KR20030082022A - The zeolites TNU-9 and TNU-10 and their manufacturing process - Google Patents

Abstract

PURPOSE: Provided are zeolites having a large surface area of at least 400m¬2/g, thermal stability and uniform size of pores, each being greater than at least 4.5Å. CONSTITUTION: The zeolite, TNU-9, has a chemical formula (I) of 1.0 Al2O3 : 10.0-200.0 SiO2. The zeolite, TNU-10, has a chemical formula of 1.0 Al2O3 : 20.0-200.0 SiO2. The method comprises the steps of (a) inputting 0.64g of (Al(NO3)3·9H2O), 1.96g of 50wt% NaOH aqueous solution and 22.48g of water into a beaker, (b) stirring things in the beaker for 5 min, (c) inputting 2.0g of amorphous silica (Degussa, Aerosil 200) into the beaker while mixing the things in the beaker, (d) adding 1.97g of MPB into the beaker, thereby obtaining a chemical compound having a chemical formula (I) of 4.5 MPB : 11.0 Na2O : 0.75 Al2O3 : 30.0 SiO2 : 1200 H2O, (e) sintering the chemical compound having chemical formula (I) at temperature of 550°C for 12 hrs while exposing it to air, thereby obtaining a chemical compound having a chemical formula (II) of 0.28 Na2O : 1.0 Al2O3 : 25.3 SiO2, (f) sintering the chemical compound obtained at the step (e) at temperature of 550°C for 12 hrs while exposing it to air, (g) inputting the chemical compound obtained at the step (f) into 1.0 mol ammonium nitrate solution and heating the mixture at temperature of 80°C for 6 hrs, and (h) sintering the compound obtained at the step (g) at temperature of 500°C for 8 hrs.

Description

The zeolites TNU-9 and TNU-10 and their manufacturing process

The present invention relates to a zeolite having a new skeleton structure and composition, and to a method of manufacturing the same. The present invention relates to a TNU-10 zeolite having the same structure as the other but having a different skeleton composition, and a method for preparing the same.

Currently, molecular sieves including zeolites are widely used as ion exchangers, separators, catalysts or catalyst supports in various fields such as fine chemistry and petrochemicals [Kirk Othmer Encyclo. Chem. Technol., 1995, Vol. 16, p. 888]. Inside the zeolite and the molecular sieve, there are pores with a uniform size within an error range of 0.1 Å or less depending on the framework structure. Therefore, these materials have unique shape selectivity not found in amorphous oxides, and thus are applied as ion exchangers, separators, catalysts, or catalyst supports in fine chemicals, petrochemical industries, etc. It has enabled the development of many important new processes [Molecular Transport and Reaction in Zeolites, VCH, 1994]. Zeolite's commercial success is due to the fact that zeolites with different pore sizes and shapes have been discovered over the last few decades and have been applied to numerous petrochemical and fine chemical processes, and have been the driving force behind technological innovation. can do.

Accordingly, the present inventors have repeatedly studied to prepare zeolites having a skeleton structure or composition completely different from those of the known zeolites, and found two new zeolite species.

The present invention provides a zeolite having a new physical property as an ion exchanger, separator, catalyst or catalyst support in fine chemicals, petrochemical industry, etc. The purpose is to provide.

The present invention for achieving the above object, the composition of the basic skeleton structure is composed of the oxide of the molar ratio as shown in the following formula (1), with a high surface area of at least 400 m ² / g or more of the skeleton at a high temperature of 500 ℃ or more It can be achieved by providing zeolites having a high thermal stability to maintain the structure and containing therein uniform pores of a size larger than at least 4.5 mm 3.

[Formula 1]

1.0 Al ₂ O ₃ : 10.0-200.0 SiO ₂

The two zeolites disclosed in the present invention are now named TNU-9 (Taejon University Number 9) and TNU-10 (Taejon University Number 10), respectively. In the case of TNU-9, zeolites having the same skeleton structure as this zeolite have not been specified in the literature so far, and TNU-10 is an example in which the skeleton is the same as that of barrerite, which is a kind of natural zeolite, but artificially synthesized the barrite. Has not been reported at all [Atlas of Zeolite Structure Types, Butterworth, 1992].

