KR100446441B1 - Method for preparing non-crystalline mesoporous molecular sieve substance using mixture of halogenated alkyltrimethyl ammonium and silicate as surfactant - Google Patents

Abstract

PURPOSE: To provide a method for preparing a non-crystalling mesoporous molecular sieve substance, which is able to improve strong hydrothermal stability of the molecular sieve substance and does not cause clogging of one dimensional linear cavities. CONSTITUTION: The method comprises the steps of (a) preparing a mixture aqueous solution of halogenated alkyltrimethyl ammonium and silicate, the halogenated alkyltrimethyl ammonium being represented by a formula 1 of CnH2n+1(CH3)3NX, wherein n is an integer of 12-18 and X is Cl or Br; (b) adding at least one organic salt or inorganic salt that is able to be coupled to a monovalent cation and dissolved into water to the mixture aqueous solution of the step (a) with mixing; (c) performing hydrothermal reaction of the mixture prepared from the step (b) to obtain a precipitate of a desired molecular sieve substance with keeping pH, temperature and time at constant; (d) filtering and drying the precipitate of the step (c); and (e) sintering the dried precipitate of the step (d).

Description

Process for preparing amorphous mesoporous molecular sieve material

The present invention relates to a method for preparing an amorphous mesoporous molecular sieve material and to the molecular sieve material, and more particularly, to the catalytic application of the M41S series of the US Mobil Corporation, a conventional mesoporous molecular sieve. A method for preparing a novel amorphous medium porous molecular sieve material in which a uniform diameter diameter cavity structure can be disordered in three dimensions while enhancing thermal stability and hydrothermal stability, which have been used as limitations, and can easily occur. A molecular sieve material produced by the present invention.

Among the solid materials known so far, materials having a uniform cavity size such as porous crystalline aluminum silicate zeolite and porous crystalline aluminum phosphate AlPO ₄ have only molecules smaller than the size of the channel inlet inside the cavity. It is defined as molecular sieve because it can be selectively adsorbed or passed through the cavity. Zeolites and AlPO ₄ materials are all crystalline materials that are characterized by a completely regular configuration of both the arrangement of constituent atoms and the arrangement of internal cavities from the point of view of crystallography. These fully crystalline molecular sieves are either produced in nature or produced through hydrothermal reactions. Hundreds of species have been discovered or synthesized so far, and due to their inherent properties such as selective adsorption, acidity and ion exchange ability, It plays an important role as a catalyst or catalyst carrier in the chemical industry. Petroleum cracking reactions using ZSM-5 or aromatic conversion reactions of paraffins using platinum-supported KL-zeolites are examples of catalytic processes utilizing the characteristics of zeolites. However, fully crystalline molecular sieves have a disadvantage that they cannot be used for the reaction of molecules larger than the cavity size because the cavity size is relatively small (1.3 mm or less). Among these, recently, Mobil researchers reported a series of mesoporous molecular sieves named M41S family including MCM-41 and MCM-48 in US Pat. Nos. 5,057,296 and 5,102,643. These molecular sieves have a structure in which mesopores of uniform size are arranged regularly. Conventional molecular sieves are prepared using inorganic cations or organic cations as template materials, whereas mesoporous molecular sieves are prepared via a liquid crystal template route using surfactants as the template material. By adjusting, the size of the cavity can be adjusted from 1.6 to 10 mm. Since then, in addition to the M41S family, Stucky and co-workers of the University of California, U.S., have reported a mesoporous molecular sieve named SBA-1,2,3 in Science, 268,1324 (1995). These mesoporous molecular sieves have a structure in which the arrangement of constituent atoms is similar to that of amorphous silica in the crystallographic view.

The mesoporous molecular sieve has a larger pore size than that of conventional zeolites and a regular arrangement of the pores, which can be applied to adsorption, separation and catalytic conversion of large molecules. The most widely studied of these mesoporous molecular sieves is the MCM-41, which has a structure in which one-dimensional linear mesopores are uniformly arranged in a hexagonal arrangement, that is, in a honeycomb shape, and the specific surface area measured by the BET method is 1000. m ² g ^-1 or so. Although slightly different depending on the synthetic conditions, the MCM-41 samples published by the early researchers produced 20-25% of the shrinkage of the structure before firing to remove the template material. This is a phenomenon caused by condensation. However, J. Chem. Soc., Journal of Chemical Society, Chem. commun., 1995 p 711 shows that the shift of the equilibrium of the silicic acid condensation reaction to the product by adjusting the pH of the reaction mixture during the hydrothermal preparation of MCM-41 results in condensation of silanol groups in the reaction mixture in advance. As a result, it has been reported that the weak thermal stability can be overcome and the uniformity of the structure can be greatly improved. The MCM-41 thus prepared has only a slight structural contraction even when heated to 900 ° C. under an oxygen atmosphere containing air or 2.3 kPa of water vapor, and has a stable structure, and has a structure up to 500 ° C. under a 100% -vapor atmosphere of 1 atmosphere. Has excellent thermal stability that does not collapse. Moreover, when aluminum is substituted in the backbone of MCM-41, it can be used in many applications requiring acid point and ion exchange properties as well as conventional zeolites.

