KR0172612B1 - Synthetic porous crystalline material, its synthesis and use - Google Patents

Abstract

The present invention exhibits an X-ray diffraction pattern with at least one peak at a d-spacing of at least 1.8 nanometers after calcination and has a benzene adsorption capacity of at least 15 g of benzene per 100 g of crystalline material at 6.7 kPa (50 Torr) and 25 ° C. A composition containing a porous, non-laminated inorganic crystalline material. Preferably, the crystalline material exhibits a hexagonal electron diffraction pattern that can be indexed as having a ^d 100 value of at least 1.8 nanometers after calcination, with uniformly sized pores of at least 1.3 nanometers in diameter.

Description

[Name of invention]

Synthetic porous crystalline material, its synthesis method and use

Detailed description of the invention

The present invention relates to synthetic porous crystalline materials, methods for their synthesis and their use as adsorbents or catalyst components.

Porous inorganic solids have been found to be very useful as industrial catalysts and separation media. The openness of the porous inorganic solids allows the molecules to contact the relatively large surface area of these materials, thereby increasing the catalytic performance and adsorptivity. Currently used porous materials can be classified into three broad categories using the substructure of these microstructures as a basis for classification. These categories are amorphous and irregular crystalline materials, crystalline molecular sieves and modified layered materials. The detailed differences in the microstructure of these materials are themselves such as the surface area of these materials, the variability in pore size and pore size, the presence or absence of X-ray diffraction patterns and the appearance of materials such as details in these patterns, etc. As can be seen, the various observable properties used to characterize them, as well as the differences in the appearance of the materials when these microstructures are examined by electron diffraction under a transmission electron microscope, are important in the catalysis and adsorption of these materials. Appears as a difference.

Amorphous and irregular crystalline materials are an important class of porous inorganic solids that have been used for industrial purposes for many years. Representative examples of these materials include amorphous silica and solid acid catalysts commonly used in catalyst formulations and irregularly crystalline transition aluminas used as petroleum reforming catalyst supports. The term amorphous is used herein to refer to a material that does not have a long range order so that the pore size of the material is distributed over a wider range. Another term used to describe these materials is X-ray indifferent, where a lack of order is also evident, which is generally uncharacteristic. The porosity of an amorphous material, such as amorphous silica, is due to the void space between each particle.

Irregular crystalline materials, such as transitional alumina, also have a wide distribution of pore sizes, but have a better defined X-ray diffraction pattern, which typically consists of several broad peaks. The microstructure of these materials consists of small crystal regions on condensed alumina, and the porosity of these materials is due to the irregular spacing between these regions (K. Wefers and Chanakya Misra, Oxides and Hydroxides of Aluminum, Technical Paper No. 19 Revised, Alcoa Research Laboratories, p. 54-59, 1987).

The size of the amorphous and irregular crystalline pores belongs to the limit region called the mesoporous range, which is 1.3 to 20 nanometers for the purposes of the present invention.

In contrast to these structurally unclear solids, there are materials with very narrow pore size distribution because the pore size is controlled by precisely repeating crystalline units in the three-dimensional backbone of the material. These materials are called molecular sieves, the most important example of which is zeolite.

The precise crystalline microstructure of most zeolites generally contains a large number of distinct values and exhibits well-defined X-ray diffraction patterns used to uniquely define the material. Similarly, the size of the pores in these materials is very regular due to the precise repetition of the crystalline microstructures. All molecular sieves found to date are generally 0.2 to 2 nanometers in size and the largest reported have a pore size in the micropore range of about 1.2 nanometers.

In the case of laminated materials, the interatomic bonds in both directions of the crystalline lattice are actually different from the interatomic bonds in the three directions, resulting in a structure containing sheets in the form of aggregated units. In general, interatomic bonds in these sheets are made of strong covalent bonds, while adjacent layers are held together by ionic force or Vander Waals interaction. Van der Waals interactions can often be neutralized by relatively weak chemical means, but the bonds between atoms in the layer remain intact and are typically unaffected.

Thus, in the case of certain laminated materials, adjacent layers may be separated by a swelling agent and then inserted into the columnar material to fix the layers in the separated locations to provide a material having a high porosity. For example, certain clays can be swollen by water, whereby layers of clay can be separated by water molecules. Other lamination materials cannot be swollen by water, but may be swollen by certain organic swelling agents such as amines and quaternary ammonium compounds. Examples of such non-water swellable laminate materials are described in US Pat. No. 4,859,648, which describes laminated silicates, magadiite, kenyaite, trititanate and perovskite. Included. Another example of a non-water swellable laminate material, which may be swelled by certain organic swelling agents, is a pore-containing titanometallate material described in US Pat. No. 4,831,006. The X-ray diffraction pattern of the columnarized laminate material can vary considerably depending on the degree to which the swelling and columnarization breaks otherwise well-ordered laminate microstructures.

In some columnarized stacking materials, the regularity of the microstructure is quite severely broken, so that the low-angle of the X-ray diffraction pattern at the d-spacing corresponding to the interlayer repetition in the columnarized material. Only one peak in the region is observed. Low-breakdown materials can exhibit several peaks in this region, which is generally the order of this basic iteration. X-ray reflections from the crystalline structure of these layers are also sometimes observed. The pore size distribution in these columnarized laminate materials is narrower than the pore size distribution of amorphous and irregular crystalline materials, but wider than the pore size distribution of crystalline framework materials.

Laminated materials sometimes exhibit a sheet-like morphology that reflects differences in the bonds present on the atomic level. Such morphology can be confirmed by transmission electron micrographs.

The present invention shows an X-ray diffraction pattern having at least one peak at a d-spacing of 1.8 nanometers or more after calcination, and has a benzene absorption capacity of at least 15 g of benzene per 100 g of the material at 6.7 kPa (50 torr) and 25 ° C. It relates to an inorganic, porous, non-laminated crystalline phase material having.

In a preferred embodiment, the present invention is an inorganic, porous, crystalline phase that exhibits a hexagonal electron diffraction pattern that has a uniform hexagonal pore size with a diameter of at least 1.3 nanometers and may have a ^d 100 value of at least 1.8 nanometers after calcination. A composition of matter consists of matter.

The pore size mentioned here is not a precise crystal size, but an effective pore size determined by adsorption measurement. Preferred methods for determining pore size use known techniques, argon physisorption described in detail in Examples 21 (a) and 21 (b). In this method, at a constant temperature, the mass of argon adsorbed by the sample is measured while varying the relative pressure on the sample and used to prepare the adsorption isotherm. The point of the isotherm corresponding to the rapid change of the gradient indicates that the pores are filled, which may be used to determine the pore size by known mathematical relations described in Example 21.

Crystalline material of the present invention (ie, it means here having sufficient regularity to provide a diffraction pattern having at least one peak after calcination, for example by X-ray, electron or neutron diffraction), is very It can be characterized by its large pore window and its unknown structure including high adsorption capacity. In general, the material of the present invention is mesoporous, which means that the material has uniform pores of 1.3 to 20 nanometers in diameter. More preferably, the material of the present invention has uniform pores of 1.8 to 10 nanometers straight. In this regard, the pore size is the maximum vertical cross sectional size of the pore.

The material of the present invention is distinguished from other porous inorganic solids by the regularity of its large open pores, the size of which is almost similar to the pore size of amorphous or irregular crystalline material, but the uniformity of its regular arrangement and size (eg For example, the pore size distribution within a single phase of ± 25%, typically ± 15% or less of the average pore size of a single phase) is more similar to the regular arrangement and size of the crystalline framework material, such as zeolites.

In a preferred arrangement, the porosity of the crystalline material of the present invention is generally provided by a hexagonal arrangement of open channels, which can be easily observed by electron diffraction and transmission electron micrographs.

In particular, transmission electron micrographs of suitably oriented samples of the material show large channels of hexagonal arrangement, and corresponding electron diffraction patterns show approximately hexagonal arrangement of diffraction maxima. The ^d 100 spacing of the electron diffraction pattern is the distance between two adjacent points on the hko projection of the hexagonal grating, which is related to the repetition distance ^a 0 between the channels observed in the electron micrograph via the relationship ^d 100 = ^a 0√3 / 2. will be. This ^d 100 interval observed in the electron diffraction pattern corresponds to the d-spacing of the low angle peak in the X-ray diffraction pattern of the material. The most highly ordered preparation of this material so far obtained has 20 to 40 distinct points that can be observed in the electron diffraction pattern. These patterns can be divided into hexagonal hk0 subsets of unique reflections such as 100, 110, 200, 210, and their symmetry-related reflections.

In this regard, it is to be understood that the hexagonal arrangement of channels includes not only mathematically perfect hexagonal symmetry, but also an arrangement surrounded by six out channels closest to each other in practically the same distance. Defects and imperfections can cause many channels to deviate from this criterion at various angles. Samples exhibiting an irregular deviation of ± 25% from the mean repeat distance between adjacent channels show a recognizable image of the maximum bubble material present.

The most regular preparation of the preferred material of the present invention exhibits a hexagonal X-ray diffraction pattern with some distinct maxima in the ultralow angle region. However, X-ray diffraction patterns are not always sufficient indicators of the presence or absence of such materials because the degree of regularity in the microstructure and the repeatability of the structures in the individual particles affect the number of peaks observed.

In fact, it has been found that preparations with one distinct peak in the low angle region of the X-ray diffraction pattern contain significant amounts of the material of the present invention.

In the calcined form, the crystalline material of the present invention is also at a position of about 1.8 nanometer d-spacing (4.090 ° 2-θ for Cu K-α radiation) corresponding to the ^d 100 value of the electron diffraction pattern of the material. It can be characterized by an X-ray diffraction pattern having at least one peak.

