SK280860B6 - Composition to be used in catalysts or porous materials, process for preparaing said composition - Google Patents

Abstract

A catalyst comprises an inorganic, porous, non-layered crystalline material exhibiting, after calcination, an X-ray diffraction pattern with at least one peak at a d-spacing greater than about 1.8 nm and having a benzene adsorption capacity of greater than 15 grams of benzene per 100 grams of the material, at a pressure of 6.7 kPa, and a temperature of 25 degrees Celsius, wherein the composition is expressed as by formula: Mn/q (Wa Xb Yc Zd Oh) wherein M is at least one ion selected from the group containing an ammonium ion or the ions of the elements stated in Groups IA, IIA and VIIA; 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 selected from the containing manganese, cobalt, nickel and magnesium; X is a trivalent element, such as aluminium, chrome, bromine, iron and gallium; Y is a tetravalent element such as silicon and germanium; Z is phosphor; 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 Z is phosphor. Also disclosed is the process for the preparation of said composition.

Description

Technical field

The invention relates to a composition based on porous synthetic materials suitable for use in catalysts or sorption materials, and to a process for preparing the composition.

BACKGROUND OF THE INVENTION

Porous inorganic materials are widely used as catalysts and release agents in industrial applications. The openness of their microstructure allows molecules to achieve relatively large surface areas of these materials, thereby increasing their sorption-catalytic effects. The currently used porous materials can be divided into three broad categories. Their inclusion in these categories is based on the details of their microstructure. These are categories of amorphous or paracrystalline materials, crystalline molecular networks and modified layer materials. Detailed differences in the microstructure of these materials result in equally important differences in their catalytic and sorption behavior, which typically characterizes them. Such characteristics include, for example, surface area, pore size and variability, the possible existence of clearly defined X-ray scans, and the appearance of the materials as observed by transmission electron microscopy and electron diffraction.

Amorphous and paracrystalline materials represent an important group of porous inorganic substances, which have been used for many years in various industrial applications for many years. Typical examples of these materials are amorphous silicates commonly used in catalytic mixtures, and para-crystalline transition aluminates used as solid acids for catalysis in refineries.

The term "amorphous" is used herein to denote materials with a slight arrangement, and the pores of the materials have a very wide pore size distribution. As an alternative term commonly used to refer to these materials, "X-ray indifferent" may be used, since the lack of alignment is noticeable on an X-ray program, which is usually without special features. The porosity of amorphous materials, such as amorphous silicates, generally arises from voids between individual particles.

Paracrystalline materials, such as transition aluminates, also have a wide pore size range, but a better defined X-ray pattern, which is usually composed of several broad peaks. The microstructure of these materials is composed of thin crystalline regions of the condensed aluminum phase and porosity of the materials given by cavities 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 pore size of amorphous and paracrystalline materials belongs to an area called the mesoporous region, for purposes of this application it is up to 1.3 to 20 nm.

In contrast to these structurally poorly defined materials, there are materials with a very narrow pore size distribution that is controlled by perfectly repeating crystalline units of the three-dimensional frame structure of the material. These materials are called “molecular sieves”. The most important examples are zeolites. The perfect microstructure of most zeolites is shown in well-defined x-ray graphs, which usually contain many sharp maxima and serve to accurately determine the material. Similarly, the pore dimensions of these materials are very regular because of perfectly repeating crystalline microstructure. All molecular sieves known to date have a pore size in the microporous region, usually bounded by 0.2 and 2 nm, with a predominant size of 1.2 nm.

In laminated materials, where the intra-atomic bonds in the two directions of the crystalline lattice are substantially different from the third direction, structures are formed which contain cohesive units similar to sheets. Usually the bond between the atoms inside these sheets is strongly covalent, while the adjacent layers are held together by ionic or van der Waals forces. These second forces can normally be neutralized by relatively simple chemical methods, while the bonds between atoms within the layer remain intact and intact.

In this way, in certain laminates, adjacent layers can be separated by swelling means, and then fixed in such a separated position of the layer by inserting posts. This results in a greater degree of porosity of the materials. For example, some clays may be swollen with water, wherein the clay layers are then separated from each other by water molecules. Other layered materials cannot be swollen with water, but can be swollen with some organic agents such as amines and quaternary ammonium compounds. Examples of such non-aqueous swelling agents are described in U.S. Patent 4,859,648 and include layered silicates, magadiles, keynets, trititanates, and perovskites. Another example of a non-water-swellable, but swellable organic material layered material is a porous titanium metal material described in U.S. Patent 4,831,006.

The x-ray of the layered materials can vary considerably depending on the degree of swelling and support of the disrupted, otherwise usually well-arranged layered structure. The regular arrangement of the microstructure in some columnar laminates is so poorly imperfectly separated that only one peak is observed in the lower angular region of the rontgenogram at a distance d corresponding to the intermediate layer repeat in the columnar material. Less distributed materials may have several peaks in this field, which are generally in line with the above-mentioned basic repeat. It is also sometimes possible to observe X-ray reflections of the crystalline structure of said layers. The pore size distribution in the columnar layered materials is substantially narrower than in the amorphous or paracrystalline materials, but wider than in the crystalline structure materials. Laminated materials often adopt plate morphology reflecting the inequality of bonds existing at the atomic level. Such morphological properties can be visualized by transmission electron microscopy.

SUMMARY OF THE INVENTION

SUMMARY OF THE INVENTION The present invention provides compositions for use in catalysts or sorption materials comprising inorganic porous, non-layered crystalline materials having, after calcination, an X-ray pattern with at least one peak at a distance d greater than 1.8 nm and having a benzene absorption capacity greater as 15 g of benzene per 100 g of material at a pressure of 6.7 kPa and a temperature of 25 ° C and whose composition corresponds to the general formula

M ^ _q (W _and X _b Y _c Z _d O _h ) in which

SK 280860 Β6

M represents at least one ion selected from the group consisting of ammonium ion and ions of elements of the group ΙΑ, IIA and VIIA of the Periodic Table of the Elements, n represents the charge of the composition with the exception of M expressed as oxides, q represents the molar mean valence M, n / q

W is at least one divalent element selected from the group consisting of manganese, cobalt, nickel and magnesium,

X is at least one three-membered element from the group consisting of aluminum, boron, chromium, gallium and iron,

Y is at least one 4-membered element from the group consisting of silicon and germanium,

Z is phosphorus, a, b, c, and d are mole fractions of W, X, Y and Z, h is from 1 to 2.5 and (a + b + c + d) equals 1.

The composition preferably comprises inorganic porous materials having a hexagonal pore arrangement of equal size with a diameter of at least 1.3 nm and having a hexagonal diffraction electron diagram having a d 10 of greater than 1.8 nm after calcination.

Preferably, the crystalline material, after calcination, has a rontgenogram with at least one peak whose distance d corresponds to the dioo value of the electron diffraction pattern.

Preferably, the crystalline material after calcination has an X-ray x-ray with two peaks at d-positions greater than 1.0 nm, one of these peaks at a d-position greater than 1.8 and no peaks with relative intensity greater than 20% of the strength of the strongest peak are at a distance d of less than 1,0.

Preferably, the material has no peaks with a relative intensity greater than 10% of the intensity of the strongest peak at a distance d of less than 1.0 nm.

Preferably, the sum of (a + b + c) is greater than d and h is equal to 2.

Preferably, W is cobalt, X is aluminum, Y is silicon, and Z is phosphorus.

Preferably a and d are zero and h is 2. Preferably X is aluminum and Y is silicon.

The present invention also relates to a process for the preparation of said composition, characterized in that crystallization is carried out at a temperature of 25 to 250 ° C and for 5 minutes to 14 days of a reaction mixture having the following composition, expressed in molar ratios of oxides

X ₂ O ₃ / YO ₂ until 0.5 X ₂ O ₃ / (Y ₂ + Z ₂ O ₅ ) 0.1 until 100 X ₂ O ₃ / (YO ₂ + WO + Z ₂ O ₅₎ 0.1 until 100 solvent / (YO ₂ + WO + Z ₂ O ₅ + X ₂ O ₃ ) 1 until 100 OH7YO ₂ until 10 (M ₂ / _e O + R ₂ / _f O) / (YO ₂ + WO + Z ₂ O ₅ + X ₂ O ₃ ) 0.01 until 20 M _{2 / e} O (YO ₂ + WO + Z ₂ O ₅ + X ₂ O ₃ ) until 10 R2 / fO / (YO ₂ + WO + Z ₂ O ₅ + X ₂ O ₃ ) 0.01 until 2.0.

where e and f are the mean valences M and R, the solvent is an alcohol or diol of 1 to 6 carbon atoms or water and R is an organic diluent of the formula R 1 R ₂ R ₃ R ₄ Q 'wherein Q is nitrogen or phosphorus and at least one R _b, R ₂ , R ₃ and R 4 are aryl or alkyl of 6 to 36 carbon atoms and each of the remaining R _b R ₂ , R ₃ and R ₄ is selected from the group consisting of hydrogen and C 1 -C 5 alkyl; atoms.

Preferably, the reaction mixture to be crystallized is a mixture of the following composition

X ₂ O ₃ / YO ₂

X ₂ O ₃ / (Y ₂ + Z ₂ O ₅ )

X ₂ O ₃ / (YO ₂ + WO + Z ₂ O ₅₎

0.001 to 0.5

0.1 to 20

0.1 to 20

solvent / (YO ₂ + WO + Z ₂ O ₅ + X ₂ O ₃ ) until 5 OH7YO ₂ until 5 (M ₂ , _e O + R, _{/ f} O) / (Y ₂ + WO + Z ₂ C) ₅ + X ₂ O ₃ ) 0.05 until 5 M _{2 / e} 0 (Y ₂ + WO + Z ₂ O ₅ + X ₂ 0 ₃ ) until 5 R / f O / fYOj + WO + + ZjOs XjOj) 0.03 until 1.0 The organic diluent is preferred le zvole né z mno-

nutrients including cetyltrimethylammonium, cetyltrimethylphosphonium, octadecyltrimethylphosphonium, benzyltrimethylammonium, cetylpyrdinium, myristyltrimethylammonium, decyltrimethylammonium, dodecyltrimethylammonium and dimethyldonium ammonium.

Preferably, R includes an additional organic diluent having the same formula as the first diluent, but each of R _b, R ₂ , R ₃ and R 4 is hydrogen or C 1 -C 5 alkyl.

Preferably, the additional organic diluent is selected from tetramethylammonium, tetraephylammonium, tetrapropylammonium, and tetrabutylammonium.

Preferably, R comprises an auxiliary organic compound selected from the group consisting of aromatic hydrocarbons and amines containing 5 to 20 carbon atoms and their halogen and alkyl groups containing 1 to 14 carbon atoms substituted derivatives, cyclic and polycyclic aliphatic hydrocarbons and amines containing 5 to 20 carbon atoms and their halogen and C1-C14alkyl substituted derivatives and straight or branched aliphatic hydrocarbons and amines of 3 to 16 carbon atoms and halogen-substituted derivatives thereof.

Preferably, the organic excipient is p-xylene, tri-methylbenzene, triethylbenzene or triisopropylbenzene.

Preferably, the molar ratio of organic excipient / YO ₂ is 0.05 to 20.

Preferably, the molar ratio of organic excipient / organic control agent (s) is from 0.02 to 100.

Preferably, the crystallization is carried out at a temperature of 50 to 175 ° C at a pH of 9 to 14 and for 5 and 300 hours.

