FI119801B - Catalytic materials and process for their preparation - Google Patents

Description

119801

FIELD OF THE INVENTION The invention relates to mesoporous lcatalysts, and more particularly to new mesoporous molecular sieve embedded in zeolite and having high thermal stability, and to a method for strengthening catalytic materials. Said catalytic materials are useful in applications in the field of hydrocarbon processing.

10

State of the art

Mesoporous molecular sieves as catalytic materials have attracted the interest of scientists for their unique properties, such as large homogeneous pores with very large surface area and size ranging from 2 to 50 nm. However, mesoporous molecular sieves known in the art are often not very thermally and hydrothermally stable, the porous walls are amorphous and have weak acidic properties. * In addition, in the regeneration of the spent catalyst after hydrocarbon processing, · .. 20 porous molecular sieve structure may collapse.

*: **: Crystalline materials with a pore size in the micronuclear region (d <2 nm), tt | i * are used as catalysts and catalyst carriers on an industrial scale, Zeolites • · ·! : are well known examples of such materials. Zeolites are widely used because of their special properties such as high surface area, high adsorption capacity and the ability to adjust adsorption capacity. Zeoliittira -: ***; it is possible to create active points, build active points and • Φ ·, · '; to adjust the acid points. intensity and volume. The zeolites have a typical pore size • * ·. ···, typically in the range of 0.4 to 1.2 nm, and the zeolites have high thermal and chemical stability. However, the ability of zeolites to process molecules with a molecular size of 119801 larger than the pore size of zeolites is limited and, in addition, zeolites are relatively rapidly reactivated in many reactions.

US 5,198,203 ships jouldco organized mesoporous Mole-5 kieselguhr sieves, known as M41S, which were developed in the early 1990s. M41S is a group of mesoporous molecular sieves formed in aqueous solution from silylca and alumina precursors with Q.H2i (CH3) N '"cations (i> 7) under hydrothermal conditions. The most prominent members of this group are hexagonal MCM-41, MCM-48 and flake-like structure 10 MCM-50 The pore size of the mesoporous molecular sieve can be adjusted to between 2 and 10 mn and the composition may include pure silicate or metal silicate (e.g., Ah, V- and Ti-substituted silicate). their pore system is organized.

US 5,246,689 and US 5,334,368 disclose a synthetic composition of a material comprising an ultra-porous crystalline phase. This material is inorganic, porous and non-layered and has pore dimensions in the range of 1.3 to 20 mn. The pore size distribution in a single phase is to some extent. regular. At least one peak in the X-ray diffraction pattern at d-distance is • 1 1 · · · · 20 greater than 1.8 nm.

• · · • · · ««

EP 0 748 652 discloses a group of mesoporous materials (MSA), 1 µl (with a narrow mesoscale size distribution. This material was amorphous and completely non-ordered. The material had a BET surface area of 672-837 m2 / g.

25 ... The synthesized mesoporous materials are not acidic or have a limited • 1 hour acidity. The number of acid sites in mesoporous materials has been increased by adding aluminum to the silica structure of the mesoporous material, • · *. 1: The acidity of the mesoporous materials described above is dry • • · * ... 1 30 tenlc lower than the acidity of the zeolites.

• · • · · ··· · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · long 373 418

Various methods of making mesoporous materials are known in the art. The tennis and hydrothermal stability and acidity of mesoporous molecular sieves have been exceeded, for example by catalytic introduction. active species in mesoporous structure. In principle, the synthesis methods involve preparing a solution of the 5 silicon source with the organic substance or substances, adjusting the p.H of the solution to a precipitation value, then recovering the precipitate and calcining. The aluminum source is added to the solution at elevated temperature at any point before the synthesis begins. Several surface-active agents and temples (organic materials), compositions, solvents and reaction conditions have been proposed.

US 5,942,208 describes a process for the preparation of a meso-maintenance material having improved hydrothermal stability over MCM-41 materials. The process used various salts and adjusted the pH of the solution with weak acids.

EP 0 795 517 provides a process for the synthesis of mesoporous materials using a mixture of a silicon source and an organic fluorine-containing template.

: ** '·· 20

U.S. Pat. No. 5,942,208 discloses the preparation of a meshblasted molecular sieve *: **: which exhibits improved thermal and hydrothermal stability compared to conventional mesoporous molecular sieves. The material could be boiled for 12 hours ··· \ · without any major structural changes.

25 ··· V · An alternative approach to the preparation of stable and active mesoporous materials is to add zeolites to the walls of meso bodies. US 09 / 764,686 describes the synthesis of mesoporous materials using Y- • .1 2 ··. zeolite seed crystal, MFI zeolite seed crystal, and beta zeolite seed seed ··· / 30 seed seed crystals.

• · · • »· • · · · • • 2 · 4 119801

CN 1349929 discloses the preparation of MSA-3 and MAS ~ 8 using solutions of the precursor L-zeolite.

Kloetstra et al. Micropor. Mesopore. Mater. 6 (1996) 287 reported in situ formation of fauja-5 sperm and MCM-41. Their approach was based on the sequential synthesis of zeolites and MCM-41.

Karlsson et al. Micropor. Mesopore. Mater. 27 (1999) 181 describe the use of a mixed-template approach for simultaneous synthesis of zeolite / MCM-41 phases.

The materials may be mixtures of two or more phases, or loosely bonded zeolite and mesoporous material, in the case of a synthesis approach to grow and lay MCM-41 on the zeolite, or zeolite. Inoculum-1S teas can be added to the gel.

Two different types of temples have been used in the synthesis of mesoporous materials. The reproducibility of such manufacturing methods can be difficult. In addition, ke- {; *. in the absence of any significant interaction between the zeolite and the meso-malignant molecular sieve, the resulting materials are thermally and hydrothermally stable. the mouth is probably low.

• · · ··· • * .i. According to the state of the art, mesoporous molecular sieves have a wide range of · ···. ***. and applications in catalysis as active phases or carriers. Many hydrocarbon Φ · # 25 conversion reactions are liappo catalysis. By focusing on its acid-catalyzed function, zeolites are known to be active at double olefin bonds and backbone. * · *. isomerization, paraffin isomerization, cracking, olefin dimerization ··. *. , olefin oligomerization, naphthene ring opening, alkylation, • m · • ·· *., * aromatic transalkylation, aromatization, etc. Bifunctional catalysts containing metal or metal oxide or sulfide phases are useful * . * · In reactions such as refluxing, paraffin isomerization, hydrocracking, decomposition 119801 lithium wax removal, sulfur removal with hydrogen, oxygen removal with hydrogen, nitrogen removal with hydrogen and several hydrogenation reactions. The main disadvantages of using zeolites are their relatively high tendency to deactivate and the limited capacity to handle bulky molecules.

5

From the foregoing, it can be seen that there is a need for thermally and hydro tennis stable catalytic materials based on meso-porous molecular sieves and for a process for the preparation of such thermally and hydrothermally stable catalytic materials. It is also apparent 10 that there is a need for a catalyst having a zeolite-like active site but where the active sites are also readily accessible to the reactants, the reactants have a short diffusion distance, and the secondary reactions and solidification of the products are limited.

Objective of the Invention

It is an object of the invention to provide a novel and active catalytic material having a mesoporous molelcyl sieve embedded in a zeolite resin, επί. *, prevented carbon 'hydrogen conversion reactions.

It is another object of the invention to provide a mechanically, thermally and hydrothermally-stable carbon molelcyl sieve embedded in a zeolite and having a zeolite-type acid-, · pamims.

It is a further object of the invention to provide a process for the preparation of said catalytic material having a mesoporous molecular sieve which is used. hon has an embedded zeolite structure.

Another object of the invention is the use of said catalytic material in hydrocarbon conversion reactions having a mesoporous molecular sieve embedded in a zeolite solution.

• · · • · • · * · * 6 119801

The characteristic features of a mesoporous molecular sieve embedded in a zeolite, a process for its preparation and the use of a mesoporous molecular sieve embedded in a zeolite are disclosed in the claims.

5

Summary of the Invention

While not limiting to the following descriptions and theoretical evaluations of the synthesis of a novel catalyst material having a mesoporous molecular sieve embedded in a zeolite structure and particularly suitable for hydrocarbon convection reactions, the essential features of the invention will be explained as follows.

The present invention relates to a novel and active catalytic material having a mesoporous molecular sieve embedded in a zeolite granule. The invention also relates to a process for preparing a mesoporous molelcyl sieve embedded in a zeolite in which the synthesis is simplified and reproducible and the product has a high catalytic activity.

• · ·,: A catalytic material having a mesoporous molecular sieve with a submerged zeolite structure is useful in hydrocarbon conversion reactions and especially in the processing of high molecular weight hydrocarbons. This new '· "· catalytic material can be used as a catalyst component in kraldcation, .. * · * hydrocracking, ring-opening, hydrogenation of aromatics, especially multiaro-, ·,., Aaates, dimerization of olefins, oligomerisation, isomers of olefins and paraffins. arylation, etherification, sulfur removal, hydrogenation and rorormorum, or as such or modified in the art, to become known.

··· • · · · · · · · · · · · · · · · · · · · · · · · · · ··· ···

Detailed Description of the Invention

It has now been found that the problems associated with prior art zeolite catalysts and meso-porous catalysts can be avoided or at least significantly reduced by the novel catalytic material of the invention, which is a mesoporous molecular sieve embedded with a high mechanical, hydro thermal stability. The new mesoporous molecular sieve immersed in zeolite is thermally stable at temperatures of at least 900 ° C in the presence of air.

10

The present invention provides a group of novel mesoporous molecular sieves embedded in zeoHites that are mechanically, thermally, and hydrothermally stable. The materials are very reproducible, as can be seen from the examples, and have superior properties in many hydrocarbon conversion reactions. A group of new mesoporous molecular sieves into which zeolites have been embedded are called mesoporous materials (MM). Mesoporous refers to materials with pores in the range of 2 to 15 nm with a regular pore system.

The meso-porous molecular sieve embedded in the zeolite comprises a meso-* porous molecular sieve selected from the M4 IS group defined on page 2 and comprises mesoporous materials having an organized pore system. Preferably, the mesoporous molecular sieve is selected from mesoporous ··· aluminosilicates known as MCM-41.

A zeolite selected from the middle porous zeolites, which are 10-membered ring zeolites such as MFI, MTT, TON, AEF, MWW, and FER structures, and large porous zeolites, • ·. ·· *. which are 12-membered ring zeolites such as BEA, FA.U, and MOR.

·· ». *. Examples of the zeolite groups mentioned are ZSM-5, ZSM-23, ZSM-22, SAFO-, f · 8 119801 11, MCM-22, femerite, beta, Y- and X-zeolites and mordenite. Preferably, the zeolite is an MFI, MTT, AEF, MWW, MOR or BEA zeolite

The catalyst material contains 0.01 to 10% by weight of aluminum (Al).

5

The catalyst, which is particularly suitable for industrial and commercial use, comprises, in accordance with the invention, a mesoborous molecular sieve embedded in a zeolite and a support selected from alumina, silica, clay and any other prior art support and combinations thereof. Preferably, the carrier comprises alumina or silica. The amount of carrier varies from 10 to 90% by weight based on the total weight of the catalyst.

The novel group of catalytic materials which, according to the invention, have meso-Imolcoin embedded zeolite molecular masses, have a high specific surface area (BET) in the range 151400-500 m2 / g, preferably 1200-600 m2 / g.

The X-ray powder diffraction pattern of the catalytic material according to the invention shows the structures of the mesoporous molecular sieve and the zeolite. The unit density of the zeolite · • * ·· 20 dimensions varies with the amount of Al in the catalytic material. The size of the overhead cabinet decreases with the amount of aluminum, from 1.982 nm for catalyst material containing 0.2 wt% Al, to 1.972 nm for catalyst material containing 3.9 wt% Al (kmi zeolite type was MFI (material code MM5). The change in unit size size · · · is the opposite of the changes generally observed with zeolites.

25: The size of the uppermost booth was 1.428 nm and 1.430 nm when the zeolite type was BEA (the material code is MMBE), the size of the unit booth was 1.406 nm and 1.436 nm when. The zeolite type was MWW (material code is MMMW22), and the unit fabric sizes are • · ·, ···. were 1,800 nm and 1,806 nm when the zeolite type was MOR (material code is 30 MMMO).

• · · • · · * · • * * · • ** ** 9 119801

The distance in the meso-porous molecular sieve MCM-41 decreases with increasing zeolite content. In MM5, the diode ranges from 4.4 nm to 3.8 nm, and in MMBEs and MMMO, d (oo ranges from 4.1 nm to 4.0 nm and MMM.W in the range 4.0 ···· 4.2.

5

Unit size and diode values are the same for pure zeolite and MCM-41 phases and their mechanical mixtures.

The changes in the distance between the dio and the unit cabinet size are a clear indication of the true 1.0 chemical bond between the mesoporous molecular sieve and the embedded zeolite in the catalytic material of the invention.

Characteristic features of the catalytic material of the invention, a mesoporous molecular sieve embedded in a zeolite, were measured by X-ray powder diffusion, ammonia scanning electron microscopy, transmission electron microscopy, oxygen scattering, and specific surface area measurement.

