Synthetic layered material mcm-56, obtain and use

 

(57) Abstract:

The invention relates to synthetic layered material MCM-56, receiving and use as a sorbent or catalyst component conversion of organic compounds. Material MCM-56 has a composition expressed as molar ratio of X2ABOUT3: (n) UO2where n has a value not exceeding about 35, X denotes a trivalent element and Y represents a tetravalent element. The material is characterized by sorption ability towards 1,3,5 - trimethylbenzene, equal to at least 35 µl per 1 g of calcined synthetic material, the initial absorption within 20 comprising 15 mg of 2,2-Dimethylbutane on 1 g of calcined synthetic material, and the x-ray calcined synthetic material has highs constant d equal to 12,40,2; 9,90,3; 6,90,1; 6,20,1; 3,550,07 and 3,420,07 . The technical result is the production of a material of high purity. 2 S. and 6 C.p. f-crystals, 13 tab., 5 Il.

The present invention relates to synthetic layered material MCM-56, the method of its production and to its use as a sorbent or catalyst component conversion of organic compounds.

Amorphous and paracrystalline materials are an important class of porous inorganic solids, which for many years used throughout the world is presented in the compositions of the catalysts, and paracrystalline transition alumina, which is used as solid acid catalysts and catalysts reforming process oil. The term "amorphous" in the context of the present invention means a material in which there is no long-range order, which can to some extent misleading, since almost all substances to some extent, are oriented, at least locally. Another term used to describe these materials - "x-ray amorphous". The microstructure of the silica particles are dense amorphous silicates size of 100 to 250 angstroms ("Kirk-Othmer Enyclopedia of Chemical Technology", 3rd Edition, Vol. 20, John Wiley & Sons, New York, p. 766-781, 1982), while the porosity is a result of the voids between the particles. Because in these materials there is no long-range order, the pores tend to spread for more distance. The absence of long-range order is also evident in radiographs, which are usually deprived of the characteristics and expressive.

Paracrystalline materials such as transition alumina, also contain pores of different sizes, but their x-rays more defined and usually contain several broad peaks. Microstructures of these materials is the result of irregular voids between these areas (K. Wafers and Chanakya Mistra, "Oxides and Hydroxides of Aluminum", Technical Paper No. 19 Revised, Alcoa Research Laboratories, p. 54-59, 1987). As for any substance pore size is defined not by long-range order, the variation of the pore size is usually very large. The pore size of these substances gets into the area of the so-called mesomorphic phase, including, for example, pores with sizes in the range from 15 to 200 angstroms.

With these solids with poorly pronounced structure contrast sharply materials, distribution of pore sizes which is very narrow, as it is strictly controlled by the crystalline nature of the microstructure of the material. For example, zeolites are ordered porous crystalline substance, usually aluminosilicates having a definite crystalline structure as determined by x-ray diffraction, within which contains many small cavities, which can be connected to each other through channels or pores of a smaller size. These cavities and pores for a particular material, zeolite have one uniform size. Since the dimensions of these pores are such that they can adsorb molecules of certain dimensions while rejecting molecules with large sizes,different properties of certain benefits.

Known methods were obtained from a variety of synthetic zeolites. Many of these zeolites designated by letter or other convenient symbols, such as zeolite A (U.S. patent 2882243); X (U.S. patent 2882244); Y (U.S. patent 3130007); ZK-5 (U.S. patent 3247195); ZK-4 (U.S. patent 3314752); ZSM-5 (U.S. patent 3702886); ZSM-11 (U.S. patent 3709979); ZSM-12 (U.S. patent 3832449); ZSM-20 (U.S. patent 3972983); ZSM-35 (U.S. patent 4016245); ZSM-23 (U.S. patent 4076842); MCM-22 (U.S. patent 4954325); MCM-35 (U.S. patent 4981663); MCM-49 (WO 92/22498) and PSH-3 (U.S. patent 4439409).