More preferably, the calcined crystalline material of the present invention has at least two peaks at positions greater than 1 nanometer d-spacing (8.842 ° 2-θ for Cu K-α radiation) and 1.8 nanometer d-spacing It is characterized by a peakless X-ray diffraction pattern with a relative intensity greater than about 20% of the strongest peak at the position below. In particular, the X-ray diffraction pattern of the calcined material of the present invention does not have a peak having a relative intensity greater than about 10% of the strongest peak at locations less than about 1 nanometer d-spacing. In a preferred hexagonal arrangement, at least one peak in the X-ray pattern will have a d-spacing corresponding to the ^d 100 value of the electron diffraction pattern of the material.

X-ray diffraction patterns herein are collected on a Scintag PAD X automated diffraction system using θ-θ geometry, Cu K-α radiation and an energy dispersive X-ray detector. The use of energy dispersive X-ray detectors can obviate the need for beam monochromators to be projected or diffracted. Both projected or diffracted X-ray beams can be parallelized by double slit projection and diffracted beam parallelism systems. The slit sizes used are 0.5, 1.0, 0.3 and 0.2 mm respectively starting from the X-ray tube. The differential slit system produces a differential intensity for the peak. Materials of the present invention with the largest pore size need to be more highly parallelized to projected X-ray beams in order to interpret low angle peaks from the transmitted projected X-ray beams.

Diffraction data is recorded by step-scanning at 0.04 ° of 2-θ, where θ is the Bragg angle and a counting time of 10 seconds for each step. The distance between planes, d's, is calculated in nanometers (nm), and the relative intensity I / Io of the line is calculated using a profile fitting routine, where Io is the intensity of the strongest line in the background. Is one hundredth of. This intensity is not corrected for Lorentz and polarization effects. Relative intensity is represented by the following terms: vs = very strong (75 to 100), s = strong (50 to 74), m = medium (25 to 49) and w = weak (0 to 24). It can be understood that diffraction data recorded as a single line consists of multiple overlapping lines that can appear as separate or partially separated lines under certain conditions such as very high experimental resolution or crystal change. In general, crystal changes may include small changes in unit lattice parameters and / or changes in crystal symmetry without substantial changes in structure.

These collateral effects, including changes in relative intensity, are the peak width / shape due to cation content, basic structural composition, nature and extent of pore filling, thermal and / or hydrothermal history, and particle size / shape effects. It may also appear due to variations, structural disorders, or differences in other factors known to those skilled in the X-ray diffraction art.

The material of the present invention should be measured on a sample free of pore blockage by accidental contaminants with an equilibrium benzene adsorption capacity of at least 15 g of benzene per 100 g of crystals at 6.7 kPa (50 Torr) and 25 ° C. For example, water can be removed by dehydration techniques such as heat treatment, and amorphous inorganic and organic materials such as silica or the like can be removed from acids or bases that can remove crushed materials without adversely affecting the materials of the present invention. It may be contacted with other chemicals and / or removed by physical means (such as calcination).

In general, the crystalline material of the present invention has the following composition:

Wherein W is the divalent transition metal in the first row of the transition metal, for example manganese, cobalt, nickel and iron and / or magnesium, preferably divalent elements such as cobalt;

X is a trivalent element such as aluminum, boron, chromium, 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, IA, IIA and VIIB ions, common hydrogen, sodium and / or fluoride ions;

n is the charge of the composition except M expressed in oxides;

q is the weighted molar average valence of M;

n / q is the mole number or mole fraction of M;

a, b, c and d are the mole fractions of W, X, Y and Z, respectively;

h is a number from 1 to 2.5,

(a + b + c + d) is one.

Preferred embodiments of the crystalline material are those where (a + b + c) is greater than d and h is 2. More preferred embodiments are substances when a and b are 0 and h is 2.

In the synthesized form, the material of the present invention has a composition represented by the following empirical formula based on anhydride:

In the above formula, R is not included in M as an ionic form and the substance is a whole organic substance used to help synthesize,

r is the coefficient for R, ie the number or mole fraction of R.

The M and R components are combined with materials due to their presence during crystallization and are easily removed or substituted in the case of M by conventional post-crystallization methods described in more detail below. For example, the first M ions, such as sodium or chloride ions, of the synthetic material of the present invention can be substituted by ion exchange with other ions. Preferred substituted ions include metal ions, hydrogen ions, hydrogen precursor ions such as ammonium ions and mixtures thereof. Particularly preferred ions are those which provide adequate catalytic activity for certain hydrocarbon conversion reactions. These include the IA (e.g., K), IIA (e.g. Ca), and VIIA (e.g., hydrogen, rare earth metals, and elements of the Periodic Table (Sargent-Welch Scientific Co. Cat. No. S-18806, 1979)). For example Mn), VIIA (e.g. Ni), IB (e.g. Cu), IIB (e.g. Zn), IIIB (e.g. In), IVB (e.g. Sn) and Metals of the VIIB group (eg F) and mixtures thereof.

Materials having a composition defined by the above structural formula can be prepared from reaction mixtures having the present composition as molar ratios of oxides within the following ranges:

In the above, e and f are the weighted average valences of M and R, respectively, and the solvent is 1-6 alcohol or diol, or more preferably mole, R is of the general formula RRRRQ Consisting of an organic aligning agent, wherein Q is nitrogen or phosphorus, and at least one of R, R, R and R is 6 to 36 carbon atoms such as, for example, -CH, -CH, -CH, -CH, etc. Aryl or alkyl group, and each of the rest of R, R, R and R is selected from hydrogen and an alkyl group having 1 to 5 carbon atoms. For example, the ammonium or phosphonium ions can be derived from compounds such as hydroxides, halides, silicates or mixtures thereof.

Compared with these other reagents known for the direct synthesis of one or more other crystal structures, it is believed that the particular effect of the alignment agent is due to its function as a template in nucleation and the growth of the desired macroporous material. Examples of these alignment agents include cetyltrimethylammonium, cetyltrimethylphosphonium, octadecyltrimethylphosphonium, benzyltrimethylammonium, cetylpyridinium, myristyltrimethylammonium, decyltrimethylammonium, dodecyltrimethylammonium and dimethyldidosilammonium compounds But not limited to these.

Preferably, the total organics R present in the reaction mixture are each selected from R, R, R and R except that hydrogen is selected from hydrogen and alkyl groups of 1 to 5 carbon atoms (two alkyl groups being linked to each other to form a cyclic compound). And a separate organic aligning agent in the form of ammonium or phosphonium ion of the above aligning agent structure. Examples of such separate organic alignment agents include tetramethylammonium, tetraethylammonium, tetrapropylammonium, tetrabutylammonium and pyrrolidinium compounds. The molar ratio of the first mentioned organic aligning agent to the separate organic aligning agent may range from 100/1 to 0.01 / 1. If a separate organic flavor is present, The molar ratio of is preferably 0.1 to 2.0, most preferably 0.12 to 1.0.

In addition, in order to change the pore size of the final crystalline material, the total organic matter R in the reaction mixture may include auxiliary organic matters in addition to the organic alignment agent (s) described above. These auxiliary organics include (1) aromatic hydrocarbons and amines having 5 to 20 carbon atoms and halogen- and C ₁ -C ₁₄ -alkyl-substituted derivatives thereof, (2) cyclic having 5 to 20 carbon atoms ( cyclic) alc polycyclic aliphatic hydrocarbons and amines and halogen- and C ₁ -C ₁₄ -alkyl-substituted derivatives thereof and (3) straight or branched chain aliphatic hydrocarbons and amines having 3 to 16 carbon atoms and their It is selected from halogen-substituted derivatives of.

In said auxiliary organics, the halogen substituent is preferably bromine. C ₁ -C ₁₄ alkyl substituents are, for example, straight or branched chain aliphatic hydrocarbons such as methyl, ethyl, propyl, isopropyl, butyl, pentyl and combinations thereof. Examples of these auxiliary organics include, for example, p-xylene, trimethylbenzene, trimethylbenzene and triisopropylbenzene.

Regarding the inclusion of the auxiliary organics in the reaction mixture, the molar ratio of the auxiliary organics / YO is 0.05 to 20, preferably 0.1 to 10, and the molar ratio of the auxiliary organics / organic alignment agent (s) is 0.02 to 100, preferably 0.05 to 35.

If a silicon source is used in the synthesis, it is preferred that at least partly an organic silicate is used, for example quaternary ammonium silicate. Examples of such silicates include, but are not limited to, tetramethylammonium silicate and tetraethylorthosilicate.

Non-limiting examples of various combinations of W, X, Y, and Z that may be considered for the reaction mixture include W is an element selected from Mg or the divalent transition metal of the first row, such as Mn, Co and Ni; X is B, Ga or Fe; Examples include the following, including combinations where Y is Ge.

The abovementioned reaction mixture is generally 5 minutes to 14 days, more preferably 1 to 300, at a temperature of 25 ° C to 250 ° C, preferably at a temperature of 50 ° C to 175 ° C, preferably at a pH of 9-14 The crystalline material of the present invention is prepared by holding it for a time until the desired crystal is produced.

When the crystalline material of the present invention is aluminosilicate, the synthesis typically comprises the following steps:

(1) The organic (R) aligning agent is mixed with the solvent or solvent mixture so that the molar ratio of solvent / R _{2 / f} O is within the range of 50 to 800, preferably 50 to 500. This mixture constitutes the primary template for this synthesis.

(2) Silica and alumina are added to the primary template mixture of step (1) so that the ratio of R _{2 / f} O / (SiO ₂ + Al ₂ O ₃ ) is within the range of 0.01 to 2.0.