The total amount of acidic sites can be measured in the catalytic material lcapasi- * «•" 20 teas to bind strongly basic molecules such as ammonia or pyridine. Total acidity was measured by ammonia temperature-programmed desorption (TP). ) and Brensted and Lewis acidity by pyridine infrared spectroscopy (FTIR.).

The acidity of the catalyst material can be customized by the amount of aluminum added in the structure and by changing the aluminum (AI) content in the zeolite, MCM-41 and • · · · · *. In the MM phases, Figures 1a and Ib show the correlation between acidity and aluminum content in the catalytic material according to the invention. Figure 1a • * shows the linearity of total acidity as a function of Al in the various MM-· ··, 30 catalyst materials and Figure Ib shows how the zeolitic and MCM-41- • *! .. * catalytic material differ in total acidity MM- • * • * 10 119801 lcataly y ttimateri of plays. Zeolites have higher levels of acid folate as a function of Al than in MM5, MMBE and MMMW samples, MCM-41 is less acidic with the same aluminum content.

5 Since there are no international standards for determining acidity, the methods used herein are described below.

The acidity assay was performed with NH3-TPD. Ico-conic acidity of the catalytic materials was measured by temperature-programmed sorption of ammonium (NH3-TPD) de-10 using an Altamira AMI-100 instrument. The sample size was 40 mg. Total acidity was measured by desorption of NH 3 as a function of temperature. The acidity of the samples was calculated from the amount of NH3 which adsorbed at 200 ° C and desorbed. between 100 ° C and 500 ° C. The NH3-TPD instrument was equipped with a thermal conductivity detector (TCD) manufactured by Gow Mac, a rise rate of 20 ° C / min was used and the temperature increased linearly to 500 ° C where it was held for 30 minutes. Quantitation was performed using pulses of known volume of 10% NH3 in helium.

: The acidity assay was also determined by pyridine FTIR. The acidity of the samples · ·· · ** · .. 20 was measured by infrared spectroscopy (ATI Mattson FTIR) using pyridine (^> 9.5%, ar) as a test molecule for both Bronsted and Lewis acid sites ··· ♦ ·; qualitative and quantitative determination. The samples were compressed into thin ··· self-supporting plates (10-12 mg / cm 2). Pyridine was first adsorbed for 30 min • ·· · • 2 1 '; at 100 ° C and then desorbed by evacuating at various temperatures (250, 300 ··· 25 and 450 ° C) to obtain a distribution of the acidic alcohols. All spectra were recorded at 100 ° C with a spectral resolution of 2 cm -1. 1 and 1450 cm-1, respectively, were used to identify Bnzmsted (BAS) and Le-1 · 1 · wis acid sites (LAS). intensities using molar extinction coefficients.

• · '·; · 1 30 • · · · · · · 2 · · 3 • · 119801 π

The acid sites are located on the surface of the catalyst material. Total surface area and pore volume were estimated using N'2 adsoipation and desorption. The average mesopore area and mesopore diameter were estimated from N2 desorption using the BJH equation (Barrer-Joyner-Halenda). The pore diameter has a size 5 limiting effect on both reactants and products. The size of the micropores depends on the structure of the zeolite. Pores less than 2 nm in diameter are defined as micropores according to iU ~ PAC, and pores in the range of 2 to 50 nm are defined as mesoporous silice.

The N2 absorption-desorption isotherms of 10 MMBE are shown in Figure 2. The diameter of the mesopore remains similar, in the range of 2.4 to 2.7 mn, in the embedded material compared to 2.6 nm in a mesh-size molecular sieve.

The BJH desorption illustrating the mesenchymal hallucin distribution at 15 MMBE is shown in the accompanying Figure 3.

The surface area and total pore volume decrease when the zeolite is immersed in meso. , into a porous molecular sieve, as can be seen in Table 1 below, · · * · *. »," · · Which gives the surface area, pore volume, and pore gray matter values for the products * * * # 20 MM5, MMBE, and MMMW, and for comparison purposes includes data for MCM-1 5 ·; 41, MPI and BEA.

• · ·· «* ·” Table 1. Surface area and porosity • · t ______ * _______ "Nftyte BET area j BJHmeso- Total BJH lmo- (m2 / g) solution area porosity-hal-ϊΤ: (m2 / g) volume echo ________ (cm3 / g) (nm) **: * 'Na-MCM-41-20__949__947__0.829 2.6V ·! Na-MM5-2ZS 896 1145 0.814 ~ 2.5 · / ”: Na -MM5-4ZS__820 1009__0J13__2.6 /. Na-MMS-4ZS-2A1 867 1069__0,794 2 ^ 5_

Na-MM5 ~ 4ZS-2A125 733 599 0.656 "" "'2.4 • · -------- ~ ------ ~ ---- 1" __---- • · 12 119801

Table 1 continues __ ___ MFIZSM-5_ 360 100 1 0.351 ~ T 20 *

Na-MMBE-4B__879__884 0.692 2 ^ 7

Na-MMB B-4B-2 AI__844__859 0.742 2.7

Na-MMBE-4B-2A.13 5,793,684 0.835 2.6 BEA_ 585 85 0.254 none H-MM-MW22__854__838 0.755 2.5 H-MM-MW22-2A1 ~ 808 772 0.703 2 ^ 5 H-MM-MW 22-2 Al-35 728 639 0.834 2.5! |: Par tilckel size of internal cavity

The zeolite is identified by X-ray diffraction (XRD). The XRD models can be riveted to the dimensions of the 5 zeolite as well as the MCM-41 phase unit cabinet using appropriate internal standards. ? -A ^ CV or TiCl? (Rutile) was used as internal standard.

The size of the .MFI unit cabinet was measured by the ASTM D 3942-97 'method, using α-AkO 4 as the internal standard.

The 10 BEA unit cubicles were measured by the modified ASTM D 3942-97 method • · *; using TiO 2, internal standard and t302] reflection at position 22 ° 2.

The MWW single bridge cabinet was measured by the modified ASTM D 3942-97 method ··· · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · theta.

* · »·» »· MMMO's single-store booth was rated for top positions without an internal standard.

· · ·

The estimate was ao = 2 * d [i0o] / \ $.

· «« E · · i · i .1. The unit cabinet size of 20 mesoporous molecular sieve (MCM-41) was estimated by J.S.

. Becker et al., JAm.Chem.Soc. 114: 10834 (1992).

The unit cabinet size of the zeolites corresponds to the amount of Al added to the zeolite backbone. AI- ·. **! the atom is larger than the Si atom, so in most zeolites the unit · ··· • * 13 119801 ko typically increases with increasing Al. In contrast, in the embedded zeolite, the dimension of the unit cabinet increases with increasing Al in the MM5 catalyst material, as can be seen in Table 2 (ao values for MFI, BEA, MWW, and MOR). The change in dimension 5 (UCD) of the MCM-41 unit cabinet does not correspond to the amount of Al, but rather decreases as the MH phase intensity increases. The changes in unit cabinet dimensions provide clear evidence of true chemical binding between the mesoporous molecular sieve and the embedded zeolite.

10 Aluminum content and unit cabinet dimensions for MCM-41 and MFI, BEA, MWW, and MOR zeolites immersed in a mesoporous molecular sieve (MCM-41) are shown in Table 2 below,

Table 2. Aluminum content and unit cabinet dimensions

Sample Al (%) MCM-41a0 MFI, BEA, MWW

_____ (nm) __ and MOR a0 (nm) MCM-41_ 2.5 3.5

Na-MM5-2ZS 0.2__4.4 1.982: Na-MM5-42S_ 0.4 4.2 1.981 · "* Na-MM5-4ZS-2A1 1.5 4.3 1.979 '! * Na-MM5-4ZS- 2A135 3.9 3.8 L972 **: \ MFI ZSM-5__1.4 - 1.978 ..... Na-MM-BE-4B _ k0 SjÖ ................ .. 1,428 ... T Na-MM-BE-4B-2A1__2.4 4.1 1,428 O Na-MM-BE-4ZS-2A135 6.0 4.1 1 ^ 30

Na-MM-MW22-2Al 2.2 4 ^ 2 ”1.426 H-MM-MW22 0.8 4.1 1.406 ·· *. ~ H-MM-MW22-2AI 2ä ζί M36 '' I * 'H-MM-MW22-2A1-3 5 3.7__4.0 MCM-22__2.4 - 1.405

Na-MM-MO 1.0 4.1 _ 1,800 15 '' • * f • · * • f 1 • Φ • · «·· 14 119801

Table 2 continues_______

Na-MM-M0-2A1 _4 ^ 6 4, "l 1,800 H-MM-MO ~ 1.0” 4.0 1.806 P1 / H-MM-MO 1.1 4.1 1.806

The thermal stability of the catalytic material according to the invention was tested by bringing the embedded material to 1000 ° C in air. The XRD diffraction pattern 5 for the rebated MM5 is shown in Figure 4. After treatment at 1000 ° C, the same pattern as shown in Figure 5 was obtained. This observation is evidence that this catalytic material of the invention is thermally stable up to at least 1000 ° C.

The nanostructure of the catalytic materials according to the invention was examined using high-resolution transmission electron microscopy (HRTEM) (Philips CM-200FEG transmission electron microscope, 0.24 nm dot resolution). The composition was measured using EDS (Noran Voyager Energy Dispersing X-ray Spectrometer). Figure 6a illustrates an HRTEM image of a meso-15 porous material embedded in beta zeolite according to the invention. Worthy-. . Therefore, Fig. 6b shows an HRTEM image of a structured MCM-41, a method of silencing a meso-mesh molecular sieve embedded in a zeolite. is described in more detail below, • ·. 20 ··· "!! Method for preparing a mesoporous molecular sieve embedded in zeolite

• S

* * * for disease includes the steps of: (a) making zeolite cores from a source of silicon and an aluminum source and a structural material (temple R), or silicate or an aluminosilicate precursor for zeolite cores, and optionally the temple is removed by: • a stepwise calcination process; B) preparing a mesoporous molecular sieve gel mixture from a source of silicon, usually a source of aluminum and a surfactant (S); C) the zeolite nuclei or precursor of silicate or aluminosilicate prepared in step a) are introduced as reagents into the gel mixture of mesohololytic molar cellulose obtained in step b) and the zeolite nuclei or the silicate or aluminosilicane precursor in silicate or aluminosilicase; d) performing, gel maturing the mixture of step c); e) performing the hydrotenic synthesis of the mixture of step d) by maintaining the mixture under suitable conditions, the iodine comprising a temperature in the range of about 100 ° C to about 200 ° C under static and dynamic mixing until crystals are formed; f) recovering the crystals; g) washing the solid product; h) drying the solid product; and i) partially or completely removing the surfactant (S) by a stepwise calcination process and optionally removing the template (R) unless removed in step a) to provide a catalyst which is a mesoporous molecular sieve embedded in a zeolite.

: · *: In step (a), zeolite cores are prepared from a source of silicon and an aluminum source and ··· · · ** ,, 20 structure control agents (Temple R). The source of silicon is selected from silicon oxides, «; Preferably, colloidal silica, solid silica and smokable silica.

··· * * · ·· * The source of aluminum is selected from aluminum sulphates (Al2 (SO4) 3'18H2O), hydrogenated alumina; · · · · · · · · · · · · · · · · · · · · · · · · · · · · · about about 25 hydroxyls, almininates, alminine isoproxide and alumina.

The appropriate temple is selected to achieve the desired zeolite structure. Example lc- ·· # /. Typically used templates include alkyl ammonium hydroxides, alkyl * ammonium halides, alkyl amine hydroxide and alkyl amine halides, # 7 30 such as tetrapropyl ammonium urea bromide, tetranylethyl ammonium hydroxide, tetra *. 1,1'-methylhammamumbromide, tetraethylanunonmmbromide, tetraethylammonium 1,169,801 hydroxide, piperidine, pyrrolidine, octylamine, ethylene amine, 1,6-diammohexane and hexaraethyleneimim.

The temperature in step b) is in the range of 40-200 ° C and the preparation is carried out in static or dynamic mode. Finally, in step a), the temple is optionally removed by a heat treatment procedure known as a stepwise calcination procedure. The treatment temperature is in the range of 350 to 900 ° C at removal. Alternatively, the temple may be removed in step i) unless it was removed in step a), but preferably the temple is removed in step a).

10

In step b), the mesohuolcome molecular sieve gel is prepared from silicon sources, optionally aluminum sources and surfactant (S). Sources of silicon are selected from silicon compounds having an organic group and inorganic sources of silicon. Sources of silicon having an organic group include tetraethoxysilane (TEOS), tetramethylammonium silylate, tetraethylammoniumurosilicate, etc. Inorganic silicon sources include sodium silicate, water glass, colloidal silica, solid silica and fumed silica. The source of aluminum is selected from aluminum sulfate (A12 (SO4) 3.18H2O), hydrogenated aluminum hydroxides, aluminates, aluminum isoproxide and aluminum oxide. Surfactants are selected to provide the desired meso-maintenance phases «· ί * ·· 20. Suitable surfactants used are alkyltrimethylammonium halide compounds of the general formula CnH2n + i (CH3) 3 * NX, where n = 12- ***** 18, X = Cl, Br. Preferably, the surfactant is selected from the group consisting of n-hexadecyltrimethyl, *: * ammonium bromide, n-hexadecyl xxymethylamine monurium chloride, cetyltriene ··· · ... · style ammonium bromide and cetyltriethylammonium bromide. The average temperature in step b) is in the range of 20-100 ° C and the preparation is carried out under stirring.