In U.S. patent 4439409 is the composition of the crystalline molecular sieve designated PSH-3, and describes its receipt from the reaction mixture containing hexamethylenimine, organic compound, which is used as a directing agent in the synthesis of layered material MCM-56 according to the present invention. The composition of the substance, which seems to be identical PSH-3 for U.S. patent 4439409, but has additional structural components, is described in European patent application 293032. It is reported that hexamethylenimine used in the synthesis of crystalline molecular sieves MCM-22 in the U.S. patent 4954325; MCM-35 in U.S. patent 4981663; MCM-49 in WO 92/22498 and ZSM-12 in U.S. patent 5021141. For the composition of molecular sieves on the basis of a substance oboznachennoj mixture, containing Quaternary ammonium ion adamantane.

Some layered materials, layers which can be separated swelling agents, serve as the basis for the very porous substances. Examples of such layered materials are clay. These clays may be saturated with water, while clay layers may be separated from each other by water molecules. Other layered materials are not able to swell in water, but can swell in certain organic substances, such as amines and Quaternary ammonium compounds. Examples of such are able to swell in organic medium layered materials are provided in U.S. patent 485948 and include layered silicates, magadia, cenat, criticality and perovskites. Another example of a layered material that can swell in certain organic agents is containing vacancies connection on the basis of Metallica titanium, which is provided in U.S. patent 4831006.

After the layered material swells, it can be strengthened by introducing a thermally resistant substances, such as silica, between the two separated layers. For example, in the above U.S. patents 4831006 and 4859648 provides a method of securing considered in this described the methods of bonding the layered materials themselves bonded materials are the U.S. patents 4216188, 4248739, 4176090 and 4367163 and European patent application 205711.

Radiographs bonded laminated materials can vary significantly depending on the degree of violation is usually well ordered layered microstructure caused by swelling and bond. The regularity of the microstructure in some bonded materials so badly broken that it is possible to observe only one peak in the low angle region of the diffraction pattern, corresponding to the interplanar d repeating element in the bonded material. Materials with less disruption can have several peaks in this area, which usually indicate the orders of this basic repeating element. Sometimes there are also x-ray reflection from the crystal structure of the layers. The distribution of pore sizes in these bonded laminated materials are narrower than the distribution of pore sizes in materials with crystal frame structure.

The aim of the present invention is a synthetic layered material, referred to in the context of the present invention as MCM-56, which corresponds to a molar ratio

X2O3

Material MCM-56 of the present invention, although resembles to some extent the materials with frame crystal structure, such as MCM-22 and MCM-49, and some other layered materials, however, differs from them. The constant value d of the unit cell of the material MCM-56 average of approximately 25.5 angstroms, while not observe the formation of interlayer bridges. When the calcination their MCM-56, for example, at a temperature of 540oC structure is not compacted, and retains a layered form. The calcined MCM-56 absorbs at least 35 mcg of 1,3,5-trimethylbenzene, i.e., at least 4 times greater than the number of 1,3,5-trimethylbenzene, which can absorb nimi MCM-22 and MCM-49, manifested in rapid initial absorption of 2,2-Dimethylbutane. MCM-56 has a unique sorption capacity and usefulness as a catalytic agent in comparison with MCM-22 and MCM-49.

Material MCM-56 according to the present invention is practically pure and impurity content of the crystalline or layered phases in it or is slightly below the detection limit, and his chest x-ray is characterized by a combination of the locations of lines and intensities of other known or their heat-treated materials, as indicated in Table I (their material) and Table II (annealed material). In these tables intensities are relative to lines of constant d at 12.4 angstroms. (All tables, see the end of the description).

The materials that are used to obtain the data shown in the table. I represent layered MCM-56 in the form of a wet cake; the material in the form of a wet cake obtained by using the same organic directing agent, which, after annealing becomes MCM-22; and a crystalline MCM-49 in the form of a wet cake. The materials used to produce the data in the table. II, represent procula is SUP>oC for 2-20 hours. The most effective from the point of view of diagnostics feature that allows you to distinguish between MCM-56 and other members of this family (materials of the type MCM-22 and MCM-49), is the value of the constant d in the range of 8.8 to 11.2 angstroms. The last of these two samples have two well-resolved peak in the range of about 8.8 - 9.2 angstroms and 10.8 - 11.2 angstroms, clearly separated from each other by a saddle. MCM-56 is characterized by a broad band with center around the value of the constant d equal to 9.9 angstroms. Although the band may have an asymmetrical profile, for example, with the inflection point, the occurrence of the saddle may indicate the beginning of the formation of MCM-49 and a reduction in the content of MCM-56.

