KR20220135693A - A manufacturing process using TEA and Zeolite using thereof - Google Patents

Abstract

The present invention relates to a method for manufacturing zeolite, and more specifically, to a method for manufacturing zeolite using TEAOH and zeolite manufactured by using the same. The method for manufacturing zeolite according to the present invention performs hydrothermal synthesis of the zeolite by using a structural inducing material comprising: the TEAOH; one or more low molecular weight alkali metal components (M) selected from a group consisting of Li, Na, and K; and one or more high molecular weight alkali metal components (N) selected from a group consisting of Rb, Cs, and Fr. According to the present invention, rho zeolite, ZK-5 zeolite, or offite zeolite are synthesized by using a low-cost structural inducing material.

Description

A zeolite manufacturing method using TEAOH and a zeolite using the same

The present invention relates to a method for producing a zeolite, and to a method for producing a zeolite using TEAOH and a zeolite produced using the same.

Zeolites and related nanoporous materials are being used as catalysts and adsorption separators in industrial fields due to their unique structures and compositions, and in particular, are attracting attention as materials capable of adsorbing carbon dioxide, which is pointed out as a cause of climate change.

As three-dimensional aluminosilicates with small pores, such as rho and ZK-5 zeolites, due to their small pore size and interstitial space and appropriate silicon-to-aluminum ratio (rho; Si/Al = 3.9 and ZK-5; Si/Al = 4.0) ) shows superior selectivity than conventional commercial zeolites in carbon dioxide nitrogen or methane separation as well as excellent carbon dioxide adsorption capacity.

However, since these zeolites are difficult to synthesize with high purity using only inorganic structure-inducing materials, expensive organic structures such as 1,4,7,10,13,16-hexaoxacyclooctadecane (hereinafter, 18-crown-6) have a complex structure. It is known that an inducer is required. In addition, 18-crown-6 has a problem in that it is not only expensive, but also has lethal toxicity in terms of the environment.

The problem to be solved in the present invention is to produce a zeolite using a cheaper and safer structure-inducing material so as to replace the manufacturing method of zeolite manufactured using an expensive organic structure-inducing material such as 18-crown-6. to provide a way

The problem to be solved in the present invention is to provide a method for manufacturing rho zeolite using a new structure-inducing material without using an expensive organic structure-inducing material such as 18-crown-6.

An object to be solved in the present invention is to provide a method for producing ZK-5 zeolite using a new structure-inducing material without using an expensive organic structure-inducing material such as 18-crown-6.

An object to be solved in the present invention is to provide a new structure-inducing material capable of synthesizing rho zeolite or ZK-5.

An object to be solved in the present invention is to provide a method for preparing another zeolite using a novel structure-inducing material capable of synthesizing rho zeolite or ZK-5.

In order to solve the above problems, the present invention

Tetraethylammonium hydroxide (hereinafter referred to as 'TEAOH') and; Li, Na, and at least one low molecular weight alkali metal component (M) selected from the group consisting of K; and Rb, Cs, and Fr. It provides a method characterized in that the zeolite is synthesized using a structure-inducing material containing one or more high molecular weight alkali metal components (N) selected from the group consisting of Fr.

In the present invention, the zeolite synthesis method comprises a hydrothermal synthesis step of reacting a silica source and an aluminum source together with a structure-inducing material (M) in water to obtain a reaction mixture represented by the following formula (1), and heating the same; can be made with

x TEAOH: y M ₂ O : z N ₂ O : 1 Al ₂ O ₃ : m SiO ₂ : n H ₂ O (1)

where x, y, z, m, n are moles,

M ₂ O is an oxide of a low molecular weight alkali metal,

N ₂ O is a high molecular weight alkali metal oxide,

x is 0.5-5.0, y is 0.25-2.0, z is 0.25-2.0, m is 2.0-50, and n is 10-200.

In the practice of the present invention, the molar ratio of Al and Si in the reaction mixture synthesized by the hydrothermal synthesis may be 1:1 to 25, preferably 1:2 to 15, and more preferably 1: It can be 3-10 days.

In the practice of the present invention, the molar ratio of Al and H 2 O in the reaction mixture synthesized by the hydrothermal synthesis may be 1:5-100, preferably 1:10-90, more preferably 1: It can be 10-80 days.

In the practice of the present invention, the molar ratio of Al and total alkali metal oxides in the reaction mixture synthesized by the hydrothermal synthesis may be 1:0.5 to 4.0, preferably 1:1 to 3.5, and more preferably may be 1:1 to 3.0.

In the practice of the present invention, the molar ratio of TEAOH and total alkali metal oxide in the reaction mixture synthesized by the hydrothermal synthesis may be 1:8 to 10:1, preferably 1:6 to 8:1, , more preferably 1:4 to 6:1.

In the practice of the present invention, in the reaction mixture synthesized by the hydrothermal synthesis, the molar ratio of M ₂ O, which is a low molecular weight alkali metal oxide, and N ₂ O, which is a high molecular weight alkali metal oxide, may be 1:8 to 8:1, Preferably, it may be 1:5-5:1, more preferably 1:2-2:1, and most preferably 1:1.

In the present invention, the difference in atomic weight between the low molecular weight alkali metal component and the high molecular weight alkali metal component may be 40 or more, preferably 50 or more, more preferably 60 or more, and most preferably 70 or more.

In the practice of the present invention, the aluminum (Al) source may be aluminum or a precursor compound containing aluminum, for example, pseudoboehmite, aluminum chloride, aluminum isopropoxide (aluminium isopropoxide), sodium aluminate, aluminum hydroxide, aluminum alkoxide, aluminum metal, aluminosilicate zeolite, aluminophosphate or silicoaluminophosphate zeolite, etc. It is possible.

In the practice of the present invention, the silicon (Si) source may be silicon or a precursor compound containing silicon, for example, fumed silica, silica sol, organosilane, Aluminosilicate to silicoaluminophosphate zeolites and the like are possible.

In the practice of the present invention, the alkali metal component may be used as a precursor, preferably a hydroxide precursor, for example, in the form of LiOH, NaOH, KOH, RbOH, CsOH, and the like.

In a preferred embodiment of the present invention, in the hydrothermal synthesis, an aqueous solution of MOH is added in a ratio of 0 to 5 moles, preferably 0.25 to 2 moles, with respect to 1 mole of metallic aluminum (Al ₂ O ₃ ), and an aqueous NOH solution is added to 0 to 5 moles, preferably 0.25 to 2 moles, and stirring for a predetermined time to prepare a first solution;

After adding and dissolving silica sol or amorphous silica in a ratio of 2 to 50 moles based on 1 mole of metallic aluminum, finally 1 to 25 moles of TEAOH, an organic structure inducing material, preferably 0.5 to 5 moles. adding and stirring for a predetermined time to prepare a second solution; and

It may consist of a step of slowly adding the prepared first solution dropwise to the prepared second solution, and then stirring at room temperature.

In the present invention, the heating step may be made at a temperature of 50 ~ 200 ℃, it may be made for 0.5 to 7 days to prevent structural change.

In the practice of the present invention, the heating may be performed in a state in which the reaction mixture is transferred to a Teflon reactor and again placed in a vessel made of stainless steel.

The zeolite formed by hydrothermal synthesis and heating according to the present invention may be a rho zeolite, a ZK-5 zeolite, or an offretite zeolite.

The present invention in one aspect,

TEAOH; Na metal component; A method for synthesizing rho zeolite using a structure-inducing material including Cs as a metal component is provided.

In one embodiment of the present invention, the rho zeolite is

To 1 mol of aluminum metal (Al ₂ O ₃ ), a +1 valent sodium hydroxide (NaOH) aqueous solution is added in a ratio of 0 to 5 mol, preferably 0.25 to 2 mol, and a cesium hydroxide (CsOH) aqueous solution is added to 0 to 5 mol. 5 moles, preferably 0.25 to 2 moles, were added and stirred for 1 hour to make a first solution, and silica sol or amorphous silica was added in a ratio of 2 to 50 moles to 1 mole of metallic aluminum and dissolved. Finally, TEAOH, which is an organic structure inducing material, is added in a ratio of 1 to 25 moles, preferably 0.5 to 5 moles, and stirred for 1 hour to make a second solution, and then slowly add the prepared first solution to the second solution After adding one drop at a time, stirring at room temperature for 24 hours to obtain a reaction mixture as shown in Formula (2); and

0.5~5.0 TEAOH:0.25~2.0 NaOH:0.25~2.0 CsOH:1.0 Al ₂ O ₃ :2.0~50 SiO ₂ :10~200 H ₂ O (2)

It can be synthesized by; transferring the reaction mixture of Formula 2 to a Teflon reactor, putting it back into a container made of stainless steel, and heating it at 50 to 200° C. for 12 hours to 7 days.

In the present invention, the rho zeolite is

TAEOH;

It has a composition ratio represented by the following formula (3)

0.1~10 A ₂ O: 1.0 Al ₂ O ₃ : 1.0~100 SiO ₂ (3)

Here, A consists of Na and Cs,

It is characterized in that it has a skeletal structure according to the XRD pattern shown in Table 1 below.

