KR102546689B1 - Pst-2 zeolite and method of preparing same - Google Patents

Abstract

The present invention relates to an aluminosilicate PST-2 zeolite of SBS and SBT symbiosis structure, a manufacturing method thereof, and the possibility of using this zeolite as a catalyst and adsorption/separation agent, and more specifically, completely different from zeolites reported so far. A large pore aluminosilicate PST-2 zeolite having a structure is prepared, and the possibility of using the PST-2 zeolite as an adsorbent in a carbon dioxide separation process and a catalyst for a fluid catalytic cracking of heavy oil is provided.

Description

PST-2 zeolite and its manufacturing method {PST-2 ZEOLITE AND METHOD OF PREPARING SAME}

The present invention relates to PST-2 zeolite and a method for producing the same, and more particularly, to PST-2 zeolite, which is an aluminosilicate having a new crystal structure of SBS and SBT symbiotic structure, and a method for producing the same.

Zeolites and related nanoporous materials contain pores of uniform shape and size due to the internal framework structure, and thus exhibit unique shape selectivity not found in generally amorphous oxides, as well as skeletal silicon charge and aluminum charge. It has acid catalytic properties due to the imbalance of Due to the above characteristics, zeolites are used in many industrial fields as catalyst supports as well as adsorption, separation and catalysts.

Due to their large pore size, large-pore zeolites (consisting of rings of 12 oxygen atoms) facilitate the diffusion of relatively large-sized reactants and products (0.9 ~ 1.0 nm) and allow the reactants to easily access the active site. In addition, it is possible to minimize the clogging of pores due to by-products (coke).

In particular, cage-based FAU zeolite having a three-dimensional structure and large pores is widely used as an ion exchanger, separator, catalyst or catalyst support in various chemical industries as well as petrochemical and fine chemistry. Among them, zeolite X (Li-X, Si/Al ratio: 1.5 or less) exchanged with Li alkali ion is used as an adsorbent for separating nitrogen and oxygen in the air, and zeolite Y with increased structural stability through steam treatment ( USY, Si/Al ratio: 1.5 or higher) is used as a commercial catalyst for fluid catalytic cracking of heavy oil.

Nevertheless, among the 253 zeolites approved by the International Zeolite Association as of 2021, only 5 structures (EMT, FAU, RWY, SBS, SBT) are known.

On the other hand, the structures of SBS and SBT among the mentioned zeolites are described in Science 19 Dec 1997: Vol. 278, Issue 5346, p. 2080-2085, 1997 Prof. It was first synthesized by Strucky's group, and they were named UCSB-6 and UCSB-10, respectively. Both zeolites were synthesized using various bimolecular long-chain amines as organic structure-inducing materials and using the charge density difference between metal frameworks.

However, since it is composed of a metal phosphate composition (UCSB-6; gallocobalt phosphate, UCSB-10; gallozinc phosphate) rather than an aluminosilicate composition, it is structurally fragile and has a disadvantage in that the structure collapses at a temperature of 300 ° C. or higher.

Therefore, the use of all of the above zeolites as catalysts and separators in the industrial field is very limited.

Recently, the present inventors purely synthesized PST-32, an SBT zeolite of aluminosilicate composition, named it PST-32, and filed a patent application for a method for manufacturing this nest-based large pore zeolite (Application No.: 10-2019-0119315) have completed

However, no aluminosilicate zeolite having an SBS structure has been synthesized yet, and the SBS/SBT intergrowth in which the SBS structure and the SBT structure grow alternately has not been identified.

Accordingly, while the present inventors were repeating research to synthesize a zeolite having a new framework and composition, a SBS/SBT intergrowth of an aluminosilicate composition having high thermal stability and three-dimensional 12-ring pores (SBS/SBT intergrowth) It has led to the discovery of zeolites having

In order to solve the above problems, an object of the present invention is to provide an aluminosilicate zeolite having a new crystal structure of SBS and SBT symbiotic structure and also to provide a manufacturing method.