However, despite the excellent thermal stability of the MCM-41, when the water temperature is 60 ° C or more in water, the silicate, which forms the structure of the molecular sieve, is hydrolyzed, and the structure starts to disintegrate slowly. Doing so will completely lose its structural characteristics. This weak hydrothermal stability is due to the catalytic conversion of the catalytically active material or the transition metal such as platinum ions, which requires hydrothermal conditions such as the use of hydrogen peroxide as the oxidant when the molecular sieve substituted by titanium is used in the partial oxidation reaction. This is a very serious limitation when temperatures above 60 ° C. are required when supported in molecular sieves. In addition, since MCM-41 has a straight cavity, it is common to prevent the formation of coke as it decomposes during the firing process to remove the mold material, thereby preventing the formation of medium pores, and to support a catalytically active material such as platinum or palladium. Even when the passage is easily blocked, the diffusion of molecules is not easy, so that the metal particles present inside the blocked passage cannot contact the reactants, and only the metal particles present at both ends exhibit catalytic activity, thereby rapidly decreasing the activity of the catalyst. Therefore, there is an urgent need to improve the hydrothermal stability of these mesoporous molecular sieves and to solve the problem of diffusion of molecules due to cavity blockage.

The present invention aims to provide a method for preparing a new mesoporous molecular sieve material without the problems of the mesoporous molecular sieve posed in the above, that is, the weak hydrothermal stability and the blockage of molecular diffusion due to the blockage of the one-dimensional linear cavity. Another object is to provide novel amorphous mesoporous molecular sieve materials produced by the process.

Figure 1 shows the X-ray diffraction pattern of the KIT-1 material prepared in one embodiment of the present invention (a) is a KIT-1 material before the firing treatment, (b) is a KIT-1 material after the firing treatment .

Figure 2 shows the X-ray diffraction pattern of the KIT-1 material prepared in another embodiment of the present invention (a) is a KIT-1 material before the firing treatment, (b) is a KIT-1 material after the firing treatment to be.

Figure 3 shows the X-ray diffraction pattern of the KIT-1 material prepared in another embodiment of the present invention (a) is a KIT-1 material before the firing treatment, (b) is a KIT-1 material after the firing treatment to be.

Figure 4 shows the X-ray diffraction pattern of the KIT-1 material prepared in another embodiment of the present invention (a) is a KIT-1 material before the firing treatment, (b) is a KIT-1 material after the firing treatment to be.

FIG. 5 shows the change of the value of d _{100 in} the form of X-ray diffraction according to the change in alkyl chain length of the surfactant of KIT-1 of FIG. 1, where (O) is the material before the firing treatment and Substance after firing.

6 is an electron micrograph of the KIT-1 sample of FIG.

7 is an electron micrograph obtained after the platinum cluster is supported on the KIT-1 sample of FIG.

8 is an adsorption-desorption isotherm of nitrogen obtained at liquid nitrogen temperature for KIT-1 synthesized using EDTANa ₄ of FIG.

9 is a cavity size distribution curve of a KIT-1 sample obtained by the method of Horvath-Kawazoe from the adsorption-desorption isotherm of nitrogen of FIG.

10 is a cavity size distribution curve obtained by the BJH method for each sample in which the alkyl chain length of the surfactant was changed as in the case of FIG.

FIG. 11 is an X-ray diffraction pattern obtained after thermal stability measurement by performing various heat treatments on the calcined KIT-1 sample of FIG.

FIG. 12 is a diagram showing the change in X-ray diffraction pattern over time by placing the calcined KIT-1 sample of FIG. 1 in boiling water at 100 ° C. FIG.

Fig. 13 shows the results of solid-state magic angular rotation (MAS) aluminum-27 nuclear magnetic resonance spectroscopy (NMR) experiments after various treatments of a KIT-2 sample according to another embodiment of the present invention.

14 shows the results of a temperature controlled desorption (TPD) experiment of ammonia gas after various treatments of a KIT-2 sample (Si / Al = 40) in another embodiment of the present invention.