· »· • · · · · ···

Zeolite cores or a silicate or aluminosilicate preparation prepared in step a) the cursor is added to the molecular sieve gel in step c) with stirring. Form- • ·. ***. the mixture is homogenized and the zeolite cores or silicate or aluminosilicate precursors are dispersed. To adjust the acidity of the product, an additional I · I m ·· *, * aluminum source may be added. This additional source of aluminum is an aluminum source of organic ligand selected from aluminum alkoxides, preferably it is achyme isopropoxide. The stirring rate in step c) is in the range of 50 to 1000 rpm. The treatment time is in the range of 10 to 500 minutes.

In step d), the gel is cooked by mixing. The mixing speed is 200-1000 ipm and the gel cooking tray is in the range of 30-1800 minutes.

In step e), the hydrothermal synthesis is carried out at a temperature in the range of 100-200 ° C. The time of I-hydrothermal synthesis can vary from 10 h to 300 h 10 depending on the desired material. The hydrothermal synthesis is carried out in dynamic mode under continuous stirring until crystals are formed.

In step f), the crystals of step e) are recovered, for example, by filtration or by any other method known in the art. If bent, adjust pH to 6-8 before recovery, such as filtration.

The solid product obtained in step f) is thoroughly washed in step g), for example using water as a washing liquid. The water temperature is in the range of room temperature • · ΐ.ί: - 60 ° C. The wash is stopped when all unwanted soluble materials have been removed 99: * · * 20 from the solid product.

• · · • * · • • t *

In step h), the solid product is dried to remove the solvent by methods known in the art.

··· 9 9 • * ··· 25 In step i), the surfactant (S) is partially or completely removed by a heat treatment, known as a step-by-step calcination. Optionally, step (i) can be removed in step (i) simultaneously with removal of the surface-active agent. The treatment temperature is in the range 350-900 ° C. The heating speed Φ ·, ··· is in the range 0.2 - 10 ° C / min. During the treatment, the atmosphere is oxidative and the final material is typically treated in air. In the final step, the catalyst, which is a mesoporous molecular sieve immersed in zeolite, is obtained.

• • · · * · 18 119801

In the manufacturing process, a gel solution of a mesoporous molecular sieve is prepared, then the zeolite nucleating agent is added under suitable synthesis conditions and the aluminum source is replaced by the zeolite nucleating agent. The source of aluminum 5 is suitably aluminum alumina and preferably aluminum isopropanolide.

Preferably, the surfactant is n-hexadecyltrimethylammonium bromide, n-hexadecyltrimethylammonium chloride, cetyltrimethylammonium bromide and acetyl diethylammonium bromide.

10

Distilled water or deionized water is preferably used as a solvent and for washing the material.

Zeolite cores are structural-free material free aluminosilicate precursors and may be partially or wholly crystalline. Due to variation in Kidelco, they can be detected by XRD, or. then no. However, their morphology can be observed by wiper electron scanning. The zeolite nucleus 11 is a metastable phase that undergoes chemical bonding with mesoporous * * ·· 20 molecular sieve walls in the presence of a pmta-active agent and during synthesis of kelp cellulite * · ·, · ·.

• «t • · · ··· *

Following intense dispersion of the aluminosilicate nuclei into the mesoporous mole,. # ί Ϊ justice.

»·· • · • · ·· *, *. # J Aluminosililcaattiprekursori for zeoliittiytimiä can be prepared zeoliittira-. * · *. body types, such as MFI, BEA, TON, MOR, MWW, ABP and FAU, according to prior art (EP 23089, U.S. Patent 3,308,069, BP 102,716, EP 23089).

• ** # *,. * Here are two examples of fabricating aluminosilicate anchors • • • • ··· 1998011 for MFI and BE A-structured zeolite cores. However, it is obvious that the other zeolites mentioned are equally suitable.

Zeolite cores made from aluminosilicate precursors are suitable for use in gel preparation. During gel maturation, chemical interactions and binding occur through the nucleation process. Gel maturation accelerates the nucleation process, and zeolite nuclei can also undergo secondary nucleation to form a complex "zeolite nucleus and surfactant mesophase" that promotes the chemical nature of the bond between the micro and mesophase mesofacies. formation.

For the formation of "zeolite cores and surfactant mesophase", it is preferred that the zeolite cores be added after the surfactant has been added to the aliquot medium or the zeolite cores are immersed in the aqueous surfactant solution followed by the gel maturation step.

For the addition of reagents, in particular surfactant and zeolite nuclei • · | t | : pretreatment of zeolite nuclei and gel maturation process. are important for the formation of the bonding between the microporous and mesoporous molecular sieve material. To obtain a highly acidic, mesoporous molecular sieve: *: ** embedded with zeolite materials, the aluminum source is added after the addition of the zeolite nuclei, but with a period of maturation of the mothers.

Vigorous mixing after the addition of the zeolite nuclei during gel preparation is important to increase the homogeneity and dispersion of the zeolite nuclei in the gel solution.

• · * * * * · **, ···. The resulting catalytic materials may optionally be converted to the corresponding proton amines by ammonium ion exchange and calcination. A suitable source for the exchange of ammonium urea is an ammonium salt such as ammonium citrate or ammonium chloride. The catalytic materials are treated with aqueous ammonium salt at temperatures in the range of 25-80 ° C for a suitable period of time, such as 1-6 hours. Ammonium cations replace alkali or alkaline earth cations of materials during processing. The degree of ion exchange can be varied by varying the 5 treatment times, ammonium solution concentration and temperature, the material obtained after the ion exchange treatment is dried and rebated to decompose the ammonium ions into proton and ammonia.

Modifications to the catalytic material of the invention, a novel meso-10 porous molecular sieve embedded in a zeolite, can be accomplished by methods selected from precipitation, deposition, encapsulation and selective removal. As well as impregnation. that ion exchange are deposition methods. In impregnation, the deposition is carried out from the liquid phase and adsorption, ion exchange and selective reaction can take place on or with the support surface. During the removal of NES-15, crystallites are formed on the surfaces rather than simple layers, diluted solutions are used for ion exchange and the desired metal lation is changed from solution to material, thereby replacing the cation or proton of the solid material. Procedures and Method Selection for Modification • · * ·: Depends on the reactions being targeted. Generally, the leaching process is preferred when a lower addition of metal and a higher dispersion are required.

• * · · * ·

Removal of the surfactant after completion of the synthesis is necessary to obtain mesoporous molecular sieves immersed in zeolite and * ** · * ··· * with high surface area and acidity. The calcination temperature, heating rate, and duration may influence the surface area, pore size distribution, and location of aluminum in the • · · '· * * frame. Synthesized, new mesoporous molecular sieve with immersed zeolite, extremely large surface area, as determined by nitrogen adsorption, and variable, high acidity, as determined by ammonia TPD, confirm that the stepwise calcification procedure is a very suitable method for the removal of surfactants.

• »t • · · * ·« «• · * * 21 119801

The removal of the temple from the mesol-sized molecular sieves into which the zeolite has been embedded is also carried out by a stepwise calcination procedure.

Synthesis of mesoporous material may be carried out with or without additional sources of aluminum. Only one template is needed for the synthesis of the catalyst material,

The catalyst material may be incorporated into or supported on the support using any of the processes known in the art.

10

The synthesis process results in an increased crystallinity of the pore walls by chemically binding the zeolite material to the mesoporous material, thereby providing the desired properties of the zeolite while preserving the mesoporous structure intact. This method requires only one type of template in gel solution.

The small crystals of the zeolite are used as "nuclei" in the synthesis of the mesoporous material, and the concentration of the "nuclei" and the size of the zeolite crystals can be varied.

• ·: This results in an increase in the concentration of zeolite nuclei and the immersion of the microporous structure in the mesoporous molecular sieve and the increased crystallinity of the mesoporous ♦ wall. It also affects the thermal and hydrotenic stability and acidity properties of the material. Variation in the size of the zeolite cores can affect the shape selectivity property of the material.

··· • · · · ··· X-ray powder diffraction patterns, scanning electron microscopy, and nitrogen adsorption * ·· v: Characterization results confirm a mesic pore molecular sieve embedded with zeolite such as MFI-, W-, BEA-, MFI-, BEA-, - Φ Λ | structures, high thermal and hydrotenic stability.

Φ · ΦΦ * • «Φ φ Φ · ·, *. In addition, complete or near complete regeneration of spent catalysts from various hydrocarbon conversion reactions such as isomerization of n-butane and 1-butene.

• M

22 119801 and the oligomerization of l-decene, and the retention of catalytic activities also indicates the stability of the catalyst material.

The manufacturing process makes it possible to design internal acidity properties in a mesolized molecular sieve. The intrinsic acidity properties of mesh-like molecular sieve materials can be designed using an aluminum source and varying the Si / Al ratio of the gel solution and various zeolite cores. The results of the calcification of the H-MM5, H-MMBE and H-MMMW catalysts with ammonia TPD and various experimental reactions such as isomerization of n-butane confirm the successful design of these materials with varying acidity.

The pore walls of the mesoporous materials are amorphous with MCM-41, but with the addition of zeolite they have increased crystallinity. In the product of the invention, the zeolite single-site copolymer is different from the unit-site copolymer in the mechanical mixture of zeolite and mesoporous molecular sieve, and has a higher mesoporous molecular sieve than the corresponding mechanical one. . in this mixture.

Another essential feature of the product is that most of the zeolite phase is chemically. bound to a mesoporous molar sieve. The product is thermally stable at least Φ Φ. at 900 ° C in the presence of air.

The mesoporous molecular sieve embedded in the invention with a zeolite ... 25 and the process for making such a material differ significantly from those described in the prior art and has numerous benefits a.

a a a · ··· a a *. * ·: A new mesoporous MM5 molecular sieve embedded in your MFI ralcet is a a a

Thermally stable up to at least 1000 ° C and MMBE at least 900 ° C

up to 30, as can be seen in the XRD and SEM images and area measurements, • 23 119801 MM5, MMBE, MMMWai and MMMO lation forms, Na conversion to the corresponding proton forms of MM5, MMBEni, MMMWai and MMMOai by ion exchange in aqueous ammonium nitrate followed by drying at 100 ° C and calcination at 500-5 ° C did not alter the structure as shown in the XRD models, thermal stability. It is known that the MCM-41 structure collapses after being brought into contact with water at high temperatures.

Metal modification of MM5, MMBE, MMMWai and MMMOai, such as noble-10 tallow modifications, and in particular platinum modifications of the examples prepared using aqueous solutions of hexachloroplatinic acid at 80 ° C for 24 hours, followed by drying at 100 ° C and calcination ° C did not affect the MM5 and MMBE structures as shown in the XRD models. This indicates that the material is stable in acidic medium.

15

The proton form of a meso-dense molecular sieve embedded in the MFI structure exhibited very high activity in the isomerization reactions of n-butane and 1-butene. The H-MM5 catalysts showed an increase in the n-butane basket version with increasing acidity.

ί *** 20 • · ♦ ** “* The proton forms of the meso-covalent molecular sieve embedded in MFI and BEA structures showed very high activity in the dimerization of l-olefins. The H-MM5 and H-MMBE catalysts showed an increase in the 1-delcein conc • ♦ * ··· ', and an increased acidity. The proton form of a meso-monolayer molecular sieve embedded in an MFI structure showed very high activity in the dimerization of isobutene, and the catalyst was not dealtivated.

· · · · · · · · · · · · · · · · · · · · · · · · · H · MM5 and H-MMBE catalyst materials were completely regenerated without: ***; in the presence of. The regenerated materials had almost the same activity n- ···. 30 butane and 1-butene isomerization and l-decene oligomerization as the product. It is well known that one of the hazards of MCM-41 catalyst is the problem of • · ··· 24 119801 which is regenerated !!, i.e. the mesoporous structure collapses after regeneration. The retention of catalytic activity in both reactions in a new mesoporous molecular sieve embedded with zeolite materials clearly indicates that the structure after regeneration is stable.

5

Pt-MM5 showed very high conversion in the isomerization of n-butane and the catalytic material retained its catalytic activity after regeneration.

Pt-MMBB showed high selectivity for ring opening products.

10

Thus, post-synthesis modification is not required for mesoporous materials MM5 and MMBE to increase thermal and hydrotenic stability. The high thermal and hydrothermal stability of the new materials is attributed to the immersion of a zeolite such as MFI and BE A in the mesh porous molecular sieve using the method described above.

This new class of mesoporous materials can be used as a catalyst for olefin dimerization, olefin oligomerization, olefin isomerization, carbon; | : in hydrocarbon cracking, aromatic alkylation, light hydrocarbon aromatization, etherification, dehydrogenation and ring-opening reactions, without: other modifications of the active material. The metal-modified material showed ·: **: high activity in light paraffin isomerization. Likewise, metal-modified materials may also be active in the isomerization of long-chained paraffins, hydrogenomn, hydrogen cracking, hydrogen desulphurisation, hydrogen deprotection, nitrogen removal with hydrogen, dehydrogenation, refomination,: T: Fisher-Tropsch- and in the oxidation reaction, when modified by a technique known in the art. The metal present in the catalyst may be present in metal, oxide or sulfide forms, or in any other form known in the art.