2θ d 100×I/I _O 8.4 to 8.5 10.5 to 10.6 VS 14.5 to 14.6 6.0 ~ 6.1 M 16.7 to 16.8 5.3 to 5.4 W 18.7 to 18.8 4.7 to 4.8 S 20.5 to 20.6 4.3 to 4.4 W 22.2 ~ 22.3 3.9 to 4.0 W 23.8 ~ 23.9 3.7 to 3.8 W 25.2 to 25.3 3.5 to 3.6 VS 26.6 ~ 26.7 3.3 to 3.4 S 28.0 ~ 28.1 3.1 to 3.2 W 29.2 ~ 29.3 3.0 to 3.1 W 30.4 to 30.5 2.9 to 3.0 M 32.8 ~ 32.9 2.7 to 2.8 M 33.8 ~ 33.9 2.6 to 2.7 W 34.9 to 35.0 2.5 to 2.6 W 36.0 to 36.1 2.4 to 2.5 W 37.0 to 37.1 2.4 to 2.5 W 39.0 to 39.1 2.3 to 2.4 W 39.9 to 40.0 2.2 to 2.3 W 40.8 to 40.9 2.2 to 2.3 W 42.7 ~ 42.8 2.1 to 2.2 W 44.4 to 44.5 2.0 to 2.1 W 45.3 ~ 45.4 1.9 to 2.0 W 47.8 ~ 47.9 1.9 to 2.0 W 48.6 ~ 48.7 1.8 to 1.9 W 49.4 to 49.5 1.8 to 1.9 W

In Table 1, θ, d, and I mean 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. - A wire tube was used. Measurements were made at a rate of 5 degrees per minute (2θ) from a horizontally compressed powder sample, and d and I were calculated from the 2θ values and peak heights of the observed X-ray diffraction peaks, where 100×I/I ₀ is W It is divided into (weak: 0-20), M (medium: 20-40), S (strong: 40-60), and VS (very strong: 60-100). According to the above results, it was confirmed that the skeletal structure has the same composition as in Chemical Formula 1, and the material having an X-ray diffraction pattern including the lattice spacings given in Table 1 is the previously reported rho zeolite [Atlas of Zeolite Structure Types, Butterworth 2007], [http://www.iza-structure.org/].

In the practice of the present invention, the ratio of Al ₂ O ₃ and SiO ₂ in the rho zeolite is preferably 1.0 Al ₂ O ₃ :1.0-100 SiO ₂ It can be expressed as, more preferably 1.0:2.0-50 , and 2θ, d, 100×I/I ₀ of Table 1 may be expressed in Table 2 below.

2θ d 100×I/I _O 8.4 to 8.5 10.5 to 10.6 95 to 100 14.5 to 14.6 6.0 ~ 6.1 25 to 30 16.7 to 16.8 5.3 to 5.4 15 to 20 18.7 to 18.8 4.7 to 4.8 35 to 40 20.5 to 20.6 4.3 to 4.4 5 to 10 22.2 ~ 22.3 3.9 to 4.0 10 to 15 23.8 ~ 23.9 3.7 to 3.8 5 to 10 25.2 to 25.3 3.5 to 3.6 80 to 85 26.6 ~ 26.7 3.3 to 3.4 45 to 50 28.0 ~ 28.1 3.1 to 3.2 5 to 10 29.2 ~ 29.3 3.0 to 3.1 10 to 15 30.4 to 30.5 2.9 to 3.0 25 to 30 32.8 ~ 32.9 2.7 to 2.8 20 to 25 33.8 ~ 33.9 2.6 to 2.7 0 to 5 34.9 to 35.0 2.5 to 2.6 0 to 5 36.0 to 36.1 2.4 to 2.5 15 to 20 37.0 to 37.1 2.4 to 2.5 0 to 5 39.0 to 39.1 2.3 to 2.4 0 to 5 39.9 to 40.0 2.2 to 2.3 0 to 5 40.8 to 40.9 2.2 to 2.3 0 to 5 42.7 ~ 42.8 2.1 to 2.2 0 to 5 44.4 to 44.5 2.0 to 2.1 0 to 5 45.3 ~ 45.4 1.9 to 2.0 0 to 5 47.8 ~ 47.9 1.9 to 2.0 5 to 10 48.6 ~ 48.7 1.8 to 1.9 5 to 10 49.4 to 49.5 1.8 to 1.9 0 to 5

In Table 2, θ, d, and I mean 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. - A wire tube was used. Measurements were made at a rate of 5 degrees per minute (2θ) from a horizontally compressed powder sample, and d and I were calculated from the 2θ values and peak heights of the observed X-ray diffraction peaks.

In a preferred embodiment of the present invention, in the rho zeolite, the ratio of A ₂ O to Al ₂ O ₃ is preferably 0 to 10.0 A ₂ O: 1.0 Al ₂ O ₃ , and more preferably 1.0 to 6.0 A ₂ O: 1.0 Al ₂ O ₃ .

In a preferred embodiment of the present invention, the rho zeolite is 1.0 ~ 6.0 A ₂ O: 1.0 Al ₂ O ₃ : 2 ~ 50 SiO ₂ .

In the present invention, the rho zeolite belongs to the space group of Im-3M of the cubic crystal system, and the crystal axis unit cell lengths a , b, and c are approximately 14.9 to 15.5 Å (Angstrom), preferably crystal It is a zeolite with axial unit cell lengths a , b and c of 14.9 Å. The structure of the rho zeolite determined through X-ray diffraction analysis is shown in FIG. 1 . The rho zeolite is a small pore material and contains various pores composed of 8 oxygen rings inside.

In the present invention, the rho zeolite may be converted into a rho (hereinafter H-rho) zeolite in which the charge of Al in the skeleton is compensated with proton (H ⁺ ) for application to acid catalysis.

In the present invention, the H-rho is a 1.0M sodium ammonium (NH ₄ NO ₃ ) solution after calcining the rho zeolite obtained using the reaction mixture of Formula (2) at 550 ° C. for 8 hours at 80 ° C. twice. After ion exchange, it can be obtained after calcination at 550 °C for 4 hours. Under the above conditions, H-rho zeolite has a crystal structure represented by the X-ray diffraction data in Table 3.

2θ d 100 × I/I _O 8.2 to 8.3 10.7 to 10.8 VS 11.7 to 11.8 7.5 to 7.6 W 14.3 to 14.4 6.1 to 6.2 W 16.6 to 16.7 5.3 to 5.4 VS 18.5 to 18.6 4.7 to 4.8 M 20.3 to 20.4 4.3 to 4.4 W 22.0 ~ 22.1 4.0 ~ 4.1 W 23.6 ~ 23.7 3.7 to 3.8 W 25.0 to 25.1 3.5 to 3.6 S 26.4 ~ 26.5 3.3 to 3.4 S 29.0 ~ 29.1 3.0 to 3.1 W 30.2 to 30.3 2.9 to 3.0 M 32.5 to 32.6 2.7 to 2.8 W 33.6 ~ 33.7 2.6 to 2.7 W 35.7 ~ 35.8 2.5 to 2.6 W 36.7 ~ 36.8 2.4 to 2.5 W 37.8 ~ 37.9 2.3 to 2.4 W 39.7 ~ 39.8 2.2 to 2.3 W 40.6 to 40.7 2.2 to 2.3 W 42.4 to 42.5 2.1 to 2.2 W 43.4 ~ 43.5 2.0 to 2.1 W 44.1 to 44.2 2.0 to 2.1 W 47.5 to 47.6 1.9 to 2.0 W 48.3 to 48.4 1.8 to 1.9 W 49.1 to 49.2 1.8 to 1.9 W

In Table 3, θ, d, and I mean 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. - A wire tube was used. Measurements were made at a rate of 5 degrees per minute (2θ) from a horizontally compressed powder sample, and d and I were calculated from the 2θ values and peak heights of the observed X-ray diffraction peaks, where 100I/Io is W (weak: 0-20), M (medium: 20-40), S (strong: 40-60), and VS (very strong: 60-100).

In a preferred embodiment of the present invention, the H-rho zeolite of Table 3 is represented in Table 4 below.

2θ d 100 × I/I _O 8.2 to 8.3 10.7 to 10.8 70 to 75 11.7 to 11.8 7.5 to 7.6 10 to 15 14.3 to 14.4 6.1 to 6.2 0 to 5 16.6 to 16.7 5.3 to 5.4 95 to 100 18.5 to 18.6 4.7 to 4.8 25 to 30 20.3 to 20.4 4.3 to 4.4 15 to 20 22.0 ~ 22.1 4.0 ~ 4.1 5 to 10 23.6 ~ 23.7 3.7 to 3.8 15 to 20 25.0 to 25.1 3.5 to 3.6 10 to 15 26.4 ~ 26.5 3.3 to 3.4 40 to 45 29.0 ~ 29.1 3.0 to 3.1 50 to 55 30.2 to 30.3 2.9 to 3.0 15 to 20 32.5 to 32.6 2.7 to 2.8 30 to 35 33.6 ~ 33.7 2.6 to 2.7 15 to 20 35.7 ~ 35.8 2.5 to 2.6 0 to 5 36.7 ~ 36.8 2.4 to 2.5 15 to 20 37.8 ~ 37.9 2.3 to 2.4 0 to 5 39.7 ~ 39.8 2.2 to 2.3 0 to 5 40.6 to 40.7 2.2 to 2.3 0 to 5 42.4 to 42.5 2.1 to 2.2 0 to 5 43.4 ~ 43.5 2.0 to 2.1 0 to 5 44.1 to 44.2 2.0 to 2.1 0 to 5 47.5 to 47.6 1.9 to 2.0 5 to 10 48.3 to 48.4 1.8 to 1.9 0 to 5 49.1 to 49.2 1.8 to 1.9 0 to 5

In Table 4, θ, d, and I mean 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. - A wire tube was used. Measurements were made at a rate of 5 degrees per minute (2θ) from a horizontally compressed powder sample, and d and I were calculated from the 2θ values and peak heights of the observed X-ray diffraction peaks.

As can be seen from the powder X-ray rotation data of the H-rho zeolite, rho is structurally stable even after heat treatment at a temperature of 550 ° C. or more for 8 hours or more, and is crystallized even after conversion to H ⁺ form for application to an acid catalyst. Since there is no significant change in the properties, its utility value is very high as an adsorbent and catalyst in various industrial processes.

The H-rho zeolite may have a BET surface area of 500 m ² /g or more, preferably 700 m ² /g or more, for example, a BET surface area of 700 to 900 m ² /g.

In another aspect of the present invention,

TEAOH; K metal component; Provided is a method for synthesizing ZK-5 zeolite using a structure-inducing material including Cs as a metal component.