TNU-9 and TNU-10 zeolites according to the present invention are SiO ₂ / Al ₂ O ₃ and NaOH / SiO in a reaction mixture containing 1,4-bis ( N- methylpyrrolidinium) butane (hereinafter referred to as MPB) dibromide, which is a diquaternary ammonium salt. After adjusting the ratio ₂ may be prepared by hydrothermal crystallization. In general, the synthesis of zeolites is accomplished through a so-called hydrothermal crystallization method in which an inorganic cation, an organic cation, or both cations are simultaneously added to an aluminosilicate gel and heat treated. Synthetic methods have been found (Handbook of Molecular Sieves, Van Nostrand Reinhold, 1992). Recently, the inventors have found that the molecular conformation of alkyl amines or alkyl ammonium ions, which are added as organic structure-inducing molecules in the synthesis of zeolites, is a molar ratio between various inorganic components in the reaction mixture, in particular SiO ₂ / Al ₂ O ₃ and NaOH / SiO. ₂ , which can vary greatly depending on the ratio, suggests in the journal that new zeolites can be synthesized by appropriately adjusting the conformation of organic structure-derived molecules [J. Phys. Chem., 2001, Vol. 105, p. 9994]. On the other hand, MPB used as the organic structure-inducing molecule in the present invention is an example used in the synthesis of MCM-47, a kind of layered silicate material is introduced in US Patent No. 5, 068, 096, zeolite using this organic structure-inducing molecule Has never been protected.

The present invention for preparing TNU-9 and TNU-10 zeolites having a skeleton structure and composition as shown in Formula 1, monovalent sodium hydroxide per 1 mole of aluminum nitrate (Al (NO ₃ ) ₃ ㆍ 9H ₂ 0) in a beaker An aqueous solution of (NaOH) is added to a ratio of 20 to 32 moles to dissolve, and then a silica sol or amorphous silica is slowly added over a period of 5 to 10 minutes at a molar ratio of 30 to 120 moles per 1 mole of aluminum oxide and stirred for 1 hour. Finally add 3 to 6 moles of MPB and then stir again at room temperature for 24 hours. The MPB used as the organic structural guide molecule was synthesized by reacting 3 moles of 1-methylpyrrolidine with 1 mole of 1,4-dibromobutane using acetone as a solvent. The composition of the reaction mixture thus obtained is shown in Chemical Formula 2.

[Formula 2]

4.0-6.0 MPB: .x Na ₂ O: 1.0 Al ₂ O ₃ : 30.0-120.0 SiO ₂ : 600-1500 H ₂ O

Where x is 10-12 and 14-16 for TNU-9 and TNU-10, respectively. The reaction mixtures obtained using the procedure and reagents described above were transferred to a Teflon reactor and placed in a stainless steel container and heated at 140-180 ° C. for 3-21 days to prepare the TNU-9 and TNU-10 zeolites. It provides a manufacturing method. In particular, when the reaction mixture has a composition as shown in Formula 3, heating at 160 ° C. for 14 days facilitates the synthesis of pure TNU-9 and TNU-10.

[Formula 3]

4.5 MPB: .x Na ₂ O: 0.75-0.25 Al ₂ O ₃ : 30.0 SiO ₂ : 1200 H ₂ O

Where x is 11 and 15 for TNU-9 and TNU-10, respectively.

X-ray diffraction measurement test of the TNU-9 zeolite according to the above production method can obtain the results shown in Table 1.

TABLE 1

In Table 1, θ, d, and I represent the Bragg angle, the lattice spacing, and the intensity of the x-ray diffraction peak, respectively. All powder X-ray diffraction data reported in the present invention, including this powder X-ray diffraction pattern, were measured using standard X-ray diffraction methods. As a radiation source, X-rays operated at 30 kV, 40 mA with copper Kα rays. A tube was used. From the horizontally compressed text sample, it was measured at a rate of 2 degrees per minute (2θ), and d and I were calculated from the 2θ value and the peak height of the observed X-ray diffraction peaks.

According to the above results, the zeolite having a X-ray diffraction pattern including a lattice interval given in Table 1 and having a skeleton structure of the formula 1 is now defined as TNU-9.

In addition, the general X-ray diffraction pattern for all TNU-9 materials is defined to fall within the range of grating intervals reported in Table 2.

TABLE 2

In addition, the present invention can obtain the results shown in Table 3 by X-ray diffraction measurement test of TNU-10 zeolite according to the above production method.

TABLE 3

According to the above results, the zeolite having the X-ray diffraction pattern including the lattice spacings of which the skeleton structure has the same composition as the formula (1) and at least given in Table 3 is defined as TNU-10.