The material of the invention can also be utilized in a variety of separation techniques, such as adsorption, absorption or selective removal.

♦ · • · ··· 25 119801

The following illustrative examples will provide a better understanding of the invention and its practical embodiments, but it will be apparent to one skilled in the art that the scope of the invention is not limited to these examples in any way.

EXAMPLES Example 1 (Reference) Preparation of ZSM-5 Zeolite according to US 3,926,784 The starting materials were aluminum silicate, aluminum sulphate, triisopropylamine bromide (TPABr), sodium chloride, sulfuric acid water. Solution A was prepared by mixing 3.5 g of aluminum silicate with 4.4 L of water. Solution B was prepared by mixing 107 g of aluminum sulfate, 438 g of TBABr, 1310 g of NaCl, 292 g of H 2 SO 4 and 6 l of water. The solutions were charged into the reactor with stirring at 250 rpm. The temperature was gradually raised to 100 ° C and the pressure increased to 8 bar. The reaction was stirred for 6 days. The reactor was cooled. Formation,. The solid product (ZSM-5) was filtered, washed with warm water and dried at 110 ° C overnight. The product was rattled to remove the temple, ion-exchanged with ammonium nitrate and rattled to prepare the zeolite proton form (H-ZSM-5).

• · ···

Examples 2-4 (Comparative) Preparation of MSA Type Materials according to EP 0 784 652 25 | * The starting materials used in the synthesis of MSA-type materials were aluminum • isopropanolide (Al-1-C 3 H 70) 3, tetraethyl cross-linked silylates (Si (C 2 H 50) / t), and tetra- • aqueous solution of propylammonium hydroxide (TPA-OH). TPA-OH, (Al-i-f *, ί, ί C3li70) 3 and water were stirred at 60 ° C for 40 minutes. The resulting solution was heated to 85 ° C to give a clear solution. Liquid • ·. * ··. ShCzHjOL) was then added via a dropping funnel. The resulting mixture was stirred on · · ♦ ·· 26 119801 for 3 hours. The reaction mixture was cooled with continuous stirring for 20 hours. After cooling, the alcohol and water formed were evaporated and the solid gel dried at 100 ° C. The dry solid was ground and calcined at 550 ° C for 8 hours.

5

The following Table 3 gives the preparation and properties of the resulting MSA-type catalysts.

Table 3

Synthesis Parameters: Example 2 Example 3 Example 4 __MSA-1 MSA-2 MSA-3

Si / Al (mol / mol) 50 12 -5_ TPA-OH / water (mol / mol) ~~ 0.18 ~~ 0.18 0.18

Product Features:

Si / Al (mol / mol) ~ 54 11.5 4.8 BET surface area (m2 / g) ___ 650 440 310

Micropore Area (ra2 / g) 380 340 210

Average pore size (nm) 1.4 1.4 1.4

Surface area of the mesoparticles (m2 / g) 270 100 80: 10 Ml ·

Example 5 (Comparison)

Preparation of Mesoporous Molecular Screen H-MCM-41 * t *

·· * Synthesis of Na-MCM-41 was performed by preparing solutions A, B and C. Solution A

· * · · · ***: 15 was prepared by mixing the fumed silylca with distilled water with continuous stirring for 15 minutes. Solution B was prepared by adding tetramethylammoniurase: * * * lilate to sodium silylate with continuous stirring, and the mixture was stirred for 20 minutes · * "; solution C was prepared by dissolving tetradecyltrimethylammonium bromide ··· * in distilled water with stirring for 20 minutes. slowly

• t ♦ J

With stirring and after the addition of solution B, the mixture was stirred for a further 20 minutes. Solution C was added slowly (20 min) to a mixture of A and B stirred. After addition of solution C and solution C, the mixture was stirred for an additional 20 min. The alumina is then added to the gel solution (A-1-B + C) with stirring and the resulting mixture is gel-cooked for 2 hours with stirring. The pH was adjusted and the gel was placed in a Teflon cup which was placed in an autoclave. Synthesis was carried out for 48 h at 100 ° C. After completion of the synthesis, the reactor was cooled and the necrotic material was filtered and washed with distilled water. The resulting Na-MCM-41 was lysed at 110 UC and calcined at 550 ° C for 10 hours. The Na-MCM-41 sodium form was ion-exchanged with an aqueous 1M ammonium nitrate solution for 2 h at 80 ° C and then the NH4-MCM-4I obtained was washed with distilled water, dried and calcined.

10

Examples 6-8

Mesoporous Molecular Screen Immersed in MFI Zeolite Zeolite Cores Preparation of three different solutions A, B, and C for the preparation of MFI zeolite cores. Solution A was prepared by adding 10.5 g of fumed silica to 81.2 ml of distilled water. Solution B was prepared by dissolving 2.2 g of NaOH and 0.3 g of Al (OH) 3 in 9.4 volumes of distilled water. Solution B was added to Solution A and the resulting gel mixture was stirred for 20 minutes. Solution C was prepared by dissolving 3.7 g of tetrapropylammonium 20 mumbromide in 3.8 g of water and stirring for 20 minutes. Solution C was added to the gel blend (A + B) and stirred for 15 minutes and 55 ml of water was added. the gel mixture was further stirred for 20 min The synthesis was carried out at 150 ° C for 18 hours After completion of the synthesis, the product was filtered, washed with distilled water, dried and calcined to give MFI zeolite cores.

25 ··· • · ·

Example 6a

• M

·

Synthesis of Na-MM5- «961i-4ZS, Mesoporous Molecular Sieve with Embedded MFI Structure, Without Aluminum Source ··· • · · · · · · ·. ; Synthesis of Na-MM5-96h-4ZS was performed by preparing solutions A, B and C. Solution • ·· * ·, ···. A was prepared by mixing 8.3 g of fuming silica with 51.7 g of distilled water • * 11> 28 119801 with continuous stirring (r.m.p. 196) for 20 minutes. Solution B was prepared by adding 18.1 g of tetrarnethylammonium silicate to 11.7 g of sodium silicate with continuous stirring (r.m.p. 180) and the mixture was stirred for 20 minutes. Solution C was prepared by dissolving 26.3 g of tetradecylthiomethylammonium bromide in 174.3 of 5 g of distilled water under vigorous stirring (r.m.p. 336) for 20 minutes. Solution B was added slowly, to solution A (15 minutes) with vigorous stirring (i.p.) 320) and after solution B was stirred for an additional 20 min. Solution C was added to the mixture (A + B) slowly (20 min) with vigorous stirring (r.m.p. 336) and after the addition of solution C, the mixture was stirred for another 20 min.

10

Thereafter, 4.2 g of the prepared MFI cores were dispersed in gel solution (A + B + C) with vigorous stirring (r.m.p. 340) for 20 minutes. The homogenome of the dispersed MFI was further subjected to vigorous agitation of the gel (340 r.m.p.) for 35 minutes. The gel solution was aged for 3 hours at ambient temperature with stirring (r.m.p, 180). The pH of the gel was adjusted and the gel was placed in a teflon cup, which was then placed in an autoclave. The synthesis was carried out for 96 h at 100 ° C.

ß,:: After completion of the synthesis, the reactor was cooled for 30 min and the resultant •; * · * 20 porous molecular sieve material embedded in the MFI granulate was mixed with distilled water, filtered and washed thoroughly with distilled water for 3 h.

The Na-MM5-96h-4ZS was dried and revolted at 450 UC using a step-by-step calcination procedure for 10 hours in a muffle furnace.

• M

Example 6b Preparation of the proton form of H-MM5-96h-4ZS, the above matrix material,

: 10 g of Na-MM5-96h-4ZS (sodium rebound, prepared above) was ion-exchanged with 1 M

• * ·. · ·. ammonium nitrate account Ammonium dehydride in water solution for 24 hours in the ambient west-···, *, 30 states. The NH4-MM5-96h-4ZS obtained after ion exchange was thoroughly washed with distilled water, dried and calcined using a stepwise calcination procedure in a muffle egg at 450 ° C.

The X-D pattern of the resulting H-MM5-96h-4ZS was similar to that of Na-MM5-96h-5ZZ, showing that the water stability of the new mesoporous material and subsequent heat treatment did not affect the stability of the structure.

Example 7

Synthesis of Na-MM5-10 96h-4ZS-2AI Mesoporous Molecular Sieve Embedded in MFI-Ralcene Using an Aluminum Source

Example 7a

Synthesis of Na-MM5-96h-4ZS-2Al Synthesis of Na-MM5-96h-4ZS-2Al was carried out by preparing solutions A, B and C.

Solution A was prepared by mixing 8.3 g of fumed silica with 51.7 g of distilled water with continuous stirring (r.m.p. 196) for 20 minutes. Solution B was prepared:. by adding 18.1 g of tetramethylammonium silicate to 11.7 g of sodium silicate • «· ··· 1 2 Ϊ1. with continuous stirring (r.m.p. 180) and the resulting mixture was stirred for 20 minutes.

Solution 11 was prepared by dissolving 26.3 g of tetradecyltrimethylamomumbum • S · 1 slide in 174.3 g of distilled water with vigorous stirring (r.m.p. 336) for 20 minutes. Solution B was slowly added (15 minutes) to solution A with vigorous stirring. After addition of solution B (r.m.p. 320) and solution B, the mixture was further stirred for 20 µm. Solution C was added slowly (20 min) to the mixture (A + B) with vigorous stirring, · · ·, 25 (r.m.p. 33 6) and after addition of solution C it was stirred for a further 20 min.

Thereafter, 4.2 g of MFI beads were dispersed in a gel solution (A + B + C) under a tin flow of 2 I with stirring (r.m.p. 340) for 20 minutes. The homogenization of the dispersed MFI was continued with vigorous agitation (r.m.p. 340) for 35 minutes! '.J for 30 years. Then 2.3 g of aluminum isopropoxide was added and stirred for 20 min. The resulting gel was allowed to mature for three Ume's under agitation (r.m.p. 180). The pH of the gel 11 119801 was adjusted and the gel was placed in a Teflon cup, which was then placed in an autoclave. Synthesis was performed for 96 L at 100 UC. After completion of the synthesis, the reactor was cooled and the resulting mesoporous material was filtered and washed thoroughly with distilled water. The resulting Na-MM5-96h-4ZS-2Al was dried and calcined using a stepwise calcination procedure for 10 h in a muffle furnace.

Example 7b Synthesis of H-MM5-961i-4ZS-2AI 10 g of Na-MM5-96h-4ZS-2Al (prepared above) was ion-exchanged with 1M aqueous ammonium nitrate solution for 24 h at room temperature. After ion exchange, the meso-porous material was washed thoroughly with distilled water, dried, and calcined for four hours using a stepwise calcination procedure in a muffle furnace at 450 ° C. The resulting H-MM5-96h-4ZS-2Al had an XRH pattern similar to that of Na-MM'5-96h-4ZS-2Al, demonstrating that the water treatment of the new meso-maintenance material and subsequent heat treatment did not affect the stability of the structure.

EXAMPLE 8 Synthesis of Na-MM5- * · * · * 96h-4ZS-2Al-3S Using a Aluminum Synthesis of 20-meso-Molecular Molecular Sieve with Embedded MFI Structure sources * · * · ♦ ·· ♦ · Example 8a '··· * Synthesis of Na-MM5-9 6h-4ZS-2 Al-35 25 ** ϊ * * · *' Na-MM5-96h-4ZS " The synthesis of 2Al-35 was carried out by preparing solutions A, B and · ** ·.

** ·. * C. Solution A was prepared by mixing 4.5 g of fumed silica with 51.7 g of distilled water with continuous stirring (r.m.p. 196) for 20 minutes. solution B was prepared by adding 18.1 g of tetramethylammonium silicate to 11.7 g of sodium silicate (ie * 30) with continuous stirring (r.m.p. 180) and the resulting mixture was stirred for 20 minutes.

Solution C was prepared by dissolving 26.3 g of tetradecyl nitromethylammonium bromide in 174.3 g of distilled water under vigorous stirring (r.m.p. 336) for 20 minutes. Solution B was added slowly (15 minutes) to solution A with vigorous stirring (r, m.p. 320) and after addition of solution B, the resulting mixture was further stirred for 20 min. Solution C was added slowly (20 min) to the mixture (A + B) with vigorous stirring (r.m.p. 336) and after the addition of solution C, the mixture was stirred for another 20 min. Thereafter, 4.2 g of the MFI cores prepared in Example 6 were dispersed in gel solution (A + B + C) with vigorous stirring (r.m.p. 340) for 20 minutes. Homogenization of the dispersed MFL was performed by vigorously stirring the gel (r.m.p. 340) for a further 35 minutes. 2.3 g of aluminum isopropoxide 10 were then added and stirred for 20 min. The resulting gel was then allowed to mature for 3 hours with stirring (r.m.p. 180). The pH of the gel was adjusted and the gel was placed in a Teflon cup, which was then placed in an autoclave. The synthesis was carried out for 96 h at 100 ° C. After completion of the synthesis, the reactor was cooled and the resulting honeycomb material was filtered and washed thoroughly with distilled water. The resulting Na-MM5-96h-4ZS-2Al-35 was dried and calcined using a stepwise calcination procedure in a muffle furnace at 450 ° C.