The recommended method for determining the pore size is using argon physical sorption, which is a known technique and described in detail in Examples 21 (a) and 21 (b). In this method, the amount of argon absorbed in the sample at a constant temperature and different relative pressure above the sample is measured, and the results are used to plot adsorption isotherms. The point on the isotherm corresponding to a sharp gradient change indicates pore filling and can be used to determine the pore size in the known mathematical relationships described in Example 21.

Crystalline (meaning a material having a sufficient order after calcination capable of providing a diffraction pattern with at least one peak, for example in X-ray, electron or neutron diffraction) the material of the invention may be characterized by its previously unknown structure, including an extremely wide range pores and high sorption capacity. In general, the material of the invention is mesoporous, meaning that the material has uniform pores with a diameter ranging from 1.3 to 20 nm. More preferably, the material of the invention has uniform pores with a diameter in the range of 1.8 to 10 nm. In this regard, the pore size is considered to be the maximum pore cross-section.

The material of the present invention can be distinguished from other porous inorganic substances by the regularity of its wide open pores, the size of which is more similar to that of amorphous or paracrystalline materials, but their regular arrangement and uniformity

Size (the pore size distribution within one phase is, for example, ± 25%, usually ± 15% or less of the average pore size of that phase) is more similar to crystalline frame construction materials such as e.g. zeolites.

In a preferred embodiment, the porosity of the crystalline materials of the present invention is given by the generally open channel hexagonal configuration, so properties can be easily compared by electron diffraction and transmission electron microscopy. In particular, a transmission electron micrograph of properly oriented samples of material shows a hexagonal arrangement of wide channels, and the respective electron diffraction diagram shows an approximately hexagonal arrangement of diffraction maxima. The distance d 10 _O on the electron diffraction diagram is the distance between adjacent points on the hk O projection of the hexagonal lattice and refers to the repeated distances a, between the channels observed on the electron micrograph using the formula d ₁₀ o = o V (3/2). This dioo distance observed in the electron diffraction pattern corresponds to the d-distance at the lower angular peak of the X-ray xenogram of this material. The maximally arranged preparation of the materials makes it possible to obtain 20 to 40 different points observable on the electron diffraction diagram. These plots may be indexed with a hexagonal hk 0 subset of a single reflection of 100, 110, 200, 210, etc. and their symmetrically connected reflections.

In this regard, it is to be understood that the appeal on hexagonal channels is meant to include not only mathematically perfect hexagonal symmetry, but also an arrangement in which most material channels are surrounded by the six closest adjacent channels substantially at the same distance. Errors and inaccuracies are caused by a significant number of channels violating this criterion at different levels. Samples having about ± 25% random deviations from the average repeating distance between adjacent channels still give an idea of the presence of ultrapore material.

Proper preparation of the material proposed by the inventor gives a hexagonal X-ray xenogram with small maximum peak variations at extremely low angle. The X-ray xenogram is not always a sufficient indicator of the presence of this material despite the degree of regularity in the microstructure and the degree of structure repeat.

However, the preparation of a material with only one significant X-ray narrow angle peak comprises a substantial amount of the material of the invention.

In calcined form, the crystalline material of the present invention can be further characterized by an X-ray pattern with at least one peak at a position greater than 1.8 nm d-distance (4.909 degrees two theta for Cu K-alpha radiation) which correlates with an SD of ₁₀₀ electron diffraction pattern of this material.

More preferably, the calcined crystalline material of the present invention is characterized by an X-ray pattern with at least two peaks at a position greater than 1 nm d-distance (8.842 degrees two-theta of Cu K-alpha radiation), at least one of which is at a greater position above 1.8 nm d-distance and without peaks at a position less than 1 nm d-distance with a relative intensity greater than 20% of the strongest peak. More precisely, the X-ray xenogram of the calcined material of the present invention does not have peaks at a position less than 1 nm of d-distance with a relative intensity greater than 10% of the strongest peak. In a preferred hexagonal arrangement, the at least one peak in the x-ray pattern will have a d-distance corresponding to the value d _d0 on the electron diffraction pattern of the material.

The X-ray diffraction data reported here was obtained on a Scintag PAD X automatic diffraction system using theta-theta geometry, Cu K-alpha radiation, and an energy X-ray scattering detector. Using this detector eliminates the need for impact or beam error. Both incident and error X-rays collimate the double slit of incident and error collimation systems. The X-ray slit used was 0.5, 1.0, 0.3 and 0.2 nm. Different slot systems can give different peak intensities. The materials of the present invention having the largest pore size may require much higher collimating incident X-rays to analyze small peak angles from the transmitted incident X-ray.

Diffraction data was recorded by a step scan of 0.04 degrees from two-theta, where theta is the Bragg angle, and the readout time for each step was 10 seconds. The interplanar distance, d s, was calculated in nm and the relative intensity of the lines, I / I _o , where I _o is one-hundredth the intensity of the strongest line above the background, was derived using a profile shape program. Intensities in Lorenz and polarization effects were inaccurate. Relative intensities are given by values in symbols vs = very strong (75 - 100), s = strong (50 - 74), m = medium (25 - 49), aw = weak (0 - 24). It should be understood that the diffraction data recorded as single lines may be composed of many overlapping lines which, under certain conditions, such as very strong experimental dissolution or crystallographic changes, may appear as blurred or partially blurred lines. It is possible that crystallographic changes may include minor changes in unit cell parameters and / or changes in crystal symmetry without substantial structural change. These small variations, including variations in relative intensities, may be due to differences in cation content, frame construction, nature and degree of pore filling, thermal and / or hydrothermal history, variations in peak shape and width, particle size and shape, structural disorder or other factors that are known to all who have good experience and knowledge in working with X-ray diffraction.

The material of the invention has an equilibrium benzene adsorption capacity of greater than 15 grams of benzene per 100 grams of crystal at 50 torr and a temperature of 25 ° C. However, the equilibrium benzene adsorption capacity shall be measured on a sample that has no pore blockage due to accidental contamination of the sample. For example, water may be removed by various dehydration technologies such as heat treatment, while inorganic amorphous materials such as silicate and organic may be removed by acid or base, or other other chemical agents and / or physical methods (e.g. calcination) such that the disrupted material is removed without disturbing the material of the present invention.

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

Wherein W is a bivalent element, such as a bivalent element of a first series of transition metals such as manganese, cobalt, nickel, iron and / or magnesium, preferably cobalt; X is a three-valent element such as aluminum, boron, chromium, iron and / or gallium, preferably aluminum;

SK 280860 Β6

Y is a four-valent element, such as silicon and / or germanium, preferably silicon; Z is a five-valent element such as phosphorus; M is one or more ions, such as ammonia, ions of groups IA, IIA and VIIB, usually hydrogen, sodium and / or fluorine ions; n is the charge of the composition, with the exception of M expressed as oxide; q is the weighted molar diameter of the valences M; n / q is the number of moles or mole fractions of M; a, b, c, and d are mole fractions of W, X,

Y and Z; h is from 1 to 2.5; and (a + b + c + d) equals 1.

Preferably said crystalline material has the following characteristic - (a + b + c) is greater than d and h = 2.

It is much better if h = 2, and = 0ad = 0.

In the as-synthesized form, the material of the present invention, on an anhydrous basis, has a composition that can be empirically expressed as follows:

rRM _n / _q (W _and X _b Y cZqOj, where R is the total organic matter used to assist in the synthesis of the material and is not included in M as the ion and r is the coefficient for R, i.e. the number of moles or mole fractions of R.

The M and R components are bonded to the material as a result of their presence during crystallization and can be easily removed or replaced in the case of M by the following crystallization methods, which are described in greater detail below. For example, the parent M, i.e., sodium or chloride ion of as-synthesized material, may be replaced by other ions by ion exchange. Preferred ion replacement includes metal ions, hydrogen ions, hydrogen precursors such as ammonium, ions and mixtures thereof. Particular preference is given to ions which modulate the catalytic activity to the reactions of some hydrocarbon conversions. These include rare earth metals, hydrogen and Group IA (eg potassium), IIA (eg calcium), IIB (eg zinc), IIIB (eg indium), IVB (eg tin) and VIIB (eg fluorine) peridic table elements (Sargent-Welch Scientific Co.Cat. No. S -18,806.1979) and mixtures thereof.

The material serving according to the above formula may be prepared from a reaction mixture having a composition in molar ratio of oxides within the following range.

reactants Possible PretRrouané Xaos / YtJa O-O, 5th 0, 001-0,5 X _and Os / <YOa ^ ZaOs) O. 1-1OQ 0. 1-20 Xaos / CYO · UO.ZaOg) 0.1-100 0.1-20 r-solvent / (YO _a * WC> Z _sl O _e * X _a (ý,) 1-1500 5-1000 ΟΗ- / ΥΟ » O-1O D-5 CM _and z.0 * R _and z _{T (} C) / <. Υ0α * Μ (Η-Ζ ₅ .0 _β * Χ ₂₀ ) 0.01-20 0.05-5 Maz-.CK YOa. + WO + ZaO + XaO,) 0-10 0-5 0. 01-2, 0 0.03-i, n

where e and f are the weighted diameters of the valencies M and R, wherein the solvent is the alcohols or diols C1; to C ₆ or better water, and wherein R comprises a pro-organic agent having the formula R. R 1 R a R q Q *, wherein Q is nitrogen or phosphorus and at least one R _b R ₂ , R ₃ , R 4 is aryl or an alkyl group having 6 to 36 carbon atoms; for example -CeH ₁₃ ; -C 10 H _2b -C 16 H ₃₃ ; C ₁₈ H ₃₇ and each of the remaining R _b R ₂ , R ₃ , R 4 is formed from hydrogen and an alkyl group having 1 to 5 carbon atoms. The compound from which the ammonia or phosphorus ion is derived may be, for example, hydroxide, halogen, silicon, or a mixture thereof.

The significant efficacy of said agents, compared to other similar agents known from the direct synthesis of one or more other crystal structures, is due to their ability to form a template for crystal formation and growth to the desired ultra-wide pore material. The number of examples of such agents is not limited, including the compounds cetyltrimethylammonium, cetyltrimethylphosphonium, octadecyltrimethylphosphonium, benzyltrimethylammonium, cetylpyridinium, myristyltrimethylammonium and dimethyldidodecylammonium. Preferably, the total organic compound present in the reaction mixture containing directly organic additives is in the form of ammonium or phosphate ions with respect to said formula, but wherein each R _b R ₂ , R ₃ and R 4 is selected from hydrogen and an alkyl group of 1; up to 5 carbon atoms (two of the alkyl groups may be linked to the cyclic compound). Examples of direct organic additives include tetramethylammonium, tetraethylammonium, tetrapropylammonium, tetrabutylammonium and pyrrolidinium. The molar ratio between the first mentioned organic reagents and organic auxiliary additives may lie in the range 100/1 to 0.01 / 1. If organic auxiliaries are present, the desired molar ratio R 2 / f / (YO ₂ + WO + Z ₂ O ₅ + X ₂ O ₃ ) in the reaction mixture is 0.1 to 2.0, preferably 0.12 -1.0.