(3) The mixture obtained in step (2) is stirred at a temperature of 20 ° C to 40 ° C, preferably for 5 minutes to 3 hours.

(4) The reaction mixture is allowed to stand, preferably with or without stirring, at a temperature of 20 ° C. to 50 ° C., preferably for 10 minutes to 24 hours.

(5) The product of step (4) is crystallized at a temperature of 50 ° C to 150 ° C, preferably for 1 to 72 hours.

When the composition of the present invention is used as an adsorbent or catalyst component, it must be further treated to remove all or some organic components.

The composition of the present invention is also used as a catalyst component in a complete blend with hydrogenated components such as tungsten, vanadium, molybdenum, rhenium, riquels, cobalt, chromium, manganese or precious metals such as platinum or palladium or mixtures thereof. It may also be used, where hydrogenation-dehydrogenation is carried out. Such components can be introduced into the composition by co-crystallization, or can be changed into a composition by the extent of Group IIIB elements, such as aluminum, present in the structure by impregnation in the composition, or physically mixed with the composition completely. have. Such components may be impregnated in or on the silicates by, for example, treating platinum with a solution comprising platinum metal-containing ions. Thus, platinum compounds suitable for this purpose include various compounds containing chloroplatinic acid, first platinum chloride and platinum amine complexes.

In particular the crystalline materials in the form of metals, hydrogen and ammonium may be advantageously transformed into other forms by heat treatment (calcination). This heat treatment is generally carried out at a temperature of 400 to 750 ° C. for at least 1 minute, generally less than 20 hours, preferably 1 to 10 hours.

Although subatmospheric pressure can be used in the heat treatment method, atmospheric pressures such as air, nitrogen and ammonia are preferred for convenience. Heat treated products are particularly useful for promoting certain hydrogen oxide conversion reactions.

If the crystalline material of the present invention is used as an adsorbent or catalyst component in an organic compound conversion reaction, it must be at least partially dehydrated. This dehydration process can be carried out by heating to a temperature of 200 ° C. to 595 ° C. for 30 minutes to 48 hours under atmospheric pressure, reduced pressure or superatmospheric pressure and atmosphere such as air, nitrogen and the like. Dehydration can also be done by leaving the composition only in vacuo at room temperature, but requires a longer time to dehydrate sufficiently.

The composition of the present invention is useful as a catalyst component in catalyzing the conversion of organic compounds such as oxygenates and hydrocarbons by acid-catalyzed reactions. Pore size minimizes the spatiospecific selectivity of transitional species in reactions such as cracking (see Chen et al., Shape Selective Catalysis in Industrial Applications, 36 CHEMICAL INDUSTRIES, P. 41-). 61 (1989). Since the pore size of the material of the present invention is very large, diffusion limiting is also minimized. For this reason, the composition of the present invention occurs in the presence of acidic moieties on the surface of the catalyst, and the molecular size is so large that conventional large pore solid catalysts such as zeolites, X, Y, L, ZSM-4, ZSM- It is particularly useful for catalyzing reactions containing reactants, products or transitional species which are unable to carry out reactions similar to large pore zeolites such as 18 and ZSM-20.

Accordingly, the catalyst compositions of the present invention are molecules having a molecular size of 1.3 nanometers or more, such as higher aromatic hydrocarbons with substituted or unsubstituted polycyclic aromatic components, steric hindrance naphthenic compounds or polysubstituted compounds with steric hindrance arrangements. Particularly useful for the conversion of large organic compounds. The catalyst composition of the present invention is particularly useful for reactions that reduce the molecular weight of the feed to smaller values, for example cracking or hydrocracking. Cracking can be carried out for a contact time of 0.1 seconds to 60 minutes at a temperature of 200 to 800 ℃ and a pressure of atmospheric pressure to 100 psig (100 to 800 kPa). Hydrocracking can be carried out with a hydrogen / hydrocarbon molar ratio of 0.1 to 100 at a temperature of 150 to 550 ° C., a pressure of 100 to 3000 psig (800 to 20800 psig), and a space time velocity of 0.1 to 100.

The catalyst composition of the present invention is a high molecular weight, high boiling point or non-distillate feed, in particular a residual feed, i.e. a non-distillable feed or a feed having an initial boiling point (5% point) of at least 1050 ° F (565 ° C). More particularly useful in reactions with. Residual feeds that may be used with the catalyst compositions of the present invention include API gravity of less than about 20, generally less than 15 and typically from 5 to 10 and at least 1% by weight of conradsen carbon content (CCR) and More generally, feeds of at least 5% by weight or more, such as 5-10% by weight, are included. Some residual fractions may contain as much as about 20 weight percent or more of CCR. The aromatic content in these feeds will be high corresponding to the content of heteroatoms such as sulfur and nitrogen as well as metals. The aromatic content in these feeds is at least 50% by weight and typically more than, generally at least 70 or 80% by weight, with the remainder being naphthenes and heterocycles. Representative petroleum refining feeds of this type include aromatic extracts, such as phenol or furural extracts, deasphalted oils, slop oils and lube processes from atmospheric and vacuum tower bottoms, asphalt and solvent extraction processes. Residual fractions from various processes, such as cocking, and the like. High boiling fractions in which the catalyst composition of the present invention can be used include gas oils such as atmospheric gas oil; Vacuum gas oil; Cycle oils, in particular heavy cycle oils; Deasphalted oil; Solvent extracts such as bright stock; And heavy gas oils such as cocker heavy gas oils. The catalytic material of the present invention can also be used as a feed of non-petroleum sources, such as synthetic oils produced by liquefaction of coal, Fischer-Tropsch waxes and heavy fractions and similar materials.

The catalyst composition of the material according to the invention is also formed for treating gases containing nitrogen oxides (NOx), for example industrial exhaust gases and hydrocarbons, especially during oxidative regeneration of catalysts used in catalytic cracking processes. It can be used to selectively convert inorganic compounds, such as nitrogen compounds, in a mixture of gases. Porous crystalline materials can be used in matrix or unmatrixed form for this purpose, suitably capable of allowing gas to pass through the catalyst with minimal degradation of extrudates, pellets or pressures. It can be molded into other forms. The crystalline material is preferably at least partially in the form of hydrogen, but a small amount of precious metals, such as catalyst components, in particular the 5 and 6 periodic metals of the VIIIA group of the periodic table, in particular platinum, palladium, ruthenium, rhodium, iridium or mixtures thereof It may be advantageous to contain. Amounts of precious metal up to about 1% by weight are common and lesser amounts, such as up to 0.1-0.5% by weight, are preferred.

NOx reduction is suitably carried out by passing a gas containing nitrogen oxides over the catalyst at elevated temperatures, typically at least 200 ° C, and generally at a temperature of 200 to 600 ° C. The gas mixture can be mixed with ammonia to promote the reduction of nitrogen oxides, and pre-mixing can be performed at temperatures up to about 200 ° C. The amount of ammonia mixed with the gas mixture is generally within the range of 0.75 to 1.25 of the stoichiometric amount, which depends on the proportion of different nitrogen oxides in the gas mixture, as shown in the following scheme:

The crystalline materials of the present invention may also be used to reduce nitrogen compounds in the gas mixture in the presence of other reducing agents such as carbon or carbon monoxide. Reducing nitrogen oxides as described above results in the use of catalysts for fluid catalytic cracking (FCC) because regeneration under suitable conditions results in the required concentration of carbon monoxide that can be used to reduce the proportion of NOx in the regeneration gas in the presence of a catalyst. It is especially useful for playing.

The compositions of the present invention can also be used as adsorbents and separation media in pharmaceuticals and fine chemicals. For example, such microporous compositions can be used to purify a medicament such as insulin or the like or can be used as a solid medium to control the release of the medicament. Other applications in which the maximum pore material can be used include waste disposal where special pore volumes are utilized. Thus, with respect to the maximum pore composition present, at least one component can be partially or completely separated from the mixture of the components having the differential adsorption by contacting the composition with the components having the differential adsorption and selectively adsorbing one component. have. Examples include contacting a mixture comprising water and at least one hydrocarbon component, where at least one hydrocarbon component is selectively adsorbed. Other examples include the selective adsorption of at least one hydrocarbon component from a mixture containing the aforementioned components and at least one other hydrocarbon component.

When the crystalline composition of the present invention is used as a catalyst, it may be desirable to impregnate it with other materials that are resistant to the temperatures and other conditions used in the organic conversion process. Such materials include active and inert materials and synthetic or natural zeolites as well as inorganic materials such as clays, silica and / or metal oxides such as alumina, titania and / or zirconia. The latter may be natural or in the form of gelatinous precipitates or gels comprising a mixture of silica and metal oxides. It is also possible to change the conversion and / or selectivity of a particular organic conversion process using a material that is bound to the new crystals, that is, a catalytically active material that is bound or present with it during the synthesis of the new bed. In order to be able to obtain the reaction product economically and consistently without having to use other means for controlling the reaction rate, a suitable diluent is provided for controlling the amount of inert material converted in a given process. These materials may be incorporated into natural clays such as bentonite and kaolin to enhance the crush strength of the catalyst under commercial process conditions. The aforementioned materials, such as clays, oxides, etc., act as binders for catalysts. When used for commercial purposes it is desirable to provide a catalyst with good fracture strength because it is desirable to prevent the catalyst from breaking down into powdery materials. These clay binders are usually used only for the purpose of enhancing the crush strength of the catalyst.

Natural clays that can be blended with the novel crystals of the present invention include montmorillonite and kaolins, which include subbentonites, and typically Dixie, Mcnamee. , Kaolin, or major mineral components, known as Georgia and Florida clays, are known as halloysite, kaolinite, dickite, nakrite, or anoxite And other substances). These clays may be used in their original mined state, or may first undergo calcination, acid treatment or chemical change.