FIG. 15 shows xenon-129 nuclear magnetic resonance measured on a 2 wt% Pt / KIT-2 sample loaded on a KIT-2 sample (Si / Al = 40) using an ion exchange method in another embodiment of the present invention. Experiment result.

The production method of the present invention for achieving the above object

A) preparing a mixed aqueous solution of alkyltrimethylammonium halide and silicate of formula (I) as a surfactant;

B) one or two or more of an organic salt or an inorganic salt which can be combined with a monovalent cation and dissolved in water is selected and added to the mixed aqueous solution of step (A) and mixed;

(C) hydrothermally reacting the mixture of step (B) by maintaining pH, temperature and time to form a precipitate of the final desired molecular sieve material;

D) filtering and drying the precipitate of the molecular sieve material formed in step (C); And

(E) firing the precipitate filtered and dried in step (D).

[Formula I]

Wherein n is an integer from 12 to 18 and X is Cl or Br.

Another manufacturing method of the present invention

(1) preparing a mixed aqueous solution of at least one selected from the group consisting of alkyltrimethylammonium halides, silicates and aluminates, boronates and 3d transition metal salts of the periodic table of formula (I) as surfactants;

(2) one or two or more organic salts or inorganic salts which can be combined with a monovalent cation and dissolved in water are selected and added to the mixed aqueous solution of step (1) and mixed;

(3) hydrothermally reacting the mixture of step (2) by maintaining pH, temperature and time to form a precipitate of the final desired molecular sieve material;

(4) filtering and drying the precipitate of the molecular sieve material formed in step (3); And

(5) the step of firing the precipitate filtered and dried in step (4).

In order to achieve another object of the present invention, the present invention provides the steps (A), (B), (C), (D) and (E) or (l), (2), (3), and (4). And amorphous medium porous molecular sieve materials prepared by step (5), wherein the cavity structure with uniform diameter is disordered in three dimensions.

Hereinafter, the present invention will be described in more detail with reference to the following examples and accompanying drawings.

As the surfactant used in the present invention, the above-mentioned halogenated alkyltrimethylammonium of formula (I) is used, preferably hexadecyltrimethylammonium chloride (HTACl), dodecyltrimethylammonium bromide (DTABr), or tetradecyl bromide. Trimethylammonium (TTABr) and octadecyltrimethylammonium bromide (OTABr). Examples of silicates used in step (A) include sodium silicate and the like, aluminate, boronate and periodic table used in step (1). Examples of salts in which one or more selected from the group consisting of 3d transition metal salts in the phase are sodium aluminate (NaAlO ₂ ). In addition, organic salts or inorganic salts that can be combined with the monovalent cations (eg, Na ⁺ , K ⁺ , NH ₄ ⁺ , etc.) used in steps (B) and (2) and dissolved in water. Salts include NaCl, KCl, CH ₃ COONa, NaBr, Na ₂ SO ₄ , NaNO ₃ , NaClO ₄ , NaClO ₃ , ethylenediaminetetraacetic acid sodium (EDTANa ₄ ), adipic acid disodium salt, 1, Sodium 3-benzenedisulfonic acid 1,3-benzendisulfonic acid disodium salt), or sodium nitrilotriacetate is preferred. In the first preparation method, based on 1 mole of alkyltrimethylammonium halide of formula (I), it may be combined with a monovalent cation (eg, Na ⁺ , K ⁺ , NH ₄ ⁺ , etc.) 1.0 to 15.0 moles of organic or inorganic salts soluble in water and 1.0 to 15.0 moles of the silicate are preferably used. Also in the second production method, based on 1 mole of alkyltrimethylammonium halide of formula (I), it may be combined with a monovalent cation (eg, Na ⁺ , K ⁺ , NH ₄ ⁺ , etc.). 1.0 to 15.0 moles of organic or inorganic salts which can be dissolved in water and 1.0 to 15.0 moles of said silicate and 0.0025 to 1.5 moles of salt selected from the group consisting of aluminates, boronates and 3d transition metal salts on the periodic table. It is good to be used. In addition, it is preferable to add an aqueous ammonia solution in steps (A) and (1) to facilitate the role of the surfactant. Also in the last step, it is preferable to perform a calcination process at between 500 and 600 ° C. under an air atmosphere.