In addition, in order to differentiate the pore sizes of the resulting crystalline material, the total organic compound R in the reaction mixture may contain an auxiliary organic compound in addition to the described direct organic reagents. These organic auxiliary agents are selected from (1) aromatic hydrocarbons and amines having five to twenty carbon atoms and their halogenated and C 1 -C ₁₄ alkyl substituted derivatives, (2) cyclic and polycyclic aliphatic hydrocarbons and amines having five to twenty carbon atoms, and their halogen and alkyl substituted derivatives; and (3) straight or branched chain aliphatic hydrocarbons and amines having three to sixteen carbon atoms, and substituted halogen derivatives thereof. ·

In said organic auxiliaries, preference is given to halogen substituents such as bromides, the alkyl substituents can be linear or branched aliphatic chains such as methyl, ethyl, propyl, isopropyl, butyl, pentyl and combinations thereof. Examples of these organic excipients include, for example, p-xyphene, trimethylbenzene, triethylbenzene and triisopropylbenzene.

When the organic auxiliaries are included in the reaction mixture, the molar auxiliary / YO ₂ ratio will be between 0.05 to 20, preferably between 0.1 and 10. The molar ratio of auxiliary / directly organic reagents (o) will be between 0.02 to 100, preferably between 0.05 to 35.

If a silicon source is used in the synthesis method, it is preferred to use at least a portion of an organic silicate, for example, a quaternary ammonium silicate. Unlimited examples include, for example, tetramethylammonium silicate and tetraethyl orthosilicate. Unlimited examples of various combinations of W, X, Y and Z contemplated for the above reaction mixtures include:

U _X Y “” ž

Al

Al

Al

CoAl

CoAl

Are you

P

Are you

Si including combinations wherein W may be Mg or an element selected from a first group of transition divalent metals such as manganese, cobalt, and nickel; X may be boron, gallium or iron; and Y may be germanium.

In order to produce the crystalline material of the present invention, the described reaction mixture is maintained at a temperature between 25 ° C to 250 ° C, preferably between 50 ° C and 175 ° C. The recommended pH is

Between 9 to 14, during crystallization, generally 5 minutes to 14 days, with a time of one hour to three hundred hours being preferred.

If the crystalline material of the present invention is aluminum silicate, the synthesis method usually comprises the following steps:

(1) The mixture of the direct organic reagent with the solvent or solvent mixture is such that the molar ratio of solvents R ₂ / fO lies in the range of 50 to 800, preferably 50 to 500. This mixture forms a "primary template" for the synthesis methods.

(2) Silicon and aluminum are added to the primary mixture of (1) so that the ratio R ₂ / fO (SiO ₂ + Al ₂ O ₃ ) is between 0.01 and 2.0.

(3) The mixture resulting from (2) is stirred at a temperature between 20 to 40 ° C for 10 minutes to 24 hours.

(4) Allow the mixture to stand either stirred or unmixed at a temperature ranging from 20 to 50 ° C for 10 minutes to 24 hours.

(5) The crystallization of the product of (4) is carried out at a temperature of 50 to 150 ° C for 1 to 72 hours.

If the mixture is to be used as a component of a sorbent or crystalline material, the composition of the present invention must be subjected to a treatment to remove some or all of the organic substances. The present composition can also be used as a catalytic component in close combination with hydrogenation components such as tungsten, vanadium, molybdenum, rhenium, nickel, cobalt, chromium, manganese or a noble metal such as platinum or palladium or mixtures thereof where the hydrogenation and dehydrogenation function. Such a component can be transformed into a composition by a co-crystallization process extended by elements of group IIIB, such as aluminum, which is impregnated inside or close to it physically in the gravel. Such a component may be impregnated into or onto, for example, as in the case of platinum, by treating the silicate with a solution containing platinum ion. Suitable platinum compounds for these purposes include chloroplatinic acid, platinum chloride and various components containing platinoamine complexes.

Said crystalline material, in particular its metallic, hydrogen or ammonium forms, can be successfully converted to other forms by thermal treatment (calcination). This heat treatment is generally carried out at a temperature of between 400 - 750 ° C for at least one minute and generally not longer than twenty hours, preferably between 1 and 10 hours. Although a pressure below atmospheric pressure can be used for thermal treatment, atmospheric pressure may be required for air, nitrogen and ammonia convenience. The thermally treated products are particularly advantageous in the catalysis of certain hydrocarbon conversion reactions.

The crystalline material of the invention, if it is to be used either as an adsorbent or as a catalyst in the conversion processes of organic compounds, should be dehydrated at least partially. The dehydration can be carried out by heating at a temperature ranging from 200 to 595 ° C in an atmosphere of air, nitrogen, etc. and at atmospheric lower or higher pressure for 30 minutes to 48 hours. Dehydration can also be carried out at room temperature, but only when placed under vacuum and a longer time is required to achieve a sufficient degree of dehydration.

The present composition is useful as a catalyst component for catalyzing the conversion of organic compounds such as oxides and hydrocarbons in acid catalyzed reactions. The pore size is such that spatial selectivity to minimize species change in reactions such as cracking is minimized. (See Chen et al., "Shape Selective Catalysis in Industrial Applications," 36, CHEMICAL INDUTRIES, pp. 41-61 (1989). Diffusion boundary is also minimized due to large pores in the material. reactions that take place in the presence of acidic sites on the surface of the catalyst and which include reactants, products or transition states that have a large molecular size, too large for similar reactions to occur with conventional solid large pore size catalysts, such as large pore zeolites such as zeolites X, Y, L, ZSM-4, ZSM -18 and ZSM-20.

The present catalyst compositions are particularly advantageous for the conversion of large molecule organic compounds such as higher aromatic hydrocarbons substituted or unsubstituted by polycyclic aromatic components or bulky naphthenic compounds or highly substituted compounds with bulky spherical configurations, for example having a molecular size from 1.3 nm upwards. The present catalyst composition is particularly effective in reactions which reduce the molecular weight of the starting material, such as cracking or hydrocracking. The cracking can be carried out at temperatures of 200-800 ° C, atmospheric to 100 psig pressure for 0.1 second to 60 minutes. The hydrocracking can be carried out at temperatures from 150 to 550 ° C, pressures of 100-300 psig and a weighted hourly space velocity of from 0.1 to 100 with a molar hydrogen / hydrocarbon ratio of from 0.1 to 100.

The present catalyst composition is particularly suitable for reactions involving high molecular weight starting materials, high boiling points, or non-distillates, in particular distillation residues, i.e. starting materials which are substantially non-distillable or have an initial boiling point (5% point). ) greater than 1050 ° F (565 ° C). The starting material residues to be used with the present catalyst composition include feeds with API weights below about 20, typically below 15, and typically between 5 and 10 with Conradsen Carbon Contents (CCR) of at least 1% by weight, more typically at least 5% or more. , such as 5-10%. In some residual fractions, the CCR may be twenty percent by weight or even more.

The aromatics content of these batches will be correspondingly higher, it may be for heteroatoms such as sulfur or nitrogen and metals.

The aroma content for these substances is usually at least 50% by weight, usually much more, and 70-80% by weight, with the principal balance of naphthanes and heterocycles. A typical refinery of this type includes atmospheric and vacuum tower residues, asphalts, aromatic extracts from the solvent extraction process, for example, fucal or phenol extraction, asphalted oils, slime oils and residual fractions from various processes such as scale production, coking and the like. The high boiling fractions with which the present composition is to be used include gas oils such as atmospheric gas oil; vacuum gas oil; cyclic oil; especially heavy cyclic oil; deasphalted oil; extraction solvents; drawing gas oil, e.g. heavy gas oil. The present catalytic material can also be used for non-petroleum materials, for example synthetic oils produced by coal liquefaction; Fischer-Tropsch waxes and heavy fractions, and other similar materials.

The catalyst composition of the present invention can also be used to selectively convert an organic compounds such as nitrogen oxides in a gas mixture containing nitrogen oxides (NO _X ), for example, industrial off-gases and gases resulting from the oxidative regeneration of catalysts used in hydrocarbon processing, especially in catalytic cracking. The porous crystalline material may be used in matrix or non-matrix form for these purposes, suitably formed into extrudates, granules, or other shapes allowing gas to pass through the catalyst with minimal pressure loss. The crystalline material is preferably or at least partially in hydrogen form, but it may be advantageous if it contains a plurality of noble metals as catalytic components, especially metals 5 and 6 of Period VIIIA of the Periodic Table, especially platinum, palladium, ruthenium, rhodium, indium and mixtures thereof . The amount of noble metals up to 1% by weight is typical in small amounts, for example 0.1 to 0.5% by weight is preferred.

The reduction of NO _x is advantageously carried out by passing the nitrogen-containing gas through the catalyst at an elevated temperature, in particular at 200 ° C, usually in the range from 200 to 600 ° C. The gas mixture may be mixed with ammonia in order to increase the nitrogen oxide reduction effect, and this pre-mixing may be performed at a temperature of up to 200 ° C. The amount of ammonia to be mixed with the gas mixture is usually in the range of 0.75 - 1.25 stoichiometric, varying according to the ratio of the different nitrogen oxides in the mixture, as shown by the equations:

NO ₂ + 8 NH ₃ = 7 N ₂ + 12 H 10

NO + 4 NH ₃ = 5 N ₂ + 6 H ₂ O

The crystalline material of the invention can also be used in a gas mixture containing in addition to nitrogen oxides also other reducing agents such as carbon or carbon monoxide. Reduction of nitrogen oxides in this way is particularly useful in the regeneration of catalysts from fluidized catalytic cracking, since the regeneration under proper conditions produces the desired concentration of carbon monoxide, which is then used to reduce the proportional portion of NO. in the regeneration gas in the presence of a catalyst.

The composition of the invention may also be used as an absorbent or release agent in the pharmaceutical industry in the manufacture of fine chemicals. For example, the ultra-large pore composition may be used in the purification of drugs such as insulin, or it may be used as a solid binder to a controlled dose of drugs.

A further application of the use of this ultra-large pore material involves the disposal of waste where extreme pore size is utilized. Thus, at least one component may be partially or totally separated from the composition having different sorption characteristics due to the presence of the ultra-large pore composition by contracting the composition with the composition which selectively sorbs one component. An example includes a composition comprising water and at least one hydrocarbon compound, wherein the at least one hydrocarbon compound is selectively sorbed. Another example involves the selective sorption of at least one hydrocarbon compound from a mixture containing the same compounds or at least one different compound.

When used as a catalyst, it may be desirable to combine the composition of the invention with another material resistant to temperature and other conditions in the organic conversion process. These materials include active and inactive materials and synthetic or natural zeolites as well as inorganic materials such as clays, silicon and / or metal oxides such as aluminum, titanium and / or zirconium. The latter may be either natural or in the form of gel precipitates or gels containing mixtures of silicon and iron oxides. The use of materials in conjunction with a new crystal, i.e., a combination thereof or its presence in the synthesis of a new crystal that is active, tends to alter the conversion and / or selectivity of catalysis of a particular organic conversion process. Inactive materials are suitable as diluents for a controlled amount of conversion of a given process, such that the product can be obtained correctly and economically without the use of other formulations and methods of controlling the degree of reaction.

These materials can be introduced into naturally occurring clays, such as bentonite or kaolin, to improve their strength when used as a catalyst under operating conditions. Said materials, i.e. clays, oxides, etc., have the function of a binder to the catalyst. It is desirable to use catalysts of good strength, since in commercial use it is desirable to protect the catalysts from being pulverized. These clay binders are normally only used to improve the strength of the catalyst.

