but accurate positions of lines in the extreme low angle region of the X-ray diffraction pattern are very difficult to determine with conventional X-ray diffractometers. Furthermore, finer collimating slits were required to resolve a peak at this low 2-theta angle. The slits used in this example, starting at the X-ray tube, were 0.1, 0.3, 0.5 and 0.2 mm, respectively. TEM indicated that the product of this example contained several materials with different -₀_ values as observed in their electron diffraction patterns. These materials were found to possess d values between about 85 A d-spacing and about 120 A d-spacing.

Example 18 To eighty grams of cetyltrimethylammonium hydroxide (CTMAOH) solution prepared as in Example 1 was added 1.65 grams of NaAlO-. The mixture was stirred at room temperature until the NaAlO- was dissolved. To this solution was added 40 grams of aqueous tetramethylammonium (TMA) silicate solution (10 wt.% Sio ) , 10 grams of HiSil, 200 grams of water and 120 grams of 1,3,5-trimethylbenzene (mesitylene) . The resulting mixture was stirred at room temperature for several minutes. The gel was then loaded into a 600 cc autoclave and heated at 105°C for ninety hours with stirring at 150 rpm. The mixture had a composition in terms of moles per mole Al 0_: 1.25 moles a₂0 27.8 moles Si0₂ 5.1 moles (CTMA) 0 2.24 moles (TMA)₂0 2256 moles H₂0

132.7 moles 1,3,5-trimethylbenzene The resulting product was filtered and washed several times with warm (60-70°C) distilled water and with acetone. The final product was calcined to 538°C in N₂/air mixture and then held in air for about 10 hours. The calcined product proved to have a surface area of 915 m 2/g and an equilbrium benzene adsorption capacity of >25 grams/100 grams. Argon physisorption data indicated an argon uptake of 0.95 cc/gram, and a pore size centered on 78 A (Dollimore-Heal Method, see

Example 22(b) ) , but running from 70 to greater than 105

Angstoms. The X-ray diffraction pattern of the calcined product of this example may be characterized as having only enhanced scattered intensity in the very low angle region of the X-ray diffraction, where intensity from the transmitted incident X-ray beam is usually observed. However, TEM indicated that the product contained several materials with different d__0Q values as observed in their electron diffraction patterns. These materials were found to possess d-₀ values between about 85 A d-spacing and about 110 A d-spacing.

Example 19

To eighty grams of cetyltrimethylammonium hydroxide (CTMAOH) solution prepared as in Example 1 was added 1.65 grams of NaA10₂. The mixture was stirred at room temperature until the NaA10₂ was dissolved. To this solution was added 40 grams of aqueous tetramethylammonium (TMA) silicate solution (10 wt.% Si0₂) , 10 grams of HiSil, and 18 grams of

1,3,5-trimethylbenzene (mesitylene) . The resulting mixture was stirred at room temperature for several minutes. The gel was then loaded into a 300 cc autoclave and heated at 105°C for four hours with stirring at 150 rpm. The mixture had a composition in terms of moles per mole A1₂0₃:

The resulting product was filtered and washed several times with warm (60-70°C) distilled water and with acetone. The final product was calcined to 538^βC in N /air mixture and then held in air for about 8 hours.

The calcined product proved to have a surface area of 975 m 2/g and an equi.lbri.um benzene adsorption capacity of >40 grams/100 grams. Argon physisorption data indicated an argon uptake of 0.97 cc/gram, and a pore size of 63 A (Dollimore-Heal Method) , with the peak occurring at P/P =0.65.

The X-ray diffraction pattern of the calcined product of this example may be characterized as including a very strong relative intensity line at 63 +

5 A d-spacing and weak lines at 36.4 + 2.0, 31.3 + 1.5

A and 23.8 + 1.0 A d-spacing. TEM indicated that the product of this example contained the ultra-large pore material.