Another object of the present invention is to prepare an aluminosilicate and PST-2 zeolite having a SBS/SBT intergrowth of a new crystal structure to be used as ion exchangers, catalysts or catalyst supports, gas separators in various industrial processes in the environment and energy fields, in particular, The purpose is to provide a PST-2 zeolite that can be used as a catalyst for catalytic cracking of heavy oil and a manufacturing method thereof.

According to one aspect of the present invention, the present invention provides a PST-2 zeolite having an SBS framework work and an SBT framework work.

The PST-2 zeolite may include an alumino silicate represented by Chemical Formula 1 below.

[Formula 1]

(M ₂ O) _x (Al ₂ O ₃ ) _y (SiO ₂ ) _z

In Formula 1,

M includes at least one alkali metal selected from the group consisting of Li, Na, K, Rb, Cs, and Fr;

x is 0.1≤x≤10, y is 1, and z is 2.0≤z≤200.

That is, the PST-2 zeolite can be expressed as the following composition.

0.1~10 M ₂ O: 1.0 Al ₂ O ₃ : 2.0~200 SiO ₂

In addition, the PST-2 zeolite may include a SBS/SBT intergrowth structure having both the SBS framework and the SBT framework in one crystal.

In addition, the SBS/SBT intergrowth structure may be a structure in which the SBS skeleton and the SBT skeleton alternately grow in one crystal.

In addition, the PST-2 zeolite may have three-dimensional nest-shaped micropores, and the micropores may include 12-ring-shaped micropores made of oxygen atoms.

The PST-2 zeolite may include a skeleton according to the XRD pattern shown in Table 1 below.

In Table 1, θ, d, and I are the Bragg angle, the interlattice spacing, and the intensity of the X-ray diffraction peak, respectively. Powder X-ray diffraction data were measured using a standard X-ray diffraction method, and copper Kα rays and an X-ray tube operating at 40 kV and 30 mA were used as radiation sources. It was measured at a rate of 5˚(2θ) per minute from a powder sample compressed horizontally, and d and I were calculated from the 2θ value and peak height of the observed X-ray diffraction peak, where 100×I/I ₀ is W (weak: 0-20), M (medium: 20-40), S (strong: 40-60), and VS (very strong: 60-100).

Also, z may be 2.0≤z≤50.

In addition, the PST-2 zeolite may include a skeleton according to the XRD pattern shown in Table 2 below.

In Table 2, θ, d, and I are the Bragg angle, the interlattice spacing, and the intensity of the X-ray diffraction peak, respectively. Powder X-ray diffraction data were measured using a standard X-ray diffraction method, and copper Kα rays and an X-ray tube operating at 40 kV and 30 mA were used as radiation sources. It was measured at a speed of 5˚(2θ) per minute from a powder sample compressed horizontally, and d and I were calculated from the 2θ value and peak height of the observed X-ray diffraction peak.

In addition, M may include one or more selected from the group consisting of Na and Cs.

In addition, the PST-2 zeolite may further include protons (H ⁺ ), and the protons may compensate for the charge amount of aluminum (Al) in the framework.

In addition, the PST-2 zeolite may be used as an ion exchanger, catalyst, acid catalyst, base catalyst, catalyst support, fluid catalytic cracking catalyst, or gas separator.

According to another aspect of the present invention, a catalyst comprising the PST-2 zeolite is provided.

According to another aspect of the present invention, an acid or base catalyst comprising the PST-2 zeolite is provided.

According to another aspect of the present invention, the method for producing a PST-2 zeolite of the present invention includes (a) preparing a mixed aqueous solution containing a structure-inducing organic material, an alumina precursor, and a silica precursor; (b) preparing a mixture by mixing one or more alkali metal salts with the mixed aqueous solution; and (c) preparing PST-2 zeolite by reacting the mixture.

In addition, the mixture may include 2.0 to 20.0 mol of the structure-inducing organic material, 0.01 to 1.0 mol of the alkali metal salt, and 10 to 600 mol of the silica precursor with respect to 1 mol of the alumina precursor.