These x-ray diffraction data obtained using x-ray diffraction system of the company "Scintag" with a germanium solid-state detector, on the strip of K-alpha copper. Registration for diffraction data was carried out step-by-step scanning from 0.02 degrees 2, where denotes the Bragg angle, and the reading time for each step is 10 seconds. The interplanar distance, d, are calculated in Angstrom, and the relative intensity of the bands I/I0, sostavlenie program profiling (the second derivative algorithm). The intensities are not corrected for the effect of LJ and polarization. Relative intensities are indicated by the symbols vs - very strong (60 - 100), s - strong (40 - 60), m - medium (20 - 40) and w - weak (0 - 20). It should be understood that the diffraction data for the specified sample as a single strip may consist of many overlapping lines, which, under certain conditions, such as differences in crystallographic changes, may appear as resolved or partially resolved lines. Crystallographic changes typically involve small changes in unit cell parameters and/or changes in the symmetry of the crystal without changing the structure. These small effects, including changes in the relative intensity can arise from differences in the content of cations, the chemical composition of the frame, nature and quantities of pores and thermal and hydrothermal history of the samples. Other changes in radiographs may be due to important differences between the materials, as observed when comparing MCM-56 with similar materials, such as MCM-49, MCM-22, PSH-3.

The degree of difference of the LMS of these materials can objavi they observed changes in radiographs, who can explain the significant changes in size along one axis. This refers not merely to the loss of organic substances used in the synthesis, and a significant change in the value of communication in the material. Precursor chemicals in this series can easily be distinguished by x-ray diffraction from calcined samples (compare, in particular, the middle column in Tables I and II). The study of radiographs as precursors and calcined forms allows to identify a number of reflections with a very similar location and intensity, while the other peaks are different from each other. Some of these differences are directly related to changes in the size of the axis and the magnitude of the connection.

The dimensions of the axes of the crystalline MCM-49 similar to the values for calcined representatives of this family and, thus, their x-rays have a match. However, the dimensions of the axes of the MCM-49 differ from the values for the calcined materials. For example, resize the axes in MCM-22 can be determined by the location of the peaks, the most sensitive to these changes. Two such peak appears at approximately 13.5 angstroms and approximately 6.75 in angstroms in the precursor MCM-22, approximately listello at 6,30 angstroms in the calcined MCM-22.

The peak at approximately 12.4 angstroms MCM-49 is located very close to the intense peak at approximately 12.4 angstroms observed for all three substances, and are often not fully resolved. Similarly, the peak at approximately 12.6 angstroms in the calcined MCM-22 is usually visible in the form of a shoulder on the background of an intense peak at 12.4 angstroms.

Other features that generally distinguish MCM-56 from similar substances, discussed earlier, are collected below in table. III (see the end of the description).

Unique layered material MCM-56 according to the present invention has a composition defined by the following molar ratios:

X2O3: (n) YO2,

where X denotes a trivalent element, such as aluminum, boron, iron and/or gallium, preferably aluminum;

Y denotes a tetravalent element such as silicon and/or germanium, preferably silicon; and n has a value not exceeding about 35, in particular from 5 to approximately less than 25, usually from 10 to less than 20, usually from 13 to 18. In their view, the substance has the formula, calculated on the anhydrous composition in terms of moles of oxides on n moles YO2expressed in the following form:

(0-2)M2O:(1-2)R:X2O3:. omponent M and R are specified for the material, because they are present during synthesis and can be easily removed after synthesis methods, which are discussed next.