In addition to the materials mentioned above, the novel crystals of the present invention are porous matrix materials such as silica-alumina, silica-magnesia, silica-zirconia, silica-toria, silica-berilia, silica-tania and silica-alumina-toria And three component materials such as silica-alumina-zirconia, silica-alumina-magnesia and silica-magnesia-zirconia. It may also be advantageous to provide at least a portion of the aforementioned matrix material in colloidal form in order to facilitate extrusion of the bound catalyst component (s).

The relative proportions of the fine crystalline material and the inorganic oxide matrix vary widely and the content of crystals is from 1 to 90% by weight of the composite, more generally from 2 to 80%, especially when the composite is made in the form of beads Range of%.

The invention is explained in more detail with reference to the following examples and the accompanying drawings:

[Brief Description of Drawings]

1 to 14 show X-ray diffraction patterns of the products of Examples 1 to 13 and 15, respectively.

FIG. 15 graphically shows isotherms of physical adsorption measured in Example 21. FIG.

FIG. 16 is a graph showing the isotherm of physical adsorption measured in Example 21, showing bubble sizes of various crystalline materials.

Figure 17 shows the electron diffraction pattern of the product of Example 4.

18 shows a transmission electron micrograph of the product of Example 4. FIG.

19 shows a transmission electron micrograph of the product of Example 5. FIG.

Figure 20 shows a transmission electron micrograph of the product of Example 18.

FIG. 21 shows the X-ray diffraction pattern of the product of Example 23.

22 shows the effect of the auxiliary organic material on the d-spacing of the first X-ray diffraction maximum for Examples 23-31.

FIG. 23 is a graphical representation of bubble size versus X-ray d-spacing for the products of Examples 23, 25, 26, 28, 29 and 31.

FIG. 24 graphically depicts bubble sizes for X-ray d-spacings for the products of Examples 23, 25, 26, 28, 29, and 31.

25-28 show X-ray diffraction patterns of the products of Examples 46-49, respectively.

In the examples, whenever adsorption data for comparison of adsorption capacities for water, cyclohexane, benzene and / or n-hexane are described they are equilibrium adsorption values measured as follows.

After calcining at about 540 ° C. for at least about 1 hour, and further treatment to remove any pore blockage contaminants, if necessary, the weighed adsorption sample is contacted with the desired pure adsorbent vapor in the adsorption chamber. . The weight increase of the adsorbent is calculated as the number of grams of adsorption capacity of the sample per 100 grams of adsorbent based on the adsorbent weight after calcining at about 540 ° C. The composition of the present invention exhibits an equilibrium benzene adsorption capacity of at least about 15 g / 100 g, in particular at least about 17.5 g / 100 g, more particularly at least about 20 g / 100 g, at 50 Torr (6.7 kPa) and 25 ° C.

A preferred method of measuring the adsorption capacity is to contact the desired pure adsorbent vapor in an adsorption chamber in which the material of the present invention is vented to less than 1 mm. During the adsorption period, the pressure is kept constant (within ± 0.5 mm) by the addition of an adsorbent vapor controlled by a monostat. As the adsorbent is absorbed by the new crystals, the pressure decreases and the valve of the hydrometer must be opened so that more adsorbent vapor is introduced into the chamber to restore the control pressure. Adsorption is complete when the pressure change is not sufficient to activate the hydrometer.

Another method of measuring the amount of benzene adsorption is to use a suitable thermogravimetric analysis system such as a computer-controlled 990/951 DuPont TGA system. For example, the adsorbent sample is dehydrated (physically sorbed water is removed) by heating it in a helium stream to a constant weight at about 350 ° C or 500 ° C. For example, if the sample is in the form as synthesized containing organic aligning agent, it is calcined in air at about 540 ° C. and maintained at a constant weight instead of treating at 350 ° C. or 500 ° C. as described above. At 25 ° C., the benzene adsorption isotherm is measured by mixing a benzene saturated helium gas stream with a pure helium gas stream at an appropriate rate to achieve the desired benzene partial pressure. Adsorption values for benzene of 50 Torr (6.7 kPa) are obtained from a graph of adsorption isotherms.

Example 1

A 100 g cetyltrimethylammonium (CTMA) hydroxide solution prepared by contacting a 29 wt% N, N, N-trimethyl-1-hexadecanaluminum chloride solution with a hydroxide-halide exchange resin was added to tetramethylammonium ( TMA) blend with 100 g of aqueous solution of silicate (10% silica) with stirring. 25 g of Hisil, precipitated hydrated silica containing about 0.02 micron of ultimate particle size and about 6% by weight free water and about 4.5% by weight combined hydrated water, is added. The resulting mixture is placed in a polypropylene bottle and kept overnight in a steam box at 95 ° C. The mixture has the following number of moles of composition per mole of Al ₂ O ₃ .

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

The calcined product has a surface area of 475 m ² / g and is expressed in g / 100 g, demonstrating having the following equilibrium adsorption capacity:

The X-ray diffraction pattern of the calcined product of this example is shown in FIG. In this and other figures, the d-spacing of 10 Angstrom units (1.0 nanometers) corresponds to 8.842 ° 2-θ (Cu K-α irradiation), and 18 Angstrom units (1.8 nanometers) is 4.909 ° Corresponds to 2-θ.

The product of this example can be characterized as showing very strong relative intensity lines at 3.78 ± 0.2 nanometer d-spacings and weak lines at 2.16 ± 0.1 and 1.92 ± 0.1 nanometers. The maximum pore material was demonstrated in the product of this example by transmission electron micrograph (TEM), where an image of hexagonal array with uniform pores and hexagonal electron diffraction pattern with ^d 100 value of 3.9 nanometers were observed. do.

Example 2

100 g of cetyltrimethylammonium (CTMA) hydroxide solution prepared in Example 1 is combined with 100 g of an aqueous solution of tetramethylammonium (TMA) hydroxide (25%) with stirring. 25 g of Hysyl, precipitated hydrated silica containing about 0.02 micron of ultimate particle size and about 6 wt% free water and about 4.5 wt% combined hydrated water, is added. The resulting mixture is placed in a static autoclave at 150 ° C. overnight. The mixture has the following moles of composition per mole of Al ₂ O ₃ :

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

The calcined product had a surface area of 993 m ² / g, expressed in g / 100 g, which proved to have the following equilibrium adsorption capacity.

The X-ray diffraction pattern of the calcined product of this example is shown in FIG.

The calcined product of this example can be characterized as showing very strong relative intensity lines at 3.93 ± 0.2 nanometer d-spacings and weak lines at 2.22 ± 0.1 and 1.94 ± 0.1 nanometers. TEM indicates that the product contains the microporous material of the present invention.

A portion of the product is contacted with 100% steam at 790 ° C. (1450 ° F.) for 2 hours. The surface area of the steamed material is 440 m ² / g, demonstrating that about 45% remain after severe steaming.

Another portion of the calcined product of this example is contacted with 100% steam at 680 ° C. (1250 ° F.) for 2 hours. The surface area of this material is 718 m ² / g, demonstrating that 725 remains intact after steaming under these conditions.

Example 3

Water, an aqueous solution of cetyltrimethylammonium hydroxide solution prepared in Example 1, aluminum sulfate, hysyl and tetrapropylammonium (TPA) bromide (35%), were combined to obtain the following moles per mole of Al ₂ O ₃ . To prepare a mixture with a composition:

The prepared mixture is placed in a polypropylene bottle and kept in a steam box at 95 ° C. for 192 hours. The sample is then cooled to room temperature and combined with 1 part by weight of the CTMA hydroxide solution prepared in Example 1 and 2 parts by weight of TMA hydroxide (25% by weight). The blended mixture is placed in a polypropylene bottle and kept overnight in a steam box at 95 ° C. The blended mixture has the following moles of composition per mole of Al ₂ O ₃ :

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

The calcined product had a surface area of 1085 m ² / g and expressed in g / 100 g, which proved to have the following equilibrium adsorption capacity.

The X-ray diffraction pattern of the calcined product of this example is shown in FIG.

The calcined product of this example can be characterized as showing very strong relative intensity lines at 3.82 ± 0.2 nanometer d-spacings and weak lines at 2.22 ± 0.1 and 1.94 ± 0.1 nanometers. TEM indicates that the product contains the microporous material of the present invention.

Example 4

200 g of cetyltrimethylammonium (CTMA) hydroxide solution prepared in Example 1 was charged with 2 g of capatal aluminum (alpha-alumina monohydrate, 74% alumina) and tetramethylammonium (TMA) silicate (10% silica). It mix | blends with 100g of aqueous solution of a). 25 g of Hysyl, precipitated hydrated silica containing about 6% by weight of free water and about 4.5% by weight of bound hydrated water, is added, with an ultimate particle size of 0.02μ. The resulting mixture is placed in a static oatclave at 150 ° C. for 48 hours. The mixture has a composition of the following moles per Al ₂ O ₃ :

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

The calcined product had a surface area of 1043 m ² / g, expressed in g / 100 g, which proved to have the following equilibrium adsorption capacity.

The X-ray diffraction pattern of the calcined product of this example is shown in FIG. The calcined product of this example can be characterized as exhibiting very strong relative intensity lines at 4.08 ± 0.2 nanometer d-spacings and weak lines at 2.31 ± 0.1 and 2.01 ± 0.1 nanometers. TEM indicates that the product contains the microporous material of the present invention (see Example 22).