Both KIT-1 and MCM-41 have a very large specific surface area (about 1000 m ² g ^-1 as measured by the BET method) and have a very uniform cavity size distribution (from Horvath-Kawazoe's method from nitrogen adsorption isotherms). Although the line width at the middle height of the cavity size distribution curve) shows a common point, the difference in the connection manner of the cavities is a characteristic difference in these structures. Invented by Mobil, MCM-41 has a cylindrical or hexagonal cavity with a uniform diameter (more than 2 mm and can be adjusted according to the manufacturing conditions) and has a hexagonal structure like a honeycomb structure. It is very large compared to the diameter. In contrast, KIT-1, which is a subject matter of the present invention, has a structure in which a passage length is short in a range of 2-10 mm, and these passages are randomly connected in three dimensions like the structure of a scrubber fiber. Due to the nature of the one-dimensional passage blockage can be prevented. KIT-1 also exhibits superior thermal and hydrothermal stability as compared to MCM-41.

Halogenated alkyltrimethylammonium used in KIT-1 forms colloidal particles as surfactants, and ions formed by dissociation of added salts (NaCl, KCl, EDTANa _4, etc.) cause electrostatic interaction with the colloidal particles. Disorganize the structure of the particles (micelle). When the silicate ion is added to the aqueous solution, the silicate ions are enclosed around the disordered liquid crystal structure in the aqueous solution, and the silicate ions are polymerized through the hydrothermal reaction to form KIT-1 of the mesoporous molecular sieve and the surfactant. do. The KIT-1 thus obtained can be removed by casting the calcination process between 500 and 600 ° C. in an air atmosphere.

1 is an X-ray diffraction of a KIT-1 material prepared in Example 1 with a molar ratio of reactants in the reaction mixture of 1 HTACl: 0.15 (NH ₄ ) ₂ O: 4 EDTANa ₄ : 4 SiO ₂ : 400 H ₂ O As a form, (a) is a KIT-1 substance before baking, and (b) is a KIT-1 substance after baking. 2 shows sodium adipate as a salt in Example 3 and the molar ratio of reactants in the reaction mixture was 1 HTACl: 0.15 (NH ₄ ) ₂ O: 8 sodium adipate: 4 SiO ₂ : 1 Na ₂ O: 400 H X-ray diffraction pattern of the KIT-1 material prepared with ₂ O, (a) is the KIT-1 material before the firing treatment, (b) is a KIT-1 material after the firing treatment. FIG. 3 shows the use of sodium 1,3-benzenedisulfonic acid salt as a salt in Example 3 and the molar ratio of the reactants in the reaction mixture was 1 HTACl: 0.15 (NH ₄ ) ₂ O: 8 1,3-benzenedisulfonic acid sodium : 4 X-ray diffraction pattern of KIT-1 material prepared by SiO ₂ : 1 Na ₂ O: 400 H ₂ O, (a) is KIT-1 material before firing treatment, (b) after firing treatment KIT-1 substance. FIG. 4 is prepared by using NaCl as a salt in Example 3 and the molar ratio of reactants in the reaction mixture is prepared by using 1 HTACl: 0.15 (NH ₄ ) ₂ O: 4 NaCl: 4 SiO ₂ : 1 Na ₂ O: 400 H ₂ O X-ray diffraction pattern of one KIT-1 material, (a) is the KIT-1 material before the firing treatment, and (b) is the KIT-1 material after the firing treatment. 1 to 4 are X-ray diffraction forms of KIT-1 synthesized using various salts. All X-ray diffraction patterns show one strong peak and two weak peaks. 5 is KIT-1 (which has 16 carbon atoms in the alkyl group of the surfactant), dodecyltrimethylammonium bromide (DTABr) having 12, 14, and 18 carbon atoms in each of the alkyl groups of Example 3 below; In the case of tetradecyltrimethylammonium (TTABr) and octadecyltrimethylammonium bromide (OTABr), i.e. the change of the value of d _{100 in} the form of X-ray diffraction with the change of the alkyl chain length of the surfactant of formula (I) is shown. (○) is a material before the baking treatment and (□) is a material after the baking treatment.

Each peak in FIGS. 1 to 4 may be represented as (100), (200), or (300) for convenience, and the value of d ₁₀₀ may be represented by the alkyl chain of the surfactant used as the template material as shown in FIG. It increases as the length gets longer. When KIT-1 was calcined at 500-600 ° C to remove the surfactant, the template material, the X-ray diffraction pattern increased only two to three times its strength than before firing, but the characteristic shape was not changed. . It can also be seen that the size of d ₁₀₀ is reduced to about 0.1 nm or less by firing. That is, only 2-3% or less of structure shrinkage was observed by the calcination treatment.