In one embodiment of the present invention, the ZK-5 zeolite is

A +1 valent potassium hydroxide (KOH) aqueous solution is added in a ratio of 0 to 5 moles, preferably 0.25 to 2 moles, with respect to 1 mole of aluminum metal (Al ₂ O ₃ ), and a cesium hydroxide (CsOH) aqueous solution is added in a ratio of 0 to 5 moles. 5 moles, preferably 0.25 to 2 moles, were added and stirred for 1 hour to make a first solution, and silica sol or amorphous silica was added in a ratio of 2 to 50 moles to 1 mole of metallic aluminum and dissolved. Finally, TEAOH, which is an organic structure inducing material, is added in a ratio of 1 to 25 moles, preferably 0.5 to 5 moles, and stirred for 1 hour to make a second solution, and then slowly add the prepared first solution to the second solution After adding one drop at a time, stirring at room temperature for 24 hours to obtain a reaction mixture as shown in Formula (4); and

0.5~5.0 TEAOH:0.25~2.0 KOH:0.25~2.0 CsOH:1.0 Al ₂ O ₃ :2.0~50 SiO ₂ :10~200 H ₂ O (4)

It can be synthesized by; transferring the reaction mixture of Chemical Formula 4 to a Teflon reactor, putting it back into a container made of stainless steel, and heating it at 50 to 200° C. for 12 hours to 7 days.

In the present invention, the ZK-5 zeolite is

TAEOH;

It has a composition ratio represented by the following formula (5)

0.1~10 A ₂ O: 1.0 Al ₂ O ₃ : 1.0~100 SiO ₂ (5)

Here, A consists of K and Cs,

It is characterized in that it has a skeletal structure according to the XRD pattern shown in Table 5 below.

2θ d 100×I/I _O 6.7 ~ 6.8 13.2 to 13.3 M 11.6 to 11.7 7.6 ~ 7.7 W 13.4 to 13.5 6.6 to 6.7 W 15.0 to 15.1 5.9 to 6.0 VS 16.4 to 16.5 5.4 ~ 5.5 M 17.7 ~ 17.8 5.0 to 5.1 W 20.1 to 20.2 4.4 to 4.5 VS 21.2 to 21.3 4.2 to 4.3 VS 22.3 ~ 22.4 4.0 ~ 4.1 W 23.3 ~ 23.4 3.8 to 3.9 VS 24.2 ~ 24.3 3.7 to 3.8 W 24.9 to 25.0 3.6 ~ 3.7 W 26.1 to 26.2 3.4 to 3.5 S 27.8 ~ 27.9 3.2 to 3.3 VS 28.6 ~ 28.7 3.1 to 3.2 W 29.4 ~ 29.5 3.0 to 3.1 VS 30.2 to 30.3 3.0 to 3.1 S 31.7 ~ 31.8 2.8 to 2.9 VS 32.5 to 32.6 2.8 to 2.9 W 33.9 to 34.0 2.6 to 2.7 M 35.2 to 35.3 2.5 to 2.6 S 35.3 ~ 35.4 2.5 to 2.6 W 36.6 ~ 36.7 2.5 to 2.6 W 37.9 to 38.0 2.4 to 2.5 W 39.1 to 39.2 2.3 to 2.4 W 40.3 to 40.4 2.2 to 2.3 W 40.9 to 41.0 2.2 to 2.3 W 41.5 to 41.6 2.2 to 2.3 W 42.1 to 42.2 2.1 to 2.2 W 43.8 ~ 43.9 2.1 to 2.2 W 44.3 to 44.4 2.0 to 2.1 W 44.9 to 45.0 2.0 to 2.1 W 46.0 ~ 46.1 2.0 to 2.1 W 47.1 to 47.2 1.9 to 2.0 W 48.1 to 48.2 1.9 to 2.0 W 48.7 ~ 48.8 1.9 to 2.0 W 49.2 to 49.3 1.9 to 2.0 W 49.7 ~ 49.8 1.8 to 1.9 W

In Table 5, θ, d, and I mean the Bragg angle, the grating 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. - A wire tube was used. Measurements were made at a rate of 5 degrees per minute (2θ) from a horizontally compressed powder sample, and d and I were calculated from the 2θ values and peak heights of the observed X-ray diffraction peaks, where 100×I/I ₀ is W It is divided into (weak: 0-20), M (medium: 20-40), S (strong: 40-60), and VS (very strong: 60-100). According to the above results, it was confirmed that the skeleton structure had the same composition as in Chemical Formula 1, and the material having an X-ray diffraction pattern including the lattice intervals given in Table 5 was ZK-5 zeolite reported previously [Atlas of Zeolite Structure Types, Butterworth 2007], [http://www.iza-structure.org/].

In the present invention, the ratio of Al ₂ O ₃ and SiO ₂ in the ZK-5 zeolite is preferably 1.0 Al ₂ O ₃ :1.0-100 SiO ₂ It may be expressed, more preferably 1.0:2.0-50 , and 2θ, d, 100×I/I ₀ of Table 1 may be expressed in Table 6 below.

2θ d 100×I/I _O 6.7 ~ 6.8 13.2 to 13.3 30 to 35 11.6 to 11.7 7.6 ~ 7.7 5 to 10 13.4 to 13.5 6.6 to 6.7 15 to 20 15.0 to 15.1 5.9 to 6.0 75 to 80 16.4 to 16.5 5.4 ~ 5.5 25 to 30 17.7 ~ 17.8 5.0 to 5.1 5 to 10 20.1 to 20.2 4.4 to 4.5 70 to 75 21.2 to 21.3 4.2 to 4.3 65 to 70 22.3 ~ 22.4 4.0 ~ 4.1 10 to 15 23.3 ~ 23.4 3.8 to 3.9 65 to 70 24.2 ~ 24.3 3.7 to 3.8 10 to 15 24.9 to 25.0 3.6 ~ 3.7 0 to 5 26.1 to 26.2 3.4 to 3.5 40 to 45 27.8 ~ 27.9 3.2 to 3.3 95 to 100 28.6 ~ 28.7 3.1 to 3.2 10 to 15 29.4 ~ 29.5 3.0 to 3.1 70 to 75 30.2 to 30.3 3.0 to 3.1 45 to 50 31.7 ~ 31.8 2.8 to 2.9 60 to 65 32.5 to 32.6 2.8 to 2.9 0 to 5 33.9 to 34.0 2.6 to 2.7 20 to 25 35.2 to 35.3 2.5 to 2.6 40 to 45 35.3 ~ 35.4 2.5 to 2.6 15 to 20 36.6 ~ 36.7 2.5 to 2.6 0 to 5 37.9 to 38.0 2.4 to 2.5 0 to 5 39.1 to 39.2 2.3 to 2.4 15 to 20 40.3 to 40.4 2.2 to 2.3 0 to 5 40.9 to 41.0 2.2 to 2.3 10 to 15 41.5 to 41.6 2.2 to 2.3 0 to 5 42.1 to 42.2 2.1 to 2.2 0 to 5 43.8 ~ 43.9 2.1 to 2.2 0 to 5 44.3 to 44.4 2.0 to 2.1 0 to 5 44.9 to 45.0 2.0 to 2.1 5 to 10 46.0 ~ 46.1 2.0 to 2.1 0 to 5 47.1 to 47.2 1.9 to 2.0 5 to 10 48.1 to 48.2 1.9 to 2.0 0 to 5 48.7 ~ 48.8 1.9 to 2.0 5 to 10 49.2 to 49.3 1.9 to 2.0 0 to 5 49.7 ~ 49.8 1.8 to 1.9 5 to 10

In Table 6, θ, d, and I mean the Bragg angle, the grating 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. - A wire tube was used. Measurements were made at a rate of 5 degrees per minute (2θ) from a horizontally compressed powder sample, and d and I were calculated from the 2θ values and peak heights of the observed X-ray diffraction peaks.

The ratio of K ₂ O to Al ₂ O ₃ is preferably 0 to 10.0 K ₂ O: 1.0 Al ₂ O ₃ , and more preferably 1.0 to 6.0 K ₂ O: 1.0 Al ₂ O ₃ .

In a preferred embodiment of the present invention, the zeolite is 1.0 ~ 6.0 K ₂ O: 1.0 Al ₂ O ₃ : 2 ~ 50 SiO ₂ .

In the present invention, the ZK-5 zeolite belongs to the space group of Im-3M of the cubic crystal system, and the crystal axis unit cell lengths a , b, and c are approximately 18.0-19.0 Å (Angstrom), preferably is a zeolite with crystal axis unit cell lengths a , b, and c of 18.6 Å. The structure of ZK-5 zeolite determined through X-ray diffraction analysis is shown in FIG. 2 . ZK-5 zeolite is a small pore material and contains various pores composed of 8 oxygen rings inside.

In the present invention, the ZK-5 zeolite may be converted into a ZK-5 (hereinafter H-ZK-5) zeolite in which the charge of Al in the skeleton is compensated with proton (H ⁺ ) for application to acid catalysis.

In the present invention, the H-ZK-5 zeolite formed from the proton (H ⁺ ) after the calcination of ZK-5 is 1.0M after calcining the ZK-5 zeolite obtained using the reaction mixture of Formula 4 at 550° C. for 8 hours. It can be obtained after ion exchange at 80°C twice with ammonium sodium (NH ₄ NO ₃ ) solution and calcined at 550°C for 4 hours. Under the above conditions, H-ZK-5 zeolite has a crystal structure represented by the X-ray diffraction data in Table 7.