Example 5

260 g of water are combined with 77 g of phosphoric acid (85%), 46 g of carpatal alumina (74% alumina) and 24 g of pyrrolidine (Pyr) with stirring. This first mixture is placed in a stirred autoclave and heated at 150 ° C. for 6 hours. The material is filtered off, washed and then air-dried. 50 g of the resulting product are slurried with 200 g of water and 200 g of cetyltrimethylammonium hydroxide solution prepared in Example 1. 400 g of an aqueous solution of tetraethylammonium silicate (10% silica) is added to prepare a second mixture, which is placed in a polypropylene bottle and kept in a steam box at 95 ° C. overnight. The first mixture has a composition of the following moles per mole of Al ₂ O ₃ :

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

The calcined product had a surface area of 707 m ² / g, expressed in g / 100 g, and proved to have the following equilibrium adsorption capacity.

The X-ray diffraction pattern of the calcined product of this example is shown in FIG. The calcined product of this example can be characterized as exhibiting very strong relative intensity lines at 2.54 ± 0.15 nanometer d-spacings. TEM indicates that the product contains the microporous material of the present invention (see Example 22).

Example 6

A solution of 1.35 g of NaAlO ₂ (43.5% Al ₂ O ₃ , 30% Na ₂ O) dissolved in 45.2 g of water was added to 17.3 g of NaOH, 125.3 g of colloidal silica (40%, Ludox ) HS-40) and 42.6 g of 40% aqueous solution of tetraethylammonium (TEA) hydroxide. After stirring overnight, the mixture is heated in a steam box (95 ° C.) for 7 days. After filtration, 151 g of filtrate is mixed with 31 g of cetyltrimethylammonium hydroxide solution prepared in Example 1 and stored in a steam box at 95 ° C. for 13 days. The mixture has the following relative water composition:

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

The calcined product composition contained 0.14 wt% Na, 68.5 wt% SiO ₂ and 5.1 wt% Al ₂ O ₃ and was proven to have a benzene equilibrium adsorption capacity of 56.8 g / 100 g.

The X-ray diffraction pattern of the calcined product of this example is shown in FIG. The calcined product of this example can be characterized as exhibiting very strong relative intensity lines at 3.14 ± 0.15 nanometer d-spacings. TEM indicates that the product contains the microporous material of the present invention.

Example 7

A mixture of 150 g of cetyltrimethylammonium (CTMA) hydroxide solution prepared in Example 1 and 21 g of colloidal silica (40%, Rutoxin HS-40) with an initial pH of 12.64 in a 300 cc oatclave at 150 ° C. Heat for 48 hours with stirring at 200 rpm. The mixture has a composition of the following moles per mole of SiO ₂ :

The resulting solid product is collected by filtration, washed with water and then calcined at 540 ° C. for 6 hours in air.

The calcined product composition contains 0.01 wt% Na, 93.2 wt% SiO ₂ and 0.016 wt% Al ₂ O ₃ , has a surface area of 992 m ² / g and is expressed in g / 100 g as follows: It has been proven to have:

The X-ray diffraction pattern of the calcined product of this example is shown in FIG. The calcined product of this example can be characterized as exhibiting very strong relative intensity lines at 4.36 ± 0.2 nanometer d-spacings and weak lines at 2.51 ± 0.15 and 2.17 ± 0.1 nanometers. TEM indicates that the product contains the microporous material of the present invention.

Example 8

Sodium aluminate (4.15 g) is added slowly to a solution containing 16 g myristyltrimethylammonium bromide (C ₁₄ TMABr) in 100 g of water. Tetramethylammonium silicate (100 g-10% SiO ₂ ), hysyl (25 g) and tetramethylammonium hydroxide (14.2 g-25% solution) are then added to the mixture. The mixture has the following relative molar composition.

The mixture is crystallized for 24 hours with stirring in an autoclave at 120 ° C. The resulting product is filtered, washed and then air-dried. Elemental analysis revealed that the product contained 53.3 wt% SiO ₂ 3.2 wt% Al ₂ O ₃ , 15.0 wt% C, 1.88 wt% Na and 53.5 wt% ash (at 1000 ° C.). FIG. 8 shows the X-ray diffraction pattern of a material calcined at 540 ° C. for 1 hour in N ₂ and then calcined for 6 hours in air. The X-ray diffraction pattern shows very strong relative intensity lines at 3.53 ± 0.2 nanometer d-spacings and weak lines at 2.04 ± 0.1 and 1.77 ± 0.1 nanometers d-spacings. TEM indicates that the product contains the microporous material of the present invention.

The washed product exchanged and calcined with 1 N ammonium nitrate solution at room temperature has a surface area of 827 m ² / g and is expressed in grams per 100 g of anhydrous adsorbent, demonstrating the following equilibrium adsorption capacity:

Example 9

Sodium silicate (8.3 g) is added slowly to a solution containing 184 g of dodecyltrimethylammonium hydroxide (C ₁₂ TMAOH, 50%) diluted with 480 g of water. An aqueous solution of Ultrasil (50 g) and tetramethylammonium silicate (200 g-10% SiO ₂ ) and tetramethylammonium hydroxide (26.38 g-25% solution) is then added to the mixture. The mixture has a composition of the following relative moles:

The mixture is crystallized for 24 hours with stirring in an autoclave at 100 ° C. The product is filtered, washed and air dried. FIG. 9 shows the X-ray diffraction pattern of a material calcined at 540 ° C. for 1 hour in N ₂ and calcined for 6 hours in air.

The X-ray diffraction pattern shows very strong relative intensity lines at 3.04 ± 0.15 nanometer d-spacing and weak lines at 1.77 ± 0.1 and 1.53 ± 0.1 nanometer d-spacing. TEM indicates that the product contains the microporous material of the present invention.

The wash product exchanged and calcined with 1N ammonium nitrate solution at room temperature has a surface area of 1078 m ² / g and is expressed in grams per 100 g of anhydrous adsorbent, demonstrating having the following equilibrium adsorption capacity:

Example 10

A solution of 4.9 g of NaAlO ₂ (43.5% Al ₂ O ₃ , 30% Na ₂ O) in 37.5 g of water was charged with 46.3 cc of 40% aqueous tetraethylammonium hydroxide solution and 96 g of colloidal silica (40%, Lu Mix with dox HS-40). The gel was stirred vigorously for 0.5 hours, mixed with eastern blood (150 mL) cetyltrimethylammonium hydroxide solution prepared in Example 1, and then reacted at 100 ° C. for 168 hours. The mixture has a composition of the following moles per mole of Al ₂ O ₃ :

The resulting solid product is collected by filtration, washed with water and then calcined at 540 ° C. for 16 hours in air.

The calcined product has a surface area of 1352 m ² / g and is expressed in g / 100 g, demonstrating having the following equilibrium adsorption capacity:

The X-ray diffraction pattern of the calcined product of this example is shown in FIG. The product of this example can be characterized as exhibiting very strong relative intensity lines at 3.58 ± 0.2 nanometer d-spacings and weak lines at 2.03 ± 0.1 nanometers. TEM indicates that the product contains the microporous material of the present invention.

Example 11

The 200 g cetyltrimethylammonium (CTMA) hydroxide solution prepared in Example 1 is combined with 4.15 g sodium aluminate and 100 g aqueous tetramethylammonium (TMA) silicate solution (10% silica) with stirring. 25 g of Hysyl, precipitated hydrated silica containing about 0.02 micron of ultimate particle size and about 6 wt% free water and about 4.5 wt% combined hydrated water, is added. The resulting mixture is left in a static autoclave at 150 ° C. for 24 hours. The mixture has a composition of the following moles per Al ₂ O ₃ :

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

TEM indicates that the product contains the microporous material of the present invention. The X-ray diffraction pattern of the calcined product of this example is shown in FIG. The X-ray diffraction pattern of the calcined product of this example can be characterized as showing very strong relative intensity lines at 4.42 ± 0.2 nanometer d-spacings and weak lines at 2.52 ± 0.15 and 2.2 ± 0.1 nanometers. .

The calcined product has a surface area of 9.32 m ² / g, expressed in g / 100 g, which proved to have the following equilibrium adsorption capacity:

The product of this example is then ammonium exchanged with a 1N NH ₄ , NO ₃ solution and calcined at 540 ° C. for 10 hours in air.

Example 12

The 200 g cetyltrimethylammonium (CTMA) hydroxide solution prepared in Example 1 is combined with 4.15 g sodium aluminate and 100 g aqueous tetramethylammonium (TMA) silicate solution (10% silica) with stirring. 25 g of Hysyl, precipitated hydrated silica containing about 0.02 micron of ultimate particle size and about 6 wt% free water and about 4.5 wt% combined hydrated water, is added. The resulting mixture is placed in a steam box at 100 ° C. for 48 hours. The mixture has a composition of the following moles per Al ₂ O ₃ :

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

The calcined product was expressed in g / 100g and proved to have the following equilibrium adsorption capacity:

The X-ray diffraction pattern of the calcined product of this example is shown in FIG. The product of this example can be characterized as showing very strong relative intensity lines at 3.91 ± 0.2 nanometer d-spacings and weak lines at 2.24 ± 0.1 and 1.94 ± 0.1 nanometers. TEM indicates that the product contains the microporous material of the present invention.

The product of this example is then ammonium exchanged with a 1N NH ₄ , NO ₃ solution and calcined at 540 ° C. for 10 hours in air.

Example 13

125 g of 29% aqueous CTMA chloride, 200 g of water, 3 g of sodium aluminate (in 50 g of H ₂ O), 65 g of Ultrasil, amorphous precipitated silica from PQ Corporation, and 21 g of NaOH (50 g of H ₂ O). Of the mixture) is thoroughly stirred and crystallized at 150 ° C. for 168 hours. The reaction product has a relative molar composition of the following moles per mole of silica:

The solid product is isolated by filtration, washed with water, dried at room temperature for 16 hours and then calcined in air at 540 ° C. for 10 hours.