Example 8b • ·: Preparation of H-MM5-96h-4ZS-2Al-35 ** '** 20 g of Na-MM5-96h-4ZS-2Al-35 (prepared above) was ion-exchanged with 1 M amine - ** * with aqueous sodium nitrate solution at room temperature for 24 h, after ion exchange, the honeycomb material was thoroughly washed, dried and calcined for four hours mmm * ... · using a stepwise calcining procedure in a muffle furnace at 450 ° C.

25 mmm V * The resulting H-MM5-96h-4ZS-2Al-35 had an XRD pattern similar to that of Na-MM5- ··· · ... · 96h-4ZS-2Al-35, indicating that the new the water treatment of the mesoporous material and the subsequent heat treatment did not affect the stability of the structure.

···. *. 30 • · «• I» • · * «· * · • t ··· 32 119801

Example 9

The platinum-modified MM5 material, Pt-H-MM5-96h-4ZS-2Al, in 5 g of H-MM5-.96h-4ZS-2Al was loaded with 2 wt% Pt using impregno intimene-5. Impregnation with 2 wt% Pt was performed in a rotary evaporator at 80 ° C for 24 h using an aqueous solution of hexachloroplatinic acid. MM5-96h-2Al impregnated with 2 wt% Pt was dried at 100 ° C and calcined at 450 ° C. The .XRD pattern for Pt-H-MM5-961i-2Al shown in Figure 5 was similar to that of the intermediate Na-MM5-96h-4ZS-2Al, showing the hydro tennis en stability of a new mesocellular mo-10 cellulose sieve embedded in zeolite.

Example 10

Preparation of Platinum-Modified MM5 Material, Pt-H-MM5-96h-4ZS-2AI-35 15 g of H-MM5-96h-4ZS-2Al-35 were loaded with 2 wt% Pt impregnation method. Impregnation with 2 wt% Pt was carried out in a rotary evaporator at 80 ° C for 24 h using hexaldloroplatic acid aqueous solution. 2 p -%:! La • · • * ·! ·! I Pt-impregnated MM5-96h-2Al-35 was dried at 100 ° C and calcined at ** 20 ° C at 450 ° C.

4 4 4 • ♦ · ··· m * * The XRD model for Pt-H-MM5-96h-2Al-3 5 was similar to the Na- ··· • * .i MM5-96h-4ZS-2Al- 35 demonstrating the hydrotenic stability of a new meso-mesh molecular sieve embedded in zeolite.

25 ··· • * · • 4 · * ··· * · • * 444 • 4 4 • 4 * • «4 • 4 44« • · • 4 • 4 4 4 4 4 4 44 4 4 444 4 4 • 4,444 33,119011

Examples 11-13

Preparation of Mesoporous Materials embedded in BEA Structure Preparation of BEA Zeolite Core 5 7.8 g of NaA102 were mixed with 60 ml of distilled water with stirring for 10 minutes and to this solution was added 74 g of tetraelylammonium hydroxide (TEA-OH, 40%) and stirred for 20 minutes. minutes. 145.4 g of colloidal silica were added to the above solution and stirred for 25 minutes.

10

The resulting gel was autoclaved and placed in Teflon cups. The synthesis was carried out at 150 ° C for 65 h in static mode. After completion of the synthesis, the product was filtered, washed with distilled water, dried at 110 ° C and calcined at 550 ° C for 7 hours to give the BEA zeolite.

15

Example 11a

Synthesis of Na-MMBE-96h-4B Mesoporous Molecular Sieve Embedded in BEA without Aluminum Source • · 1 2 3 ♦ · ♦ ··· ··· 9 9 ί · 1 20 Na-MMBE-96h-4B Synthesis was carried out by preparing solutions A, B and C. Solution 9 M.1 A was prepared by mixing 8.3 g of fumed silica with 51.7 g of distilled water *: with continuous stirring (rmp 196) for 20 minutes. Solution B was prepared by adding

by heating 18.1 g of tetramethylammonium silicate to 11.7 g of sodium silicate * ..1 · with continuous stirring (r.m.p. 180) and the mixture was stirred for 20 minutes. Liuos C

25 was prepared by dissolving 26.3 g of tetradecyltrimethylamomumbumbide in 174.3 g of distilled water with vigorous stirring (r.m.p. 336) for 20 minutes. Solution B 1 was added slowly to solution A (15 minutes) with vigorous stirring (r.m.p.

After addition of solution B, the resulting mixture was stirred for an additional 20 min. The solution was added to A + B slowly (20 min) with vigorous stirring (r.m.p.

After addition of solution C, the mixture was stirred for an additional 20 minutes.

• · »• · i1 •» 2 • · 3 34 119801

Thereafter, 3.7 g of the precursor BEA zeolite nucleus prepared above was added to the gel solution (A + B + C) with vigorous stirring (r.m.p. 350) and the gel matured with stirring (r.m.p. 180). The pH of the gel was adjusted and the gel was placed in a teflon cup, which was then placed in an autoclave.

5

The synthesis was carried out for 96 h at 100 UC. After completion of the synthesis, the reactor was cooled and the resulting mesoporous material was filtered and washed thoroughly with distilled water. The resulting Na-MMBE ~ 96h-4B was dried and calcined using a stepwise calcination procedure.

10

Example 11b Preparation of H-MMBE-96h-4B 10 g of Na-MMBE-96h-4B (prepared above) in an ion exchanger with 1 M aqueous ammonium iodine-15 solution for 24 h at room temperature. after ion exchange, the mesoporous material was washed thoroughly, dried and calcined using a stepwise calcination procedure.

* · Ί ·! The XRD pattern of the H-MMBE-96h-4B was similar to that of Na-MMBE-96h-4B, demonstrating that the water treatment of the new mesoporous material and subsequent *.!. * except the heat treatment did not affect the stability of the structure.

• ·

Example 12 ** ** · ... * Synthesis of a mesoporous molecular sieve embedded in BEA, synthesis of Na-MMBE-9 6U-4B-2AI using an aluminum source ··· # * ... · Example 12a • Synthesis of Na-MMBE-96h-4B-2Al • · · · · · · · · · ·. Synthesis of Na-MMBE-96h-4B-2Al was performed by preparing solutions A, B and C.

Solution A was prepared by mixing 8.3 g of smokable silica with 51.7 g of distilled water while stirring continuously (r.m.p. 196) for 20 minutes. Solution B was prepared by adding 18.1 g of tetramethylammonium silicate to 11.7 g of sodium silicate with continuous stirring (r.m.p. 180) and the resulting mixture was stirred for 20 minutes. Solution C was prepared by dissolving 26.3 g of tetradecyltrimethylammonium bromo-5 dia in 174.3 g of distilled water with vigorous stirring (r.m.p. 336) for 20 minutes. Solution B was added slowly (15 minutes) to solution A with vigorous stirring (r.m.p. 320) and after addition of solution B, the mixture was further stirred for 20 min. Solution C was added slowly (20 min) to mixture (A + B) with vigorous stirring (r.m.p. 336) and after addition of solution C it was stirred for a further 20 min.

10

Subsequently, 3.7 g of the precursor of BEA zeolite cores was added to the gcel solution (A + B + C) with vigorous stirring (r.m.p. 350) and stirred for 25 minutes, followed by addition of 1.9 g of aluminum isopropoxide and stirred for 20 min. The resulting gel was allowed to mature for three hours with stirring (r.m.p. 180). The pH of the gel was adjusted and the gel was placed in a Teflon cup, which was then placed in an autoclave. The synthesis was carried out for 96 L at 100 ° C. After completion of the synthesis, the reactor was cooled and the resulting mesoporous material was filtered and washed thoroughly with distilled water. The resultant Na-MMBE-96h-4B-2Al was dried and bleached using a stepwise calcination procedure for 10 h.

• ··:. ·. 20 • · ·

Example 12b Preparation of H-MMBE-96h-4B-2Al 10g Na-MMBE-96h-4B-2Al (prepared above) was ion-exchanged with 1M ammonia-25. aqueous nitrate solution for 24 hours at ambient temperature. After ion-exchange, the mesh molecular sieve material was washed thoroughly with distilled water, dried, and calcined in a muffle furnace using a stepwise calcination procedure.

The XRD pattern of the obtained H-MMBE-96h-4B-2Al was similar to that of Na-MMBE-96h-4B-2Al, showing that water treatment of the new mesoporous material and subsequent heat treatment did not affect the stability of the structure.

36 119801

Example 13

Synthesis of Na-MMBE-96h-4B-2Al-35 mesolymphatic molecular sieve embedded in BEA using aluminum source 5

Example 13a

Synthesis of Na-MMBE-96h-4B-2Al-35

Synthesis of Na-MMBE-96h-4B-2Al-35 was performed by preparing solutions A, B and 10 C. Solution A was prepared by mixing 4.4 g of fuming silicate with 51.7 g of distilled water with continuous stirring (rmp 196) for 20 minutes. . Solution B was prepared by adding 18.1 g of tetramethylammonium silicate to 11.7 g of natxmmsilicate with constant stirring (r.m.p. 180) and the mixture was stirred for 20 minutes. Solution C was prepared by dissolving 26.3 g of tetradecyltrimethylamomumbumide 174.3 in 15 g of distilled water with vigorous stirring (r.m.p. 336) for 20 minutes. Solution B was slowly added (15 minutes) to solution A with vigorous stirring (r.ra.p. 320) and after addition of solution B, the resulting mixture was further stirred for 20 min. Solution C was added slowly (20 min) to the mixture (A + B) with vigorous stirring and then after addition of solution C, the mixture was stirred for a further 20 minutes * 1: 2 3-20 volumes. Thereafter, 3.7 g of BE A-zeo fusion precursor (prepared above) was added to the gel solution (A + B + C) with vigorous stirring (rmp 340) and the mixture was stirred for 25 minutes. , 9 g of aluminum isopropoxide and stirred for 20 min. The resulting gel was then allowed to mature for 3 hours with stirring · · · (rmp 180) The pH of the gel was adjusted and the gel was placed in a Teflon cup which was then placed in an autoclave. at a temperature of 100 "C. After completion of the synthesis, the reactor was cooled and the resulting mesoporous material was filtered and washed thoroughly with distilled water. The resulting Na-MMBE-96h-4B-2Al-35 was dried and calcinylated using a stepwise calcination procedure.

• · · 30 • · 1 • · · * · 1 · • · 2 · 3 37 119801

Example 13b Preparation of H-MMBE-96h-4B-2AI-35 10 g of Na-MMBE-96h-4B-2Al-35 (prepared above) was ion-exchanged with 1M aqueous ammonium nitrate solution for 24 h at ambient temperature. After ion exchange, the mesoporous molecular sieve material was thoroughly washed, dried and calcined in a muffle furnace using a stepwise calcination procedure.

The resulting H-MMBE-96h-4B-2Al-35 had an XRD pattern similar to that of Na-MMBB-10 96h-4B-2Al-35, showing that the new mesoporous material was not affected by water treatment and subsequent heat treatment. stability of ralcene.

Example 14

Platinum Modified MMBE Material, Pt-H-MMBE-96h-4B-2AI

5 g of H-MMBE-96h-4B-2Al were charged with 2 wt% Pt using the impregnation method. Impregnation with 2 wt% Pt was performed in a rotary evaporator at room temperature. , at 80 ° C for 24 hours using an aqueous solution of hexaldoraplatinic acid. 2% by weight of Pt • * * * * * impregnated with H-MMBE-96h-2Al was dried and calcined. The XRD pattern of Pt-H-MMBE-96h-4B-? * * * Was similar to that of Na-MMBE-96h-4B-2Al * * * ** * starting material, demonstrating the hydrothermal stability of the new mesoporous molecular sieve. Modification of H-MMBE-96h-4B-2Al with Pt also did not affect the original · · · · * · * structure.

Example 15 · »«: · ** * 'Platinum-Modified MMBE Material, Pt-H-MMBE-96h-4B-2Al-35 • * · 1 • *' ·· ** Preparation • 5 g H-MMBE-96h-4B-2Al-35 was loaded with 2 wt% Pt with impregnation; 30 methods. Impregnation with 2 wt.% Pt was performed in a rotary evaporator at a heat. at 80 ° C for 24 h using an aqueous solution of helcsaldor platinum acid. 2 p -%; lla • · • a · 38 119801

Pfca-impregnated H-MMBE-96h-2Al-35 was dried and calcined. The XRD pattern of Pt-H-MMBE -96h-2Al-35 was similar to that of the parent product Na-MMBE-96h-4B-2A1-35, demonstrating the hydrotenic stability of the new mesoporous molecular sieve, In addition, H-MMBE-96h-4B-2Al-35 modification of Pt with Pt did not affect the allcu-5 derived structure.

Examples 16-18

Preparation of Pt-H-MMBE ion exchange 10 g of each H-MMBE material: H-MMBB-96h-4B (Example 16), H-MMBE-96h-4B-2Al (Example 17) and H-MMBE-96h -4B-2Al-35 (Example 18) was weighed into 2 liter bottles. 1 L of deionized water was added. A reflux condenser was placed on the flask. The flasks were placed in a water bath at 70 ° C and shaking at 110 ° C. The bottles were kept under these conditions for one hour. The reflux-15 condenser was then replaced with a drip funnel with a vent. 52 ml of 0.01 M Pt solution was measured into a dropping funnel. The Pt solution was slowly dropped (about 15 drops per minute) into a flask at 70 ° C with shaking at 110. Pt addition took 53 minutes. The dropping funnel was replaced by a fair condenser and the flask was left in these · · # · · * ..