Material MCM-56 according to the present invention may be subjected to heat treatment and in calcined form, has a large surface area (more than 300 square meters/g) and usually a large sorption capacity in relation to some large molecules compared to previously known materials such as calcined PSH-3, SSZ-25, MCM-22 and MCM-49. Unlike MCM-49, which is not able to swell, MCM-56 in the form of a wet cake, i.e. their MCM-56, able to swell, indicating the absence of the interlayer bridges.

If necessary, in their substance, the original cations of the alkali or alkaline earth metals such as sodium, can be at least partially replaced by other cations, if you use known from the technical field of methods of ion exchange. The preferred cations for substitution are metal ions, hydrogen ions, the precursor of hydrogen, in particular ammonium ions and mixtures thereof. The most preferred cations are those which possess catalytic act is Alla Groups IIA, IIIA, IVA, IB, IIB, IIIB, IVB and VIII of the Periodic table of elements.

When using as a catalyst layered material MCM-56 according to the present invention may be subjected to processing, typically, calcination in order to remove some or all of the organic components. In cases when you want to give it a hydrogenating and dehydrating properties, the crystalline material may also be used as catalyst in combination with a hydrogenating component such as tungsten, vanadium, molybdenum, rhenium, Nickel, cobalt, chromium, manganese, or a noble metal such as platinum or palladium. These components may be introduced into the composition through co-crystallization, by replacing in the structure of some element of IIIA group, in particular aluminum, by a thorough mechanical mixing, the specified component can be entered by impregnation, as, for example, in the case of platinum, by treating the silicate with a solution containing platinum ions. Thus, suitable platinum compounds are chloroplatinate acid, platinum chloride and various compounds containing amine complex of platinum.

You can expose MCM-56 heat treatment without disturbing it is in General carried out by heating at a temperature at least 370oC for at least 1 minute and generally not more than 20 hours. Although you can use a pressure less than atmospheric, it is more convenient to carry out the process at atmospheric pressure. The heat treatment can be carried out when a temperature of approximately 925oC. the Product after heat treatment, especially in its metal, hydrogen or ammonium form, is particularly useful for catalyzing a reaction of conversion of certain organic compounds, particularly hydrocarbons. Examples of such reactions, which do not limit the present invention include the reaction described in U.S. patents 4954325, 4973784, 4992611, 4956514, 4962250, 4982033, 4962257, 4962256, 4992606, 4954663, 4992615, 4983276, 4982040, 4962239, 4968402, 5000839, 5001296, 4986894, 5001295, 5001283, 5012033, 5019670, 5019665, 5019664 and 5013422.

Layered material MCM-56 of the present invention, if it is used as adsorbent or catalyst in the conversion of organic compounds, must be at least partially dehydration. This can be done by heating to a temperature in the range from 200 to 370oC in air, in nitrogen atmosphere, etc., at atmospheric pressure, reduced pressure or increased pressure within from 30 minutes to 48 hours. Dehydration can also be done by the first degree of dehydration will require more time.

Layered material MCM-56 according to the present invention can be obtained from a reaction mixture containing a source of the cation of the alkali or alkaline earth metal (M), in particular sodium or potassium, an oxide of trivalent element X, in particular of aluminum, an oxide of tetravalent element Y, in particular silicon, directing agent (R) and water, with the specified reaction mixture has a composition expressed as molar ratios of oxides intervals of the values shown in the table. XIII.

To obtain the crystalline product of the present invention, the source YO2in the applicable method of synthesis should be a preferably solid YO2for example, at least about 30 wt%. solid YO2. If YO2denotes silica, a source of silicon oxide containing at least about 30 wt%. solid silicon oxide, in particular of ultrasil (besieged obtained by spray dried silica containing about 90 wt%. silica) or Hisil (a precipitated hydrogenated SiO2containing about 87 wt%. silica, about 6 wt%. free water and about 4.5% of bound hydration water and having a particle size of occii, the crystalline MCM-56. So YO2in particular, the source of silicon oxide that contains at least about 30 wt%. solid YO2in particular, silicon oxide, and more preferably at least about 40 wt%. solid YO2in particular, silicon oxide.