Naturally occurring clays that may be associated with the new crystals include the montmorillonites and a kaolin group that includes the subbentonites and kaolins commonly known as Dixie, Mc Namee Georgia and Florida and others in which the major mineral constituents are calloysite, kaolinite, dickite, nacrit or enauxite, such clays may be used as originally extracted or after treatment by calcination, acid treatment or chemically modified.

In addition, said materials, new crystals may be composed with porous backing materials such as aluminum silicate, magnesium silicate, zirconium silicate, thorium silicate, beryllium silicate, titanium silicate, as well as quaternary compounds such as aluminum silicate aluminum - zirconium silicate, aluminum magnesium silicate and magnesium - zirconium silicate. It may be desirable to prepare at least a portion of the material in a holoid format to facilitate the extrusion of the catalyst components to be coupled.

The relative proportions of the final distribution of the crystalline material and the inorganic oxide matrix vary widely, with a crystal content ranging from 1 to 90 percent by weight, but more commonly, especially when the composition is prepared in the form of spheres, ranging from 2 to 80 percent by weight.

BRIEF DESCRIPTION OF THE DRAWINGS

The invention will now be described in more detail with reference to the examples and accompanying graphs in which:

Figures 1-14 are X-ray patterns of the products of Examples 1-13 and 15 respectively.

Figure 15 is an isothermal diagram of the physical sorption measurement of Example 15.

Figure 16 is a diagram of the measurement of the physical sorpcic of Example 21, which shows the pore size of various crystalline materials.

Chart 17 is an electron diffraction chart of the product of Example 4.

Figure 18 is a transmission electron micrograph of the product of Example 4.

Figure 19 is a transmission electron micrograph of the product of Example 5.

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

Figure 21 is a rontgenogram of the product of Example 23.

SK 280860 Β6

Figure 22 shows the effects of the external organism on d-spacings at the first X-ray diffraction maximum of Example 23-31.

Figure 23 is a pore size diagram against the d-layer X-ray beam for the product of Examples 23, 25, 26, 28, 29 and 31.

Figure 24 is a plot of pore volume versus d-distance X-ray beam for the product of Examples 23, 25, 26, 28, 29 and 31.

Graphs 25-28 are X-ray diffraction graphs of the products of Examples 46-49.

DETAILED DESCRIPTION OF THE INVENTION

In the examples where sorption data is given to further compare the sorption capacity for water, cyclohexane, benzene and / or n-hexane, the equilibrium absorption values are determined as follows:

A weighed sample of adsorbent, after calcination at about 540 ° C for at least one hour and a longer treatment if necessary, which removes all pore blocking contaminants, is in contact with suitable clean adsorbable vapors in the adsorption chamber. From the increased weight of the adsorbent, the adsorption capacity of the sample is calculated in grams per 100 grams of adsorbent-based adsorbent after calcination at about 540 ° C. The present composition has an equilibrium benzene adsorption capacity at 50 torr (6.7 kPa) and a temperature of 25 ° C of greater than 15 grams / 100 grams, more specifically greater than 17.5 grams / 100 grams, much more precisely 20 grams / 100 grams.

A preferred method of measuring adsorption capacity is by contacting the material of the present invention with the net vapors of adsorbed substance in an adsorption column evacuated to less than 1 mm. The pressure is kept constant (within ± 0.5 mm) by controlling the adsorbed vapors by the manostat throughout the adsorption period. If a new crystal is used, when the pressure drops, the manostat opens the valve and allows the adsorbed vapors to enter and set the pressure again. Sorption is complete when the pressure change is so small that it does not initiate the action of the manostat.

Another method for measuring benzene adsorption is a suitable thermogravimetric analysis system, such as a computer-controlled 990/951 du Pont TGA system. The sample is dehydrated (removal of sorbed water) by heating at, for example, 350 or 500 ° C to a constant weight in flowing helium. If the sample is in an as-synthesized form, that is, it contains direct organic substances, it is calcined at 540 ° C in air to constant weight, instead of the previously described treatment at 350-500 ° C. The benzene adsorption isotherm is measured at 25 ° C in a mixture of a stream of benzene saturated with benzene and a stream of pure helium in the correct proportions to achieve the desired benzene partial pressure. The adsorption value at 50 torr of benzene is taken from the adsorption isotherms diagram.

Example 1

One hundred grams of the cetyltrimethylammonium (CTMA) basic solution prepared by mixing 29% by weight of a solution of N, N, N-trimethyl-1-hexadecanamine hydrochloride with a halogen ion exchange resin was mixed with aqueous tetramethylammonium (TMA) silicate solution (10% silicate). Twenty-five grams of HiSil, a precipitated hydrated silicate containing about 6% by weight of free water and about 4.5% by weight of bound hydration water and having an approximate particle size of about 0.02 microns, was added. The resulting mixture was placed in a polypropylene bottle and placed in a steam box at 95 ° C overnight. This mixture had a composition in moles per mole of Al ₂ O ₃ :

2.7 moles Na ₂ O

392 mol of SiO ₂

35.7 moles (CTMA) ₂ O

61.7 mol (TMA) ₂ O 6231 mol H ₂ O

The resulting solid product was filtered and air dried at ambient temperature. The product was then calcined at 540 ° C for one hour in a nitrogen atmosphere and then for an additional six hours in air.

The calcined product must be shown to have a surface area of 475 m ² / g and has approximately the following adsorption capacity in grams per gram: H ₂ O 8,3 cyclohexane 22,9 n-hexane 18,2 benzene 21,5

The X-ray xenogram of this calcined product is shown in FIG. 1. In this graph and the following graph, it is significant that ten Angstrom units (1.0 nm) d-distance corresponds to 8.842 degrees 2-theta (Cu K-alpha radiation) and eighteen Angstrom units (1.8 nm) corresponds to 4.909 degrees .

The product of this example can be characterized by comprising a line with very strong intensity at 3.78 ± 0.2 nm d-spacing and weak lines at 2.16 ± 0.1 nm and 1.92 ± 0.1 nm. The presence of ultra-large pores of the material was demonstrated on a transmission electron microscope (TEM), which gives an idea of the hexagonal ordering and uniformity of the pores, and the hexagonal electron diagram with a _d10 of 3.9 nm.

Example 2

100 grams of an aqueous solution of cetyltrimethylammonium hydroxide prepared as in Example 1 was mixed with 100 grams of an aqueous solution of tetramethylammonium (TMA) hydroxide (25%). 25 g of HiSil precipitated hydrated silicon containing 6% by weight loose and 4.5% bound water were added. The resulting mixture had a composition in moles per mole of Al ₂ O ₃ after heating in an autoclave at 150 ° C overnight:

2.7 mol Na ₂ 0

291 mol SiO ₂

35.7 moles (CTMA) ₂ O

102 mol (TMA) ₂ O

The resulting solid product was filtered and air dried at ambient temperature. It was then calcined at 540 ° C for one hour in nitrogen and 6 hours in air.

The calcined product had a surface area of 993 m ² / g and the following equilibrium adsorption capacities in g / g:

H ₂ O 7,1 cyclohexane 47.2 n-hexane 36.2 benzene 49.5

The X-ray xenogram of the calcined product of this example is shown in Figure 2. This includes a very thick line at 3.93 ± 0.2 nm and a weak line at 2.22 ± 0.1 and 1.94 ± 0.1 nm, respectively. TEM shows that the product contains ultra-large pore material.

A portion of the product was then contacted with steam at 790 ° C (1450 ° F) for two hours. The surface area of the evaporated material was 440 m ² / g, indicating that about 45% remained after steaming. Another portion of the calcined product was in contact with steam for two hours at 680 ° C (1250 ° F). The surface area was 718 m ² / g, indicating that 72% remained after evaporation under these conditions.

Example 3

Water, cetyltrimethylammonium hydroxide of Example 1, aluminum sulfate, HiSil and aqueous tetrapropylammonium (TPA) bromide solution (35%) were mixed and the resulting mixture had a molar composition per mole of Al ₂ O ₃ :

0.65 molNa ₂ 0 mol SiO ₂

8.8 mol (CTMA) 10

1.22 mol (TPA) ₂ O 1336 mol H ₂ O

The resulting mixture was placed in a polypropylene bottle and placed in a steam box for 192 hours at 95 ° C. The sample was cooled at room temperature and mixed with the CTMA hydroxide prepared in Example 1 and TMA hydroxide (25%) with weight ratios of 3 parts mixture, 1 part CTMA hydroxide and 2 parts TMA hydroxide. The combined mixture was placed in a polypropylene bottle and placed in a steam box at 95 ° C overnight. The resulting mixture had a molar composition per mole of Al ₂ O ₃ :

0.65 mol Na ₂ O mol SiO ₂ mol (CTMA) ₂ O

1.22 mol (TPA) ₂ O

35.6 moles (TMA) ₂ O

The resulting solid product was filtered, air dried at normal temperature and then calcined at 540 ° C for 1 hour under nitrogen and 6 hours under air.

The calcined product had a surface area of 1085 m ² / g

and equilibrium adsorption capacity in g / g: H ₂ O 11.5 cyklhexán 50 n-hexane 39.8 benzene 62

The X-ray diffraction pattern of the calcined product is shown in Figure 3. The product can be characterized by a very thick line at 3.82 ± 0.2 nm d-spacing and thin lines at 2.22 ± 0.1 and 1.94 ± 0.1 nm, respectively. TEM shows that the product contains ultra-large pore material.

Example 4

200 grams of cetyltrimethylammonium (CTMA) hydroxide from Example 1 was mixed with 2 grams of Catapalaluminium (alpha-aluminum monohydrate 74% Al) and 100 grams of an aqueous solution of tetramethylammonium (TMA) silicate (10% Si). 25 grams of HiSil precipitated hydrated silicon containing 6% by weight free and 4.5% bound water and a particle size of 0.02 nm was added. The resulting mixture was placed in a static autoclave for 48 hours at 150 ° C. The mixture had a composition in moles per mole of A1 ₂ O ₃ :

0.23 mol Na ₂ O

33.2 mol of SiO ₂

6.1 mole (CTMA) ₂ 0

5.2 mol (TMA) ₂ O

780 mol H ₂ O

The resulting product was filtered and air dried at normal temperature. It was then calcined at 540 ° C for 1 hour in nitrogen and 6 hours in air.

The calcined product had a surface area of 1043 m ² / g and an equilibrium adsorption capacity of g / g:

H ₂ O 6.3 cyclohexane> 50 n-hexane 49.1 benzene 66.7

The X-ray xenogram of the calcined product is shown in Figure 4. It contains a very thick line at 4.08 ± 0.2 nm d-spacing and weak lines at 2.31 ± 0.1 and 2.01 ± 0.1 nm, respectively. TEM shows that the product contains ultra-large pore material (see Example 22).

Example 5

260 grams of water was mixed with 77 grams of phosphoric acid (85%), 46 grams of Catapolalumina (74% aluminum) and 24 grams of pyrrolidine (pyr). The mixture was placed in a stirred autoclave for 6 days at 150 ° C. The material was filtered, washed and air dried. 50 grams of the product was mixed with 200 grams of water and 200 grams of cetyltrimethylaluminium hydroxide of Example 1. Then 400 grams of an aqueous solution of tetraethylammonium silicate (10% Si) was added to form a secondary mixture which was placed in a polypropylene bottle and placed in a steam box overnight 95 ° C. The first mixture had a composition in moles per mole of A1 ₂ O ₃ :

mol P ₂ O ₅

0.51 mol (pyr) ₂ O

47.2 mol H ₂ O

The resulting solid product was filtered and air dried at normal temperature. It was then calcined at 540 ° C for one hour in nitrogen and 6 hours in air.