The reason why each peak is wide in the X-ray diffraction pattern is that the cavities of KIT-1 are connected in a disordered manner without making a uniform arrangement. This can also be observed in an electron micrograph of KIT-1 of FIG. 1 (see FIG. 6). In this electron micrograph, KIT-1 has an isotropic structure with no directivity in structure because the cavity with a diameter of about 3 nm is connected very shortly in three dimensions of about 2-5 nm and the connection method is like a disordered plastic sponge. . In addition, the electron diffraction pattern (not shown) showed that KIT-1 formed a disordered structure, similar to the X-ray diffraction pattern or electron micrograph, but it was very short on the cavity array picture shown in the electron micrograph. It is difficult to tell whether the passages are connected to each other or the long linear cavities are entangled like noodle rhythms.The electron micrograph of Fig. 7 shows metal platinum along the cavity formed inside the structure of KIT-1 of Fig. 1. From the picture, it was found that the cavity of KIT-1 is irregularly connected to each other in three dimensions, and that KIT-1 is completely different from MCM-41 which has long straight cavity structure. .

Figure 8 is an adsorption of the nitrogen obtained at liquid nitrogen temperatures for a KIT-1 synthesis using 1 EDTANa ₄ to a salt-desorption isotherm inde adsorption of nitrogen in the vicinity of P / P ₀ of 0.4, similar to the case of MCM-41 Shows sudden metastasis of dose. 9 is a cavity size distribution curve obtained by the method of Horvath-Kawazoe from the adsorption isotherm of nitrogen. In FIG. 9, the cavity size of the KIT-1 is disorderly connected, but the cavity size shows a very narrow cavity size distribution curve (line width of 1 nm or less at medium height) at 3.4 nm. FIG. 10 is a cavity size distribution curve obtained by the BJH method for each sample in which the alkyl chain length of the surfactant is changed as in the case of FIG. 5. This shows a similar pattern to the change in the size of d ₁₀₀ obtained by X-ray diffraction analysis.

FIG. 11 is an X-ray diffraction pattern obtained by measuring the thermal stability by performing the following various heat treatments on the calcined KIT-1 sample of FIG. 1, and (a) shows the calcined KIT-1 without any heat treatment. (B) is a sample after raising the temperature at a rate of 100 ° C. per hour to 900 ° C. under an oxygen atmosphere containing 2.3 kPa of water vapor, and holding it for 2 hours, and (c) 100% − of 1 atm. After the temperature was raised at a rate of 100 ° C. per hour to 750 ° C. under a steam atmosphere, the sample was held for 2 hours. 11 shows that the structure of KIT-1 is maintained as it is at least 900 ° C under these conditions. In addition, it can be seen that the structure of KIT-1 is stable up to at least 750 ° C. even when maintained for 2 hours in a 100% water vapor atmosphere.

12 is a diagram showing the change in X-ray diffraction pattern over time by placing the calcined KIT-1 sample of FIG. 1 in boiling water at 100 ° C., (a) after 1 hour, (b) After 6 hours, (c) after 12 hours, (a) after 24 hours (e) means after 48 hours. KIT-1 of the present invention has almost no change in structure even after at least 48 hours, whereas conventional porous porous sieves such as MCM-41 and MCM-48 are completely collapsed within 12 hours under these conditions. Can be observed. That is, KIT-1 has a very excellent hydrothermal stability compared to other mesoporous molecular sieves.