In addition, a general X-ray diffraction pattern for all TNU-10 materials is defined to fall within the range of grating intervals reported in Table 4.

TABLE 4

Hereinafter, the present invention will be described for a detailed understanding of several exemplary embodiments, for example, the preparation method of TNU-9 and TNU-10 zeolites, which are only intended to illustrate the embodiments and to limit the scope of the present invention. It is not.

<Example 1>

Preparation of TNU-9 Zeolite

In a plastic beaker, first, 1.96 g of 50 wt% aqueous sodium hydroxide (NaOH) solution and 0.64 g of aluminum nitrate (Al (NO ₃ ) ₃ ㆍ 9H ₂ O) were added to 22.48 g of water and stirred for 5 minutes, followed by 2.0 g of Slowly add amorphous silica (Degussa, Aerosil 200) and stir for 30 minutes, add 1.97 g of MPB to obtain a reaction mixture represented by the following formula (4), transfer the reaction mixture obtained above to a Teflon reactor, and then again stainless steel It was put in a container made of heated to rotate 100 times per minute at 160 ℃ for 14 days, and then the obtained solid product was repeatedly washed with water and dried at room temperature.

[Formula 4]

4.5 MPB: .11.0 Na ₂ O: 0.75 Al ₂ O ₃ : 30.0 SiO ₂ : 1200 H ₂ O

X-ray diffraction measurement test was carried out with the solid powder obtained in Example 1, and the results are shown in Table 5.

TABLE 5

<Example 2>

Preparation of TNU-9 Zeolite

In a plastic beaker, first, 5.87 g of 50% by weight aqueous sodium hydroxide (NaOH) solution and 1.28 g of aluminum nitrate (Al (NO ₃ ) ₃ ㆍ 9H ₂ O) were added to 67.72 g of water and stirred for 5 minutes, followed by 6.0 g of Slowly add amorphous silica (Degussa, Aerosil 200) and stir for 30 minutes, add 5.91 g of MPB to obtain a reaction mixture represented by Formula 5 below, transfer the reaction mixture obtained above to a Teflon reactor, and then again stainless steel It was heated in a container made of a rotating 100 times per minute at 160 ℃ for 14 days and then, the obtained solid product was repeatedly washed with water and dried at room temperature.

[Formula 5]

4.5 MPB: .11.0 Na ₂ O: 0.5 Al ₂ O ₃ : 30.0 SiO ₂ : 1200 H ₂ O

X-ray diffraction measurement test with the powder of the solid product obtained in Example 2 was the same as the X-ray data given in Table 5, no other phase was observed.

When a portion of the sample obtained in Example 2 was fired for 12 hours under air at 550 ° C., and the X-ray diffraction pattern was measured again, the fired sample exhibited essentially the same X-ray pattern as in Example 1. It was observed, and the results obtained by performing elemental analysis to identify the composition of this sample are shown in the formula (6).

[Formula 6]

0.28 Na ₂ O: 1.0 Al ₂ O ₃ : 25.3 SiO ₂

A part of the sample obtained in Example 2 was calcined under air at 550 ° C. for 12 hours, put in a 1.0 molar ammonium nitrate solution, heated at 80 ° C. for 6 hours, and calcined again at 500 ° C. for 8 hours for nitrogen adsorption test. TNU-9 zeolite was observed to have a BET surface area of about 500 m ² / g.

<Example 3>

Preparation of TNU-10 Zeolite

In a plastic beaker, 3.69 g of 50% by weight aqueous sodium hydroxide (NaOH) solution and 0.29 g of aluminum nitrate (Al (NO ₃ ) ₃ ㆍ 9H ₂ O) were added to 30.80 g of water and stirred for 5 minutes, followed by 2.77 g of Slowly add amorphous silica (Degussa, Aerosil 200) and stir for 30 minutes, add 2.73 g of MPB to obtain a reaction mixture represented by the following formula (7), transfer the reaction mixture obtained above to a Teflon reactor, and then again stainless steel It was heated in a container made of a rotating 100 times per minute at 160 ℃ for 12 days, and then the obtained solid product was repeatedly washed with water and dried at room temperature.

[Formula 7]

4.5 MPB: .15.0 Na ₂ O: 0.25 Al ₂ O ₃ : 30.0 SiO ₂ : 1200 H ₂ O

X-ray diffraction measurement test was carried out with the solid powder obtained in Example 3, and the results are shown in Table 6.