In addition, the step (a) may include (a-1) preparing a first aqueous solution containing the structure-inducing organic material and the alumina precursor; (a-2) preparing a mixed aqueous solution containing the first aqueous solution and the silica precursor; and (a-3) maintaining the mixed aqueous solution at a temperature of 70 to 90 °C for 12 to 24 hours to prepare an aged mixed aqueous solution; can include

In addition, the step (c) is (c-1) stirring the mixture at a temperature of 90 to 110 ℃; and (c-2) preparing PST-2 zeolite by reacting the stirred mixture at a temperature of 90 to 110 °C for 1 to 30 days.

In addition, the structure-inducing organic material may include tetraethylammonium hydroxide (TEAOH).

In addition, the alumina precursor may include aluminum tri-sec butoxide.

In addition, the silica precursor may include colloidal silica sol.

In addition, the PST-2 zeolite has an SBS framework and an SBT framework, and may be represented by Formula 1 below.

[Formula 1]

(M ₂ O) _x (Al ₂ O ₃ ) _y (SiO ₂ ) _z

In Formula 1,

M includes one or more alkali metals selected from the group consisting of Li, Na, K, Rb, Cs, and Fr;

x is 0.1≤x≤10, y is 1, and z is 2.0≤z≤200.

That is, the PST-2 zeolite can be expressed as the following composition.

0.1~10 M ₂ O: 1.0 Al ₂ O ₃ : 2.0~200 SiO ₂

According to another aspect of the present invention, the present invention is a carbon dioxide mixture comprising the step of contacting a mixed gas containing carbon dioxide with the PST-2 zeolite according to claim 1 to selectively adsorb the carbon dioxide to the PST-2 zeolite. A selective separation method is provided.

According to another aspect of the present invention, the present invention provides a heavy oil reforming method comprising the step of reforming heavy oil by catalytic cracking using a catalyst containing the PST-2 zeolite.

As described above, the present invention is a novel aluminosilicate PST-2 zeolite having a previously unknown SBS and SBT symbiosis structure and a method for preparing the same, and utilization as a catalyst and adsorption/separation agent using the PST-2 zeolite can provide.

1 is a structure of PST-2 zeolite of Example 1.
2 is an X-ray diffraction (XRD) result of aluminosilicate PST-2 zeolite made according to Example 1.
3 is a scanning microscope (SEM) image of aluminosilicate PST-2 made according to Example 1.
4 is an X-ray diffraction (XRD) result of a product containing a large amount of zeolite Y as an impurity made according to Example 2.
5 is an X-ray diffraction (XRD) result of impure PST-2 zeolites made according to Example 3.
6 is an X-ray diffraction (XRD) result of an offretite structure made according to Example 4.
7 is an X-ray diffraction (XRD) result of aluminosilicate PST-2 prepared according to Example 5.
8 is an X-ray diffraction (XRD) result of aluminosilicate PST-2 prepared according to Example 6.
9 is a surface area measurement (BET) result of aluminosilicate PST-2 prepared according to Example 6.
10 is a result of selective adsorption and separation performance for carbon dioxide gas of PST-2 zeolite prepared according to Example 6.
11 is a result of the catalytic cracking reaction of heavy oil of PST-2 zeolite prepared according to Example 6.

Since the present invention can apply various transformations and have various embodiments, specific embodiments are exemplified and described in detail in the detailed description. However, it should be understood that this is not intended to limit the present invention to specific embodiments, and includes all transformations, equivalents, and substitutes included in the spirit and scope of the present invention. In describing the present invention, if it is determined that a detailed description of related known technologies may obscure the gist of the present invention, the detailed description will be omitted.

Also, terms including ordinal numbers such as first and second to be used below may be used to describe various components, but the components are not limited by the terms. These terms are only used for the purpose of distinguishing one component from another. For example, a first element may be termed a second element, and similarly, a second element may be termed a first element, without departing from the scope of the present invention.

Also, when a component is referred to as “on another component,” “formed on another component,” or “laminated on another component,” directly on the front surface or one side of the surface of the other component. It may be formed attached or stacked, but it should be understood that other components may further exist in the middle.