: conditions for 24 inches.

• m: * ·· 20 φ

The reaction mixture from the flask was suction filtered using a sintered glass crucible. The resulting * "** material was washed in a flask with one liter of deionized water and filtered again. This was done twice. After the second wash, a sintered glass crucible with the material was placed in an oven at 80 ° C for 16 hours.

25

«M

After drying for 16 hours, the material was transferred to a crucible and calcined in an oven. The temperature was raised from 21 ° C to 300 ° C. *. J 0} 2 ° C / min.

# φφ 7 m φ • ΦΦ Φ Φ Φ ΦΦΦ 30 φ Φ Φ ΦΦ • ΦΦ φφφ φφφ φφφ φ φφφ 39 119801

Examples 19-28

Meso porous molecular sieve with embedded MWW-zeolite structure Preparation of MWW-zeolite nuclei 5

Two solutions A and B were prepared for the preparation of MWW zeolytic cores. Solution A was prepared by adding 87.58 g of sodium silicate to 42 cups of distilled water with stirring for 15 minutes and to this solution was added 16.7 g of hexamethylene dropwise over 25 minutes and the mixture was stirred for 20 minutes. Solution B was added to 7.4 g of concentrated sulfuric acid in 224 ml of distilled water and stirred for 10 minutes, followed by the addition of 8.9 g of aluminum sulphate and stirring for 20 minutes. Solution B was slowly added to solution A and stirred vigorously. The gel was placed in Teflon cups and placed in 300 ml delivery bowls. Synthesis was carried out for 96 h in a rotary mode at 150 ° C. After completion of the synthesis, the product was filtered, washed with distilled water, dried at 110 ° C and calcined at 550 ° C for 8 hours to give a precursor of MWW zeolite cores.

·:; Example 19a Synthesis of 20 mesoporous molecular sieve with embedded MWW structure Na-ϊφ; # ϊ MM-4MW22 without aluminum source

tt * · * Synthesis of Na-MM-4MW22 was carried out by preparing solutions A, B and C. Solution A

• · · ίι> # ί was prepared by mixing 8.3 g of a smoky bridge with 51.7 g of distilled water and stirring (r.m.p. 196) for 20 minutes. Solution B was prepared by adding 18% g of tetramethylammonium silicate to 11.7 g of sodium silicate continuously by stirring (r.m.p.180) and stirring for 20 minutes. Solution C was prepared, · j; by dissolving 26.3 g of tetradecyltrimethylammonium bromide in 174.3 g of water and * · **, ···] with vigorous stirring (r.m.p. 336) for 20 minutes. Solution B was added slowly (15 *

30 minutes) to solution A with vigorous stirring (r.m.p. 320), and law solution B

Was completely added, the resulting mixture was stirred for an additional 20 min. Solution C was added slowly (20 min) to the mixture (A + B) again under vigorous stirring (r.m.p. 336) and after the addition of solution C, the mixture was stirred for another 20 min.

Thereafter, 4.22 g of the precursor MWW zeolite nucleus prepared above was added to 5 gels (A + B + C) with vigorous stirring (r.m.p. 340) for 20 minutes.

Homogenization of the dispersed MWW was accomplished by further agitation of the gel (r.m.p. 340) for 35 minutes. The gel was then allowed to mature for three hours with stirring (r, m.p. 180) at ambient temperature. The pH of the gel was adjusted and the gel was placed in Teflon cups, which were then placed in an autoclave. The synthesis was carried out at 10 ° C for 100 hours for 96 hours.

After completion of the synthesis, the reactor was cooled for 30 min and the meso-care molecular sieve material embedded in the MWW structure was mixed with distilled water, filtered and washed thoroughly with distilled water for 3 h.

The synthesized Na-MM-4MW22 was dried at 110 ° C and calcined for 10 h in a muffle furnace at 550 ° C using a stepwise calcinom procedure.

Example 19b J Preparation of H-MM-4MW22? ··· 20 g of Na-MM-4MW22 (sodium form prepared above) was ion-exchanged with 1 M: ··; aqueous solution of ammonium nitrate or ammonium chloride for 24 hours at ambient temperature. The mesoporous molecular sieve M-J4-MM-4MW22 obtained after ion exchange was washed thoroughly with distilled water, dried at 110 ° C for 12 hours and calcined at 450 ° C for four hours in a muffle furnace: T: stepwise calcinom.

* ··•••••••••••••••••••••••••••••••••••••••••• 41 119801

Example 20

Synthesis of Na-MM-4MW22-2Al Mesoporous Molecular Sieve Embedded in MWW Using Aluminum Source 5 Example 20a

Synthesis of Na-MM-4MW22-2Al

Synthesis of Na-MM ~ 4MW22-2Al was accomplished by fortifying solutions A, B and C. Solution A was prepared by mixing 8.3 g of fumed silica with 51.7 g of distilled 10 water with continuous stirring (r.m.p, 196) for 20 minutes. Solution B was prepared by adding 18.10 g of tetramethylammonium silicate to 11.7 g of sodium silicate with continuous stirring (r.m.p. 180) and the resulting mixture was stirred for 20 minutes. Solution C was prepared by dissolving 26.3 g of tetradecyltrimethylammonium bromide in 174.3 g of distilled water with vigorous stirring (r.m.p. 336) for 20 minutes. Solution B was added slowly (15 minutes) to solution A with vigorous stirring (r.m.p, 320) and after addition of solution B, the mixture was further stirred for 20 min. Solution C was added slowly (20 min) to mixture (A + B) with vigorous stirring (r.m.p. 336) and after addition of solution C it was stirred for a further 20 min.

4.2 g of the precursor of MWW zeolite cores was prepared in a gel blend with 4.2 g (A + B + C) under vigorous stirring (rmp 340). minutes. The homogenization of the dispersed MWW was further carried out with vigorous agitation of the gel (r.m.p, 340) for 35 minutes. Thereafter, 2.3 g of aluminum isopropoxide was added and stirred for 20 min. The resulting gel was allowed to mature for 3 hours with stirring (r.m.p. 180) at ambient temperature. The pH of the gel was adjusted and the gel was placed in Teflon cups, which were then placed in 300 ml autoclaves. The synthesis was carried out at 100 ° C for 96 h.

After completion of the synthesis, the reactor was cooled and mesoporous.,; The 30 molecular sieve material embedded in the MWW structure was filtered and washed with carefully distilled water for 3 h. The resulting Na-MM-4MW22-2A1 was dried at 42 119801 at 110 ° C and were rebelled at 550 ° C using a stepwise calcification procedure for 10 h.

Example 20b Preparation of H-MM-4MW22 ~ 2Al 10 g of Na-MM-4MW-2Al (sodium form, prepared above) was stained with 1M aqueous ammonium nitrate or ammonium chloride for 24 h at ambient temperature. After ion exchange, the mesoporous molecular sieve material NH? 1 -10 MM-4MW22-2A1 obtained was thoroughly washed with distilled water, dried at Π0 ° C for 12 hours, and re-cured at 450 ° C for four hours in a muffle calcination procedure.

The resulting H-MM-4MW22-2Al had an XRD pattern similar to that of Na-MM-15 4MW22 ~ 2Al, showing that the water treatment of the new mesoporous material and subsequent heat treatment did not affect the stability of the structure.

Example 21 ···

Synthesis of Nn-itJti 20 MM-4MW22 ~ 2Al-35 Mesoporous Molecular Sieve with Embedded MWW Structure Using Aluminum Source Φ • · *: · Example 21a «···

Synthesis of Na-MM-4MW22-2Al-35: * · *: Synthesis of Na-MM-4MW22-2Al-35 was carried out by preparing solutions A, B and C.

: ***: Solution A was prepared by mixing 4.5 g of a smoky bridge with 51.7 g of distilled **. with continuous stirring of water (r, m.p. 196) for 20 minutes. Solution B was prepared by adding 18.10 g of tetramethylammonium silicate to 11.7 g of sodium silicate • · with continuous stirring (r.m.p. 180) and the resulting mixture was stirred for 20 minutes.

Solution C was prepared by dissolving 26.3 g of tetradecyltrimethylammonium bromide in *** 174.3 g of distilled water under vigorous stirring (r.m.p. 336) for 20 minutes 4311901. Solution B was added slowly (15 minutes) to solution A with vigorous stirring (r.m.p, 320), and when solution B was completely added, the resulting mixture was further stirred for 20 min. Solution C was added slowly (20 min) to the mixture (AH-B) with vigorous stirring (r.m.p. 336) and after addition of solution C, the mixture was stirred for an additional 20 min.

4.2 g MWW The zeolite cores prepared in Example 19 were dispersed in the gel mixture (A + B + C) with vigorous stirring (rmp 340) for 20 minutes. The homogenization of the dispersed MWW was performed by further mixing (rmp 340) gee-10 35 minutes. Then 2.3 g of aluminum isopropoxide was added and stirred for 20 min. The gel was then allowed to mature at ambient temperature with stirring for three inches (r.m.p, 180). The pH of the gel was adjusted and the gel was placed in teflon cups which were then placed in a 300 ml autoclave. The synthesis was carried out for 96 h at 100 ° C.

15

After completion of the synthesis, the reactor was cooled and the resulting mesoporous molecular sieve material embedded in the MWW structure was mixed with distilled water, filtered and washed thoroughly with distilled water for 3 h. Synthetated Na-MM-4MW22-2Al-35 was dried at 110 ° C. ° C and calcined · *: * · * 20 at 550 ° C in a muffle furnace using a stepwise calcining procedure for 10 h.

• · *

Example 21b Preparation of H-MM-4MW22-2AI-35 25 ··· V 10 10 g Na-MM-4MW22-2Al-35 (Natile form, prepared above) ion exchange- · * · * ... · brick 1 M aqueous ammonium nitrate for 24 h at ambient temperature. Ioni- • \ f; mesoporous molecular sieve material obtained after exchange NKL-MM- • ·. ***. 4MW22-2A1-35 was washed thoroughly with distilled water, dried at 110 ° C. *. 30 ° C for 12 hours and calcined at 450 ° C for four hours using a stepwise · · ·

• M

* .. * calcination procedure in muffle liquors.

• ψ • · ··· 44 119801

The resulting H-MM ~ 4MW22-2Al-35 had an XRD pattern similar to that of Na-MM-4MW22-2Al-35, showing that the water treatment of the new mesoporous material and subsequent heat treatment did not affect the stability of the structure.

5

Example 22

Preparation of Platinum-Modified H-MM-4MW22-2Al 5 g of H-MM-4MW22-2A1 were loaded with 2 wt% Pt using the impregnation procedure. Impregnation with 2 wt% Pt was performed in a rotary evaporator at 80 ° C for 24 h using an aqueous solution of hexalcloroplatinum alpha. MM-4MW22-2A1 impregnated with 2 wt% Pt was dried at 100 ° C and calcined at 450 UC. The XRD pattern for Pt-H-MM-4MW22-2A1 was similar to that of the parent product Na-MM-4MW22-2A1, showing a new mesoporous molecular sieve embedded in MWW structure} hydrotheemic stability.

Example 23

Preparation of Platinum-Modified H-MM-4MW22-2AI-35 20 g of H-MM-4MW22-2Al-35 was loaded with 2 wt% Pt using the impregnation method. Impregnation with 2 wt% Pt was carried out in a rotary evaporator at 80 ° C for 24 h using an aqueous solution of hexachloroplatinum acid. H-MM-4MW22-2A1-35 impregnated with 2 wt% Pt was dried at 110 ° C and calcined ··· * ... · at 450 ° C. The XRD pattern for Pt-H-MM-4MW22-2Al-35 was similar to that for the parent product Na-MM-4MW22-2Al-35, showing a new mesoporous ···: · · · · · · · · · · · · · · · · · · · stability.

«* · • m • 4 • · · • · a · • a 444 • 4 • 4 4aa • 4 · mmm • ·· 4 a 4aa • 4 4» ··· 45 119801

Examples 24-28

Mesoporous Molecular Sieve with Embedded MOR Zeolite Structure Preparation of MOR Zeolite Thin 5

Two solutions A and B were made to prepare a precursor of MOR zeolite cores. Solution A was prepared by adding 37.8 g of Ludox AS 30 to 6.7 g of piperidine and stirred for 15 min. Solution B was prepared by adding 44 ml of distilled water to 4.6 g of sodium hydroxide and stirred for 10 minutes, followed by addition of 5.9 g of aluminum sulphate and further stirring for 15 minutes. Solution B was slowly added to solution A and stirred vigorously for 15 minutes. The gel was placed in teflon cups and placed in a 300 ml autoclave. Synthesis was carried out for 48 h in a rotary mode at 200 ° C. After completion of the synthesis, the product was filtered, washed with distilled water, dried at 110 ° C and calcined at 550 ° C for 10 hours to give a pre-cursor of MOR zeolite cores.