The calcined product was shown to have a surface area of 840 m ² / g, and g / 100 g, having the following equilibrium adsorption capacity:

The X-ray diffraction pattern of the product of this example, shown in FIG. 13, can be characterized as exhibiting very strong relative intensity lines at 4.05 ± 0.2 nanometer d-spacings. TEM indicates that the product contains the microporous material of the present invention.

Example 14

For comparison purposes, a very stable zeolite Y which is usually prepared is obtained. This zeolite has a benzene equilibrium adsorption capacity of 20.7 g / 100 g. Its X-ray diffraction pattern shows the line of all zeolites Y, showing the highest peak at a d-spacing of about 1.40 nanometers.

Example 15

To prepare the first template mixture for this example, 240 g of water was added to 92 g of a solution of 50% dodecyltrimethylammonium hydroxide, 36% isopropyl alcohol (IPA) and 14% water to give a solvent / R _{2 / f} Let the molar ratio of O be 155. The molar ratio of H ₂ O / R _{2 / f} O in this mixture is 149 and the molar ratio of IPA / R _{2 / f} O is 6. To the first template mixture is added 4.15 g sodium aluminate, 25 g hysyl, 100 g tetramethylammonium silicate solution (10% SiO ₂ ) and 13.2% 25% tetramethyl ammonium hydroxide aqueous solution. The molar ratio of R _{2 / f} 0 / (SiO ₂ + Al ₂ O ₃ ) to the mixture is 0.28.

The mixture is stirred at 25 ° C. for 1 hour. The resulting mixture is placed in an autoclave at 100 ° C. and stirred at 100 rpm for 24 hours. The mixture in the autoclave has the following relative molar composition per mole of SiO ₂ :

The resulting solid product is collected by filtration, washed with water and dried in air at ambient temperature. The product is then calcined at 540 ° C. for 1 hour in nitrogen, followed by 6 hours in air.

The calcined product is represented by a surface area of 1223 m ² / g and g / 100 g, having the following equilibrium adsorption capacity:

The X-ray diffraction pattern of the calcined product of this example is shown in FIG. The product of this example can be characterized as exhibiting very strong relative intensity lines at 3.08 ± 0.15 nanometer d-spacings and weak lines at 1.79 ± 0.1 and 1.55 ± 0.1 nanometers. TEM indicates that the product contains the microporous material of the present invention.

Example 16

50.75 g of decyltrimethylammonium hydroxide (prepared by contacting about 29% by weight solution of decyltrimethylammonium bromide with hydroxide-halide exchange resin) is combined with 8.75 g of tetraethylorthosilicate. The mixture is stirred for about 1 hour and then left in the steam box for about 24 hours. The mixture has a composition of the number of moles per mole SiO ₂ as follows:

The resulting solid product is filtered, washed several times with warm (60-70 ° C.) distilled water and several times with acetone. The final product is calcined at 538 ° C. in the N ₂ / air mixture and held for 8 hours in air.

The calcined product was demonstrated to have a surface area of 915 m ² / g and an equilibrium benzem adsorption capacity of 35 g / 100 g. Argon physisorption data indicated that 0.34 cc / g of argon was adsorbed and the pore size was 1.5 nanometers.

The X-ray diffraction pattern of the calcined product of this example can be characterized as showing very strong relative intensity lines at 2.75 ± 0.15 nanometers and weak lines at 1.58 ± 0.1 and 1.37 ± 0.1 nanometers. TEM indicates that the product contains the microporous material of the present invention.

Example 17

80 g of cetyltrimethylammonium hydroxide (CTMAOH) solution prepared in Example 1 was added to 1.65 g of NaAlO ₂ . The mixture is stirred at room temperature until NaAlO ₂ is dissolved. To this solution is added 40 g of tetramethylammonium (TMA) silicate aqueous solution (10 wt% SIO ₂ ), 10 g of Hysyl, 200 g of water and 70 g of 1,3,5-trimethylbenzene (TMB). The resulting mixture is stirred at room temperature for a few minutes. The gel is then placed in a 600 cc autoclave and heated for 68 hours with stirring at 105 rpm. The mixture has the following moles of composition per mole of Al ₂ O ₃ :

The resulting product is filtered off and washed several times with warm (60-70 ° C.) distilled water and then several times with acetone. Calcined to 538 ° C. in the final product N ₂ / air mixture and then held in air for about 10 hours.

The calcined product proved to have an equilibrium benzene adsorption capacity of 25 g / 100 g.

The X-ray diffraction pattern of the calcined product of this example can be characterized as exhibiting a broad and very strong relative intensity line at about 0.2 nanometer d-spacings, but using X-ray diffractometers using conventional X-ray diffractometers. It is very difficult to determine the exact line position in the national angle region of the diffraction pattern. In addition, the fin collimating slit is required to separate the peak at the national 2-θ angle. The slit sizes used in this example are 0.1, 0.3, 0.5 and 0.2 mm respectively starting from the X-ray tube. TEM indicates that the product of this example contains several materials with different ^d 100 values as observed in the electron diffraction pattern. This material was found to have a ^d 100 value between 8.5 and 12 mm d-.

Example 18

80 g of cetyltrimethylammonium (CTMAOH) solution prepared in Example 1 was added to 1.65 g of NaAlO ₂ . The mixture is stirred at room temperature until NaAlO ₂ is dissolved. To this solution is added 40 g of tetramethylammonium (TMA) silicate aqueous solution (10 wt% SIO ₂ ), 10 g of Hysyl, 200 g of water and 120 g of 1,3,5-trimethylbenzene (TMB). The resulting mixture is stirred at room temperature for a few minutes. The gel is then placed in a 600 cc autoclave and heated for 90 h with stirring at 105 ° C. at 150 rpm. The mixture has the following moles of composition per mole of Al ₂ O ₃ :

The resulting product is filtered off and washed several times with warm (60-70 ° C.) distilled water and then several times with acetone. Calcined to 538 ° C. in the final product N ₂ / 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 equilibrium benzene adsorption capacity of 25 g / 100 g. The argon physisorption data shows that the argon adsorption amount is 0.95 cc / g, the pore size is mainly 7.8 nanometers (Dollimore-Heal method, see Example 21 (b)), and ranges from 7 to At least 10.5 nanometers.

The X-ray diffraction pattern of the calcined product of this example can be characterized as having enhanced scattering intensity only in the local angle region of the X-ray diffraction, where the intensity from the transmitted incident X-ray beam is generally Is observed. However, TEM indicates that the product of this example contains several materials with different ^d 100 values as observed in the electron diffraction pattern. This material was found to have a ^d 100 value between 8.5 and 11 nanometer d-spacings (eg Example 22).

Example 19

80 g of cetyltrimethylammonium hydroxide (CTMAOH) solution prepared in Example 1 was added to 1.65 g of NaAlO ₂ . The mixture is stirred at room temperature until NaAlO ₂ is dissolved. To this solution is added 40 g of tetramethylammonium (TMA) silicate aqueous solution (10 wt% SIO ₂ ), 10 g of Hysyl and 18 g of 1,3,5-trimethylbenzene (TMB). The resulting mixture is stirred at room temperature for a few minutes. The gel is then placed in an autoclave of 300 cc and heated for 4 h with stirring at 105 ° C. and 150 rpm. The mixture has the following moles of composition per mole of Al ₂ O ₃ :

The resulting product is filtered off and washed several times with warm (60-70 ° C.) distilled water and then several times with acetone. Calcined to 538 ° C. in the final product N ₂ / 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 equilibrium benzene adsorption capacity of 40 g / 100 g. Argon physical adsorption data demonstrates that the argon adsorption amount is 0.97 cc / g, the pore size is 6.3 nanometers (Dolimore-Hill method, see Example 21 (b)), and this peak appears at P / Po = 0.65. do.

The X-ray diffraction pattern of the calcined product of this example shows very strong relative intensity lines at 6.3 ± 0.5 nanometer d-spacings and weak lines at 3.64 ± 0.2, 3.13 ± 0.15 and 2.38 ± 0.1 nanometers d-spacings. It may be characterized as represented. TEM indicates that the product of this example contains the microporous material of the present invention.

Example 20

The dealkylation in which tri-t-butylbenzene (TTBB) is converted to di-t-butylbenzene for the final products of Examples 1 to 14 is measured to assess the catalytic properties of the present invention. This evaluation may be performed under one or both of the following conditions: (i) a temperature of 225 ° C., a weight spacetime velocity of 100 hours ⁻¹ , or (ii) a temperature of 200 ° C., a weight spacetime velocity of 200 hours ⁻¹ Performed under both conditions. The pressure uses atmospheric pressure. The feed consists of 6.3 / 93.7 TTBB / toluene. Conversion rate is measured after 30 minutes on stream.

The result is as follows:

Example 21 (a)

Argon Physical Adsorption on Porous Systems up to about 6.0 Nanometers in Diameter

To determine the pore diameter of a product of the invention having pores up to about 6.0 nanometers in diameter, 0.2 g of a sample of the products of Examples 1-16 were placed in a glass sample tube as described in US Pat. No. 4,762,010. Input and mounted on a physical adsorption device. The sample is heated in vacuo to 300 ° C. for 3 hours to remove adsorbed water. The sample is then cooled to 87 ° K by immersing the sample tube in liquid argon. The basis gas argon is introduced into the sample in a stepwise manner as described in US Pat. No. 4,762,010, column 20. The amount of argon adsorbed can be calculated from the amount of argon introduced into the sample and the amount of argon remaining in the gas space on the sample. In this calculation, ideal gas law and assayed sample volume are used (see, eg, S. J. Gregg et al., Adsorption, surface Area and Porosity, 2nd ed., Academic press, 1982). In each case, the graph of the adsorption volume of the sample versus the relative pressure on the sample forms an adsorption isotherm at equilibrium as shown in FIG. 15 for the product sample of Example 4. FIG. It is common to use the relative pressure obtained by measuring the ratio of the equilibrium pressure of the adsorbent to the vapor pressure Po at the temperature at which the isotherm is observed. A small amount of argon is added to each stage to get 168 data points in the relative pressure range of 0 to 0.6. About 100 points are needed to define an isotherm with sufficiently detailed data.