Singular expressions include plural expressions unless the context clearly dictates otherwise. In this application, the terms "include" or "have" are intended to designate that there is a feature, number, step, operation, component, part, or combination thereof described in the specification, but one or more other features It should be understood that the presence or addition of numbers, steps, operations, components, parts, or combinations thereof is not precluded.

The PST-2 zeolite according to the present invention may have an SBS framework and an SBT framework.

PST-2 zeolite may have a composition represented by Formula 1 below.

[Formula 1]

(M ₂ O) _x (Al ₂ O ₃ ) _y (SiO ₂ ) _z

In Formula 1,

M contains at least one alkali metal selected from the group consisting of Li, Na, K, Rb, Cs, and Fr, x is 0.1≤x≤10, y is 1, and z is 2.0≤z≤200 am.

That is, the PST-2 zeolite can be expressed as the following composition.

0.1~10 M ₂ O: 1.0 Al ₂ O ₃ : 2.0~200 SiO ₂

Here, the zeolite of the present invention is characterized in that it has a skeleton structure according to the XRD pattern shown in Table 1 below.

2θ d 100×I/I _O 5.9 to 6.0 15.0 to 15.1 VS 6.5 to 6.6 13.7 to 13.8 VS 10.2 to 10.3 8.7 to 8.8 M 12.0 to 12.1 7.4 to 7.5 W 18.7 to 18.8 4.7 to 4.8 W 20.3 to 20.4 4.4 to 4.5 W 21.3 to 21.4 4.2 to 4.3 W 21.8 to 21.9 4.1 to 4.2 W 24.1 to 24.2 3.7 to 3.8 VS 25.7 to 25.8 3.5 to 3.6 M 26.0 to 26.1 3.4 to 3.5 M 27.0 to 27.1 3.3 to 3.4 S 28.2 to 28.3 3.2 to 3.3 S 29.5 to 29.6 3.0 to 3.1 VS 30.7 to 30.8 2.9 to 3.0 W 31.3 to 31.4 2.9 to 3.0 W 33.1 to 33.2 2.7 to 2.8 W 34.2 to 34.3 2.6 to 2.7 W 35.6 to 35.7 2.5 to 2.6 W 36.2 to 36.3 2.5 to 2.6 W 37.4 to 37.5 2.4 to 2.5 W 39.0 to 39.1 2.3 to 2.4 W 41.3 to 41.4 2.2 to 2.3 W 43.5 to 43.6 2.1 to 2.2 W 45.9 to 46.0 2.0 to 2.1 W 47.2 to 47.3 1.9 to 2.0 W 48.9 to 49.0 1.9 to 2.0 W

In Table 1, θ, d, and I mean the Bragg angle, the interlattice 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 sun tube was used. It was measured at a speed of 5 degrees (2θ) per minute from a powder sample compressed horizontally, and d and I were calculated from the 2θ value and peak height of the observed X-ray diffraction peak, where 100×I/I ₀ is W (weak: 0-20), M (medium: 20-40), S (strong: 40-60), VS (very strong: 60-100).

According to the above results, a zeolite having a skeleton structure composed of the same composition as Formula 1 and having an X-ray diffraction pattern including the lattice spacings given in Table 1 is named PST-2 (POSTECH Number 2). According to the reported literature, there is no zeolite with a framework structure similar to PST-2 yet (Atlas of Zeolite Structure Types, Butterworth 2007, http://www.iza-structure.org/).

In the present invention, PST-2 may be a symbiotic structure of SBS and SBT (SBS/SBT intergrowth). Both SBS and SBT structures consist of only double 6-ring and 11-sided Cancrinite structural units, which are classified into SBS and SBT zeolites according to the way they are arranged. However, at this time, a zeolite having an arrangement of these structural units can exist in one crystal, which is called a symbiosis structure, or intergrowth. The symbiotic structure may or may not have a certain rule, and preferably may have a certain rule. However, until now, the synthesis of SBS/SBT intergrowth in aluminosilicate and metal phosphate compositions has not been elucidated at all.

In the present invention, PST-2 has a nest-based SBS and SBT structure with a 12-ring pore entrance that can be accessed in three dimensions, but it is not a simple physical mixture of SBS and SBT zeolites, so SBS and SBT Another physicochemical property different from that of the zeolite in the structure can be expressed.