Example 24a • · ί .: Synthesis of Na-MM-ft: Meso-Maintenance Molecular Sieve with Embedded MOR Structure: ** 20 MO-4MO-96h Without Aluminum Source ·

Synthesis of Na-MM-MO-4MO-96h was carried out by preparing solutions A, B and C. Solution A was prepared by mixing 8.3 g of fumed silica with 51.7 g of distilled water with continuous stirring (rmp 196). . Solution B was prepared by adding 18.10 g of tetramethylammonium silicate to 11.7 g of sodium silicate by continuous clarification (r.m.p.180) and the mixture was stirred for 20 minutes. Solution C was prepared by dissolving 26.3 g tetradecyltrimethylammonium bromide (Flulca) in 174.3 g distilled water with vigorous stirring (r.m.p. 336) for 20 minutes. Solution B was added f · slowly (15 minutes) to solution A with vigorous stirring (r.m.p. 320) and • f ·. *. After the addition of solution B, the resulting mixture was stirred for an additional 20 min. Solution C li-

f · S

The 119801 was slowly (20 min) adjusted to A + B with vigorous stirring (r.m.p, 336) and stirred for a further 20 min after adding C.

Subsequently, 3.7 g of the precursor of the MOR zeolite cores prepared above was added to the gel-5 mixture (A + B + C) with vigorous stirring (r.m.p. 350) for 20 minutes. Homogenization of the Dispergoidim MOR was performed by further agitation of the gel (r.m.p. 350) for 30 minutes. The gel was then allowed to mature for three hours with stirring (r.m.p. 180) at ambient temperature. The pH of the gel was adjusted and the gel was placed in a tefion cup which was then placed in a 300 ml autoclave. Synthesis 10 was performed at 100 ° C for 96 nuclei.

After completion of the synthesis, the reactor was cooled and the resulting mesoporous molecular sieve material immersed in MOR-ralceime was mixed with distilled water, filtered and washed thoroughly with distilled water. The synthesized-15 Na-.MM-MO-4MO-96h was dried at 110 ° C and rebelled at 550 ° C using a stepwise calcination procedure for 10 h.

,. Example 24b • · · * Preparation of H-MM-MO-4MO-96h 9 9 • 99 _ * 20 µ · · * ··· 10 g Na-MM-M0-4M'0-96h (sodium form) , prepared above) was ion-exchanged with 1M aqueous solution of ammonium nitrate or ammonium chloride for 24 h at ambient temperature, the mesoporous molecular sieve obtained after ion exchange * * * · 'NH4-MM-MO-4MQ-96h was washed thoroughly with distilled water, dried at 110 ° C. 12 hours and calcined at 450 ° C for four hours in a muffle bath using a stepwise calcination procedure.

• · • ♦ 9 99 9 1 * · X The XRD pattern of the resulting H-MM-MO-4MO-96h was similar to that of Imin Na-MM-MO- • ·:: 4MO ~ 96h; water treatment of the material. . : 30 ly and subsequent heat treatment did not affect the stability of the structure.

• ·· • · · · · · · ··· 47 119801

Example 25

Synthesis of Na-MM-MO-4MO-96h-2Al Mesoporous Molecular Sieve Embedded in MOR Using Aluminum Source 5 Example 25a

Synthesis of Na-MM-MO? 4MO-2Al

Synthesis of Na-MM-MO-4MO-96h-2Al was performed by preparing solutions A, B and C. Solution A was prepared by mixing 8.3 g of fumed silica with 51.7 g of distilled water while stirring continuously (rmp 196). minutes. Solution B was prepared by adding 18.10 g of letramethylanimonium silicate to 11.7 g of sodium silicate with continuous stirring (r.m.p. 180) and the resulting mixture was stirred for 20 minutes. Solution C was prepared by dissolving 26.34 g of tetradecyltrinethyl anxmonium bromide in 174.3 g of distilled water with vigorous stirring (r.m.p. 336) for 20 minutes. Solution B was added slowly (15 minutes) to junction A with vigorous stirring (r.m.p. 320) and after addition of solution B, the mixture was further stirred for 20 min. Solution C was added slowly (20 min) to mixture (A + B) with vigorous stirring (r.m.p. 336) and after addition of solution C it was stirred for a further 20 min.

• · • · · • * · ··· * • · • * ·. Thereafter, 3.7 g of the MOR zeolite nucleated precursor i, j #! was added to the gel mixture (A + B + C) with vigorous stirring (r.m.p. 350) for 25 minutes * and then 1.9 g of aluminum isopopoxide was added to the gel and stirred for 30 minutes. The gel was then allowed to mature at ambient temperature with stirring for 3 hours (r.m.p. 180). The pH of the gel was adjusted and the gel was placed in a Teflon cup mirror placed in 300 ml autoclaves. The synthesis was carried out for 96 h at iT at 100 ° C.

• · · · *: After completion of the synthesis, the reactor was cooled for 30 min and heated. · ·. the porous molecular sieve material embedded in the MOR structure was mixed with distilled water, filtered, and washed thoroughly with distilled water for 3 h.

* · "The synthesized Na-MM-MO-4MO-96h-2Al was dried at 110 ° C and lcal-1 · · · · 48119801 was sintered at 550 ° C using a stepwise calcining procedure for 10 h.

Example 25b Preparation of 5 H-MM-MO-4MO-96h-2Al 10 g of Na-MM-MO-4MO-96h-2Al (sodium form prepared above) was deionized with 1M aqueous ammonium nitrate or ammonium chloride for 24 h at ambient temperature. temperature. Homemaker Uceen meso-maintenance molecular sieve material 10 NH4-MM-MO4M0-96h-2Al was washed thoroughly with distilled water, dried at 110 ° C for 12 hours and calcined at 450 ° C for four hours in a batch furnace using a stepwise calcination procedure.

The XRD pattern of the resulting H-MM-MO-4MO-96h-2Al was similar to that of Na-MM-15 MO-4MO-96h-2Al, showing that the water treatment of the new mesoporous material and subsequent heat treatment did not capture structure stability .

• · M: Example 26 • Φ i ** Synthesis of Na-MM- ♦ M. Meso-pore Molecular Sieve with MOR Granule Immersion * MO-4MO-9 611-2A1-35 using an aluminum source Φ φφ ·· φ Φ · Φ

Example 26a Synthesis of O Na-MM-MO-4MO-96h-2Al-35 25 • Φ Φ

Synthesis of V * Na-MM-MO-4MO-96h-2Al-35 was carried out by preparing solutions A, B

φ φ φ and C. Solution A was prepared by mixing 4.4 g of fumed silica with 51.7 g of distilled water with continuous stirring (r.m.p. 196) for 20 minutes. Solution B was prepared by adding 18.10 g of tetramethylammonium silicate to 11.7 g of sodium silicate, 30 curves with continuous stirring (r.m.p. 180) and the resulting mixture was stirred for 20 minutes. Solution C was prepared by dissolving 26.3 g of tetradecyltrimethylamine ammonium 49 119801 bromide in 174.3 g of distilled water with vigorous stirring (r.m.p. 336) for 20 minutes. Solution B was added slowly (15 minutes) to solution A with vigorous stirring (r.m.p. 320) and after addition of solution B, the resulting mixture was further stirred for 20 min. Solution C was added slowly (20 min) to the mixture (A + B) with vigorous stirring (r.m.p. 336) and after the addition of solution C, the mixture was stirred for an additional 20 min.

3.7 g of the MOR zeolite nucleus precursor prepared in Example 45 was added to the gel mixture (A + B + C) with vigorous stirring (r.m.p. 320) for 25 minutes.

1.9 g of aluminum isopropoxide were then added and stirred for 20 min. The Saadim gel was then allowed to mature at ambient temperature for 3 hours with stirring (r.m.p. 180). The pH of the gel was adjusted and the gel was placed in Teflon cups which were then placed in a 300 ml autoclave. The synthesis was carried out for 96 h at 100 ° C.

15

After completion of the synthesis, the reactor was cooled for 30 min, and the meso-porous molarcyl sieve material embedded in the MOR granule was mixed with distilled water, filtered and washed thoroughly with distilled water for 3 h. Syn-· ·: tetrazed Na-MM-MO-4MO-96 The -35 was dried at 110 ° C and the · · ·: * · * 20 was sintered at 550 ° C using a stepwise calcination procedure for 10 h.

• · ..! · * Example 26b *.,. Preparation of H-MM "MO-4MO-96h-2Al-35 25 ·· · 10 g of Na-MM-MO-4MO-96h-2Al-35 (sodium form, prepared above) was ion-exchanged A 1 M aqueous solution of ammonium nitrate or ammonium chloride at ambient temperature for 24 hrs., The mesoporous molecular weight material obtained after the ion exchange was washed thoroughly with distilled water ···, *. was dried at 110 ° C for 12 hours and calcined at 450 ° C in a muffle furnace using a stepwise calcination procedure.

• · • · ··· 50 119801

Example 27

Preparation of Platinum-Modified H-MM-MO-4MO-96h-2Al-35 5 g of H-MM-MO-4MO-96h-2Al-35 was loaded with 2 wt% Pt using the impregnation method . Impregnation with 2 wt% Pt was carried out in a rotary shaker at 80 UC for 24 h using an aqueous solution of hexaldoraplatinic acid. MM-MO-4MO-961i-2Al-35 impregnated with 2 wt% Pt was dried at 100 ° C and calcined at 450 ° C. The XRD pattern for Pt-H-MM-MO-4MO-96h-10 2Al was similar to that of the Na-MM-MO-4MO-96h-2Al aged product, demonstrating the hydrothermal stability of a new mesoporous molecular sieve embedded in MOR-ralcene. .

Example 28 Preparation of Platinum Modified H-MM-MO-4MO-9611-2AI-35 To 5 g of H-MM-MO-4MO-96h-2Al-35 was loaded with 2 wt% Pt of impreg. -. . synchronization techniques. Impregnation with 2 wt% Pt was performed in a rotary evaporator at t · · "* * at 80 ° C for 24 h using an aqueous solution of hexaldoraplatinic acid. 2 p- · · *" 20% Pt impregnated with H-MM-MO- 4MO-96h-2Al-35 was dried at 100 '···] UC and calcined at 450 ° C. The XRD pattern for Pt-H-MM-MO-4MO-96h-2Al-35 was similar to that for the parent extract Na-MM-MO-4MO-96h-2Al-35, showing a new mesoporous molecular sieve with an embedded MOR structure, • ♦ * · · · * hydrothermal stability.

25 ··· • · ·

EXAMPLE 29 Thermal Stability Test *: The Thermal Stability Test was conducted by heating the inventive materials to a temperature of 700 ° C, 800 ° C. , 900 ° C and 1000 ° C in the air for 24 hours.

• m m m ··· After this treatment, the materials were analyzed using BET and XRD.

• · ··· 51 119801

An example of XRD diagnosis for 1000 µC treated samples is given in Figure 5. No differences in material structure were observed with BET or XRD.

Example 30 5 Mechanical stability test

The mechanical stability test of the materials according to the invention was carried out by compressing the material powder with a force of 20,000 Newton. The formed tablets were crushed and screened to different particle sizes. XR..D and BET measurements of different fractions of screened material 10 were analyzed using XRD and BBT. No differences were found in the XIID charts or BET areas and the pore size. The results are shown in Table 4 below, which provides examples of the results of N2 adsorption measurements of mechanical stability experiments.

15 Table 4

Area and BET BJH BET BJH BET BJH

porosity N2 area by pore-pore-pore adsorption (m2 / g) (m2 / g) volume volume diameter diameter: _ (cm3 / g) (cm3 / g) (A) __ (A) j \ * H- MM5-96h-4ZS 775 731 0.594 0.513 32 28 * '0.6 -0.85 __________: · ί- | H-MM5-96h-4ZS 748,682 0.563 0.489 31 29 ·: **: <0.007 ···: * "· Example 31 ···

Repeatability of methods ··· • «· * * · · 1. 20 Same procedure for the production of Ices-like material (Example 8) · * ·. *. was repeated on different scales. The batches had very similar properties as 1 · t · · · shown in Table 5, which gives the results of the repeatability test.

• * • · ·· »t · • ·» • · • · · · # # 52 119801

Table 5

Si (w-%) AI (w-%) Si / AI MCM-41 a0 MFI a0 _____________ (A) _ (ÄO__

Example 8 42.3 3.9 ___ 10/1 ___ 38 ___ 1.9.72

Example 8 42.7 3.8 10.9 36 19.73 (10x larger scale) _

EXAMPLES 32-41 1-Decene Oligomerization Using Catalysts of the Invention Oligomerization of 1-delceene using materials of the invention as catalysts showed high activity, deactivation and regenerability of the catalysts of the invention. Invented catalyst materials and 10 prior art control catalysts were tested in 1-deceme oligomerization. The experiments were performed in a batch reactor with stirring. The reaction temperature was 200 ° C. The reaction time was 24 h. The pressure in the reactor was about 20 bar.

The reaction products were analyzed by gas chromatography and GC distillation and the peaks. 15 were identified based on the number of carbons in the molecule. Molecules having a number of carbonyls above 20 were identified as lubricant components in GC analysis.

t 'Molecules that boiled above 343 ° C were identified by a lubricant component in GC distillation.

The catalysts used in the experiments were regenerated in a muffle furnace at 540 ° C in air at 9 9 9 V *.