2θ D 100 × I/I _O 6.7 ~ 6.8 13.2 to 13.3 W 9.5 ~ 9.6 9.3 ~ 9.4 VS 13.4 to 13.5 6.6 to 6.7 W 15.0 to 15.1 5.9 to 6.0 S 16.5 to 16.6 5.4 ~ 5.5 S 19.0 to 19.1 4.7 to 4.8 W 20.2 to 20.3 4.4 to 4.5 S 21.3 to 21.4 4.2 to 4.3 M 22.4 to 22.5 4.0 ~ 4.1 W 23.4 ~ 23.5 3.8 to 3.9 M 24.3 ~ 24.4 3.7 to 3.8 W 26.1 to 26.2 3.4 to 3.5 W 27.9 ~ 28.0 3.2 to 3.3 S 29.5 ~ 29.6 3.0 to 3.1 M 30.3 to 30.4 2.9 to 3.0 M 31.8 ~ 31.9 2.8 to 2.9 M 32.6 ~ 32.7 2.7 to 2.8 W 34.0 to 34.1 2.6 to 2.7 W 35.4 ~ 35.5 2.5 to 2.6 W 36.7 ~ 36.8 2.4 to 2.5 W 39.2 to 39.3 2.3 to 2.4 W 41.1 to 41.2 2.2 to 2.3 W 41.6 ~ 41.7 2.2 to 2.3 W 42.3 ~ 42.4 2.1 to 2.2 W 44.0 to 44.1 2.1 to 2.2 W 44.5 to 44.6 2.0 to 2.1 W 45.1 to 45.2 2.0 to 2.1 W 47.3 to 47.4 1.9 to 2.0 W 48.9 to 49.0 1.9 to 2.0 W

In Table 7, θ, d, and I mean the Bragg angle, the grating 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. - A wire tube was used. Measurements were made at a rate of 5 degrees per minute (2θ) from a horizontally compressed powder sample, and d and I were calculated from the 2θ values and peak heights of the observed X-ray diffraction peaks, where 100I/Io is W (weak: 0 to 20), M (medium: 20 to 40), S (strong: 40 to 60), and VS (very strong: 60 to 100). In a preferred embodiment of the present invention, H- ZK-5 zeolite is represented in Table 8 below.

2θ D 100 × I/I _O 6.7 ~ 6.8 13.2 to 13.3 15 to 20 9.5 ~ 9.6 9.3 ~ 9.4 95 to 100 13.4 to 13.5 6.6 to 6.7 5 to 10 15.0 to 15.1 5.9 to 6.0 50 to 55 16.5 to 16.6 5.4 ~ 5.5 40 to 45 19.0 to 19.1 4.7 to 4.8 5 to 10 20.2 to 20.3 4.4 to 4.5 40 to 45 21.3 to 21.4 4.2 to 4.3 25 to 30 22.4 to 22.5 4.0 ~ 4.1 15 to 20 23.4 ~ 23.5 3.8 to 3.9 20 to 25 24.3 ~ 24.4 3.7 to 3.8 0 to 5 26.1 to 26.2 3.4 to 3.5 10 to 15 27.9 ~ 28.0 3.2 to 3.3 40 to 45 29.5 ~ 29.6 3.0 to 3.1 25 to 30 30.3 to 30.4 2.9 to 3.0 20 to 25 31.8 ~ 31.9 2.8 to 2.9 20 to 25 32.6 ~ 32.7 2.7 to 2.8 5 to 10 34.0 to 34.1 2.6 to 2.7 5 to 10 35.4 ~ 35.5 2.5 to 2.6 5 to 10 36.7 ~ 36.8 2.4 to 2.5 0 to 5 39.2 to 39.3 2.3 to 2.4 0 to 5 41.1 to 41.2 2.2 to 2.3 0 to 5 41.6 ~ 41.7 2.2 to 2.3 0 to 5 42.3 ~ 42.4 2.1 to 2.2 0 to 5 44.0 to 44.1 2.1 to 2.2 0 to 5 44.5 to 44.6 2.0 to 2.1 0 to 5 45.1 to 45.2 2.0 to 2.1 0 to 5 47.3 to 47.4 1.9 to 2.0 0 to 5 48.9 to 49.0 1.9 to 2.0 0 to 5

In Table 8, θ, d, and I mean the Bragg angle, the grating 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. - A wire tube was used. Measurements were made at a rate of 5 degrees per minute (2θ) from a horizontally compressed powder sample, and d and I were calculated from the 2θ values and peak heights of the observed X-ray diffraction peaks. As can be seen from the powder X-ray rotation data of the H ^- ZK-5 zeolite, ZK-5 is structurally stable even after heat treatment at a temperature of 550 ° C. Since there is no significant change in crystallinity even after conversion, it is expected to have very high utilization value as an adsorbent and catalyst in various industrial processes.

The H-ZK-5 zeolite may have a BET surface area of 400 m ² /g or more, preferably 500 m ² /g or more, for example, a BET surface area of 500 to 700 m ² /g.

In another aspect, the present invention

TEAOH; Li metal component; Provided is a method for synthesizing offretite zeolite using a structure-inducing material containing Rb as a metal component.

In one embodiment of the present invention, the offretite zeolite is

To 1 mol of aluminum metal (Al ₂ O ₃ ), a +1 valent lithium hydroxide (LiOH) aqueous solution is added in a ratio of 0 to 5 moles, preferably 0.25 to 2 moles, and a rubidium hydroxide (RbOH) aqueous solution is added in a ratio of 0 to 5 moles. 5 moles, preferably 0.25 to 2 moles, were added and stirred for 1 hour to make a first solution, and silica sol or amorphous silica was added in a ratio of 2 to 50 moles to 1 mole of metallic aluminum and dissolved. Finally, TEAOH, which is an organic structure inducing material, is added in a ratio of 1 to 25 moles, preferably 0.5 to 5 moles, and stirred for 1 hour to make a second solution, and then slowly add the prepared first solution to the second solution After adding one drop at a time, stirring at room temperature for 24 hours to obtain a reaction mixture as shown in Formula (6); and

0.5~5.0 TEAOH:0.25~2.0 LiOH:0.25~2.0 RbOH:1.0 Al ₂ O ₃ :2.0~50 SiO ₂ :10~200 H ₂ O (6)

It can be synthesized by; transferring the reaction mixture of formula (6) to a Teflon reactor and putting it back into a stainless steel container and heating it at 50-200° C. for 12 hours to 7 days.

In the present invention, the offretite zeolite is

TAEOH;

It has a composition ratio represented by the following formula (7)

0.1~10 A ₂ O: 1.0 Al ₂ O ₃ : 1.0~100 SiO ₂ (7)

Here, A consists of Li and Rb,

It is characterized in that it has a skeletal structure according to the XRD pattern shown in Table 9 below.

2θ d 100×I/I _O 7.8 ~ 7.9 11.3 to 11.4 VS 11.8 to 11.9 7.5 to 7.6 W 13.5 to 13.6 6.6 to 6.7 M 15.6 to 15.7 5.7 ~ 5.8 W 17.9 to 18.0 5.0 to 5.1 W 19.5 to 19.6 4.5 to 4.6 W 20.6 to 20.7 4.3 to 4.4 M 23.4 ~ 23.5 3.8 to 3.9 M 23.8 ~ 23.9 3.7 to 3.8 VS 24.9 to 25.0 3.6 ~ 3.7 M 26.2 ~ 26.3 3.4 to 3.5 W 27.1 ~ 27.2 3.3 to 3.4 W 28.4 to 28.5 3.1 to 3.2 S 30.6 to 30.7 2.9 to 3.0 W 31.3 to 31.4 2.9 to 3.0 S 31.5 to 31.6 2.8 to 2.9 S 33.5 to 33.6 2.7 to 2.8 W 36.3 to 36.4 2.5 to 2.6 M 38.3 ~ 38.4 2.4 to 2.5 W 39.4 to 39.5 2.3 to 2.4 W 41.0 to 41.1 2.2 to 2.3 W 41.5 to 41.6 2.2 to 2.3 W 42.8 ~ 42.9 2.1 to 2.2 W 43.6 ~ 43.7 2.1 to 2.2 W 45.8 ~ 45.9 2.0 to 2.1 W 46.5 ~ 46.6 2.0 to 2.1 W 48.2 to 48.3 1.9 to 2.0 W

In Table 9, θ, d, and I mean 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. - A wire tube was used. Measurements were made at a rate of 5 degrees per minute (2θ) from a horizontally compressed powder sample, and d and I were calculated from the 2θ values and peak heights of the observed X-ray diffraction peaks, where 100×I/I ₀ is W It is divided into (weak: 0-20), M (medium: 20-40), S (strong: 40-60), and VS (very strong: 60-100).

According to the above results, it was confirmed that the skeleton structure had the same composition as in Chemical Formula 1, and the material having an X-ray diffraction pattern including the lattice intervals given in Table 9 was the previously reported offretite zeolite [Atlas of Zeolite Structure Types, Butterworth 2007], [http://www.iza-structure.org/].

In the present invention, the ratio of Al ₂ O ₃ and SiO ₂ in the zeolite is preferably 1.0 Al ₂ O ₃ : 1.0 ~ 100 SiO ₂ It can be expressed, more preferably 1.0: 2.0 ~ 50, the 2θ, d, 100×I/I ₀ of Table 9 may be expressed in Table 10 below.

2θ d 100×I/I _O 7.8 ~ 7.9 11.3 to 11.4 70 to 75 11.8 to 11.9 7.5 to 7.6 5 to 10 13.5 to 13.6 6.6 to 6.7 30 to 35 15.6 to 15.7 5.7 ~ 5.8 0 to 5 17.9 to 18.0 5.0 to 5.1 5 to 10 19.5 to 19.6 4.5 to 4.6 0 to 5 20.6 to 20.7 4.3 to 4.4 25 to 30 23.4 ~ 23.5 3.8 to 3.9 20 to 25 23.8 ~ 23.9 3.7 to 3.8 95 to 100 24.9 to 25.0 3.6 ~ 3.7 30 to 35 26.2 ~ 26.3 3.4 to 3.5 5 to 10 27.1 ~ 27.2 3.3 to 3.4 5 to 10 28.4 to 28.5 3.1 to 3.2 45 to 50 30.6 to 30.7 2.9 to 3.0 0 to 5 31.3 to 31.4 2.9 to 3.0 50 to 55 31.5 to 31.6 2.8 to 2.9 45 to 50 33.5 to 33.6 2.7 to 2.8 5 to 10 36.3 to 36.4 2.5 to 2.6 20 to 25 38.3 ~ 38.4 2.4 to 2.5 0 to 5 39.4 to 39.5 2.3 to 2.4 0 to 5 41.0 to 41.1 2.2 to 2.3 5 to 10 41.5 to 41.6 2.2 to 2.3 0 to 5 42.8 ~ 42.9 2.1 to 2.2 0 to 5 43.6 ~ 43.7 2.1 to 2.2 0 to 5 45.8 ~ 45.9 2.0 to 2.1 0 to 5 46.5 ~ 46.6 2.0 to 2.1 0 to 5 48.2 to 48.3 1.9 to 2.0 5 to 10

In Table 10, θ, d, and I mean the Bragg angle, the grating 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. - A wire tube was used. Measurements were made at a rate of 5 degrees per minute (2θ) from a horizontally compressed powder sample, and d and I were calculated from the 2θ values and peak heights of the observed X-ray diffraction peaks.