Directing agent R is chosen from the group comprising cyclamen, azacycloheptan, disallowance and mixtures thereof, the alkyl contains from 5 to 8 carbon atoms. Not limiting the invention, examples of R are cyclopentylamine, cyclohexylamine, cycloheptylamine, hexamethylenimine, heptamethylnonane, homopiperazin and combinations thereof.

Crystallization of the layered material according to the present invention can be carried out both in static conditions and with stirring in a suitable reaction vessel, such as vessel made of polypropylene or coated with Teflon or steel autoclaves. The crystallization is preferably carried out at a temperature from 80 to 225oC. For the synthesis of MCM-56 from the above mixture is however important to stop and terminate the reaction prior to the formation of MCM-49 through MCM-56. Then MCM-56 is released from the liquid and produce. The time required for the synthesis of MCM-56, within which there is znachitelnaya to observe the course of the reaction using x-rays for the value of the constant d in the range of 9 - 11 angstroms. Thus, Table I shows that MSM-56 gives a single peak with a constant value d equal to 9.9 +/- 0,3, while MCM-49 has two peaks with the center for values of the parameter d 9.0 11.2 angstroms.

Layered material MCM-56 according to the present invention can be used as an adsorbent used for selecting at least one component from a mixture of components steam or liquid phase, with different sorption characteristics with respect to MSM-56. Consequently, at least one component may be partially or almost completely isolated from the mixture of components having different sorption characteristics with respect to MSM-56, when contacting this mixture with MSM-56, for selective absorption of one component.

Layered material MCM-56 according to the present invention can be used as a catalyst for a wide range of catalytic reactions chemical conversion, including many important at this time of industrial processes. Examples of chemical conversion processes which are effectively catalyze the MSM-56 either by itself or in combination with one or more other catalytically active substances in totalisator. Specific examples include:

(1) alkylation of aromatic hydrocarbons, in particular benzene, olefins with long chains, for example C14 olefins with reaction conditions include a temperature of from 340oC to 500oC, a pressure from 100 to 20000 kPa (from atmospheric to 200 atmospheres), average hourly feed rate of 2 to 2000 1/h and the ratio of aromatic hydrocarbon/olefin from 1:1 to 20:1, with the aim of obtaining aromatic hydrocarbons with long alkyl chains, which can then undergo reaction of sulfonation for more detergents;

(2) alkylation of aromatic hydrocarbons with gaseous olefins with the aim of obtaining aromatic hydrocarbons with short chains, particularly the alkylation of benzene with propylene in obtaining cumene, with reaction conditions include a temperature of from 10oC to 125oC, a pressure of from 100 to 3000 kPa (1 to 30 atmospheres), average hourly feed rate of aromatic hydrocarbon of 5 to 50 1/h;

(3) alkylation of the product of reforming containing significant amounts of benzene and toluene with fuel gas containing C5 olefins, with the aim of obtaining including products of mono - and dialkylamino, with reaction conditions vklyuchayu feed rate of the olefin from 0.4 to 0.8 1/h, average hourly feed rate of the product of the reformer 1 to 2 1/hour and recycling the gas mixture is from about 1.5 to 2.5/about the amount of incoming fuel gas;

(4) alkylation of aromatic hydrocarbons, in particular benzene, toluene, xylene and naphthalene, with olefins long chains, for example C14 olefins, with the aim of obtaining raw materials for the manufacture of lubricating oils on the basis of alkyl aromatic hydrocarbons with reaction conditions include a temperature of from 160oC to 260oC and pressure from 2510 to 3200 kPa (350 to 450 pounds per square inch);

(5) alkylation of phenols with olefins or the corresponding alcohols with the aim of obtaining phenols with long alkyl chains, and the reaction conditions include a temperature of from 200oC to 250oC, a pressure of from 1480 to 2170 kPa (200 to 300 pounds per square inch), the total average hourly feed rate of 2 to 10 1/hour; and

(6) the alkylation of ISO-alkanes, in particular ISO-butane, olefins, such as 2-butene, with reaction conditions include temperatures from minus 25oC to 400oC, in particular from 75oC to 200oC, a pressure from below atmospheric to 35,000 kPa (5000 psi), in particular from 100 to 7000 kPa (1 to 1000 and the molar ratio of the total number of ISO-alkane to the total amount of olefin, equal to from 1: 2 to 100:1, in particular from 3:1 to 30:1.