The calcined product has a surface area of 707 m ² / g and an equilibrium adsorption capacity in g / g:

H ₂ O 33.2 cyclohexane 19.7 n-hexane 20.1 benzene 23.3

The X-ray of the calcined product is shown in the graph. 5. It contains a very thick line at 2.54 ± 0.15 nm d-distance. TEM shows that the product contains ultra-large pore material (see Example 22).

Example 6

A solution of 1.35 g NaA10 ₂ (43.5% Al ₂ O ₃ , 30% Na ₂ O) dissolved in 45.2 g water was mixed with 17.3 g NaOH, 125.3 g colloidal silicon ( 40% Ludox HS-40) and 42.6 grams of an aqueous solution of tetraethylammonium (TEA) hydroxide. The mixture was stirred overnight and then placed in a steam box for 7 days at 95 ° C. After filtration, 151 grams of the solution were mixed with 31 grams of cetyltrimethylammonium hydroxide of Example 1 and placed in a steam box for 13 days at 95 ° C. The mixture had a relatively molar composition:

0.25 mol of Al ₂ O ₃ molNa ₂ O mol of SiO ₂

0.95 mol (CTMA) ₂ O

445 mol H ₂ O

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

The calcined product contains 0.14% Na, 86.5% SiO ₂ , 5.1% Al ₂ O ₃ (w / w) and has an equilibrium benzene adsorption capacity of 58.6 g / 100 g.

The X-ray diffraction pattern of the calcined product is shown in Figure 6. The product may be characterized by the presence of a very thick line at 3.14 ± 0.15 d-distances. TEM shows that the product contains ultra-large pore material.

Example 7

A mixture of 150 grams of cetyltrimethylammonium (CTMA) hydroxide of Example 1 and 21 grams of colloidal silicon (40% Ludox HS-40) with an initial pH of 12.64 was heated in a 300 cc autoclave to 150 ° C and stirred for 48 hours at 200 rpm. The composition was composed of:

0.5 mol (CTMA) ₂ O

46.5 mol H ₂ O

The resulting solid product was filtered, washed with water, and then calcined at 540 ° C for 6 hours in air. The calcined product contained 0.01% Na, 93.2% SiO ₂ and 0.016% Al ₂ O ₃ (w / w) and had a surface area of 992 m ² / g with the following equilibrium adsorption capacity (grams / 100 grams):

H ₂ O _4, 6 cyclohexane> 50 n-hexane> 50 benzene 62.7

The X-ray of the calcined product is shown in Figure 7. The product may be characterized by a line with a very strong relative intensity of 4.36 ± 0.2 nm d-spacing and weak lines of 2.51 ± 0.15 and 2.17 ± 0.1 nm. TEM shows that the product contains ultra-large pore material.

Example 8

Sodium aluminate (4.15 g) was slowly added to a solution containing 16 grams of myristyltrimethylammonium bromide (CuTMABr) in 100 grams of water. To the mixture was then added tetramethylammonium silicate (100 g - 10% SiO ₂ ), HiSil (25 g) and tetramethylammonium hydroxide (14.2 g - 25% solution). The mixture had the following relative molar composition:

1.9 moles A1 ₂ O ₃

3.0 mol Na ₂ O mol SiO ₂

2.4 mol (C ₁₄ TMA) ₂ O

6.1 mol (TMA) ₂ O

628 mol H ₂ O

The mixture crystallized in a stirred autoclave at 120 ° C for 24 hours. The resulting product was filtered, washed and air dried. Elemental analysis showed that the product contained 53.3% SiO ₂ , 3.2% Al ₂ O ₃ , 15.0% C, 1.88% N, 0.11% Na and 53.5% ash and at 1000 ° C. C. Figure 8 shows a X-ray of a material that was calcined at 540 ° C for 1 hour under nitrogen and 6 hours in air. It contains a line with very strong relative intensity at 3.53 ± 0.2 nm d-distance and weak lines at 2.04 ± 0.1 and 1.77 ± 0.1 nm d-distance. TEM shows that the product contains ultra-large pore material.

The washed product, which was converted with a 1N ammonium nitrate solution at room temperature, then calcined, has a surface area of 827 m ² / g and the following equilibrium adsorption capacities in g / 100 g of dehydrated sorbent:

H ₂ O 30.8 cyclohexane 33.0 n-hexane 27.9 benzene 40.7

Example 9

Sodium aluminate (8.3 g) was slowly added to a solution containing 184 g dodecyltrimethylammonium hydroxide (C ₁₂ TMAOH, 50%) diluted with 480 g water. UltraSil (50 g) and an aqueous solution of tetramethylammonium silicate (200 g - 10% SiO ₂ ) and tetramethylammonium hydroxide (26.38 g 25% solution) were then added to the solution. He had the following molar composition:

394 mol H ₂ O

11.1 mol of isopropanol

The solution was crystallized in an autoclave at 100 ° C with stirring for 24 hours. The resulting product was filtered, washed and dried. Figure 9 shows a X-ray of a substance that was calcined at 540 ° C for 1 hour under nitrogen and for 6 hours in air. The X-ray diffraction pattern of the substance shows a line with a very strong d-distance intensity of 3.04 ± 0.15 nm and faint lines at a d-distance of 1.77 ± 0.1 nm and 1.53 ± 0.1 nm, respectively. TEM shows that ultra-large pore material is present in the product. The washed product was converted with an ammonium nitrate solution at room temperature, then calcined and showed a surface area of 1.078 m ² / g and the following equilibrium adsorption capacity in g / 100 g of anhydrous sorbent: H ₂ O 32.6 cyclohexane 38.1 n-hexane 33.3 benzene 42.9

Example 10

A solution of 4.9 grams of NaA10 ₂ (43.5% Al ₂ O _3> 30% NaO ₂ ) in 37.5 grams of water was combined with 46.3 cc of a 40% aqueous solution of tetraethylammonium hydroxide and 96 grams of colloidal silicate (40%, Ludox) HS-40). The gel was vigorously stirred for half an hour, mixed with an equal volume (150 mL) of the cetyltrimethylammonium hydroxide solution prepared in Example 1 and reacted at 100 ° C for 168 hours. This compound had the following composition in moles per mole of Al ₂ O ₃ :

1.1 molNa ₂ O

30.6 mol of SiO ₂

3.0 mol (TEA) ₂ O

3.25 mol (CTMA) ₂ O

609 mol H ₂ O

The resulting solid product was filtered, washed in water, and then calcined for 16 hours at 540 ° C in air.

The calcined product shows a surface area of 1325 m ² / g and has an equilibrium adsorption capacity in g / 100 g:

H ₂ O 23.6 cyclohexane> 50 n-hexane 49 benzene67.5

An X-ray of the calcined product is shown in Figure 10. The product of this example can be characterized by containing a line with a very strong intensity at 3.85 ± 0.2 nm d-distance and a weak line at 2.03 ± 0.1 nm. TEM shows that the product contains ultra-large pore material.

Example 11

200 grams of the cetyltrimethylammonium (CTMA) hydroxide solution prepared in Example 1 was combined with 4.15 grams of sodium aluminate and 100 grams of an aqueous solution of tetramethylammonium silicate (10% aluminum) with stirring. 25 grams of HiSil, a precipitated hydrated silicate containing 6% by weight of free and

4.5% bound water with a largest particle size of about 0.02 microns. The resulting mixture was placed in a static autoclave for 24 hours at 150 ° C. The mixture had a composition in moles per mole of A1 ₂ O ₃ :

1.25 moles Na ₂ O

27.8 mol of SiO ₂

5.1 mol (CTMA) ₂ O

4.4 mol (TMA) ₂ O

650 mol H ₂ O

The resulting solid product was filtered and air dried at normal temperature. The product was then calcined at 540 ° C for 1 hour under nitrogen and for 6 hours in air. TEM shows that this product contains ultra-large pore material. The X-ray of this calcined product is shown in FIG. 11. The product can

SK 280860 byť6 be characterized in that it contains a line with a very strong d-distance intensity of 4.42 ± 0.2 nm and weak lines at a distance of 2.52 ± 0.15 and 2.2 ± 0.1 nm.

The calcined product has a surface area of 932 m ² / g and the following equilibrium adsorption capacity in grams / 100 g:

H ₂ O 39.3 cyclohexane 46.6 n-hexane 37.5 benzene 50

The product of this example was converted with a 1N ammonium nitrate solution, then calcined at 540 ° C for 10 hours in air.

Example 12

The 200 grams of cetyltrimethylammonium (CTMA) hydroxide prepared in Example 1 was combined with 4.15 grams of sodium aluminate and 100 grams of an aqueous solution of tetramethylammonium (TMA) silicate (10% aluminum) with stirring. 25 grams of HiSil, a precipitated hydrated silicate containing 6% by weight of free and about

4.5% bound water with a largest particle size of about 0.02 microns. The resulting mixture was placed in a steam box for 48 hours at 100 ° C. The mixture had a composition in moles per mole of A1 ₂ O ₃ :

1.25 moles Na ₂ O

27.8 mol of SiO ₂

5.1 mol (CTMA) ₂ O

4.4 mol (TMA) ₂ O

650 mol H ₂ O

The resulting solid product was filtered and air dried at normal temperature. The product was then calcined at 540 ° C for 1 hour under nitrogen and for 6 hours in air.

The calcined product has the following equilibrium adsorption capacity in grams / 100 g: H ₂ O 35.2 cyclohexane 50 n-hexane 40.8 benzene 53.5

The X-ray xenogram of this calcined product is shown in FIG. 12. The product may be characterized by comprising a line of very strong intensity at 3.91 ± 0.2 nm d-spacing and weak lines at 2.24 ± 0.1 and 1.94 ± 0.1 nm.

TEM shows that this product contains ultra-large pore material.

The product was then converted with a 1N ammonium nitrate solution, then calcined at 540 ° C for 10 hours in air.

Example 13

125 grams of a 29% aqueous solution of CTMA chloride, 200 grams of water, 3 grams of sodium aluminate (in 50 grams of water) 65 grams of Iltrasil, amorphous precipitated silicate obtained from PQ Corporation and 21 grams of NaOII (in 50 grams of water) were thoroughly mixed and crystallized at 150 ° C for 168 hours. The reaction compound had the following molar composition in moles per mole of Al:

0.1 mol (CTMA) ₂ O

21.89 mol H ₂ O

0.036 mol NaA10 ₂

0.53 mol of NaOH

The solid product was filtered, washed with water and dried for 16 hours at room temperature and calcined at 540 ° C for 10 hours in air.

The calcined product has a surface area of 840 m ² / g and the following equilibrium adsorption capacity in grams / 100 g:

H ₂ O 15.2 cyclohexane 42.0 n-hexane 26.5 benzene 62

The X-ray diffraction pattern of the product is shown in FIG. 13 and may be characterized by containing a line with a very strong intensity at 4.05 ± 0.2 nm d-distance. TEM shows that the product contains ultra-large pore material.

Example 14

For comparison purposes, an ultra-stable zeolite Y having a benzene adsorption capacity of 20.7 grams per 100 grams was obtained. The X-ray xenogram of this product had all lines with the highest peak value at 1.4 nm d-distance.