TABLE 6

Compared with the previously reported X-ray diffraction patterns of zeolites, TNU-10 was found to have the same structure as barite, a kind of natural zeolite [Collection of Simulated XRD Patterns fro Zeolites, Elsevier, 1996].

<Example 4>

Preparation of TNU-10 Zeolite

In a plastic beaker, 2.67 g of 50 wt% aqueous sodium hydroxide (NaOH) solution and 0.43 g of aluminum nitrate (Al (NO ₃ ) ₃ ㆍ 9H ₂ O) were added to 22.22 g of water and stirred for 5 minutes, followed by 2.0 g of Slowly add amorphous silica (Degussa, Aerosil 200) and stir for 30 minutes, add 1.97 g of MPB to obtain a reaction mixture represented by the following formula (8), transfer the reaction mixture obtained above to a Teflon reactor, and then again stainless steel It was heated in a container made of a rotating 100 times per minute at 160 ℃ for 14 days, and then the obtained solid product was repeatedly washed with water and dried at room temperature.

[Formula 8]

4.5 MPB: .15.0 Na ₂ O: 0.50 Al ₂ O ₃ : 30.0 SiO ₂ : 1200 H ₂ O

As a result of X-ray diffraction measurement test with the powder of the solid product obtained in Example 4, it was the same as the X-ray data given in Example 3, and no other phase was observed.

When a portion of the sample obtained in Example 4 was fired for 12 hours under air at 550 ° C., and the X-ray diffraction pattern was measured again, the fired sample showed the same X-ray pattern as in Table 6. In order to identify the composition of the sample, elemental analysis was performed to show the results of the general formula (9).

[Formula 9]

0.40 Na ₂ O: 1.0 Al ₂ O ₃ : 13.0 SiO ₂

Within the framework of the Barre light kind of natural zeolite which has the same structure and TNU-10 of the present invention, SiO ₂ / Al ₂ O ₃ of TNU-10 compared to the ratio (6.8) SiO ₂ / Al ₂ O ₃ ratio (13.0) Was found to be higher.

A portion of the sample obtained in the above example was calcined under air at 550 ° C. for 12 hours, put in a 1.0 mol ammonium nitrate solution, heated at 80 ° C. for 6 hours, and calcined again at 500 ° C. for 8 hours under nitrogen adsorption test. The -10 zeolite was observed to have a BET surface area of about 440 m ² / g.

As described above, the present invention has the same structure as that of TNU-9 zeolite having a new structure and composition different from the known zeolites, and a barite which is a kind of natural zeolite, but the SiO ₂ / Al ₂ O ₃ ratio in the skeleton It is a useful invention to make larger TNU-10 zeolites and to provide new zeolites and methods for their preparation that can be used as solid acid catalysts with unique shape selectivity or as a separator for certain molecules.

Claims (3)

TNU-9 zeolite, characterized in that the basic skeleton structure is composed of the oxide composition of the molar ratio as shown in the following formula (1) and has an X-ray diffraction pattern including the lattice intervals given in Table 1. <Formula 1> 1.0 Al ₂ O ₃ : 10.0-200.0 SiO ₂ <Table 1> TNU is characterized by having an X-ray diffraction pattern comprising the lattice spacings given in Table 2 because the composition is composed of an oxide composition having a molar ratio such as that of Chemical Formula 2, so that the SiO ₂ / Al ₂ O ₃ ratio in the skeleton is greater than or equal to 10. -10 zeolites. <Formula 2> 1.0 Al ₂ O ₃ : 20.0-200.0 SiO ₂ <Table 2> A solution of monohydric sodium hydroxide (NaOH) in an amount of 20 to 32 moles is dissolved in a beaker with respect to 1 mole of aluminum nitrate (Al (NO ₃ ) ₃ .H ₂ O), followed by melting a silica sol or amorphous silica. Slowly add 1 mol of aluminum oxide at 30 to 120 molar ratio over 5 to 10 minutes and stir for 1 hour, and then add 3 to 6 moles of 1,4-bis ( N -methylpyrrolidinium) butane dibromide as an organic structural guide molecule. The reaction mixture obtained by transferring to a Teflon reactor and put in a stainless steel container again and heated at 100 to 180 ℃ for 3 to 21 days, characterized in that the TNU-9 and TNU-10 zeolite manufacturing method.