As in the case of many other catalysts, it is necessary to enter the MCM-56 in the structure of other substances, resistant to temperature and other conditions in which carry out chemical conversion of organic compounds. Such substances include active and inactive materials and synthetic or natural zeolites as well as inorganic substances such as clay, silica and/or metal oxides, such as alumina. The latter may be either of natural origin, and in the form of a gel-like precipitation or gels including mixtures with silica and metal oxides. The chemicals in combination with MSM-56, in particular, obtained by mixing or introduction in the synthesis of MCM-56, which is an active connection, leads to changes in the degree of conversion and/or selectivity of the catalyst in certain organic conversion processes connections. Inactive substances perform a useful function thinners and serve to control the degree of conversion in a given process, in order to economically obtain the right products without using other means of controlling the reaction rate. These substances can vluchteling during the performance of industrial processes. These materials, particularly clays, oxides, etc., play a role of a binder for the catalyst. It is desirable that the catalyst had a resistance to crushing, because when industrial use is necessary to protect the catalyst from destruction with the formation of the powdery material. Such binder based on clays and/or oxides are usually used to increase the stability of the catalyst with respect to crushing.

Natural clay from which it is possible to obtain composites with new crystalline substances include compounds of the family of the montmorillonite and kaolin, while these families include abbandonati, and kaolin are usually known clay Dixie, MNamee, Georgia and Florida or others in which the main mineral component is halloysite, kaolinite, dicit, nacrite or anoxic. These clays can be used in raw form after extraction from the mine or initially subjected to calcination, acid treatment or chemical modification. Binder, useful for preparation of compositions with a layered material MCM-56 according to the present invention are inorganic oxides, notably alumina.

P is used as the matrix, such as silica - alumina, silica - magnesia, silica - Zirconia, silica - oxide, thorium oxide, silicon oxide, beryllium, silicon oxide - titanium oxide, as well as ternary compositions, the silicon oxide - aluminum oxide - thorium oxide, silica - alumina - Zirconia, silica - alumina - magnesia and silica - magnesia - Zirconia.

The relative proportions thoroughly mixed material MCM-56 and matrix on the basis of inorganic oxides can vary within wide limits, the content of MCM-56 is from 1 to 90 wt%, and usually, especially in cases when the composite is prepared in the form of beads, in the range from 2 to 80% by weight of the composite.

The invention is described in more detail using the following examples and relevant drawings, where

in Fig. 1 shows a radiograph of a dried product MCM-56 in Example 1;

in Fig. 2 presents the x-ray calcined product MCM-56 according to Example 2;

in Fig. 3 shows a radiograph of a dried product MCM-56 in Example 9;

in Fig. 4 shows a radiograph of a calcined product MCM-56 in Example 10;

the nafta in Example 3;

in Fig. 5(c) presents the x-ray product according to Example 4;

in Fig. 5(d) presents the x-ray product in Example 5.

In Examples where there is determined the value of alpha indicates that the alpha value roughly indicates the catalytic cracking activity of the catalyst compared to a standard catalyst and corresponds to the relative rate constant (rate of conversion of n-hexane by volume of catalyst per unit time). The basis for the definition is the activity of the cracking catalyst based on silica - alumina, the value of alpha for which is set to unity (constant speed 0,016 1/sec). Alpha test is described in U.S. Patent 3354078 and in publications Journal of Catalysis, Vol. 4, p. 527 (1965); Vol. 6, p. 278 (1966); Vol. 61, p. 395 (1980). Experimental conditions during the tests, which are given in the present description, include a constant temperature of 538oC and variable flow rate, which is described in detail in Journal of Catalysis, Vol. 61, p. 395.