Example 15

The primary exemplary solution for this example was formed by adding 240 grams of water to 92 grams of a solution containing 50% dodecyltrimethylammonium hydroxide, 36% isopropyl alcohol (IPA) and 14% water so that the molar ratio of solvent / Rj / fO was 155. The molar H ₂ O ratio The R _{2 / f} O in this solution was 149 and the IPA / R _{2 / f} O was 6. 4.15 grams of sodium aluminate, 25 grams of HiSil, 100 grams of an aqueous solution of tetramethylammonium silicate (10% SiO ₂ ) were added to the primary sample solution. and 13.2 grams of a 25% solution of tetrametalammonium hydroxide. The molar ratio RmO / SiO + + AIA) was 0.28.

This solution was stirred for 1 hour at 25 ° C. The resulting mixture was placed in an autoclave at 100 ° C, stirred at 100 rpm. for 24 hours. The autoclave mixture had the following molar composition in moles per mole of SiO ₂ : 0.05 moles of Na ₂ O

0.036 moles A1 ₂ O ₃

0.18 mol (C ₁₂ TMA) ₂ O

0.12 mol (TMA) ₂ O

36.0 mol H ₂ O

1.0 mol IPA

The resulting solid product was filtered, washed with water and air dried at normal temperature. The product was then calcined at 540 ° C for 1 hour under nitrogen, then 6 hours in air.

The calcined product has a surface area of 1223 m ² / g and an equilibrium adsorption capacity in grams / 100 g: H ₂ O 25.5 cylohexane 41.1 n-hexane 35.1 benzene 51

The X-ray X-ray of this product is shown in graph no. 14. The product may be characterized by comprising a line with a very strong intensity at 3.08 ± 0.15 nm d-spacing and weak lines at 1.79 ± 0.1 and 1.55 ± 0.1 nm. TEM shows that the product contains ultra-large pore material.

Example 16

50.75 grams of decyltrimethylammonium hydroxide (prepared compounds of a 29% solution of decyltrimethylammonium hydroxide with hydroxide) was combined with 8.75 grams of tetraethyl orthosilicate. The compound was stirred for about 1 hour and then transferred to a polypropylene bottle which was placed in a steam box for 24 hours. The compound had a composition in moles per mole of SiO ₂ :

0.81 mol (C ₁₀ TMA) ₂ O

47.6 mol H ₂ O

SK 280860 Β6

The resulting solid product was filtered and washed several times with 60-70 ° C with warm distilled water and acetone. The final product was calcined in a nitrogen-air mixture at 538 ° C, and then held in the air for about 8 hours.

The calcined product has a surface area of 915 m ² / g and a benzene adsorption capacity of 35 grams / 100 grams.

The x-ray of this product can be characterized by containing a very strong intensity at 2.75 ± 0.15 nm d-spacing and a weak line at 1.58 ± 0.1 and 1.37 ± 0.1 nm, respectively. TEM shows that this product contains ultra-large pore material.

Example 17

To 80 grams of the cetyltrimethylammonium hydroxide (CTMAOH) solution prepared as in Example 1 was added

1.65 grams of NaA10 ₂ . The compound was stirred at room temperature until the aluminate was soluble. To this solution were added 40 grams of an aqueous solution of tetramethylammonium (TMA silicate (10% SiO ₂ ), 10 grams of HiSil, 200 grams of water and 70 grams of 1,3,5-trimethylbenzene (TMB) .The resulting mixture was stirred at room temperature for several minutes. The gel was then placed in a 600 cc autoclave and heated to 105 ° C for 68 hours with constant stirring at 100 rpm This compound had a molar composition per mole of Al ₂ O ₃ :

1.25 moles Na ₂ O

27.8 mol of SiO ₂

5.1 mol (CTMA) ₂ O

2.24 mol (TMA) ₂ O

2256 mol H ₂ O

80.53 mol TMB

The resulting solid product was filtered and washed several times with 60-70 ° C with warm distilled water and then with acetone. The final product was calcined in a nitrogen-air mixture at 538 ° C, and then held in the air for about 10 hours.

The calcined product has a benzene adsorption capacity of 25 grams / 100 grams.

The X-ray xenogram of this product can be characterized by containing a line with a very strong intensity at a d-distance of about 10.2 nm, but the exact position of the lines in the region of extremely small angles of the X-ray xenogram is very difficult to distinguish using a conventional X-ray meter. In addition, finer collimation slits were required to distinguish the peak at this small 2-theta angle. The slits in this case were 0.1, 0.3, 0.5, 0.2 nm. TEM showed that the product of this example contained several substances with different _d10 values, as determined by observing their electron diffraction pattern. These substances were found at positions d ₁₀₀ values between 8.5 and 12 nm d-distances.

Example 18

Up to 80 grams of a solution of cetyltrimethylammonium hydroxide (CTMAOH) prepared as in example no. 1 was added

1.65 grams of NaA10 ₂ . The compound was stirred at room temperature until aluminate was dissolved. To this solution were added 40 grams of an aqueous solution of tetramethylammonium (TMA silicate (10% SiO ₂ )), 10 grams of HiSil, 200 grams of water and 120 grams of 1,3,5-trimethylbenzene (TMB), and the resulting mixture was stirred for several minutes at room temperature. The gel was then placed in a 600 cc autoclave and heated to 105 ° C for 90 hours with constant stirring at 150 rpm This mixture had a molar composition per mole of Al ₂ O ₃ :

1.25 mol of Na ₂ O

27.8 mol of SiO ₂

5.1 mol (CTMA) ₂ O

2.24 mol (TMA) ₂ O 2256 mol H ₂ O

132.7 mol TMB

The resulting solid product was filtered, and then washed with 60-70 ° C with warm distilled water and acetone. The resulting product was calcined in a nitrogen-air mixture at 538 ° C, and then held in an air atmosphere for about 10 hours.

The calcined product has a surface area of 915 m ² / g and an adsorption benzene capacity of 25 g / 100 gTam. Argon physical sorption data shows an increase in argon to 0.95 cc / g and a pore size concentrated around 7.8 nm (Dollimore-Heal Method, see Example 21b), but ranging from 7 nm to more than 10.5 nm.

The X-ray calcined product can be characterized by having only scattered intensity in the region of a very small X-ray angle where the intensity of the beam of transmitted incident X-rays was usually observed. TEM showed that the product of this example contained several substances with different _d10 values, as determined by observing their electron diffraction pattern. These substances were in positions d _{1 ()} of between

8.5 and 11 nm d-distances (see Example 22).

Example 19

To 80 grams of cetyltrimethylammonium hydroxide prepared as in example no. 1, 1.65 grams of NaA10 ₂ was added. The mixture was stirred at room temperature until dissolution. To the solution were added 40 grams of an aqueous solution of tetramethylammonium silicate (10% SiO ₂ ), 10 grams of HiSil and 18 grams of 1,3,5-trimethylbenzene (TMB). The resulting mixture was stirred for several minutes. The gel was then placed in a 300 cc autoclave for 4 hours at 105 ° C and stirred at 150 rpm. This mixture had a composition in moles per mole of A1 ₂ O ₃ :

1.25 mol of Na ₂ O

27.8 mol SiO ₂

5.1 mol (CTMA) ₂ O

2.24 mol (TMA) ₂ O

650 mol H ₂ O

19.9 mol TMB

The resulting product was filtered, washed several times with 60-70 ° C warm distilled water and acetone. The resulting product was calcined in a nitrogen-air mixture at 538 ° C, and then held in the air for about 8 hours.

The calcined product has a surface area of 975 m ² / g and an equilibrium benzene adsorption capacity of 40 grams / 100 grams. Argon physical sorption data shows an increase in argon to 0.97 cc / g and a pore size of 6.3 nm (Dollimore-Heal Method, see Example 21b), with a peak at P / Po = 0.65.

The X-ray xenogram of the calcined product may be characterized by a line with a very strong intensity at 6.3 ± 0.5 nm d-spacing and weak lines at 3.64 ± 0.2, 3.13 ± 0.15 and 2.38 ± 0, 1 nm. TEM shows that the product contains ultra-large pore material.

Example 20

In order to improve the catalytic values, the product of the present invention of Examples 1-14 was evaluated by dealkylation from tri-tert-butylbenzene and di-tert-butylbenzene. The evaluation was performed under one or both sets of conditions: (i) a temperature of 225 ° C, a mass hourly space velocity of 100 h ^-1 or (ii) a temperature of 200 ° C, a mass hourly space velocity of 200 h ^-1 .

SK 280860 Β6

The pressure was atmospheric. The inlet was composed of 6.3 / 93.7 TTBB / toluene. The conversion was measured for 30 minutes.

Catalyst from Example X mass conversion. 225 'C / 100 h' ¹ 200 C / 200 hrs First 0 - 2 6. 2 - 3 53 »9 - 4 10. 4 - 5 68. 9 6 100, O - 7 5. 3 - 8 - 61.2 9 - 5Θ. 9 10 86. 3 11 96. 7 - 12 92, 8 - 13 - 37.7 14 12. 0 ABOUT

Example 21

Argon physical sorption of porous systems over 6.0 nm in diameter

In order to determine the pore diameter of the products of the present invention with pores greater than 6.0 nm in diameter, 0.2 grams of samples of the products of Examples 1 to 16 were placed in a glass sample tube and attached to the physical sorption apparatus described in U.S. Pat. . 4 762 010,

The sample was heated at 300 ° C for 3 hours under vacuum to remove adsorbed water. The sample was then cooled to 87 ° C by immersing the sample in liquid argon. Thereafter, a measured amount of argon gas was added to the samples in a stepwise manner as described in U.S. Pat. No. 4,762,010, column 20. The adsorbed amount of argon can be calculated from the amount of argon gas added to the sample and the remaining amount of argon in the gas phase above the sample. The ideal gas rule and calibrated sample volumes are used for this calculation (see also S.J. Gregg et al., Adsorption, Surface Area and Porosity, 2nd Edition, Academic Press, 1982). In any case, a graph of adsorbed amount and relative pressure above the sample at equilibrium creates an adsorption isotherm, as shown in Figure 15 of the sample of the product of Example 4. Usually, the relative pressure given by the ratio of equilibrium pressure to vapor pressure of adsorbent is used. In addition to the temperature at which isotherm is measured. Sufficient small amounts of argon are added at each stage to give 168 points in the relative pressure range from 0 to 0.6. At least 100 points are required for an isotherm to be sufficiently defined.

An isothermal jump (inflexion), in this case (product of Example 4) at P / Po = 0.4, indicates the filling of the porous system. The size of the step indicates the adsorbed amount, while the position of the step in the P / Po values indicates the size of the pores in which adsorption took place. Larger pores are filled at higher P / Po. A log derivative (PZPo) is used to better determine the position of the grade. This can be seen in Figure 16. Figure 16 also shows data obtained in an identical form of crystalline material from U.S. Pat. No. 4,880,611 and other other crystalline materials. Furthermore, there is a physical scale on the axis that converts the positions on the adsorption peak in log (P / Po) values to the physical pore diameter. This conversion was obtained using the following formula:

To 's' s * s

109 (PZPo >), d-O. 38 3CL-D / 2) '3CDZ21' 3 (11/2) 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 Horvath and Kawazoe methods (G. Horvath et al., J. Chem. Eng. Japan 16 (6) 470 (1983)). The constants required to use this formula were determined from the measurement of the ALPO-5 isotherm and its known pore sizes. This method is particularly suitable for microporous materials having pores greater than 6.0 nm in diameter.