Example 20

Argon Physisorption Determination

To determine the pore diameters of the mesoporous products with pores up to about 60 A in diameter, 0.2 gram samples of the products of Examples 1 through 17 were placed in glass sample tubes and attached to a physisorption apparatus as described in U.S. Patent No.

4,762,010.

The samples were heated to 300°C for 3 hours in vacuo to remove adsorbed water. Thereafter, the samples were cooled to 87°K by immersion of the sample tubes in liquid argon. Metered amounts, of gaseous argon were then admitted to the samples in stepwise manner as described in U.S. Patent No. 4,762,010, column 20. From the amount of argon admitted to the samples and the amount of argon left in the gas space above the samples, the amount of argon adsorbed can be calculated. For this calculation, the ideal gas law and the calibrated sample volumes were used. (See also S.J. Gregg et al., Adsorption. Surface Area and Porosity. 2nd ed. , Academic Press, 1982). In each instance, a graph of the amount adsorbed versus the relative pressure above the sample, at equilibrium, constitutes the adsorption isotherm. It is common to use relative pressures which are obtained by forming the ratio of the equilibrium pressure and the vapor pressure P of the adsorbate at the temperature where the isotherm is measured. Sufficiently small amounts of argon were admitted in each step to generate 168 data points in the relative pressure range from 0 to 0.6. At least about 100 points are required to define the isotherm with sufficient detail.

The step (inflection) in the isotherm, indicates filling of a pore system. The size of the step indicates the amount adsorbed, whereas the position of the step in terms of P/ reflects the size of the pores in which the adsorption takes place. Larger pores are filled at higher P/P-** In order to better locate the position of the step in the isotherm, the derivative with respect to log (P/P ) is formed. The adsorption peak (stated in terms of log (P/P ) ) may be related to the physical pore diameter (A) by the following formula:

K .10 .10 log(P/P_o)=. d-0.38|3(L-D/2)³ 9(L-D/2)⁹ 3(D/2)³ 9(D/2)⁹

where d = pore diameter in nanometers, K = 32.17, S = 0.2446, L = d + 0.19, and D = 0.57. This formula is derived from the method of Horvath and Kawazoe (G. Horvath et al., J. Chem. Eng. Japan. 16 (6) 470(1983)). The constants required for the implementation of this formula were determined from a measured isotherm of ALP0-5 and its known pore size. This method is particularly useful for microporous materials having pores of up to about 60 A in diameter.

The results of this procedure for the samples from Examples 1 through 16 are tabulated below. The samples from Examples 10, 13 and 15 gave two separate peaks, believed to be the result of two separate ultra-large pore phases in the products.

Examples Pore Diameter. A

1 32.2

2 35.4

3 42.5

4 39.6

5 16.9

6 27.3

7 36.6

8 42.6

9 28.3

10 22.8, 30.8

11 36.8

12 36.1

13 35.0, 42.1

14 40.0

15 22.4, 30.4

16 15.0

By way of comparison, a commercially prepared sample of zeolite USY (equilibrium benzene sorption capacity of 20.7 grams/100 grams, X-ray diffraction pattern with all the lines of zeolite Y and with the highest d-spacing at about 14 A) had a pore diameter of about 8.3 A as determined by the above method.

The method of Horvath and Kawazoe for determining pore size from physisorption isotherms was intended to be applied to pore systems of up to 20 A diameter; but with some care as above detailed, its use can be extended to pores of up to 60 A diameter.

In the pore regime above 60 A diameter, the Kelvin equation can be applied. It is usually given as:

-2_V

In(P/P ) = cos θ r_kRT where: θ = surface tension of sorbate

V = molar volume of sorbate θ = contact angle (usually taken for practical reasons to be 0)

R = gas constant

T = absolute temperature r, = capillary condensate (pore) radius

P/P = relative pressure (taken from the physisorption isotherm)

The Kelvin equation treats adsorption in pore systems as a capillary condensation phenomenon and relates the pressure at which adsorption takes place to the pore diameter through the surface tension and contact angle of the adsorbate (in this case, argon) . The principles upon which the Kelvin equation are based are valid for pores in the size range 50 to 1000 Angstrom diameter. Below this range the equation no longer reflects physical reality, since true capillary condensation cannot occur in smaller pores; above this range the logarithmic nature of the equation precludes obtaining sufficient accuracy for pore size determination.