In this case (product of Example 4) the step (inflection) of the isotherm at about P / Po = 0.4 indicates the filling of the porous system. The size of the step represents the amount of adsorption, while the position of the step in terms of P / Po represents the size of the pores where adsorption takes place. Larger pores are filled at higher P / Po. To specify a better location of the phase of the isotherm, take the derivative of log (P / Po). This is shown in FIG. Figure 16 also shows the data obtained in the same way for the crystalline material from US Pat. No. 4,880,611 and several other crystalline materials. It also provides a physical scale on the axis where the position of the adsorption peak, expressed in log (P / Po), is converted to the physical pore diameter. This conversion is obtained using the following formula.

Where

d is the diameter of the pores in nanometers,

K is 32.17

S is 0.2446

L is d + 0.19

O is 0.57.

The above formula is derived from the methods of Horvath and Kawazoe (G. Horvath et al., J. Chem. Eng. Japan 16 (6) 470 (1983)). Constants needed to perform the transplant are determined from the measured isotherm of ALPO-5 and its known pore size. This method is particularly useful for microporous materials having pore sizes up to about 6.0 mm straight.

As shown in FIG. 16, the pore size of the material of Example 4 is 3.96 nanomers with a peak appearing in log (P / Po) =-0.4 or P / Po = 0.4, whereas the material of US Pat. No. 4,880,611 The pore size is 1.2 nanometers or P / Po = 0.02. In other materials, the peak was penetrated at P / Po = 0.015, indicated separately in FIG. This peak represents adsorption to the walls of the pores and does not vary the pore size of a given material. A P / Po value of 0.03 corresponds to a pore size of 1.3 nanometers.

The results of this method for the samples of Examples 1-16 are shown in the table below. The samples of Examples 9, 12 and 15 show two separate peaks, which are believed to be the result of two individual maximum porosity in the product.

Example 21 (b)

Argon Physical Adsorption on Porous Systems Larger than about 6.0 Nanometers in Diameter

For porous regimes larger than about 6.0 nanometers in diameter, the Kelvin equation can be applied. Kelvin is usually expressed as

In the above formula,

γ is the surface tension of the adsorbent,

V is the molar volume of the adsorbent,

θ is the contact angle (generally 0 for practical reasons),

R is a gas constant,

T is the absolute temperature,

γ _k is the capillary condensation (pore) radius,

P / P _o is the relative pressure (taken from the physical adsorption system).

In Kelvin's equation, adsorption in a porous system is considered to be capillary condensation, and the pressure at which adsorption occurs is related to the pore diameter through surface tension and the contact angle of the adsorbent (argon in this case). The principle based on the Kelvin equation is valid only when the pore diameter is between 5 and 100 nanometers. When the diameter is smaller than the above range, there is no physical meaning because capillary condensation cannot occur in small pores; When the diameter is larger than this range, due to the algebra of the above formula, it is not possible to determine sufficiently accurate pore size.

Kelvin equations, often selected to measure pore size, were reported by Dolimore and Hill in particular (D. Dollimore and GR Heal, J. Applied Chem., 14, 108 (1964)). However, the effect of the surface layer of the adsorbent on the pore wall was corrected, so that the pore diameter could be measured more accurately. The Dollymore and Hill methods are derived using desorption isotherms, but the same applies to adsorption isotherms by simply inverting the data set.

As mentioned, the Dollymore and Hill methods are applied to the argon physisorption data of the Examples 18 and 19 products.

Example 22

[Transmitted electronic brown rice technology]

To further explain the properties of the hexagonal crystalline product of the present invention, samples of the products of Examples 1 to 13, 15 to 19, 23 to 31 and 38 were subjected to the above mentioned transmission electron microscopy (TEM). Was investigated. Transmission electron microscopy is a kind of technology used to reveal the microstructure of materials including crystalline materials.

To describe the microstructure of the material, the electron beam should be thin enough to penetrate the sample, typically about 50 to 100 nanometers. Crystal morphology of the material generally requires the preparation of the material for irradiation by ultramicrotomy. Although time consuming, these sample preparation techniques are very familiar to those skilled in the art of electronic microscopy. This material is embedded in a resin, in this case commercially available acrylic resin LR WHITE (hard), having a viscosity, and then about 80 for about 1 hour 30 minutes. Cure at 캜. Thin slices of this block are cut using diamond knives on an ultramicrotome, and flakes ranging in thickness from 50 to 100 nanometers are collected on micromesh electron microscope support grit. For this material, LKB model microtome with 45 ° C. diamond blade is used; The support grid is a 400 mesh copper grid. Once the thin carbon coating on the sample has been evaporated (light white on the white side of the paper next to the sample in the evaporator) to prevent charging in the transmission electron microscope, the sample to be irradiated in the TEM is prepared.

It is merely to prove the existence of the material of the present invention, and simple sample preparation techniques used in most synthetics can be used. This includes the deposition of the dispersion of material on carbon-coated laced Formvar electron microscope supports after grinding and disintegration by high frequency sound in propanol. Pieces or regions of sufficient thickness to obtain electron diffraction patterns and lattice images are found near the edges of the individual crystals. Samples for analysis of the products of Examples 23-31 and 38 can be prepared by this dispersion technique.

High resolution transmission electron micrographs show the projection of the structure along the direction in which the sample is captured. For this reason, it is necessary for a sample to have a specific directivity in order to view specific details of the microstructure of the material. For the crystalline materials, these directivity can be selected very easily by observing electron diffraction patterm (EDP) generated simultaneously with the electron microscope image. Such electron diffraction patterns can easily be made with modern TEM instruments using, for example, selected area field limiting aperture techmiques familiar to those skilled in the art of electron microscopy. If an electron diffraction pattern with diffraction points in the desired arrangement is observed, the corresponding image of the crystal representing the electron diffraction pattern will show details of the microstructure along the direction of projection represented by the electron diffraction pattern. In this way, different projections of the crystal structure can be observed and distinguished using the TEM.

In order to observe the salient features of the crystalline products of the invention, it is necessary to observe the material in one direction, where the corresponding electron diffraction pattern represents the hexagonal arrangement of diffraction points from a single individual crystal. When multiple crystals exist within the field confinement aperture, an overlap diffraction pattern that is very difficult to interpret occurs. The hexagonal pattern from individual crystals from the product of Example 4 is shown in FIG. 17. The number of diffraction points observed depends, among other things, on the degree of regularity of the array of formations in the material. However, at least the innermost ring of bright spots should be observed to obtain a good image. Individual crystals can be controlled by the sample slope controller on the TEM during this orientation. Usually, it is easy to take advantage of the fact that the sample contains irregularly oriented crystals, and also to simply examine through the sample while the crystal exhibiting the desired electron diffraction pattern is located. This latter technique is used to make the electron micrograph described below.

Microtomeized samples of the materials of Examples 1-13 and 15-19 were in place according to the technique described above, having a effective objective diameter of 0.2 nanometers and operating at 200,000 volts. Irradiate with a 200 (X) transmission electron microscope The instrument has a point-to-point resolution of 0.45 nanometers Underfocus side of minimum contrast lens current setting If the objective lens can be carefully maintained, the equivalent image can be generated using other experimental spirits, etc., which are familiar to those skilled in the art of high resolution (phase) microscopy TEM. Electron micrographs from microtomized thin fragments of the product, which show a fairly regular arrangement of large channels in the hexagonal array.

The repetition distance between the channels is about 4.5 nanometers, which corresponds to the location of the first peak of the material's X-ray diffraction pattern layer (4.1 nanometers / √3 / 2. This observation is also consistent with the pore size measured at about 3.96 nanometers, calculated from the argon physisorption measurements of the materials of Example 16.

19 is an electron micrograph taken from microtomized thin fragments of the crystalline product of Example 5. FIG. This electron micrograph shows a fairly regular array of somewhat smaller channels in the hexagonal array. The repetition distance between these channels is about 3.0 nanometers, which corresponds to the position of the first peak (2.5 nanometers / √3 / 2) of the X-ray diffraction pattern layer of the material. The smaller pore size of this material is also demonstrated by the argon physisorption measurements reported in Example 21 (a), where a value of 1.69 nanometers is calculated for the material of Example 5.

FIG. 20 is an electron micrograph from the crystalline microtomized thin fragment of Example 18. This in-phase channel is very large and more irregular, but it is evident that it is a particular hexagonal arrangement of the material of the invention.

Example 23

1.65 g of 80% cetyltrimethylammonium hydroxide (CTMAOH) solution prepared by contacting a 29 wt% N, N, N-trimethyl-1-hexadecanaluminum chloride solution with a hydroxide-halide exchange resin It is added to NaAlO ₂ . The mixture is stirred until NaAlO ₂ is completely dissolved. To this solution is added 40.4 g of tetramethylammonium silicate aqueous solution (10 wt% SIO ₂ ) and 10.0 g of Hysil (HiSil: 90 wt% SiO ₂ ). The resulting mixture is stirred for several minutes at temperature. The gel is then placed in a 300 ml autoclave and heated to 105 ° C. with stirring at 150 rpm. After heating for about 4 hours, the reaction is quenched with cold water and the contents are removed. The product is filtered off and washed several times with warm (60-70 ° C.) distilled water and acetone. The final product is calcined at 538 ° C. for 8 hours in N ₂ / air mixture.