Also, a structure (named KIT-2, Si / Al * 5-200) in which a part of silicon was substituted with aluminum in the backbone of the medium-porous molecular sieve KIT-1, which is the present invention, was also prepared. X-ray diffraction patterns and electron micrographs showed that the structure of KIT-2 was identical to that of KIT-1. 13 and 14 show solid-state magic angular rotation (MAS) aluminum after various thermal stability and hydrothermal stability experiments with a sample having a Si / Al ratio of 40 (z value corresponds to 0.05 in Example 4 to be described later). 27 Nuclear Magnetic Resonance Spectroscopy (NMR) Experimental Results and Temperature Programmed Desorption (TPD) of Ammonia Gas for Each Sample As shown in FIG. 13, FIG. 13 shows a solid state MAS aluminum-27 nuclear magnetic material obtained after various treatments as follows. As a result of the resonance experiment, (a) before the firing treatment, (b) after the firing treatment, (c) the temperature was raised to a temperature of 100 ° C. to 500 ° C. in an oxygen atmosphere containing 2.3 kPa of water vapor, and then 2 After holding for a period of time, (d) raises the temperature at a rate of 100 ° C. to 900 ° C. under an oxygen atmosphere containing 2.3 kPa of water vapor, and then maintains it for 2 hours, followed by (e) 100 ° C. boiling water. Kept for 12 hours in the It means after. Like KIT-1, the KIT-2 hardly collapses the structure by heat treatment or hydrothermal treatment, and the aluminum contained in the structure maintains the tetrahedral structure. FIG. 14 shows the results of temperature controlled desorption of ammonia adsorbed on a sample obtained after various treatments on a fired KIT-2 sample (Si / Al = 40), (a) after firing, (b) After raising the temperature at a rate of 100 ℃ per hour to 500 ℃ in an oxygen atmosphere containing 2.3 kPa of water vapor, and maintained for 2 hours, (c) to 900 ℃ under an oxygen atmosphere containing 2.3 kPa of water vapor After raising the temperature at a rate of 100 ℃ per hour, after holding for 2 hours, (d) means after holding for 12 hours in boiling water of 100 ℃. The TPD results show that KIT-2 has both weak and strong scatters. In FIG. 14, KIT-2 was almost maintained even after treatment for 2 hours in an oxygen atmosphere containing 2.3 kPa of water vapor at 900 ° C. or at least 12 hours in boiling water at 100 ° C. with respect to KIT-2. It can be seen that has high thermal stability and hydrothermal stability. KIT-2, like zeolites, is suitable for supporting materials having catalytically active sites because of its ion exchange capacity. Table 1 below shows various metal ions in KIT-2 (Si / Al = 40, which corresponds to a Z value of 0.05 in Example 4 to be described later) by wt% of Table 1, and then in air 550 After firing at 10 ° C. for 10 hours, hydrogen or oxygen adsorption experiments were carried out after reduction under a hydrogen atmosphere to form metal clusters. z value is 0.05) xenon-129 nuclear magnetic resonance of (1) of Table 1 obtained after supporting 2wt% of platinum ions through ion exchange to form a platinum cluster through the above-described firing and reduction treatment As the spectral spectrum, (a) is KIT-2 (Si / Al = 40, which corresponds to a z value of 0.05 in Example 4 to be described later), and (b) is 2 wt% of (1) of Table 1 below. Pt / KIT-2. In each result, very small metal clusters of 1 nm size can be formed in KIT-2.

TABLE 1

Hydrogen or oxygen adsorption results of metal clusters supported on KIT-2

Example 1

Solution A was prepared by mixing 20 g of 25 wt% aqueous solution of hexadecyltrimethylammonium chloride (HTACl) with 0.29 g of 28 wt% aqueous ammonia and 33.3 wt% sodium ethylenediaminetetraacetate (EBTANa ₄ ) solution as shown in Table 2 below. Solution B was prepared by mixing 31 g of 1.0 M aqueous sodium hydroxide solution with 9.4 g of Ludox HS40 (colloidal silica, trade name of Du Pont) and heating at 80 ° C. for 2 hours. The solution A was placed in a polypropylene bottle, and the two solutions were mixed at room temperature for 1 hour while dropping the solution B dropwise while stirring strongly using a magnetic stirrer. The molar ratio of the reactants in the reaction mixture was HTACl: (NH ₄ ) ₂ O is 1: 0.05, EDTANa ₄ / HTACl is shown in Table 2, HTACl: SiO ₂ : Na ₂ O was 1: 4: 1 was. The reaction mixture was reacted at 100 ° C. for 2 days and then cooled to room temperature. The pH of the reaction mixture was titrated to 10.2 using an aqueous 30 wt% acetic acid solution. The mixture was reacted again at 100 ° C. for 2 days, cooled to room temperature, and then repeated twice to adjust the pH to 10.2. The precipitate was filtered off, washed thoroughly with secondary distilled water and dried at 100 ° C. It was calcined at 550 ° C. for 10 hours in air to remove the surfactant contained in the dried sample. The KIT-1 materials thus prepared are all X-ray diffraction forms as shown in FIG. 1 (molar ratio of reactants prepared with 1 HTACl: 0.15 NH ₄ ) ₂ O: 4 EDTANa ₄ : 4 SiO ₂ : 400 H ₂ O There was little difference in the form of X-ray diffraction before and after firing treatment. The d ₁₀₀ value in the X-ray diffraction results for each KIT-1 material and the surface area determined by the BET method from nitrogen adsorption were 1000 ± 50 m ² g ⁻¹ and the respective values are listed in Table 2. Co-size of KIT-1 material obtained by Horvarth-Kawaxoe method (molar ratio of reactants prepared from 1 HTACl: 0.15 (NH ₄ ) ₂ O: 4 EDTANa ₄ : 4 SiO ₂ : 400 H ₂ O) from nitrogen adsorption results The distribution curve is shown in FIG. 9 and each material showed similar results.

[Table 2]

The amount of EDTANa ₄ aqueous solution used in Example 1 and the d ₁₀₀ value and surface area in the form of X-ray diffraction for each prepared material.