As shown in Figure 16, the pore size of the material of Example 4 is 3.96 nm with a peak located at log (P / Po) = -0.4 or P / Po = 0.4, while the pore size of the material of US No. 4,880,611 is 1.2 nm or P / Po = 0.02. On other materials, a peak was observed at P / Po = 0.015, which is indicated by an asterisk in Figure 16. This peak shows adsorption on the pore walls and does not indicate in any way the pore size of the material. P / Po = 0.03 corresponds to a pore size of 1.3 nm.

The results of this procedure for the samples of Examples 1 to 16 are shown in the table below. The samples of Examples 9, 12 and 15 provided two separate peaks, which could be assumed to be due to two separate phases with ultra-large pores in the products.

Example

Fiction

1S

Pore diameter. nm

3. 22

3:54

4.25

3, 96

1.63

2.73

4.26

2.83

2. 28.

3.68

61

3:50

4, O

O. 83

2, 24

J. 50

3, 08

4, 21

3. 04

Example 21 (b)

Argon physical sorption for porous system over 6 nm in diameter

In the porous mode above 6.0 nm, the Kelvin equation can be applied. It is usually given by:

-2V ln <P / Pq) - cos 9, r _K RT where ln = surface tension of sorbent

V = molar volume of sorbent = constant angle (usually for practical reasons O)

R = gas constant

T = absolute temperature r _k = capillary condensation radius

P / Po = relative pressure (taken from the physical sorption isotherm)

The Kelvin equation adjusts adsorption in porous systems as a capillary condensation phenomenon and the relationship of pressure at which adsorption takes place to the pore diameter through surface tension and the constant angle of the adsorbent (in this case argon). The principles on which the Kelvin equation is based apply to pore sizes lying in the 5 to 100 nm range. Below this range, the equation does not depict physical reality, since at the small pore sizes there is no first capillary condensation, above this region the natural logarithm of the equation allows to obtain a pore size resolution with sufficient accuracy.

A particular use of the Kelvin equation often chosen for measuring pore size is reported by Dollimor and He.

SK 280860-6 alom (D. Dollimore and G. R. Heal, J. Applied Chem., 14, 108 (1964)). This method, adapted to the pore wall adsorbent surface layer effects where the Kelvin equation is not sufficient, provides a more accurate measurement of the pore size. Although derived from desorption isotherms, this method can also be used for adsorption isotherms. The products of Examples 18 and 19 were subject to the Dollimor and Heal methods for physical argon sorption data.

Example 22

Transmission electron microscopy

To further illustrate the nature of the hexagonal crystalline product of this invention, samples of the products of Examples 1-12, 13, 15-19, 23-31 and 36-38 were studied by transmission electron microscopy (TEM). TEM is a method allowing to know the microscopic structure of a material, including porous.

To illustrate the microstructure, the sample must be thin enough to pass through an electron beam, generally about 50-100 nm. The crystal morphology of the present material usually requires the preparation of ultramicrotomias. This method is quite common for those involved in electron microscopy. The material is embedded in a resin, in this case a commercial low viscosity acrylic resin, L. R. WHITE (hard), which is then treated at 80 ° C for 1.5 hours. The thin layer from the block is cut off by ultramicrotomy using a diamond incisor and the layers at 50-100 nm thickness are deposited on a fine electron microscope grid. For these materials, the LKB microtomy model with a 45 ° C blade, a 400 mesh grid was used. After evaporating the thin carbon coating of the sample, which protects the sample when placed in the microscope (gray staining of the sample paper in the evaporator), the sample is prepared for TEM.

If only verification of the presence of the material of the invention is required, a simpler sample preparation can be used. This includes placing the dispersion on the material on a carbon-coated Formvar electron microscope after grinding and sonication in propanol. Area fragments sufficiently thin to obtain an electron diffraction diagram, and the image of a lattice can normally be found near the crystal edge. Samples for the analysis of the products of Examples 23-31 and 36-38 were prepared by this dispersion technique.

The high resolution TEM shows the structure along the direction in which the sample is viewed. For this reason, specific sample orientation is required in order to observe certain details of the sample and its microstructure. For crystalline materials, this orientation is much easier to determine when observing an electron diffraction pattern (EDP) formed in parallel to the electron image. Such EDPs are generated on modern TEM instruments, for example, by selecting regions limited by the size and technique well known to those skilled in electron microscopy. If EDP is observed with the desired alignment of the diffraction points, the corresponding crystal image shows that EDP displays microstructure details in the direction of projection indicated by EDP. In this way, various crystal structures can be observed and identified using TEM.

Observing the features of the crystalline product protrusions of the present invention, a material orientation is required which, in the corresponding EDP, gives the hexagonal arrangement of the diffraction points of the individual crystal. Diffraction diagrams of multiple crystals may overlap, making interpretation difficult. An example of the individual crystal hexagonal diagram of Example 4 is shown in the graph

17. The number of diffraction points depends on the degree of regularity of the crystalline structure of the material, inter alia. At least one can observe the inner circle of the bright spot to obtain a good image. Individual crystals can be adjusted in the TEM so that the correct orientation is achieved. Much more often, it is possible to take advantage of the fact that the sample contains a plurality of differently oriented crystals, and it is easy to view the sample until the desired EDP (and thus orientation) is found. This technique was used to obtain said electron micrograph.

Microtome samples of the materials of Examples 1-13 and 15-19 were examined by the technique described in JEOL 200 CX TEM at 200,000 volts with a 0.2 nm objective grid. The instrument has a dot resolution of 0.45 nm. Other experimental arrangements known to those skilled in the art of high-resolution (phase contrast) TEM, which give an equivalent image, can be used, the objective lens in the lower experiment being in minimal contrast to the lenses of the conventional setting. Figure 18 is an electron micrograph of a microtome thin layer of crystalline material of Example 4. This micrograph shows a regular series of broad channels in hexagonal configuration. The recurrent channel spacing is 4.5 nm, which is consistent with the position of the first X-ray peak (4.1 nm / 3/2) of this material. If the channels have walls between them, this observation is also consistent with an approximate pore size of 3.96 nm calculated from the argon physical sorption measurements of the material in Example 16.

Figure 19 is an electron micrograph of the microtome thin layer of the crystalline product of Example 5. This micrograph shows a regular row of a few smaller channels in hexagonal configuration. The recurring spacing between channels is 3.0 nm, which is consistent with the position of the X-ray peak (2.5 nm / 3/2) of this material. The smaller pore size was also verified by the argon physical sorption shown in Example 21 (a), where 1.69 nm was calculated from the material of Example 5.

Figure 20 is an electron micrograph of the microtome layer of the crystalline product of Example 18. The channels in this image are fairly large and considerably irregular, but the characteristic hexagonal arrangement of the material of the invention is apparent.

Example 23

1.65 g NaA10 ₂ was added to a solution of 80 g cetyltrimetylamóniumhydroxidu (CTMAOH) formed by combining N, N, N-trimethyl-l-hexadekanamínium chloride hydroxide. The mixture was stirred until the NaAlO ₂ dissolved. To this solution were added 40 grams of tetramethylammonium silicate solution and 10 grams of HiSil (90% SiO ₂ ). The resulting mixture was stirred for several minutes at room temperature. The gel was then placed in a 300 ml autoclave and heated to 105 ° C with stirring at 150 rpm. After 4 hours of heating, the reaction was quenched with cold water and the contents were removed. The product was filtered and washed several times with warm distilled water (60-70 ° C) and acetone. The resulting product was calcined at 538 ° C in an N / air mixture for 8 hours. The gel reaction mixture has a composition in moles per mole of Al ₂ O ₃ :

1.25 moles Na ₂ O

27.8 mol of SiO ₂

5.1 mol (CTMA) ₂ O

2.24 mol (TMA) ₂ O

650 mol H ₂ O

SK 280860 Β6

The calcined product of this example has a surface area of 1187 m ² / g and an adsorption benzene capacity of 66 grams / gram.

The x-ray of the calcined product of this example is shown in Figure 21, which shows that the product has a very strong relative line intensity at 3.68 ± 0.2 nm d-spacing and weak lines at 2.21 ± 0.1 and 1.83 ± 0.1 nm. The product of this example was examined by a transmission electron microscope (TEM), which gives an image of a hexagonal arrangement of uniform pore sizes and a hexagonal electron diffraction pattern with a d ₁₀ value of 3.8 nm.

Examples 24 -31

Eight separate experiments were performed according to the procedure of Example 23, but with the addition of the auxiliary organic to the initial reaction scheme. In all cases, the adjuvant 1,3,5-trimethylbenzene (TMB) was added as the last ingredient. The concentration of TMB was different in each experiment, as shown in Table A. Table A also shows pore sizes, pore volumes in cc / g and equilibrium sorption value. The pore size and volume of Examples 24, 27 and 30 were extrapolated from the d-distance plots to measure the pore size and volume of the other examples (see Charts 23 and 24). The strongest X-rays are also indicated for comparison purposes. Figure 22 evaluates the effect of TMB on the d-distance of the first X-ray maximum in TMB moles / mole of SiO ₂ in the reaction mixture. As the concentration of the auxiliary organism increases, the size and volume of the pores in the crystalline material increases.

TEM examination of each calcined product of Examples 24-31 gives a picture of the hexagonal uniform pore arrangement and a hexagonal diffraction pattern with a d ₁₀₀ value corresponding to the d-distance of the rontgenogram peak.

Table A

TMB primers EXAMPLE TMB / You are about,. <blade> TMB / d-distance- CTHA + laziness size (Nm) benzene sorpcia <g / 100 g at 6.7 kPa) <md— (Nm) 23 ABOUT ABOUT 0 3. 68 3, 2, 3, 77 66 24 0,025 0.12 D. 32 3.4 4. 15 rl 25 0. 050 0.23 0.65 4, 53 4, 51 62 26 0075 0.35 0. 37 4. 01 5. 25 46 27 0,1d 0. 46 1. 30 5, 48 5. 80 37 2Θ 0.150 O. 7D 1. 95 6.22 6, 30 43 23 Π, 15Π O, 70 1.95 6. 22 6, 90 36 30 0,183 O, 85 2, 38 6. 37 6. Hl 32 31 0, 2.1 G 1. OO 2. 80 6. 51 7. 02 38

Example 32-45

In order to determine which organic compounds are suitable as auxiliary organs for use in the present invention, Example 23 was repeated, but in each case 10 grams of the potential auxiliary organ was added to the reaction mixture before the addition of HiSil. The results are shown in Table B, which shows that n-octadecane (Example 40), 1-pentanol (Example 43) and phenol (Example 44) distorted the results of changes in the d-distance of the strongest X-ray line or gave amorphous materials. All of the remaining materials listed in Table B give valid changes in the position of the strongest X-ray line and thus are useful as auxiliary organisms.

The TEM examination of the calcined product of each of Examples 36-38 gives a picture of the hexagonal arrangement of the individual pores and a hexagonal electron diffraction pattern with a d value of ₁₀₀ generally corresponding to the d-distance of the X-ray peak.