If PST-2 zeolite, a SBS/SBT intergrowth of aluminosilicate composition with high thermal stability, is synthesized and applied as a new catalyst or adsorption and separation agent, both SBS and SBT zeolites are among the most widely used zeolites industrially. Like the phosphorus FAU zeolite, it can be a zeolite with very high utility value industrially.

In addition, since PST-2 zeolite is a nest-based structure with 3-dimensionally accessible 12-ring pore entrances, and the size of these 12-ring pore entrances is similar to that of FAU zeolite, SBS/SBT with aluminosilicate composition Intergrowth zeolite has very high utility values not only academically but also practically.

In the present invention, the ratio of Al ₂ O ₃ to SiO ₂ in the zeolite is preferably 1.0 Al ₂ O ₃ : 2.0 to 200 SiO ₂ , more preferably 1.0: 2.0 to 50, and the 2θ, d, 100×I/I ₀ in Table 1 can be expressed in Table 2 below.

2θ d 100×I/I _O 5.9 to 6.0 15.0 to 15.1 95 to 100 6.5 to 6.6 13.7 ~ 13.8 80 to 85 10.2 to 10.3 8.7 to 8.8 20 to 25 12.0 to 12.1 7.4 to 7.5 5 to 10 18.7 to 18.8 4.7 to 4.8 15 to 20 20.3 to 20.4 4.4 to 4.5 5 to 10 21.3 to 21.4 4.2 to 4.3 5 to 10 21.8 to 21.9 4.1 to 4.2 10 to 15 24.1 to 24.2 3.7 to 3.8 70 to 75 25.7 to 25.8 3.5 to 3.6 20 to 25 26.0 to 26.1 3.4 to 3.5 20 to 25 27.0 to 27.1 3.3 to 3.4 40 to 45 28.2 to 28.3 3.2 to 3.3 40 to 45 29.5 to 29.6 3.0 to 3.1 90 to 95 30.7 to 30.8 2.9 to 3.0 10 to 15 31.3 to 31.4 2.9 to 3.0 15 to 20 33.1 to 33.2 2.7 to 2.8 15 to 20 34.2 to 34.3 2.6 to 2.7 0 to 5 35.6 to 35.7 2.5 to 2.6 15 to 20 36.2 to 36.3 2.5 to 2.6 5 to 10 37.4 to 37.5 2.4 to 2.5 5 to 10 39.0 to 39.1 2.3 to 2.4 0 to 5 41.3 to 41.4 2.2 to 2.3 10 to 15 43.5 to 43.6 2.1 to 2.2 0 to 5 45.9 to 46.0 2.0 to 2.1 0 to 5 47.2 to 47.3 1.9 to 2.0 0 to 5 48.9 to 49.0 1.9 to 2.0 5 to 10

In Table 2, θ, d, and I mean the Bragg angle, the interlattice 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 sun tube was used. It was measured at a speed of 5 degrees (2θ) per minute from a powder sample compressed horizontally, and d and I were calculated from the 2θ value and peak height of the observed X-ray diffraction peak. In the present invention, the monovalent metal is preferably an alkali metal, and Li, Na, K, Rb, Cs and the like may be used.

The ratio of M ₂ O to Al ₂ O ₃ is preferably 0.1 to 10 M ₂ O: 1.0 Al ₂ O ₃ , and more preferably 0.1 to 5.0 M ₂ O: 1.0 Al ₂ O ₃ .

In a preferred embodiment of the present invention, the zeolite is 0.1 to 5.0 M ₂ O: 1.0 Al ₂ O ₃ : 2.0 to 50 SiO ₂ .

In the present invention, the PST-2 zeolite is hydrothermal by controlling the type and amount of SiO ₂ /Al ₂ O ₃ and alkali metal in the reaction mixture, and using tetraethylammonium (TEA) as an organic structure-inducing material. It can be produced through synthetic methods.

In the practice of the present invention, heating conditions may be heating at 50 to 150 ° C for 12 hours to 30 days.