The gel reaction mixture has the following moles of composition per mole of Al ₂ O ₃ :

The calcined product of this example was demonstrated to have a surface area of 1187 m ² / g and a benzene adsorption capacity of 66 g / 100 g.

The X-ray diffraction pattern of the calcined product of this example is shown in FIG. 21 from which the product exhibits very strong relative intensities at 3.68 ± 0.2 nanometer d-spacings and weak at 2.12 ± 0.1 and 1.83 ± 0.1 nanometers. It can be seen that the line represents. The product of this example was observed by transmission electron micrograph (TEM), where an image of hexagonal array with uniform pores and hexagonal electron diffraction pattern with ^d 100 value of about 3.8 nanometers were observed.

[Examples 24 to 31]

Except for adding the auxiliary organics to the initial reaction mixture, eight separate experiments were performed by repeating the method of Example 23. In each case, the auxiliary organic material is 1,3,5-trimethylbenzene (TMB) added to the reaction mixture as final component. The concentration of TMB varies from experiment to experiment, as described in Table A. Table A also lists the size of the product, pore boosting in cc / g and equilibrium benzene adsorption values. Pore size and pore volume values for Examples 24, 27 and 30 are extrapolated from d-spacing graphs for pore size and pore volume measured in other examples (see FIGS. 23 and 24). The strongest X-ray diffraction lines are also indicated for comparison purposes. FIG. 22 shows the effect of TMB auxiliary organics on the d-spacing of the first X-ray diffraction pattern, expressed in moles of TMB / moles of SiO ₂ in each reaction mixture. As the concentration of auxiliary organics increases in the reaction mixture, the pore size and volume for the product crystalline material increases.

Each calcined product of Examples 24 to 31 was observed by TEM, where the hexagonal electron diffraction pattern with ^d 100 values corresponding to the ^d -spacing of the peaks in the X-ray diffraction pattern and the image of the hexagonal array with uniform pores This is observed.

[Examples 32 to 45]

The procedure of Example 23 is repeated to illustrate that the organic compound provides an auxiliary organic material suitable for use in the present invention, in which case 10 g of auxiliary organic material is added directly to the reaction mixture before the hysyl is added. The results are shown in Table B, from which n-octadecane (Example 40), 1-pentanol (Example 43) and phenol (Example 44) significantly reduced the d-spacing of the strongest X-ray diffraction lines. It can be seen that it does not change or forms an amorphous product. All other materials listed in Table B significantly change the position of the strongest X-ray lines and are therefore suitable auxiliary organic materials.

The calcined products of each of Examples 36 to 38 were observed by TEM, where the images of the hexagonal array with uniform pores and the d-spacing of the peaks in the X-ray diffraction pattern A hexagonal electron diffraction pattern with a value of 100 is observed.

Example 46

A solution was prepared by dissolving in 1.08 g of 10 g of cobalt nitrate hexahydrate. In this solution, 40 g of 29 wt% CTMA hydroxide solution, 10 g of tetrabutylammonium (TBA) silicate solution (prepared by combining 168 g of tetraethylorthosilicate with 270 g of 55 wt% TBA hydroxide solution) and 5 g of hysyl silica is stirred. The resulting mixture has the following moles of composition per mole of silica.

The mixture is placed in a polypropylene bottle and placed in a steam box for 72 hours.

The resulting solid product is washed by filtration, air-dried and then calcined at 540 ° C. for 10 hours in air. The calcined product has an equilibrium benzene adsorption capacity of 40% by weight and an X-ray diffraction pattern shown in FIG. It can be seen from this that the X-ray diffraction pattern includes very strong lines at d-spacings of 3.7 ± 0.2 nanometers and weak lines at d-spacings of 2.1 ± 0.1 and 1.9 ± 0.1 nanometers.

Example 47

The procedure of Example 46 is repeated using 1.08 g nickel nitrate hexahydrate instead of the cobalt compound. The resulting calcined product had an equilibrium benzene adsorption capacity of 60% by weight and an X-ray diffraction pattern shown in FIG. 26 (a very strong line at d-spacings of 3.7 ± 0.2 nanometers and weak at d-spacing of 2.1 ± 0.1 nanometers). Line).

Example 48

4.5 g of chromium sulfate. The solution is prepared by dissolving hexahydrate in 20 g of water. 200 g of 29 wt% CTMA hydroxide solution, 50 g of tetrabutylammonium (TBA) silicate solution (prepared by combining 168 g of tetraethylorthosilicate with 270 g of 55 wt% TBA hydroxide solution) and 5 g of hysyl silica is stirred. The resulting mixture has the following molar composition per mole of silica;

The mixture is placed in a polypropylene bottle and placed in a steam box for 72 hours.

The resulting solid product is filtered off, air-dried and then calcined at 540 ° C. for 10 hours in air. The calcined product has an equilibrium benzene adsorption capacity of 40% by weight and an X-ray diffraction pattern shown in FIG. It can be seen from this that the X-ray diffraction pattern includes very strong lines at d-spacings of 3.9 ± 0.2 nanometers and weak lines at d-spacings of 2.1 ± 0.1 nanometers.

Example 49

50 g of cetyltrimethylammonium hydroxide prepared in Example 1 is combined with 5 g of tetraethylorthosilicate and 14.5 g of tetramethylammonium silicate solution (10% silica) with stirring. After stirring was continued for 1 hour, the resulting solution was added a gallium nitrate solution prepared by dissolving 1.2 g of Ga (NO ₃ ) ₃ XH ₂ O in 10 g of water. Assuming that the surfactant has been fully edified, the mixture has a composition of the following moles per mole of silica:

The mixture is placed in a polypropylene bottle and placed in a steam box at about 95 ° C. for 48 hours. The resulting solid product is washed by filtration, air-dried and then calcined (in nitrogen, for 1 hour at 540 ° C., then for 6 hours in air). The X-ray diffraction pattern of the calcined product is shown in FIG. 28 and includes very strong lines at d-spacings of 3.4 ± 0.2 nanometers and weak lines at d-spacings of 2.1 ± 0.1 and 1.8 ± 0.1 nanometers. The chemical composition of the product as synthesized is as follows:

40 wt% carbon

2.5 wt% nitrogen

15% by weight of silicone

2.8% by weight gallium

0.07% of aluminum

39.9 wt% ash (1000 ° C)

Claims (10)

A ratio of porosity with X-ray diffraction pattern with at least one peak at d-spacings of 1.8 nanometers or more after calcination, with a benzene adsorption capacity of at least 15 g of benzene per 100 g of crystalline material at 6.7 kPa (50 Torr) and 25 ° C. A composition containing a layered inorganic crystalline material. The porous inorganic crystalline phase of claim 1, wherein the uniformly sized pores having a diameter of at least 1.3 nanometers form a hexagonal array and exhibit a hexagonal electron diffraction pattern that can be indexed as having a d ₁₀₀ value of at least 1.8 nanometers after calcination. A composition containing a substance. The method of claim 1 or 2, wherein the crystalline material exhibits at least two peaks at positions greater than or equal to 1.0 nanometers d-space after calcination, wherein at least one of the peaks is present at a position greater than or equal to 1.8 nanometers d-spacing, Sculptures with X-ray diffraction patterns that do not exhibit peaks with relative intensities greater than 20% of the strongest peaks at locations less than about 1.0 nanometer d-spacing. The composition according to claim 1 or 2, wherein the crystalline material has a composition represented by the following general formula. M _{n / q} (WaX _b Y _c Z _d O _h ) Wherein M is one or more ions; n is the charge of the composition excluding M expressed in oxides; q is the weighted molar average valence of M; n / q is the mole number 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 and a, b, c and d are the mole fractions of W, X, Y and Z, respectively; h is a number from 1 to 2.5; a + b + c + d is 1. The composition of claim 1 having an X-ray diffraction pattern substantially as shown in any of FIGS. 1 to 14, 21 and 25 to 28. A process for synthesizing the composition of claim 1 characterized by crystallizing the reaction mixture having a composition in the range as indicated below, expressed in molar ratios of oxides. Wherein e and f are the weighted average valences of M and R, respectively, the solvent is C ₁ -C ₆ alcohol or diol, or water, and R is an organic orientation having the general formula R ₁ R ₂ R ₃ R ₄ Q ⁺ Zero, wherein Q is nitrogen or phosphorus, at least one of R ₁ , R ₂ , R ₃ and R ₄ is an aryl or alkyl group having 6 to 36 carbon atoms, and R ₁ , R ₂ , R ₃ and R _The rest of ₄ are each selected from hydrogen and a C ₁ -C ₅ alkyl group. 7. An additional organic alignment agent according to claim 6, wherein R comprises an additional organic alignment agent having the same structural formula as the above-mentioned alignment agent each of R ₁ , R ₂ , R ₃ and R _{4 is} selected from hydrogen and a C ₁ -C ₅ alkyl group. Way. Contacting the organic compound-or inorganic compound-containing feedstock with a catalyst comprising the active form of the composition according to claim 1 under catalytic conversion conditions, thereby catalytically How to switch. The method of claim 8, wherein the feedstock consists of a hydrocarbon and the conversion reaction comprises a cracking or hydrocracking reaction that reduces the molecular weight of the hydrocarbon. A composition according to claim 1 for selectively adsorbing one component from a mixture of components.