In the practice of the present invention, the ratio of A ₂ O and Al ₂ O ₃ is preferably 0 to 10.0 A ₂ O: 1.0 Al ₂ O ₃ , and more preferably 1.0 to 6.0 A ₂ O: 1.0 Al It is ₂ O ₃ .

In a preferred embodiment of the present invention, the zeolite is 1.0 to 6.0 A ₂ O: 1.0 Al ₂ O ₃ : 2 to 50 SiO ₂ .

In the present invention, the offretite zeolite belongs to the space group of P- 6m2 of the hexagonal crystal system, and the crystal axis unit cell lengths a and b are approximately 12.8 to 13.3 Å (Angstrom), and c is approximately 7.2 to 7.8 Å, preferably a zeolite having crystal axis unit cell lengths a and b of 13.1 Å and c of 7.5 Å. The structure of the offretite zeolite determined through X-ray diffraction analysis is shown in FIG. 3 . Offretite zeolite is a large pore material and contains various pores composed of 12 oxygen rings inside.

In the present invention, the offretite zeolite can be prepared through hydrothermal synthesis by controlling the types and amounts of SiO ₂ /Al ₂ O ₃ , Rb/Li and alkali metals in the reaction mixture, and using TEAOH as an organic structure inducing material. have.

In the practice of the present invention, the heating conditions may be heating for 12 hours to 14 days at 50 ~ 200 ℃.

In the present invention, the offretite zeolite may be converted into an H-offretite (hereinafter H-offretite) zeolite in which the charge of Al in the skeleton is compensated with proton (H ⁺ ) in order to be applied to the acid catalysis.

In the present invention, the H-offretite zeolite is obtained by calcining the offretite zeolite obtained using the reaction mixture of Chemical Formula 6 at 550 ° C. for 8 hours. After ion exchange at 80 ° C. twice with 1.0M sodium ammonium (NH ₄ NO ₃ ) solution. It can be obtained after calcining again at 550 °C for 4 hours. Under the above conditions, the H-offretite zeolite has a crystal structure represented by the X-ray diffraction data in Table 11.

2θ D 100 × I/I _O 7.8 ~ 7.9 11.3 to 11.4 VS 11.7 to 11.8 7.5 to 7.6 W 13.5 to 13.6 6.6 to 6.7 S 14.1 to 14.2 6.3 to 6.4 W 15.6 to 15.7 5.7 ~ 5.8 W 19.5 to 19.6 4.5 to 4.6 W 20.7 to 20.8 4.3 to 4.4 M 23.5 ~ 2.6 3.8 to 3.9 M 23.8 ~ 23.9 3.7 to 3.8 VS 24.9 to 25.0 3.6 ~ 3.7 S 26.3 to 26.4 3.4 to 3.5 W 27.2 ~ 27.3 3.3 to 3.4 W 28.4 to 28.5 3.1 to 3.2 S 30.7 to 30.8 2.9 to 3.0 W 31.5 to 31.6 2.8 to 2.9 VS 33.7 ~ 33.8 2.7 to 2.8 W 35.7 ~ 35.8 2.5 to 2.6 W 36.2 to 36.3 2.5 to 2.6 W 36.4 ~ 36.5 2.5 to 2.6 W 38.3 ~ 38.4 2.4 to 2.5 W 39.7 ~ 39.8 2.3 to 2.4 W 41.2 to 41.3 2.2 to 2.3 W 43.0 ~ 43.1 2.1 to 2.2 W 43.7 ~ 43.8 2.1 to 2.2 W 46.0 ~ 46.1 2.0 to 2.1 W 46.6 to 46.7 2.0 to 2.1 W 48.2 to 48.3 1.9 to 2.0 W 48.8 ~ 48.9 1.9 to 2.0 W

In Table 11, θ, d, and I mean the Bragg angle, the grating 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. - A wire tube was used. Measurements were made at a rate of 5 degrees per minute (2θ) from a horizontally compressed powder sample, and d and I were calculated from the 2θ values and peak heights of the observed X-ray diffraction peaks, where 100I/Io is W (weak: 0 to 20), M (medium: 20 to 40), S (strong: 40 to 60), and VS (very strong: 60 to 100). In a preferred embodiment of the present invention, H- Offretite zeolites are represented in Table 12 below.

2θ D 100 × I/I _O 7.8 ~ 7.9 11.3 to 11.4 95 to 100 11.7 to 11.8 7.5 to 7.6 15 to 20 13.5 to 13.6 6.6 to 6.7 55 to 60 14.1 to 14.2 6.3 to 6.4 5 to 10 15.6 to 15.7 5.7 ~ 5.8 5 to 10 19.5 to 19.6 4.5 to 4.6 15 to 20 20.7 to 20.8 4.3 to 4.4 30 to 35 23.5 ~ 2.6 3.8 to 3.9 25 to 30 23.8 ~ 23.9 3.7 to 3.8 75 to 80 24.9 to 25.0 3.6 ~ 3.7 45 to 50 26.3 to 26.4 3.4 to 3.5 0 to 5 27.2 ~ 27.3 3.3 to 3.4 15 to 20 28.4 to 28.5 3.1 to 3.2 40 to 45 30.7 to 30.8 2.9 to 3.0 0 to 5 31.5 to 31.6 2.8 to 2.9 65 to 70 33.7 ~ 33.8 2.7 to 2.8 10 to 15 35.7 ~ 35.8 2.5 to 2.6 0 to 5 36.2 to 36.3 2.5 to 2.6 10 to 15 36.4 ~ 36.5 2.5 to 2.6 10 to 15 38.3 ~ 38.4 2.4 to 2.5 0 to 5 39.7 ~ 39.8 2.3 to 2.4 0 to 5 41.2 to 41.3 2.2 to 2.3 5 to 10 43.0 ~ 43.1 2.1 to 2.2 0 to 5 43.7 ~ 43.8 2.1 to 2.2 0 to 5 46.0 ~ 46.1 2.0 to 2.1 0 to 5 46.6 to 46.7 2.0 to 2.1 0 to 5 48.2 to 48.3 1.9 to 2.0 5 to 10 48.8 ~ 48.9 1.9 to 2.0 0 to 5

In Table 12, θ, d, and I mean the Bragg angle, the grating 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. - A wire tube was used. Measurements were made at a rate of 5 degrees per minute (2θ) from a horizontally compressed powder sample, and d and I were calculated from the 2θ values and peak heights of the observed X-ray diffraction peaks.

As can be seen from the powder X-ray rotation data of the H-offretite zeolite, offretite is structurally stable even after heat treatment at a temperature of 550° C. or higher for 8 hours or more, and is crystallized even after conversion to H ⁺ form for application to an acid catalyst Since there is no significant change in the properties, its utility value is very high as an adsorbent and catalyst in various industrial processes.

The H-offrete zeolite may have a BET surface area of 300 m ² /g or more, preferably 400 m ² /g or more, for example, a BET surface area of 400 to 500 m ² /g.

In the present invention, they belong to the space group of Im -3 m of the cubic crystal system, and the crystal axis unit cell lengths a, b, c are 14.9 Å (Angstrom) and rho and ZK with a new silicon-aluminum ratio of 18.6 Å. -5 zeolite, and an offretite zeolite belonging to the space group of P-6m2 of the hexagonal crystal system, with a new silicon-aluminum ratio with crystal axis unit cell lengths a and b of 13.1 Å and c of 7.5 Å We provide a new method for manufacturing using low-cost derivatives, and provide new zeolites containing these derivatives.

1 is the structure of a rho zeolite.
2 is the structure of ZK-5 zeolite.
3 is the structure of an offretite zeolite.
4 is an X-ray diffraction (XRD) result of an aluminosilicate rho zeolite prepared according to Example 1. FIG.
5 is a scanning microscope (SEM) image of the aluminosilicate rho made according to Example 1. FIG.
6 is an X-ray diffraction (XRD) result of a product containing a large amount of ECR-1 and phillipsite zeolite as impurities instead of rho prepared according to Comparative Example 1-1.
7 is an X-ray diffraction (XRD) result of an analcime product prepared according to Comparative Example 1-2.
8 is an X-ray diffraction (XRD) result of aluminosilicate rho made according to Example 2. FIG.
9 is an X-ray diffraction (XRD) result of aluminosilicate rho made according to Example 3. FIG.
10 is a surface area measurement (BET) result of aluminosilicate rho made according to Example 3. FIG.
11 is an X-ray diffraction (XRD) result of aluminosilicate ZK-5 made according to Example 4.
12 is a scanning microscope (SEM) image of aluminosilicate ZK-5 made according to Example 4.
13 is an X-ray diffraction (XRD) result of a product containing L and a small amount of erionite zeolite as impurities instead of ZK-5 made according to Comparative Example 4-1.
14 is an X-ray diffraction (XRD) result of aluminosilicate ZK-5 prepared according to Example 5;
15 is a surface area measurement (BET) result of aluminosilicate ZK-5 made according to Example 5. FIG.
16 is an X-ray diffraction (XRD) result of aluminosilicate offretite prepared according to Example 6.
17 is a scanning microscope (SEM) image of aluminosilicate offretite prepared according to Example 6.
18 is an X-ray diffraction (XRD) result of a product containing a large amount of amorphous (H ₄ Li ₂ O ₇ Si ₂ ) impurities along with ZSM-12 zeolite instead of offretite made according to Comparative Example 6-1. .
19 is an X-ray diffraction (XRD) result of a product containing a small amount of L zeolite as an impurity together with offretite prepared according to Comparative Example 6-2.
20 is an X-ray diffraction (XRD) result of aluminosilicate offretite prepared according to Example 7. FIG.
21 is a surface area measurement (BET) result of aluminosilicate offretite prepared according to Example 7.