Zeolite according to a preferred embodiment of the present invention is aluminum trisec butoxide (Al[OCH(CH ₃ )C ₂ H ₅ ] ₃ ) with respect to 1.0 mole A hydroxyl organic structure-inducing substance, TEAOH, is slowly added dropwise in an amount of 2 to 50 moles, preferably 4 to 20 moles, and stirred for 1 hour. To a solution prepared by stirring, silica sol or amorphous silica is added as described above. 2 to 200 mol, preferably 2 to 50 mol, was added to the solution and stirred for 1 hour, and the resulting solution was aged at 80° C. for 18 hours. Finally, +1 sodium nitrate (NaNO ₃ ) is added at a ratio of 0.1 to 10 moles, preferably 0.1 to 5 moles, and cesium nitrate (CsNO ₃ ) is added in an amount of 0.1 to 10 moles, preferably 0.1 to 5 moles. After adding to a ratio of, it was stirred at room temperature for 24 hours to obtain a reaction mixture having the following composition.

[Reaction mixture composition]

4.0~20.0 TEAOH:0.1~5.0 NaNO ₃ :0.1~5.0 CsNO ₃ :1.0 Al ₂ O ₃ :2.0~50 SiO ₂ :10~600 H ₂ O

PST-2, characterized in that the reaction mixture obtained by using the above-described procedure and reagents is transferred to a Teflon reactor, put into a container made of stainless steel, heated and stirred at 50 to 150 ° C, and reacted for 12 hours to 30 days. A method for producing zeolite is provided. When the heating time is too long, there is a risk that the structure may be deformed by heating for a long time.

Seed synthesis method using PST-2 zeolite with a mass fraction of about 4% to silicon before stirring at room temperature for 24 hours after adding hydroxylated structure-inducing organic TEA to increase the purity of PST-2 Through this, the purity of PST-2 zeolite can be increased. In the case of the seed synthesis method, it is one of the commonly used methods of zeolite synthesis, and induces rapid crystallization of the zeolite, increases the yield of the zeolite, and increases the purity of the material.

In one aspect, the present invention can prepare PST-2 (hereinafter referred to as H-PST-2) zeolite in which charge compensation of Al in the framework is performed with protons (H ⁺ ) to be applied to acid catalysis.

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

2θ d 100×I/I _O 6.0 to 6.1 14.8 to 14.9 S 6.4 to 6.5 13.8 to 13.9 VS 10.3 to 10.4 8.6 to 8.7 M 12.2 ~ 12.3 7.3 to 7.4 W 15.7 to 15.8 5.6 to 5.7 W 17.9 to 18.0 5.0 to 5.1 W 19.0 ~ 19.1 4.7 to 4.8 W 20.7 to 20.8 4.3 to 4.4 W 21.6 to 21.7 4.1 to 4.2 W 22.1 to 22.2 4.0 to 4.1 W 24.4 to 24.5 3.7 to 3.8 W 26.4 to 26.5 3.4 to 3.5 W 27.4 to 27.5 3.3 to 3.4 W 28.5 to 28.6 3.1 to 3.2 W 30.0 to 30.1 3.0 to 3.1 W 31.2 to 31.3 2.9 to 3.0 W 33.7 to 33.8 2.7 to 2.8 W 36.4 to 36.5 2.5 to 2.6 W 42.1 to 42.2 2.1 to 2.2 W

In Table 3, θ, d, and I mean the Bragg angle, the interlattice 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 sun tube was used. It was measured at a speed of 5 degrees (2θ) per minute from a powder sample compressed horizontally, and d and I were calculated from the 2θ value and peak height of the observed X-ray diffraction peak, where 100×I/I ₀ is W (weak: 0-20), M (medium: 20-40), S (strong: 40-60), VS (very strong: 60-100).

In a preferred practice of the present invention, the H-PST-2 zeolite of Table 3 is represented by Table 4 below.