Example 2

In Example 2, the alkyl chain lengths of the surfactants in Solution A in Example 1 were changed to 12, 14 and 18. That is, Solution A is 0.29 g of 25 wt% aqueous dodecyl trimethylammonium bromide (DTABr) solution, 25 wt% aqueous tetradecyl trimethyl ammonium bromide (TTABr) solution and 25 wt% octadecyl trimethyl ammonium bromide (OTABr) solution, respectively, as shown in Table 3. A 28 wt% aqueous ammonia solution and 71.3 g of a 33.3 wt% EDTANa ₄ aqueous solution were mixed. Solution B used the aqueous sodium silicate solution prepared in Example 1 (using Ludox HS40). The rest of the preparation is the same as in Example 1 and the molar ratio of the reactants in the reaction mixture is shown in Table 1 below: Surfactant (NH ₄ ) ₂ O: EDTANa ₄ : SiO ₂ : Na ₂ O: H ₂ O in Table 1 is 1: 0.15: 4: 4: 400. The X-ray diffraction pattern of the sample thus obtained was similar to that of FIG. 1, and the change of the value of d ₁₀₀ according to the alkyl chain length is shown in FIGS. 5 and 3. The surface area determined by BET method from nitrogen adsorption was 1000 ± 50m ² g ^-1 and the values are shown in Table 3. According to the alkyl chain length, the cavity size determined by the BJH method was changed as shown in FIG. 10.

TABLE 3

Type and amount of aqueous alkyltrimethylammonium bromide solution used in Example 2 and d ₁₀₀ value and surface area in X-ray diffraction pattern for each prepared material.

Example 3

KIT-1 was synthesized using sodium adipic acid, sodium 1,3-benzenedisulfonic acid, NaCl and KCl instead of EDTANa ₄ , a salt used in Example 1. Solution A was prepared by adding 0.29 g of 28 wt% aqueous ammonia and 30 wt% of each aqueous salt solution to 20 g of 25 wt% HTACl aqueous solution. At this time, the amount of each aqueous salt solution is shown in Table 4. The solution B used the aqueous sodium silicate solution used in Example 1. The molar ratio of reactants in the reaction mixture is HTACl: (NH ₄ ) ₂ O: SiO ₂ : Na ₂ O: H ₂ O is 1: 0.15: 4: 1: y and the ratio of salt / HTACl is shown in Table 4 below And y is the amount of water used. The rest of the preparation was the same as in Example 1. The X-ray diffraction pattern of each KIT-1 material thus obtained was as shown in Figs. 2 to 4, and the surface area determined by BET method from nitrogen adsorption was 1000 ± 50 m ² g ^-1 as shown in Table 4.

TABLE 4

Type and amount of 30 wt% salt aqueous solution used in Example 3 and d ₁₀₀ value and surface area in X-ray diffraction pattern for each prepared material.

Example 4

Solution A was prepared by mixing 0.29 g of 28 wt% aqueous ammonia solution and 71 g of 33.3 wt% EDTANa ₄ aqueous solution in 20 g of 25 wt% HTACl aqueous solution, and solution B was an aqueous sodium silicate solution used in Example 1. Solution C was prepared by dissolving sodium aluminate (NaAlO ₂ ) to 5wt% in distilled water. The solution A was mixed in a polypropylene bottle while mixing the two solutions at room temperature for 1 hour while dropping the solution B dropwise by using a magnetic stirrer while dropping the solution B dropwise. The molar ratio of reactants in the reaction mixture is HTACl: (NH ₄ ) ₂ O: EDTANa ₄ : SiO ₂ : Na ₂ O: Al ₂ O ₃ : H ₂ O is 1: 0.15: 4: 4: 1: z: y, Where z is in Table 5 below and y was 400-500. The rest of the preparation was the same as in Example 1. The X-ray diffraction pattern of the sample thus obtained was similar to that obtained in Example 1, and the surface area obtained by BET method from nitrogen adsorption was shown in Table 5. In the sample (z value corresponds to 0.05), the solid phase MAS aluminum-27 nuclear magnetic resonance experiment of FIG. 13 confirmed that all the aluminum had a rectangular structure, from which all the aluminum was present in the structure. there was. The other z showed similar results. In addition, in the sample (z value corresponds to 0.05), it was found from the TPD results of the adsorbed ammonia of FIG. 14 that the weak acid point of 100-200 ° C. and the strong acid point of 400-700 ° C. existed. The other z showed similar results. KIT-2 thus prepared was able to form small metal clusters as shown in Table 5 and FIG. 15 through ion exchange, reduction and calcination of metal ions.

TABLE 5

The amount of 5 wt% NaAlO ₂ aqueous solution used in Example 4 and the d ₁₀₀ value and surface area in X-ray diffraction behavior for each of the prepared materials.