Table B

The addition of Pr./SiDa fl. Cmolar sloth · * - «- (nm>)

Renzyne scrp <g / 100 and at e, 7 kPa

23 zero 0 0 63 66 32 p-xylan O. 094 0. 44 4. 98 39 33 1. 3. 5-Trimethylhenzene 0. 083 O, 39 1.2 38 34 1,3-5-trimethylbenzene O. 062 0. 29 4, 01 3S 35 1. 3. 5-Trisopropyl- 049 0, 23 4. 49 43 benzene 36 1,3-diethylenedamantane 0 061 and 28 4. 89 42 37 n peiitán O, 139. 64 4. 72 31 38 n-decane O. 070 64 48 39 ri — dodecane □. 059 O, 27 4. 28 48 40 n-octadecane O. 039 3. 70 54 41 1-phenylnonan O. 049 O, 23 64 34 42 1.B-dlbrómoktán O. 037 4, 49 33 43 1-pentanol O. 113 O, 53 amorphous 28 44 • Phenol O. 106 amorphous ON THE 45 pyridine 0, 126 O, 59 64 ON THE

Example 46

The solution was prepared by dissolving 1.08 grams of cobalt nitrate hexahydrate in 100 grams of water. To this solution were mixed 40 grams of 29% by weight CTMA aqueous hydroxide solution, 100 grams of tetrabutylammonium (ΤΒΛ) silicate solution (prepared by mixing 168 grams of tetraethyl orthosilicate with 270 grams of 55% TBA aqueous solution and hydroxide) and 5 grams of HiSil silicate. The resulting mixture had the following composition in moles per mole of silicon:

0.21 mol (CTMA) ₂ O

0.07 mol (TBA) ₂ O

0.04 mol CoO

25.7 molH ₂ O

The mixture was placed in a polypropylene bottle and placed in a steam box for 72 hours. The resulting solid product was filtered, washed, air dried, and then calcined in air at 540 ° C for 10 hours. The calcined product had an equilibrium benzene sorption capacity of 40% by weight and the rontgenogram shown in Figure 25. It can be seen that the graph includes a very thick line at d-distances

3.7 ± 0.2 nm and thin lines at d-spacing 2.1 ± 0.1 a

1.9 ± 0.1 nm.

Example 47

The procedure of Example 46 was repeated, but 1.08 grams of nickel nitrate hexahydrate was added instead of cobalt. The resulting calcined product has a benzene sorption capacity of 60% by weight and the X-ray graph shown in Figure 26 (with a very thick line at d-distance)

3.7 ± 0.2 nm and a thin line at a d-distance of 2.1 ± 0.1 nm).

Example 48

The solution was prepared by dissolving 4.5 grams of chromium sulfate hydrate in 20 grams of water. To this solution were mixed 200 grams of an aqueous solution of 29% by weight CTMA hydroxide, 50 grams of tetrabutylammonium (TBA) silicate prepared by mixing 168 grams of tetraethyl orthosilicate with 270 grams of an aqueous solution of 55% by weight TBA hydroxide) and 25 grams of HiSil silicate. The resulting mixture had a molar composition per mole of silicon:

0.21 mol (CTMAtyO

0.07 mol (TBA) ₂ O

0.02 mol of Cr ₂ O ₃

22.0 mol H ₂ O

SK 280860 Β6

The mixture was placed in a polypropylene bottle and placed in a steam box for 72 hours. The resulting solid was filtered, washed, air dried, and then calcined at 540 ° C for 10 hours. The calcined product had an equilibrium benzene sorption capacity of 40% by weight and the X-ray graph shown in Figure 27. It can be seen that the graph includes a very thick line at d-distance

3.9 ± 0.2 nm and a weak line at a d-distance of 2.1 ± 0.1 nm.

Example 49 grams of cetyltrimethylammonium hydroxide prepared in Example 1 was mixed with 5 grams of tetraethyl orthosilicate and 14.5 grams of a solution of tetramethylammonium silicate (10% silicate). Stirring was continued for 1 hour and gallium nitrate prepared by dissolving 1.2 grams of Ga (NO ₃ ) ₃ xH ₂ O in 10 grams of water was added to the resulting solution. The resulting mixture had the following composition in moles per mole of silicon:

0.5 mol (CTMA) ₂

0.05 mol Ga ₂ O ₃ mol H ₂ O

The mixture was placed in a polypropylene bottle and placed in a steam box for 48 hours at 95 ° C. The resulting solid product was filtered. washed, air dried, and then calcined (1 hour at 540 ° C under a stream of nitrogen, then 6 hours in air). The X-ray xenogram of the resulting calcined product is shown in Figure 28 with a very thick line at a d-distance of 3.4 ± 0.2 nm and weak lines at a d-distance of 2.1 ± 0.1 and 1.8 ± 0.1 nm. Chemical analysis of the product:

% carbon by weight

2.5 wt% nitrogen wt% silicon

2.8% by weight of gallium

0.07% aluminum by weight

39.9% by weight of ash (1000 ° C).

Claims (19)

PATENT CLAIMS A composition for use in catalysts or sorption materials, characterized in that it comprises inorganic porous non-layered crystalline materials having, after calcination, a rontgenogram having at least one peak at a distance d greater than 1.8 nm and having a benzene absorption capacity greater than that. as 15 g of benzene per 100 g of material at a pressure of 6.7 kPa and a temperature of 25 ° C and whose composition corresponds to the general formula M ^ WÄYeZA) in which M represents at least one ion selected from the group consisting of ammonium ion and ions of the elements of the group ΙΑ, IIA and VIIA of the Periodic Table of the Elements, n represents the charge of the composition with the exception of M expressed as oxides, q represents the molar mean valence M, n / q W is at least one divalent element selected from the group consisting of manganese, cobalt, nickel and magnesium, X is at least one three-membered element from the group consisting of aluminum, boron, chromium, gallium and iron, Y is at least one 4-membered element from the group consisting of silicon and germanium, Z is phosphorus, a, b, c, and d are mole fractions of W, X, Y and Z, h is from 1 to 2.5 and (a + b + c + d) equals 1. Composition according to claim 1, characterized in that it comprises inorganic porous materials having a hexagonal pore arrangement of equal size with a diameter of at least 1.3 nm and having, after calcination, a hexagonal diffraction electron diagram having a d ₁₀₀ value of greater than 1.8 nm . Composition according to claim 2, characterized in that the crystalline material, after calcination, has an X-ray xenogram with at least one peak whose distance d corresponds to the value d | _{00 of the} electron diffraction diagram. The composition of claim 1 or 2, wherein the crystalline material has, after calcination, a two-peak rontgenogram at positions d greater than 1.0 nm, one of these peaks at a position d greater than 1.8 and no peaks with a relative intensity greater than 20% of the strength of the strongest peak are at a distance d of less than 1.0. The composition of claim 4, wherein the material has no peaks with a relative intensity greater than 10% of the intensity of the strongest peak at a position d of less than 1.0 nm. 6. The composition of claim 1 wherein the sum of (a + b + c) is greater than d and h is equal to 2. 7. The composition of claim 1 wherein W is cobalt, X is aluminum, Y is silicon, and Z is phosphorus. 8. The composition of claim 6, wherein h and d are zero and h is 2. 9. The composition of claim 1 wherein X is aluminum and Y is silicon. Process for preparing a composition according to claim 1 or 2, characterized in that crystallization is carried out at a temperature of 25 to 250 ° C and for 5 minutes to 14 days of a reaction mixture having the following composition expressed in molar ratios of oxides X ₂ O ₃ / YO ₂ until 0.5 X ₂ O ₃ / (Y ₂ + Z ₂ O ₅ ) 0.1 until 100 X ₂ O ₃ / (YO ₂ + WO + Z ₂ O ₅₎ 0.1 until 100 solvent / (Y0 ₂ + WO + Z ₂ 0 ₅ + X ₂ 0 ₃ ) 1 until 100 OH7YO ₂ until 10 (M _{2 / e} O + R _{2 / f} O) / (YO ₂ + WO + Z ₂ O ₅ + X ₂ O ₃ ) 0.01 until 20 M _{2 / e} O (Y ₂ + W ₂ + Z ₂ 0 ₅ + X ₂ 0 ₃ ) until 10 R _{2 / f} O / (YO2 + WO + _Z2 O5 + _{X2 O3)} 0.01 until 2.0. where e and f are the mean valences M and R, the solvent is an alcohol or diol of 1 to 6 carbon atoms or water and R is an organic diluent of the formula R ₁ R ₂ R ₃ R ₄ Q ⁺ , wherein Q is nitrogen or phosphorus and at least one of R "R ₂ , R ₃ and R" is an aryl or alkyl group having 6 to 36 carbon atoms and each of the remaining R _b R ₂ , R ₃ and R 4 is selected from the group consisting of hydrogen and C 1 -C 5 alkyl . Method according to claim 10, characterized in that a mixture having a composition expressed in molar ratios of oxides is used as the starting mixture to effect crystallization. X ₂ O ₃ / YO ₂ 0,001 until 0.5 X ₂ O ₃ / (Y ₂ + Z ₂ O ₅ ) 0.1 until 20 X ₂ O ₃ / (YO ₂ + WO + Z2O ₅₎ 0.1 until 20 solvent / (YO ₂ + WO + Z ₂ O ₅ + X ₂ O ₃ ) until 5 OH7YO ₂ until 5 (M _{2 / e} O + R ₂ , A / (Y ₂ + WO + Z ₂ O <± X ₂ O ₃ ) 0.05 until 5 M _{2 / e} O (YO ₂ + WO + Z ₂ O ₅ + X ₂ O ₃ ) until 5 SK 280860 Β6 Rj (fO / iaa + WO + ZjOs + XzOj) 0.03 to 1.0 The method according to claim 10 or 11, wherein the organic diluent is selected from the group consisting of cetyltrimethylammonium, cetyltrimethylphosphonium, octadecyltrimethylphosphonium, benzyltrimethylammonium, cetylpyridinium, myristyltrimethylammonium ammonium ammonium ammonium ammonium ammonium ammonium ammonium ammonium ammonium ammonium ammonium ammonium ammonium ammonium ammonium ammonium ammonium ammonium ammonium. The method of claim 10 or 11, wherein R comprises an additional organic diluent having the same formula as the first said diluent, but each of R _b R ₂ , R ₃ and R ₄ is hydrogen or alkyl. a group containing 1 to 5 carbon atoms. 14. The method of claim 13 wherein the additional organic diluent is selected from the group consisting of a tetramethylammonium, tetraethylammonium, tetrapropylammonium, and tetrabutylammonium compound. A process according to claim 10 or 11, wherein R comprises an organic auxiliary selected from the group consisting of aromatic hydrocarbons and amines containing 5 to 20 carbon atoms and their halogen and alkyl groups containing 1 to 14 carbon atoms substituted derivatives, cyclic and polycyclic aliphatic hydrocarbons and amines containing 5 to 20 carbon atoms and their halogen and alkyl groups containing 1 to 14 carbon atoms substituted derivatives and straight or branched aliphatic hydrocarbons and amines containing 3 to 16 carbon atoms and halogen substituted derivatives thereof. 16. The method of claim 15 wherein the adjuvant is p-xylene, trimethylbenzene, triethylbenzene or triisopropylbenzene. 17. The method of claim 17, characterized in characterized in that the molar ratio of auxiliary organic / YO ₂ is equal to 0.05 to 20. 18. The process of claim 17 wherein the molar ratio of organic excipient / organic control agent (s) is from 0.02 to 100. The process according to claim 10, wherein the crystallization is carried out at a temperature of 50 to 175 ° C, at a pH of 9 to 14 and for 5 and 300 hours.