Example 1

A mixture of 258 g of water, 6 g of a 50% aqueous sodium hydroxide solution, and 13.4 g of sodium aluminate solution (25.5% of Al2O3and 19.5% Na2O), 51,4 g ultrasil (VN3) and 27.1 g of hexamethyleneimine (HMI) is injected into usaimage the reaction mixture has the following composition in mole fractions:

SiO2/Al2O3= 23

OH/SiO2= 0,21

Na/SiO2= 0,21

HMI/SiO2= 0,35

H2O/SiO2= 20

After 34 hours the reaction is stopped. The product is filtered, washed with water to obtain a wet cake and part of it is dried in an oven at a temperature of 110oC.

Part of the product in the form of a wet cake and dried part of the product is subjected to x-ray analysis and identified as MCM-56. Radiograph dried MCM-56 is shown in Table IV and shown in Fig. 1.

The chemical composition of the product of example 1, % wt.:

N = 1,61

Na = 1,1

Al2O3= 6,6

SiO2= 70,5

The solids content = 78,2

The molar ratio of SiO2/Al2O3in the specified product is 18.

Example 2

Part of the product of example 1 is substituted for ammonium, exposing three interaction with 1 M solution of ammonium nitrate, and calcined in air for 6 hours at a temperature of 540oC. Radiograph of the calcined product of this example shows that it is a MSM-56; she is given in table V and shown in Fig. 2.

Example 3

For comparison, repeat the example 1 according to the patent With resistant or form of the precursor MCM-22, examined by x-ray diffraction analysis. X-rays are given in table VI and shown in Fig. 5(b).

Example 4

The product from example 3 calcined at a temperature of 538oC for 20 hours. Radiograph of this calcined product is shown in table VII and shown in Fig. 5(c).

Example 5

In the autoclave of 2.24 parts of 45% of aluminate sodium are added to a solution containing 1.0 part of a 50% aqueous NaOH solution and 43.0 parts of water. Add with stirring to 8.57 parts ultrasil, and then 4,51 part of hexamethylenimine (HMl).

The resulting reaction mixture has the following composition in mole fractions:

SiO2/Al2O3= 23

OH-/SiO2= 0,21

Na/SiO2= 0,21

HMl/SiO2= 0,35

H2O/SiO2= 19,3

The mixture was crystallized with stirring at a temperature of 150oC for 84 hours. The product is identified as MCM-49, and his chest x-ray are shown in table VIII and shown in Fig. 5(d).

Chemical product composition, wt%:

N = 1,70

Na = 0.70 and

Al2O3= 7,3

SiO2= 74,5

The solids content = 84,2

The molar ratio of SiO2/Al2O3in the specified product costs is made, in % weight.:

Cyclohexane, 40 top - 10,0

n-Hexane, 40 top - 13,1

Water, 12 top - 15,4

The portion of the sample calcined in air at a temperature of 538oC for 3 hours. Radiograph of this substance are listed in table IX.

Example 6

The product from example 2 is subjected to alpha test and get a value of alpha equal to 106.

Example 7

In order to compare microporosity and the degree of opening of the pores for materials, MCM-56, MCM-22 and MCM-49 for samples calcined MCM-56, MCM-22 and MCM-49 received in accordance with the techniques described in the examples, which are presented in the publication by E. L. Wu., G. R. Landolt and A. W. Chester, "New Developments in zeolite science and Technology", Studies in Surface Science and Catalysis, 28, 547 (1986), consistently absorb hydrocarbons with increasing size of the molecules. The payroll results to Fi dynamic absorbance values obtained in these studies are presented in table X.

The results of sorption studies clearly indicate differences between the tested materials. The sorption capacity of MSM-56 relative to 1,3,5-trimethylbenzene, hydrocarbon with the most sterically hindered molecule, at least 4 times greater than that of MCM-22 and MCM-49. MSM-56 also has the highest initial rate of absorption 2,2-dim the R 2,2-Dimethylbutane in the stream at a temperature of 373 K) compared with MCM-22 and MCM-49. The corresponding times for the samples submitted materials MCM-56, MCM-22 and MCM-49 is 12, 252 and 233 seconds respectively. Initial rate of absorption of n-hexane represents the time required for absorption of 40 mg of n-hexane per gram of sorbent, and for 1,3,5-trimethylbenzene is the time required to absorb the first 7 mg of 1,3,5-trimethylbenzene per gram of sorbent.