Hereinafter, the following examples describe in detail the essence of the present invention and a method for implementing the same. The following examples are intended to illustrate the present invention, but do not limit the present invention.

Example 1. Preparation of rho zeolite

In a plastic beaker, 1.40 g of 50 wt% sodium hydroxide (NaOH) and 0.75 g of 50 wt% cesium hydroxide (CsOH) were first put in 2.82 g of water, stirred for 30 minutes, and then 0.27 g of metallic aluminum was added. Stir for 1 hour. Then, after adding 1.05 g of TEAOH at 35 wt %, 7.51 g of colloidal silica sol (Ludox HS-40) was slowly added thereto, followed by stirring for 24 hours to obtain a reaction mixture having the composition shown in Chemical Formula 8 below.

[Formula 8]

0.5 TEAOH : 1.75 Na ₂ O : 0.25 Cs ₂ O : 1.00 Al ₂ O ₃ : 10 SiO ₂ : 100 H ₂ O

Then, the reaction mixture obtained above was transferred to a Teflon reactor, put into a stainless steel vessel, and heated at 120° C. for 2.75 days. Then, the obtained solid product was repeatedly washed with water and dried at room temperature.

As a result of performing an X-ray diffraction measurement test with the solid powder obtained in Example 1, it was confirmed that it was similar to rho zeolite when compared with the X-ray diffraction patterns of previously reported zeolites (Atlas of Zeolite Structure). Types, Butterworth 2007, http://www.iza-structure.org/). The results of the X-ray diffraction measurement test using the solid powder obtained in Example 1 are shown in Table 13 and FIG. 4 .

2θ d 100×I/I _O 8.4 to 8.5 10.5 to 10.6 100 14.5 to 14.6 6.0 ~ 6.1 27 16.7 to 16.8 5.3 to 5.4 16 18.7 to 18.8 4.7 to 4.8 39 20.5 to 20.6 4.3 to 4.4 8 22.2 ~ 22.3 3.9 to 4.0 15 23.8 ~ 23.9 3.7 to 3.8 9 25.2 to 25.3 3.5 to 3.6 84 26.6 ~ 26.7 3.3 to 3.4 46 28.0 ~ 28.1 3.1 to 3.2 7 29.2 ~ 29.3 3.0 to 3.1 10 30.4 to 30.5 2.9 to 3.0 26 32.8 ~ 32.9 2.7 to 2.8 23 33.8 ~ 33.9 2.6 to 2.7 2 34.9 to 35.0 2.5 to 2.6 2 36.0 to 36.1 2.4 to 2.5 18 37.0 to 37.1 2.4 to 2.5 2 39.0 to 39.1 2.3 to 2.4 One 39.9 to 40.0 2.2 to 2.3 4 40.8 to 40.9 2.2 to 2.3 One 42.7 ~ 42.8 2.1 to 2.2 4 44.4 to 44.5 2.0 to 2.1 2 45.3 ~ 45.4 1.9 to 2.0 One 47.8 ~ 47.9 1.9 to 2.0 5 48.6 ~ 48.7 1.8 to 1.9 5 49.4 to 49.5 1.8 to 1.9 3

In Table 13, θ, d, and I mean the Bragg angle, the grating 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. - A wire tube was used. Measurements were made at a rate of 5 degrees per minute (2θ) from a horizontally compressed powder sample, and d and I were calculated from the 2θ values and peak heights of the observed X-ray diffraction peaks. As a result of thermogravimetric analysis and elemental analysis, it was confirmed that the solid powder obtained in Example 1 contained about 9.7% by weight of water and 4.7% by weight of TEA cations in rho zeolite. In addition, it was confirmed that the Si/Al ratio of the produced zeolite was about 3.5 using Inductive Coupled Plasma (ICP).

In addition, as a result of measuring a scanning electron microscope (SEM) to confirm that rho is a pure substance without impurities (Fig. 5), a very uniform square crystal shape was observed, and other crystal shapes were not observed.

Comparative Example 1-1. Use only NaOH in the reaction mixture

Under the same conditions as in Example 1, only 50 wt% sodium hydroxide (NaOH) was added in an amount of 1.6 g to prepare a reaction mixture having the composition shown in Chemical Formula 9 below, and a solid product obtained after heating at 120° C. for 7 days was repeatedly washed with water and dried at room temperature.

[Formula 9]

0.5 TEAOH : 2.00 Na ₂ O : 1.00 Al ₂ O ₃ : 10 SiO ₂ : 100 H ₂ O

As a result of performing an X-ray diffraction measurement test with the solid powder obtained in Comparative Example 1-1 (FIG. 6), a large amount of phillipsite zeolite along with ECR-1 could be obtained instead of rho zeolite.

Comparative Example 1-2. Use only CsOH in the reaction mixture

Under the same conditions as in Example 1, only 50 wt% cesium hydroxide (CsOH) was added at 6.00 g to prepare a reaction mixture having the composition shown in the following formula (10), and the solid product obtained after heating at 120 °C for 3 days was repeatedly washed with water and dried at room temperature.

[Formula 10]

0.5 TEAOH : 2.00 Cs ₂ O : 1.00 Al ₂ O ₃ : 10 SiO ₂ : 100 H ₂ O

As a result of performing an X-ray diffraction measurement test with the solid powder obtained in Comparative Example 1-2 (FIG. 7), only a zeolite having an analcime structure was produced as a mixture.

Example 2. Preparation of rho zeolite

In a plastic beaker, 0.60 g of 50 wt% sodium hydroxide (NaOH) and 0.75 g of 50 wt% potassium hydroxide (CsOH) were first added to 0.27 g of water and stirred for 30 minutes, then 0.90 g of sodium aluminate (Na ₂ O·Al ₂ O ₃ ·0.8H ₂ O) was added and stirred for 1 hour. Then, after adding 1.05 g of TEAOH at 35 wt %, 7.51 g of colloidal silica sol (Ludox HS-40) was slowly added thereto, followed by stirring for 24 hours to obtain a reaction mixture having the composition shown in Chemical Formula 11 below.

[Formula 11]

0.5 TEAOH : 1.75 Na ₂ O : 0.25 Cs ₂ O : 1.00 Al ₂ O ₃ : 10 SiO ₂ : 100 H ₂ O

As a result of performing an X-ray diffraction measurement test with the solid powder obtained in Example 2 (FIG. 8), an X-ray diffraction pattern of pure rho was observed in the same manner as in Example 1.

Example 3. Preparation of H-rho zeolite

After calcining the rho zeolite prepared in Example 1 under air at 550 degrees for 8 hours, 1.0 g of zeolite was placed in 100 mL of 1.0 M sodium ammonium (NH ₄ NO ₃ ) solution, and ion exchange was performed at 80° C. for 6 hours. The solid product obtained after the repetition was repeatedly washed with water and dried at room temperature, and then calcined for 4 hours under air at 550 ° C. It was observed to exhibit essentially the same X-ray pattern as in the case of , and the results are shown in Table 14 and FIG. 9 . As a result of thermogravimetric analysis and elemental analysis, it was confirmed that all of the organic structure-inducing material (TEA) in the H-rho zeolite was burned and contained only 11.0 wt% of water. In addition, as a result of the nitrogen adsorption experiment, it was observed that the H-rho zeolite had a BET surface area of about 820 m ² /g, which is shown in FIG. 10 .

2θ d 100 × I/I _O 8.2 to 8.3 10.7 to 10.8 74 11.7 to 11.8 7.5 to 7.6 12 14.3 to 14.4 6.1 to 6.2 100 16.6 to 16.7 5.3 to 5.4 27 18.5 to 18.6 4.7 to 4.8 18 20.3 to 20.4 4.3 to 4.4 5 22.0 ~ 22.1 4.0 ~ 4.1 20 23.6 ~ 23.7 3.7 to 3.8 13 25.0 to 25.1 3.5 to 3.6 44 26.4 ~ 26.5 3.3 to 3.4 52 29.0 ~ 29.1 3.0 to 3.1 16 30.2 to 30.3 2.9 to 3.0 31 32.5 to 32.6 2.7 to 2.8 17 33.6 ~ 33.7 2.6 to 2.7 2 35.7 ~ 35.8 2.5 to 2.6 16 36.7 ~ 36.8 2.4 to 2.5 0 37.8 ~ 37.9 2.3 to 2.4 One 39.7 ~ 39.8 2.2 to 2.3 One 40.6 to 40.7 2.2 to 2.3 One 42.4 to 42.5 2.1 to 2.2 2 43.4 ~ 43.5 2.0 to 2.1 0 44.1 to 44.2 2.0 to 2.1 5 47.5 to 47.6 1.9 to 2.0 5 48.3 to 48.4 1.8 to 1.9 4 49.1 to 49.2 1.8 to 1.9 3

In Table 14, θ, d, and I mean the Bragg angle, the grating 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. - A wire tube was used. Measurements were made at a rate of 5 degrees per minute (2θ) from a horizontally compressed powder sample, and d and I were calculated from the 2θ values and peak heights of the observed X-ray diffraction peaks.

Example 4. Preparation of ZK-5 zeolite

In a plastic beaker, 2.18 g of 45 wt% potassium hydroxide (KOH) and 0.75 g of 50 wt% cesium hydroxide (CsOH) were first put in 2.32 g of water, stirred for 30 minutes, and then 0.27 g of metallic aluminum was added. After stirring for 1 hour. Then, after adding 1.05 g of TEAOH at 35 wt %, 7.51 g of colloidal silica sol (Ludox HS-40) was slowly added thereto, followed by stirring for 24 hours to obtain a reaction mixture having the composition shown in Chemical Formula 12 below.