As described above, the molecular sieve material of the present invention, the KIT-1 also exhibits excellent thermal stability and hydrothermal stability as compared to MCM-41, there is no molecular diffusion barrier due to blockage of one-dimensional linear cavity.

Claims (17)

(A) preparing a mixed aqueous solution of alkyltrimethylammonium halide and silicate of formula (I) as the surfactant; (B) one or two or more of an organic salt or an inorganic salt which can be combined with a monovalent cation and dissolved in water is selected and added to the mixed aqueous solution of step (A) and mixed; (C) hydrothermally reacting the mixture of step (B) by maintaining pH, temperature and time to form a precipitate of the final desired molecular sieve material; (D) filtering and drying the precipitate of the molecular sieve material formed in step (C); And (E) A method for producing an amorphous medium porous molecular sieve material consisting of calcining the precipitate filtered and dried in step (D). [Formula I] Wherein n is an integer from 12-18 and X is Cl or Br. The method according to claim 1, wherein the surfactant is hexadecyltrimethylammonium chloride, dodecyltrimethylammonium bromide, tetradecyltrimethylammonium bromide, or octadecyltrimethylammonium bromide. The method for producing an amorphous medium porous molecular sieve material according to claim 1, wherein the silicate is sodium silicate. According to claim 1, Organic salts or inorganic salts which can be combined with the monovalent cation and soluble in water NaCl, KCl, CH3COONa, NaBr, Na2SO4, NaNO3, NaClO4, NaClO3, Sodium ethylenediaminetetriacetic acid, Adipic acid A method for producing an amorphous medium-porous molecular sieve, characterized in that it is sodium (adipic acid disodium salt), 1,3-benzendisulfonic acid disodium salt, or nitrilotriacetic acid sodium. . According to claim 1, 1.0 to 15.0 moles of an organic or inorganic salt which can be combined with a monovalent cation and dissolved in water based on 1 mole of the alkyl (I) halide alkyltrimethylmethylammonium and 1.0 to 15.0 of the silicate A method for producing an amorphous medium porous molecular sieve material, characterized in that moles are used. The method of claim 1, wherein the aqueous ammonia solution is added in the step (A). The method of claim 1, wherein the firing temperature is between 500 and 600 ° C. 6. The method according to any one of claims 1 to 7, wherein the molecular sieve material is a three-dimensional disordered cavity structure having a uniform diameter. (1) preparing a mixed aqueous solution of one or two selected salts from the group consisting of alkyl halides and silicates of the formula (I) with silicates and aluminates, boronates and 3d transition metal salts of the periodic table as surfactants; (2) one or two or more organic salts or inorganic salts which can be combined with a monovalent cation and dissolved in water are selected and added to the mixed aqueous solution of step (1) and mixed; (3) hydrothermally reacting the mixture of step (2) by maintaining pH, temperature and time to form a precipitate of the final desired molecular sieve material; (4) filtering and drying the precipitate of the molecular sieve material formed in step (3); And (5) A method for producing an amorphous medium porous molecular sieve material, comprising calcining the precipitate filtered and dried in step (4). [Formula I] Wherein n is an integer from 12-18 and X is Cl or Br. 10. The method of claim 9, wherein said aluminate is sodium aluminate (NaAlO2). 10. The organic salt or inorganic salt which can be combined with a monovalent cation and dissolved in water based on 1 mole of the alkyltrimethylammonium halide of Formula (I) is 1.0 to 15.0 moles and the silicate 1.0. To 15.0 moles and 0.0025 to 1.5 moles of one or more salts selected from the group consisting of aluminates, boronates and 3d transition metal salts on the periodic table are used in the preparation of amorphous mesoporous molecular sieve material. 10. The method of claim 9, wherein the surfactant is hexadecyltrimethylammonium chloride, dodecyltrimethylammonium bromide, tetradecyltrimethylammonium bromide or octadecyltrimethylammonium bromide. 10. The method of claim 9, wherein said silicate is sodium silicate. The organic or inorganic salt of NaCl, KCl, CH3COONa, NaBr, Na2SO4, NaNO3, NaClO4, NaClO3, sodium ethylenediaminetetracetate, adipic acid A method for producing an amorphous medium-porous molecular sieve, characterized in that it is sodium (adipic acid disodium salt), 1,3-benzendisulfonic acid disodium salt, or nitrilotriacetic acid sodium. . 10. The method of claim 9, wherein the aqueous ammonia solution is added in step (1). 10. The method of claim 9, wherein the firing temperature is between 500 and 600 ° C. The method according to any one of claims 9 to 16, wherein the molecular sieve material is a three-dimensional disordered cavity structure having a uniform diameter.