Example 8

Repeat example 1, except that the reaction is interrupted after 40 hours. Data of x-ray phase analysis confirmed that the product is a MSM-56.

Example 9

A mixture of 258 g of water, to 20.5 g of sodium aluminate solution (25.5% of Al2O3and 19.5% Na2O), 51,4 g ultrasil (VN3) and 50 g of hexamethyleneimine (HMI) enter into interaction in an autoclave with a capacity of 600 ml with stirring (400 rpm) at a temperature of 154oC.

The resulting reaction mixture has the following composition in mole fractions:

SiO2/Al2O3= 15

OH-/SiO2= 0,17

Na/SiO2= 0,17

HMI/SiO2= 0,66

H2O/SiO2= 19

After 130 hours the reaction is stopped. The product is filtered, washed with water to obtain a wet cake and part of it is dried in an oven at a temperature of 110

The chemical composition of the product according to example 9, % wt.:

N = 1,42

Na = 2,3

Al2O3= 9,3

SiO2= 70,7

The solids content = 82,3

The molar ratio of SiO2/Al2O3in the specified product is 13.

Example 10

The portion of the product from example 9 as opposed to ammonium, exposing three interaction with 1 M solution of ammonium nitrate, and calcined in a nitrogen atmosphere for 3 hours at a temperature of 482oC, cooled to a temperature of approximately 130oC, and then calcined in air at a temperature of 538oC for 5 hours. Radiograph of this material are given in table XII and shown in Fig. 4.

Roentgenogram products according to examples 2-5 is shown in Fig. 5. In Fig. 5(a) shows a radiograph of a product MCM-56 according to example 2; Fig. 5(b) shows a radiograph of a product according to example 3. Radiograph for product MCM-22 in example 4 shown in Fig. 5(c), and the radiograph in Fig. 5(d) corresponds to the product MCM-49 in example 5. These radiographs are presented in these figures in order to compare. X-rays 5(b) and (c) the ri annealing, and for the crystalline MCM-22, respectively.

1. Synthetic layered material, the composition of which corresponds to a molar ratio

X2ABOUT3: (n) YO2,

where n has a value not exceeding about 35;

X denotes a trivalent element;

Y denotes a tetravalent element,

characterized in that said material is characterized by sorption ability towards 1,3,5-trimethylbenzene, equal to at least 35 µl per 1 g of calcined synthetic material, the initial absorption within less than about 20, comprising 15 mg of 2,2-Dimethylbutane on 1 g of calcined synthetic material, and the x-ray calcined synthetic material has a maximum constant d equal to 12,4 0,2, 9,9 0,3, 6,9 0,1, 6,2 0,1, 3,55 0,07 and 3,42 0,07 .

2. The material under item 1, characterized in that X represents aluminum, boron, iron and/or gallium and Y is silicon and/or germanium.

3. The material under item 1, characterized in that X represents aluminum and Y is silicon.

4. The material under item 1, characterized in that the value of n is from 5 to not more than 25.

5. The material under item 1, characterized in, is calculated on the anhydrous basis when the ratio of moles of oxides on n moles YO2expressed by the following formula:

(K)M2O : (1 - 2)R : X2O3: (n)YO2,

where K has a value of not more than 2;

M denotes an alkali or alkaline earth metal;

R denotes an organic fragment.

7. The material on p. 6, wherein R is chosen from the group including cycloalkylation, azacycloheptan, disallowance and mixtures thereof, the alkyl contains from 5 to 8 carbon atoms.

8. A method of converting a source material containing organic compounds to conversion products by contacting the specified starting material with a catalyst containing an active form of synthetic layered material, characterized in that the synthetic layered material using material on p. 1.

 

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