[Formula 12]

0.5 TEAOH : 1.75 K ₂ O : 0.25 Cs ₂ O : 1.00 Al ₂ O ₃ : 10 SiO ₂ : 100 H ₂ O

Then, the reaction mixture obtained above was transferred to a Teflon reactor, put into a stainless steel vessel again, heated at 120° C. for 7 days, and then the obtained solid product was repeatedly washed with water and dried at room temperature.

As a result of performing an X-ray diffraction measurement test with the solid powder obtained in Example 4, it was confirmed that it was similar to the ZK-5 zeolite when compared with the X-ray diffraction patterns of the previously reported zeolites (Atlas of Zeolite Structure Types, Butterworth 2007, http://www.iza-structure.org/). The results of the X-ray diffraction measurement test using the solid powder obtained in Example 4 are shown in Table 15 and FIG. 11 .

2θ d 100×I/I _O 6.7 ~ 6.8 13.2 to 13.3 32 11.6 to 11.7 7.6 ~ 7.7 6 13.4 to 13.5 6.6 to 6.7 15 15.0 to 15.1 5.9 to 6.0 80 16.4 to 16.5 5.4 ~ 5.5 27 17.7 ~ 17.8 5.0 to 5.1 7 20.1 to 20.2 4.4 to 4.5 71 21.2 to 21.3 4.2 to 4.3 65 22.3 ~ 22.4 4.0 ~ 4.1 11 23.3 ~ 23.4 3.8 to 3.9 69 24.2 ~ 24.3 3.7 to 3.8 13 24.9 to 25.0 3.6 ~ 3.7 2 26.1 to 26.2 3.4 to 3.5 44 27.8 ~ 27.9 3.2 to 3.3 100 28.6 ~ 28.7 3.1 to 3.2 13 29.4 ~ 29.5 3.0 to 3.1 73 30.2 to 30.3 3.0 to 3.1 47 31.7 ~ 31.8 2.8 to 2.9 61 32.5 to 32.6 2.8 to 2.9 3 33.9 to 34.0 2.6 to 2.7 22 35.2 to 35.3 2.5 to 2.6 41 35.3 ~ 35.4 2.5 to 2.6 19 36.6 ~ 36.7 2.5 to 2.6 4 37.9 to 38.0 2.4 to 2.5 2 39.1 to 39.2 2.3 to 2.4 17 40.3 to 40.4 2.2 to 2.3 2 40.9 to 41.0 2.2 to 2.3 12 41.5 to 41.6 2.2 to 2.3 2 42.1 to 42.2 2.1 to 2.2 2 43.8 ~ 43.9 2.1 to 2.2 3 44.3 to 44.4 2.0 to 2.1 2 44.9 to 45.0 2.0 to 2.1 7 46.0 ~ 46.1 2.0 to 2.1 One 47.1 to 47.2 1.9 to 2.0 6 48.1 to 48.2 1.9 to 2.0 4 48.7 ~ 48.8 1.9 to 2.0 8 49.2 to 49.3 1.9 to 2.0 4 49.7 ~ 49.8 1.8 to 1.9 7

In Table 15, θ, d, and I mean the Bragg angle, the grating 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. - A wire tube was used. Measurements were made at a rate of 5 degrees per minute (2θ) from a horizontally compressed powder sample, and d and I were calculated from the 2θ values and peak heights of the observed X-ray diffraction peaks. As a result of thermogravimetric analysis and elemental analysis of the solid powder obtained in Example 4, it was confirmed that the rho zeolite contained about 13.2% by weight of water and 2.9% by weight of TEA cations. In addition, it was confirmed that the Si/Al ratio of the produced zeolite was about 3.5 using Inductive Coupled Plasma (ICP).

At the same time, as a result of measuring a scanning electron microscope (SEM for short) to confirm that ZK-5 is a pure substance without impurities ( FIG. 12 ), a very uniform square crystal shape was observed, and other crystals No shape was observed.

Comparative Example 4-1. Use only KOH in the reaction mixture

Under the same conditions as in Example 4, only 45 wt% potassium hydroxide (KOH) was added in an amount of 2.5 g to prepare a reaction mixture having the composition shown in the following formula (13), and a solid product obtained after heating at 120 °C for 7 days was repeatedly washed with water and dried at room temperature.

[Formula 13]

0.5 TEAOH : 2.00 K ₂ O : 1.00 Al ₂ O ₃ : 10 SiO ₂ : 100 H ₂ O

As a result of performing an X-ray diffraction measurement test with the solid powder obtained in Comparative Example 4-1 (FIG. 13), it was possible to obtain a small amount of erionite zeolite together with LTL instead of ZK-5 zeolite.

Example 5. Preparation of H-ZK-5 zeolite

After calcining the ZK-5 zeolite prepared in Example 4 under air at 550° C. for 8 hours, 1.0 g of zeolite was placed in 100 mL of 1.0 M sodium ammonium (NH ₄ NO ₃ ) solution, and ions were placed at 80° C. for 6 hours. After repeating the exchange twice, the solid product obtained was repeatedly washed with water and dried at room temperature, and then calcined for 4 hours under air at 550° C. to convert to H-ZK-5 zeolite. The sample was observed to exhibit essentially the same X-ray pattern as that of Example 4, and the results are shown in Table 16 and FIG. 14 . As a result of thermogravimetric analysis and elemental analysis, it was confirmed that all of the organic structure-inducing material (TEA) in the H-ZK-5 zeolite was burned and only contained 12.6 wt% of water. In addition, as a result of the nitrogen adsorption experiment, it was observed that the H-ZK-5 zeolite had a BET surface area of about 580 m ² /g, which is shown in FIG. 15 .

2θ D 100 × I/I _O 6.7 ~ 6.8 13.2 to 13.3 18 9.5 ~ 9.6 9.3 ~ 9.4 100 13.4 to 13.5 6.6 to 6.7 7 15.0 to 15.1 5.9 to 6.0 53 16.5 to 16.6 5.4 ~ 5.5 41 19.0 to 19.1 4.7 to 4.8 7 20.2 to 20.3 4.4 to 4.5 44 21.3 to 21.4 4.2 to 4.3 28 22.4 to 22.5 4.0 ~ 4.1 17 23.4 ~ 23.5 3.8 to 3.9 20 24.3 ~ 24.4 3.7 to 3.8 5 26.1 to 26.2 3.4 to 3.5 14 27.9 ~ 28.0 3.2 to 3.3 45 29.5 ~ 29.6 3.0 to 3.1 29 30.3 to 30.4 2.9 to 3.0 24 31.8 ~ 31.9 2.8 to 2.9 22 32.6 ~ 32.7 2.7 to 2.8 5 34.0 to 34.1 2.6 to 2.7 8 35.4 ~ 35.5 2.5 to 2.6 7 36.7 ~ 36.8 2.4 to 2.5 2 39.2 to 39.3 2.3 to 2.4 2 41.1 to 41.2 2.2 to 2.3 3 41.6 ~ 41.7 2.2 to 2.3 2 42.3 ~ 42.4 2.1 to 2.2 One 44.0 to 44.1 2.1 to 2.2 3 44.5 to 44.6 2.0 to 2.1 One 45.1 to 45.2 2.0 to 2.1 3 47.3 to 47.4 1.9 to 2.0 One 48.9 to 49.0 1.9 to 2.0 4

In Table 16, θ, d, and I mean the Bragg angle, the grating 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. - A wire tube was used. Measurements were made at a rate of 5 degrees per minute (2θ) from a horizontally compressed powder sample, and d and I were calculated from the 2θ values and peak heights of the observed X-ray diffraction peaks.

Example 6. Preparation of offretite zeolite

In a plastic beaker, 0.06 g of 98 wt% lithium hydroxide (LiOH) and 3.59 g of 50 wt% rubidium hydroxide (RbOH) were first added to 2.10 g of water, stirred for 30 minutes, and then 0.27 g of metallic aluminum was added. Stir for 1 hour. Then, after adding 1.05 g of TEAOH at 35 wt %, 7.51 g of colloidal silica sol (Ludox HS-40) was slowly added thereto, followed by stirring for 24 hours to obtain a reaction mixture having the composition shown in Chemical Formula 14 below.

[Formula 14]

0.5 TEAOH : 1.75 Rb ₂ O : 0.25 Li ₂ O : 1.00 Al ₂ O ₃ : 10 SiO ₂ : 100 H ₂ O

Then, the reaction mixture obtained above was transferred to a Teflon reactor, put into a stainless steel vessel, and heated at 120° C. for 7 days, and then the obtained solid product was repeatedly washed with water and dried at room temperature.

As a result of performing an X-ray diffraction measurement test with the solid powder obtained in Example 6, it was confirmed that it was similar to the offretite zeolite when compared with the X-ray diffraction patterns of previously reported zeolites (Atlas of Zeolite Structure). Types, Butterworth 2007, http://www.iza-structure.org/). The results of the X-ray diffraction measurement test using the solid powder obtained in Example 6 are shown in Table 17 and FIG. 16 .