999 The results of the 1-decene oligomerization reaction experiments are summarized in Table 6 below.

J ...: 25 • · • · · • 99 • · · · · · · 999 53 119801

Table 6 _______________ _

Example Catalyst Conversion Selectivity% Lubricant to Lubricant Yield ____% __% 32 ZSM-5 20 3 0.5 (e.g. 1) 33 MSA-1 0.5 87 0.4 (e.g. 2) 34 MSA-3 1 87 0, 9 (Ex. 4) 35 MCM-41 45 97 29 (Ex. 5) 36 H-MM5-96h-4ZS-71 97 69 __2A1-35 (Ex. 9) _ 37 H-MMBE-96h-4B-2Al 78 94 7 ~ 3 (e.g. 12) 38 H-MMBE-96-4B -2 AI- 80 ~ 93 74 35 (e.g. 13) 39 H-MM5-96h-4ZS- 70 98 ~ 69 2A1-35, Regenerated 40 HMMBE-96h-4B -2A1 76 96 ~ 73 Regenerated: 41 H-MMBE-96h-4B- 79 93 72 ··· · j ·. 2A1-3 5, regenerated • · · .............. I 1 ----- 1— ................... .

«• 1 · * 1 1. Examples 42 and 43 * ·. Reaction of isobutene using the materials of the invention as catalysts * 1 · · · · · c

· 1φ J

Using the materials of the invention as catalysts, the reaction reactions of isobutene were performed, which showed high activity and low deactivation of the catalysts of the invention. The catalysts were tested in a fixed bed reactor at a reaction temperature of 100 ° C at 20 bar with WHSV 20. High activity of the catalyst was observed, but no dealctivation was observed. As an example of the isobutene reaction, the catalyst of Example 8 is stretched to the reference catalyst (Example 1) in Figure 7: dimerization of isobutene.

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M

• «• · • · · 54 119801

Examples 44-47

Paraffin Isomerization Experiments Using Catalysts of the Invention The object of the 5-n-butane isomerization column was to confirm the chemical nature of the interaction in the mesoporous molecular sieve of the invention embedded in the MFI structure, the formation of strong Bmnsted acid sites and hydrothermic new material. The isomerization of n-butane was used as a test reaction to evaluate the acidity of the catalysts. Isomerization of n-Bulan was performed with proton forms of novel mesoporous molecular sieve catalysts to evaluate the acidic properties. It was found that the H-form (H-MM5 ~ 96h-4ZS-2A1-35) catalyst with the lowest Si / Al ratio had the highest conversion of n-butane, clearly indicating that strong Bnefnsted acid sites were formed and that a mesoporous molecular sieve embedded in the MFI structure with 15 real chemical bonds.

Regeneration of the H-form and Pt-H-MM5 catalysts was carried out in the presence of air at 450 ° C for two hours. The objective of the regeneration was to evaluate the feasibility of recovering the activity of the catalyst and also to evaluate the hydrothermal stability of the catalyst during regeneration of the catalyst because of the formation of water during the regeneration process. It was confirmed that both the H- * 'form and the Pt-modified catalyst retained their catalytic ... activity almost completely, ensuring hydrothermal stability of the structure.

The isomerization of 25 n-butane to isobutane was investigated with a proton-form catalyst and ··· V * 2 wt% Pt-H-MM5-96h-4Zs-2Al catalysts in a fixed bed microreactor which was ···: · Made of quartz. The experiments were carried out at almost atmospheric pressure and the amounts of the catalysts used were in the range of 0.3 to 1.0 g. The n-butane reactant was fed to the reactor using hydrogen as carrier gas. Product analysis was performed in real time ···. *. 30 gas chromatography equipped with an FI detector and a capillary column.

The results of the n-butane isomerisation test reactions are shown in Table 7 which shows the isomerization of n-butane at 450 ° C, WHSV 1.23 h'1, n-butane / hydrogen in a 1: 1 ratio.

Table 7. Conversion of n-butane

Example no. catalyst Conversion (w-%) 44 H -MM5-96h-4ZS-2Al 40_45_H-MM5-96h-4ZS-2 Al-3 5__70_ _46_ Pt-H-MM5-96h-4ZS-2Al-35-C- fresh__87_ 47 Pt-H-MM5-9 6h-4ZS-2 Al-3 5-C-Regen. 85 5

Examples 48 and 4.9 1-Butene Isomerisation Experiments Using the Materials of the Invention as catalysts The purpose of the 10 1-butene isomerization bridge was to ensure the Bransted acidic structure of the strong Brinsted acidic structure of the interaction, the chemical nature of the mesenchymal mesoporous molecular sieve embedded in the MFI structure.

The isomerization of 1-butene was also used as an experimental assay for the study of the iso- isomer of 1-butene. mercerization to isobutene. In addition, the aim was to explore the possibility of regeneration

• »I

* ·· catalyst used and evaluate whether the catalyst retains its catalytic activity after regeneration. It was found that the catalyst used could be regenerated 1- * · **. · ··. after isomerization of butene. In addition, the conversion of 1-butene (97.2 mol%) with the regenerated catalyst was almost the same as with the corresponding fresh catalyst (97 mol%), which also showed the hydrolytic stability of the catalyst.

The isomerization of f butene-1-butene to isobutene was investigated with a proton-form H ~ MM5-96h- · · ** "4Zs-2Al catalyst in a quartz solid bed reactor. Experiments ··· *, '··· * 25 was performed under near atmospheric pressure at 350 ° C WHSV for 10 h. The 1: 1-butene reagent was fed to the reactor using hydrogen as carrier gas at a ratio of * ··········· 119801 1: 1. equipped with an FI detector and a capillary column, a condenser was placed after the GC for the sampling of heavier compounds, liquid products. The first sample was taken after 10 minutes of use (TOS) .The first 5 10 samples were taken every 1 hour and subsequent samples every 3 hours.

Example 50

Hole opening assay using material of the invention as catalyst 10 The activity and selectivity of the catalyst of the invention in a decalin ring opening assay were tested in 50 ml autoclave at 250 ° C in 20 bar hydrogen. Decalin (10 mL ~ 9.0 g) was added to a reactor containing 1 g of the reduced catalyst at 250 ° C at room temperature. The pressure was increased to 10 bar with hydrogen. The reactor was then placed in an oil bath at 250 ° C. When the temperature of the 15 reactors reached 250 ° C, the hydrogen pressure was adjusted to 20 bar. Reaction time 011 five tute. The reactor was then rapidly cooled to -10 ° C. The reactor was weighed after cooling. The pressure was released from the autoclave. Kata-,. the lithium product was taken into a sample container and the GC sample was filtered as a filter with a needle. The conversion of decalin was 81% and the selectivity for the ring-opening products was 32% with the catalyst prepared according to the invention. »» · • · · * * *.

Examples 51 and 52 ... 25 Hydrocracking experiments using the material of the invention as a catalyst The catalyst according to the invention (Example 17). catalyst) activity and selectivity in the hydrocracking reaction were tested in an autoclave at 300 ° C (Example 51) and ··· 350 µC (Example 52) at 30 bar hydrogen pressure. A paraffin mixture (about · * ·, {30 80 g) was added to the reactor containing 2 g of reduced catalyst at 450 ° C at room temperature. The pressure was increased with hydrogen to 30 bar when the reactor temperature reached 300 ° C (Example 51) or 350 ° C (Example 51). Example 52), the hydrogen pressure was adjusted to 30 bar, the reaction time was 65 hours, the reactor was weighed after cooling, the pressure was released from the autoclave, the products were analyzed by gas chromatography, the paraffin conversion was 60% (Example 51) and 65% (e.g. Erkki 52) and se-5 had a 100% selectivity for cracking products in both cases.

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• ·· • · · • 1 ♦ * · ♦ • · «*» »·· ♦ 1 · # · • · · · · · · · · · · · · · · · · · 9 9 9 9 9 9 • 99 9 9 999 9 9 9 9 999 9 9 9 9 9 9 9 · 1 • · ·· • · »« 1 ·

Claims (16)

119801 Catalytic material, characterized in that the catalytic material is a meso-porous molecular sieve embedded in zeolite and the catalytic material 5 is thermally stable at a temperature of at least 900 ° C. Catalytic material according to claim 1, characterized in that the catalytic material has a specific surface area in the range of 1400 to 500 m / g, preferably 1200 to 600 m 2 / g. 10 Catalytic material according to claim 1 or 2, characterized in that the catalytic material comprises a mesoporous molecular sieve selected from the group M41S, preferably a mesoporous molecular sieve selected from the group consisting of MCM-41 or MCM-48. 15 Catalytic material according to any one of claims 1 to 3, characterized in that the catalytic material comprises a middle pore zeolite selected from the group consisting of MFI, MTT, TON, AEF, MWW and FER zeolites, or large pores. a zeolite selected from BEA, FAU, MOR zeolites, preferably zeolite !! 20 ti is zeolite of MFI, MTT, AEF, BEA, MWW or MOR. • * • ·· «• · · • · · ***. Catalytic material according to any one of claims 1 to 4, characterized by · ·. because the mesoporous molecular sieve is MCM-41 or MCM-48 and the zeolite is · ♦ · * ”* MFI or BEA zeolite. • · • · · * · 25 ... Catalytic material according to any one of claims 1 to 5, characterized in that the catalyst is in prototype, repentant or modified metal. • · • · · · · · · · 30 7. Catalyst, characterized in that the catalyst comprises 90 to 10% by weight of the catalytic material according to any one of claims 1 to 6 and 10 to 90% by weight of a support. • * ·· • · • · · »* 119801 A process for the preparation of a mesoporous molecular sieve embedded in a zeolite, characterized in that the process comprises the steps of: a) preparing zeolite cores from a silicon source and an aluminum source and a directional agent, or a silicate or aluminosilicate precursor for a zeolite core; the material is removed by a stepwise calcination procedure; b) preparing a gel mixture of a mesoporous molecular sieve from a source of silicon, optionally an aluminum source, and a surfactant (S); c) introducing the zeolite cores or the silicate or submicosilicate precursor prepared in step a) into the mesoporous molecular sieve gel mixture obtained in step b) and the zeolite cores or silicate or. the aluminosilicate precursor is homogenized and dispersed on molecular sieve gel; d) subjecting the mixture of step c) to gel maturation in a mixed blend; e) performing the hydrothermal synthesis of the mixture of step d) while maintaining the mixture: under suitable conditions including a temperature in the range of about 100 ° C to about 200 ° C, under static and dynamic mixing until crystals form. (F) collecting the crystals; (g) washing the solid; (h) drying the solid; and (i) surfactant (S); ) is partially or completely removed in a stepwise · · · · · 25 calcining procedure and optionally the structural agent is removed unless removed in step a) to give a catalyst which is a · · · · · mesoporous molecular sieve, embedded in zeolite • · · • M A process for the preparation of a mesoporous molecular sieve embedded in a zeolite according to claim 8, characterized in that the source of silicon is in the form of a). selected from silicon oxides, preferably colloidal silica, solid silica or smoky silica. A process for the preparation of a mesoporous macromolecular sieve embedded in zeolite according to claim 8 or 9, characterized in that the silicon source or sources in step b) is selected from silicon compounds having an organic group and an inorganic silicon source, having an organic group is tetraethoxysilane, tetramethylammonium silylate or tertraelylammonium silylate, and the inorganic source of silicon is sodium silicate, water glass, colloidal silica, solid silylca or fumed silica, Process for the preparation of a mesoporous molecular sieve embedded in a zeolite according to any one of claims 8 to 10, characterized in that the source of aluminum is selected from aluminum sulphate (Al 2 (SO 4) 3 '18 H 2 O), hydrogenated aluminum hydroxides, aluminates, aluminum isopropoxide. and alumina, A method according to any one of claims 8 to 11 for mesoporous moles! for the manufacture of a sieve embedded in a zeolite sieve, characterized in that the i *** 20 surfactant is selected from alkyl trimethylammonium halide compounds of the general formula C "H2n + i (CH3) 31NX, where n = 12-18, X = Cl , Br, and preferably ^ · · "1 surfactant is n-hexadecylthiomethylanimmonium bromide, n-helcadecyltrimethylammonium chloride, cetyltrimethylammonium bromide and« · «cetyltriethylammonium bromide. Process for the preparation of a mesoporous molecular sieve embedded in zeolite according to any one of claims 8 to 12, characterized in that: 1 additional source of aluminum is selected from alumina, preferably it is · ·, ···. aluminum-isopropolcsidi. ·· 2 30 ♦ · • ·· • · · 2 • · 119801 Use of a catalytic material according to any one of claims 1 to 6 or a mesoporous molecular sieve embedded in a zeolite prepared by the process according to claim 7 or one of claims 8 to 13, in the treatment of hydrocarbons, preferably o dimerization, oligomerization of olefins, olefins. in hydrocarbon cracking, aromatic allcylation, light hydrocarbon aromatization, etherification, dehydrogenation and ring-opening reactions. Use of the catalytic material according to claim 6 in the isomerization of light paraffins, isomerization of long chain paraffins, hydrogenation, hydrocarbons, desulfurization with hydrogen, hydrogen removal with hydrogen, dehydrogenation, reforming, Fisher-Tropsch. Use according to claims 13 or 14 for oligomerization of 1-decene, dimerization of isobutene, isomerization of n-butane, isomerization of 1-butene and ring opening of decalin. · · * «· ** ** M M ** M M M M M M M M M M M M M M M M M M M M M M M M M M M M * · # • · · «*« It It It It It It It It M M M M M M M M M M M M M M M M M M M M M M M M M M M M M M * * 119801