The particular implementation of the Kelvin equation often chosen for measurement of pore size is that reported by Dollimore and Heal (D. Dollimore and G.R. Heal, J. Applied Chem. 14. 108 (1964)). This method corrects for the effects of the surface layer of adsorbate on the pore wall, of which the Kelvin equation proper does not take account, and thus provides a more accurate measurement of pore diameter. While the method of Dollimore and Heal was derived for use on desorption isotherms, it can be applied equally well to adsorption isotherms by simply inverting the data set. Transmission Electron Microscopy

In order to illuminate the microstructure of materials by transmission electromicroscopy (TEM) , samples must be thin enough for an electron beam to pass through them, generally about 500-1000 A or so thick. The crystal morphology of the present materials usually required that they be prepared for study by ultramicrotomy. While time consuming, this technique of sample preparation is quite familiar to those skilled in the art of electron microscopy. The materials are embedded in a resin, in this case a commercially available low viscosity acrylic resin L.R. WHITE (hard), which is then cured at about 80°C for about 1 1/2 hours. Thin sections of the block are cut on an ultramicrotome using a diamond knife and sections in the thickness range 500-1000 A are collected on fine mesh electron microscope support grids. For these materials, an LKB model microtome with a 45°C diamond knife edge was used; the support grids were 400 mesh copper grids. After evaporation of a thin carbon coating on the sample to prevent charging in the microscope (light gray color on a white sheet of paper next to the sample in the evaporator) , the samples are ready for examination in the TEM.

High resolution TEM micrographs show projections of structure along the direction that the sample is viewed. For this reason, it is necessary to have a sample in specific orientations to see certain details of the microstructure of the material. For crystalline materials, these orientations are most easily chosen by observing the electron diffraction pattern (EDP) that is produced simultaneously with the electron microscope image. Such EDPs are readily produced on modern TEM instruments using, e.g. the selected area field limiting aperture technique familiar to those skilled in the art of electron microscopy. When an EDP with the desired arrangement of diffraction spots is observed, the corresponding image of the crystal giving that EDP will reveal details of the microstructure along the direction of projection indicated by the EDP. In this way, different projections of a crystal's structure can be observed and identified using TEM.

In order to observe the salient features of the crystalline product of the present invention, it is necessary to view the material in an orientation wherein the corresponding EDP gives a hexagonal arrangement of diffraction spots from a single individual crystal. If multiple crystals are present within the field limiting aperture, overlapping diffraction patterns will occur that can be quite difficult to interpret. The number of diffraction spots observed depends to a degree upon the regularity of the crystalline arrangement in the material, among other things. At the very least the inner ring of bright spots should be observed to obtain a good image. Individual crystals can be manipulated by specimen tilt adjustments on the TEM until this orientation is achieved. More often, it is easier to take advantage of the fact that the specimen contains many randomly oriented crystals and to simply search through the sample until a crystal giving the desired EDP (and hence orientation) is located. This latter technique was used to produce the electron micrographs discussed below.

Microtomed samples of materials from the Examples were examined by the techniques described above in a JEOL 200 CX transmission electron microscope operated at 200,000 volts with an effective 2 A objective aperture in place. The instrument has a point-to-point resolution of 4.5 A. Other experimental arrangements familiar to one skilled in the art of high resolution (phase contrast) TEM could be used to produce equivalent images provided care is taken to keep the objective lens on the underfocus (weak leans) side of the minimum contrast lens current setting.

Example 21 This example illustrates the activity of the mesoporous catalyst of the invention for the ethylation of benzene.