2θ D 100×I/I _O 7.8 ~ 7.9 11.3 to 11.4 74 11.8 to 11.9 7.5 to 7.6 7 13.5 to 13.6 6.6 to 6.7 33 15.6 to 15.7 5.7 ~ 5.8 One 17.9 to 18.0 5.0 to 5.1 8 19.5 to 19.6 4.5 to 4.6 4 20.6 to 20.7 4.3 to 4.4 27 23.4 ~ 23.5 3.8 to 3.9 21 23.8 ~ 23.9 3.7 to 3.8 100 24.9 to 25.0 3.6 ~ 3.7 34 26.2 ~ 26.3 3.4 to 3.5 9 27.1 ~ 27.2 3.3 to 3.4 7 28.4 to 28.5 3.1 to 3.2 50 30.6 to 30.7 2.9 to 3.0 3 31.3 to 31.4 2.9 to 3.0 55 31.5 to 31.6 2.8 to 2.9 49 33.5 to 33.6 2.7 to 2.8 8 36.3 to 36.4 2.5 to 2.6 24 38.3 ~ 38.4 2.4 to 2.5 4 39.4 to 39.5 2.3 to 2.4 2 41.0 to 41.1 2.2 to 2.3 8 41.5 to 41.6 2.2 to 2.3 2 42.8 ~ 42.9 2.1 to 2.2 3 43.6 ~ 43.7 2.1 to 2.2 One 45.8 ~ 45.9 2.0 to 2.1 3 46.5 ~ 46.6 2.0 to 2.1 One 48.2 to 48.3 1.9 to 2.0 9

In Table 17, θ, d, and I mean the Bragg angle, the grating 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. - A wire tube was used. Measurements were made at a rate of 5 degrees per minute (2θ) from a horizontally compressed powder sample, and d and I were calculated from the 2θ values and peak heights of the observed X-ray diffraction peaks. As a result of thermogravimetric analysis and elemental analysis of the solid powder obtained in Example 6, it was confirmed that the offretite zeolite contained about 8.3% by weight of water and 6.3% by weight of TEA cations. In addition, it was confirmed that the Si/Al ratio of the produced zeolite was about 4.1 using Inductive Coupled Plasma (ICP).

At the same time, as a result of measuring a scanning electron microscope (SEM) to confirm that the offretite is a pure substance without impurities (FIG. 17), a very uniform cylindrical crystal shape was observed, and a different crystal shape was observed. was not observed.

Comparative Example 6-1. Use only LiOH in the reaction mixture

Under the same conditions as in Example 6, only 98 wt% lithium hydroxide (LiOH) was added at 0.49 g to prepare a reaction mixture having the composition shown in Chemical Formula 15 below, and the solid product obtained after heating at 120° C. for 7 days was repeatedly washed with water and dried at room temperature.

[Formula 15]

0.5 TEAOH : 2.00 Li ₂ O : 1.00 Al ₂ O ₃ : 10 SiO ₂ : 100 H ₂ O

As a result of performing an X-ray diffraction measurement test with the solid powder obtained in Comparative Example 6-1 (FIG. 18), a large amount of amorphous (H ₄ Li ₂ O ₇ Si ₂ ) was obtained with ZSM-12 zeolite instead of offretite zeolite. can be obtained

Comparative Example 6-2. Use only RbOH in the reaction mixture

Under the same conditions as in Example 6, only 50 wt% rubidium hydroxide (RbOH) was added in an amount of 4.10 g to prepare a reaction mixture having the composition shown in the following formula (16), and a solid product obtained after heating at 120 °C for 7 days was repeatedly washed with water and dried at room temperature.

[Formula 16]

0.5 TEAOH : 2.00 Rb ₂ O : 1.00 Al ₂ O ₃ : 10 SiO ₂ : 100 H ₂ O

As a result of performing an X-ray diffraction measurement test with the solid powder obtained in Comparative Example 6-2 (FIG. 19), a small amount of L zeolite was produced as a mixture together with offretite.

Example 7. Preparation of H-offretite zeolite

After calcining the offretite zeolite prepared in Example 1 under air at 550° C. for 8 hours, 1.0 g of zeolite was placed in 100 mL of 1.0 M sodium ammonium (NH ₄ NO ₃ ) solution, and ion exchange was performed at 80° C. for 6 hours. After repeating twice, the solid product obtained was repeatedly washed with water and dried at room temperature, and then calcined for 4 hours under air at 550 ° C. It was observed that the X-ray pattern was essentially the same as in the case of 6, and the results are shown in Table 18 and FIG. 20 . As a result of thermogravimetric analysis and elemental analysis, it was confirmed that all of the organic structure-inducing material (TEA) in the H-offretite zeolite was burned and only contained 15.8% by weight of water. In addition, as a result of the nitrogen adsorption experiment, it was observed that the H-offretite zeolite had a BET surface area of about 500 m ² /g, which is shown in FIG. 21 .

2θ d 100 × I/I _O 7.8 ~ 7.9 11.3 to 11.4 100 11.7 to 11.8 7.5 to 7.6 18 13.5 to 13.6 6.6 to 6.7 57 14.1 to 14.2 6.3 to 6.4 7 15.6 to 15.7 5.7 ~ 5.8 5 19.5 to 19.6 4.5 to 4.6 19 20.7 to 20.8 4.3 to 4.4 33 23.5 ~ 2.6 3.8 to 3.9 29 23.8 ~ 23.9 3.7 to 3.8 77 24.9 to 25.0 3.6 ~ 3.7 47 26.3 to 26.4 3.4 to 3.5 4 27.2 ~ 27.3 3.3 to 3.4 19 28.4 to 28.5 3.1 to 3.2 40 30.7 to 30.8 2.9 to 3.0 5 31.5 to 31.6 2.8 to 2.9 68 33.7 ~ 33.8 2.7 to 2.8 10 35.7 ~ 35.8 2.5 to 2.6 3 36.2 to 36.3 2.5 to 2.6 11 36.4 ~ 36.5 2.5 to 2.6 14 38.3 ~ 38.4 2.4 to 2.5 2 39.7 ~ 39.8 2.3 to 2.4 One 41.2 to 41.3 2.2 to 2.3 5 43.0 ~ 43.1 2.1 to 2.2 4 43.7 ~ 43.8 2.1 to 2.2 2 46.0 ~ 46.1 2.0 to 2.1 3 46.6 to 46.7 2.0 to 2.1 2 48.2 to 48.3 1.9 to 2.0 8 48.8 ~ 48.9 1.9 to 2.0 2

In Table 18, θ, d, and I mean the Bragg angle, the grating 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. - A wire tube was used. Measurements were made at a rate of 5 degrees per minute (2θ) from a horizontally compressed powder sample, and d and I were calculated from the 2θ values and peak heights of the observed X-ray diffraction peaks.

Claims (11)

In the method for hydrothermal synthesis of zeolite using a structure-inducing material,
TEAOH; Li, Na, and at least one low molecular weight alkali metal component (M) selected from the group consisting of K; and Rb, Cs, and Fr. A method characterized in that using a structure-inducing material containing one or more high molecular weight alkali metal components (N) selected from the group consisting of. According to claim 1,
The zeolite synthesis method comprises a hydrothermal synthesis step of reacting a silica source and an aluminum source together with a structure-inducing material (M) in water to obtain a reaction mixture represented by the following formula (1), and heating the same how to do it with
x TEAOH: y M ₂ O : z N ₂ O : 1 Al ₂ O ₃ : m SiO ₂ : n H ₂ O (1)
where x, y, z, m, n are moles,
M ₂ O is an oxide of a low molecular weight alkali metal,
N ₂ O is a high molecular weight alkali metal oxide,
x is 0.5-5.0, y is 0.25-2.0, z is 0.25-2.0, m is 2.0-50, and n is 10-200. 3. The method of claim 1 or 2,
A method, characterized in that the difference in atomic weight between the low molecular weight alkali metal component and the high molecular weight alkali metal component is 40 or more. 3. The method of claim 2,
The heating step is a method, characterized in that made at a temperature of 50 ~ 200 ℃ for 0.5 to 7 days. 3. The method of claim 1 or 2,
The method, characterized in that the zeolite is rho zeolite, ZK-5 zeolite, or offretite zeolite. 3. The method of claim 1 or 2,
The rho zeolite is TEAOH; Na metal component; Method characterized in that it is synthesized using a structure-inducing material containing a Cs metal component. 3. The method of claim 1 or 2,
The ZK-5 zeolite is TEAOH; K metal component; Method characterized in that it was synthesized using a structure-inducing material containing a Cs metal component. 3. The method of claim 1 or 2,
The offretite zeolite is TEAOH; Li metal component; A method, characterized in that it is synthesized using a structure-inducing material containing an Rb metal component. TAEOH;
It has a composition ratio represented by the following formula (3)
0.1~10 A ₂ O: 1.0 Al ₂ O ₃ : 1.0~100 SiO ₂ (3)
Here, A consists of Na and Cs,
A roh zeolite, characterized in that it has a skeletal structure according to the XRD pattern shown in Table 1 below.
[Table 1]

In Table 1, θ, d, and I mean 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. - A wire tube was used. Measurements were made at a rate of 5 degrees per minute (2θ) from a horizontally compressed powder sample, and d and I were calculated from the 2θ values and peak heights of the observed X-ray diffraction peaks, where 100×I/I ₀ is W It is divided into (weak: 0-20), M (medium: 20-40), S (strong: 40-60), and VS (very strong: 60-100). TAEOH;
It has a composition ratio represented by the following formula (5)
0.1~10 A ₂ O: 1.0 Al ₂ O ₃ : 1.0~100 SiO ₂ (5)
Here, A consists of K and Cs,
zk-5 zeolite, characterized in that it has a skeletal structure according to the XRD pattern shown in Table 5 below.
[Table 5]

In Table 5, θ, d, and I mean the Bragg angle, the grating 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. - A wire tube was used. Measurements were made at a rate of 5 degrees per minute (2θ) from a horizontally compressed powder sample, and d and I were calculated from the 2θ values and peak heights of the observed X-ray diffraction peaks, where 100×I/I ₀ is W It is divided into (weak: 0-20), M (medium: 20-40), S (strong: 40-60), and VS (very strong: 60-100). TAEOH;
It has a composition ratio represented by the following formula (5)
0.1~10 A ₂ O: 1.0 Al ₂ O ₃ : 1.0~100 SiO ₂ (5)
Here, A consists of Li and Rb,
Offretite zeolite, characterized in that it has a skeletal structure according to the XRD pattern shown in Table 9 below.
[Table 9]

In Table 9, θ, d, and I mean 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. - A wire tube was used. Measurements were made at a rate of 5 degrees per minute (2θ) from a horizontally compressed powder sample, and d and I were calculated from the 2θ values and peak heights of the observed X-ray diffraction peaks, where 100×I/I ₀ is W It is divided into (weak: 0-20), M (medium: 20-40), S (strong: 40-60), and VS (very strong: 60-100).

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