Benzene was reacted with ethylene in a fixed-bed pilot plant unit at 300-500 psig (2170 to 3550 kPa) pressure and 10:1 mole ratio of benzene of ethylene. The catalyst was composed of 65 wt% H-form MCM-41 prepared by the method described in Example 13 above, in 35 wt percent 1₂0 (Versal 250 - trademark) . The catalyst was prepared by mulling and pelletizing the MCM-41/alumina mixture followed by calcination in air after which the calcined product was exchanged with ammonium nitrate solution and calcined to bring the mesoporous material in the binder to its hydrogen form for the desired catalytic activity. For a comparison, a typical ZSM-5 catalyst containing 65 wt percent zeolite was also evaluated in a similar manner. The catalyst performance is tabulated as follows:

Process Conditions:

Temp, °F(°C)

C₂= WHSV

C = Conversion, wt. pet. Product Selectivity, Wt%

Xylenes/EB

DEB/EB

C_g+/EB

As shown, the MCM-41 catalyst achieved a complete ethylene conversion at gas phase conditions. Although less active than ZSM-5 for ethylbenzene synthesis, the MCM-41 catalyst does not produce undesirable by-product xylenes; consistent with its pore dimensions, MCM-41 provided slightly higher polyalkylated products than those obtained with ZSM-5 (0.112 vs. 0.083 C.+/EB) .

Example 22 This example illustrates the activity of the ultra-large pore size catalyst of the invention for the alkylation of naphthalene. Catalyst Preparation

The following mixture was charged to an autoclave: 9965g Cetyltrimethylammonium (CTMA) hydroxide solution prepared by contacting a 29 wt. pet. N,N,N-trimethyl-1-hexdecylammonium chloride solution with a hydroxide-for-halide exchange resin, 208g Sodium aluminate, 492g Tetramethylammonim silicate (10% aqueous solution) , 1245g Precipitated hydrated silica (HiSil ♦)

The mixture was crystallized at 100°C for 20 hrs. with stirring under autogeneous pressure. The resulting product was recovered by filtration and dried in air at ambient temperature. A sample of the product was calcined at 540° C in nitrogen and then in air.

The calcined product had a surface area of 1120 m2/g and the following equilibrium absorption capacities in grams/100 grams:

H20 10.8

Cyclohexane >50 n-hexane >50

Benzene 67

This product exhibited a very strong relative intensity line at 38.4 + 2.0 Angstroms d-spacing, and weak lines at 22.6 + 1.0, 20.0 + 1.0, and 15.2 +1.0A.

A catalyst composed of 100% H-MCM-41 was prepared by pelletizing the MCM-41 produced by this method. The catalyst pellets were calcined successively in nitrogen and air, followed by exchange with ammonium nitrate solution, after which the exchanged, pelletized catalyst was calcined in air.

A naphthalene alkylation reaction was carried out in a 1 1. autoclave using 150g (0.612 moles) of a C..

1-olefin and 39 g (0.306 moles) of naphthalene with 5.4 g of the MCM-41 catalyst (2.85 wt%) at 400°F (200°C) for 6 hours under 50 psig (450 kPa) nitrogen pressure. After decanting and filtering the catalyst, the total liquid product was vacuum distilled at 650°F (343°C) to obtain a lube range material. For comparison purposes, a USY zeolite catalyst was also evaluated for naphthalene alkylation reaction under identical conditions. A comparison of the catalyst performance is shown in the following table:

Table

Viscosity Index 102 98 • As shown, the ultra-large pore size catalyst achieved a complete conversion of naphthalene similar to the USY catalyst, but had much higher conversion of olefin (90 vs 68 wt%) . This is reflected in the increased alkylated naphthalene lube yield obtained with the ultra-large pore size catalyst (90 wt% vs 73 wt%) . Consistent with its ultra large pore dimensions, the MCM-41 catalyst promoted the formation of tri- and tetra-alkylated naphthalene products that could not be obtained with a conventional large pore USY catalyst. As a result, the product obtained from the MCM-41 catalyst, containing a higher level of the polyalkylated naphthalenes, has much higher viscosity than that obtained with USY (10.19 vs 5.58 cS @100°C) . In addition to its high viscosity, the polyalkylated naphthalene lubricant has a very low pour point (-48°C) and high VI (102 VI) . The use of a combination of the ultra-large pore materials in combination with conventional alkylation catalysts such as USY therefore has the potential to provide alkylated naphthalene synthetic lubes with a wide range of viscosities, thus providing flexibility in product application.

Claims

Claims :

1. A process for preparing an alkyl-substituted aromatic compound by reacting the aromatic compound with an alkylating agent in the presence of a catalyst comprising an inorganic, porous, non-layered crystalline phase material exhibiting, after calcination, an X-ray diffraction pattern with at least one peak at a d-spacing greater than about 18 Angstrom Units and having a benzene adsorption capacity of greater than 15 grams of benzene per 100 grams of said material at 6.7 kPa (50 torr) and 25°C.

2. A process acccording to claim 1 in which the crystalline phase material of the alkylation catalyst has, after calcination, a hexagonal arrangement of uniformly-sized pores with diameters of at least 13 A and exhibits a hexagonal electron diffraction pattern that can be indexed with a d_1Q_ value greater than about 18 A.

3. A process according to claim 1 in which the crystalline phase has an X-ray diffraction pattern following calcination with at least one peak whose d-spacing corresponds to the d_₀₀ value from the electron diffraction pattern.

4. A process according to claim 1 in which the crystalline phase has a composition expressed as follows:

^Mn/q^(Wa^Xb^Yc^Zd°h> wherein M is one or more ions; n is the charge of the composition excluding M expressed as oxides; q is the weighted molar average valence of M; n/q is the number of moles or mole fraction of M; W is one or more divalent elements; X is one or more trivalent elements; Y is one or more tetravalent elements; Z is one or more pentavalent elements; a, b, c, and d are mole fractions of W, X, Y, and

Z, respectively; h is a number of from 1 to 2.5; and (a+b+c+d) = 1.

5. A process according to claim 4 wherein W comprises a divalent first row transition metal or magnesium; X comprises aluminum, boron, gallium or iron; Y comprises silicon or germanium; and Z comprises phosphorus.

6. A process according to claim 5 wherein a and d are 0 and h = 2.

7. A process according to claim 6 wherein X comprises aluminum and Y comprises silicon.

8. A process according to claim 1 in which the reaction is conducted at a temperature of 90°C to 500°C, a pressure of 100 to 25000 kPa, a feed weight hourly space velocity (WHSV) of 0.1 to 10

—₁ hr and an alkylatable aromatic compound to alkylating agent mole ratio of 0.1:1 to 50:1.

9. ^• A process according to Claim 8 wherein the reaction is the alkylation of naphthalene or a substituted naphthalene and is conducted at a temperature of 90° to 315°C, a pressure of 450 to 7000 kPa, a WHSV of 0.1 to 5.0 and an alkylatable aromatic compound to alkylating agent mole ratio of 0.5:1 to 5:1.

10. A process according to Claim 8 wherein the reaction is the ethylation of benzene and is conducted in the vapor phase at a temperature of 315 to 430°C, a pressure of 1480 to 3550 kPa, a space velocity of 1 to 10 WHSV based on the ethylene and with the weight ratio of benzene to ethylene being 15:1 to 25:1.

11. A process according to Claim 8 wherein the reaction is the ethylation of benzene and is conducted in the liquid phase at a temperature of 150 to 315°C, a pressure of 2860 to 5620 kPa, a space velocity of 1 to 10 WHSV based on the ethylene and with the weight ratio of benzene to ethylene being 15:1 to 25:1.