2θ d 100 × I/I _O 6.0 to 6.1 14.8 to 14.9 55 to 60 6.4 to 6.5 13.8 to 13.9 95 to 100 10.3 to 10.4 8.6 to 8.7 35 to 40 12.2 ~ 12.3 7.3 to 7.4 5 to 10 15.7 to 15.8 5.6 to 5.7 5 to 10 17.9 to 18.0 5.0 to 5.1 0 to 5 19.0 ~ 19.1 4.7 to 4.8 0 to 5 20.7 to 20.8 4.3 to 4.4 5 to 10 21.6 to 21.7 4.1 to 4.2 5 to 10 22.1 to 22.2 4.0 to 4.1 5 to 10 24.4 to 24.5 3.7 to 3.8 10 to 15 26.4 to 26.5 3.4 to 3.5 5 to 10 27.4 to 27.5 3.3 to 3.4 5 to 10 28.5 to 28.6 3.1 to 3.2 5 to 10 30.0 to 30.1 3.0 to 3.1 15 to 20 31.2 to 31.3 2.9 to 3.0 0 to 5 33.7 to 33.8 2.7 to 2.8 0 to 5 36.4 to 36.5 2.5 to 2.6 0 to 5 42.1 to 42.2 2.1 to 2.2 0 to 5

In Table 4, θ, d, and I mean the Bragg angle, the interlattice 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 sun tube was used. It was measured at a speed of 5 degrees (2θ) per minute from a powder sample compressed horizontally, and d and I were calculated from the 2θ value and peak height of the observed X-ray diffraction peak.

As can be seen from the powder X-ray rotation data of the H-PST-2 zeolite, PST-2 is structurally stable even after heat treatment at a temperature of 550 ° C or higher for 8 hours or more, and in the form of H ⁺ for application as an acid catalyst. Since there is no significant change in crystallinity after conversion, its utilization value as an adsorbent and catalyst in various industrial processes is expected to be very high.

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

Hereinafter, the present invention will be described in more detail using examples. These examples are only for exemplifying the present invention, and the present invention is not limited thereto.

[Example]

Example 1: Preparation of PST-2 zeolite

In a plastic beaker, 0.51 g of aluminum trisec butoxylate (Al[OCH(CH ₃ )C ₂ H ₅ ] ₃ ) 35% by weight and 6.73 g of TEAOH were first added and stirred for 1 hour. To the resulting aqueous solution, 2.40 g of colloidal silica It was put in sol (Ludox AS-40) and 2.92 g of tertiary distilled water, stirred for 1 hour, and then aged at 80℃ for 18 hours. Finally, 0.022 g of sodium nitrate (NaNO ₃ ) and 0.15 g of cesium nitrate (CsNO ₃ ) were added and stirred for 24 hours to obtain a reaction mixture having the following composition.

[Reaction mixture composition]

16.0 TEAOH : 0.26 NaNO ₃ : 0.76 Cs NO ₃ : 1.0 Al ₂ O ₃ : 16 SiO ₂ : 480 H ₂ O

Subsequently, the reaction mixture obtained above was transferred to a Teflon reactor, put into a container made of stainless steel, stirred and heated at 100 ° C. for 14 days, and the obtained solid product was repeatedly washed with water and dried at room temperature to obtain PST-2 solid powder. Got it.

Referring to FIGS. 1 and 2, in order to confirm that the zeolite is not a physical mixture but a SBS / SBT symbiotic structure, the SBS and SBT structures were determined using a transmission electron microscope (TEM) and X-ray diffraction analysis. It can be seen that the zeolite contained at the same time.

As a result of the transmission electron microscope test with the solid powder obtained in Example 1, referring to the left drawing of FIG. It was confirmed that the SBS layer structure and the SBT layer structure, which have (12-ring) and are not physically mixed, exist simultaneously in one crystal. To express this a little more easily, the 12-ring pores are marked with circles with each color, and the structure with the order of green, blue, orange, blue, green circles means SBT, and the order of purple and yellow circles Having means SBS structure. Therefore, referring to the right drawing of FIG. 1, it can be seen that the PST-2 zeolite is a zeolite containing SBS and SBT structures at the same time.

In addition, as a result of an X-ray diffraction measurement test with the solid powder obtained in Example 1, no pattern identical to that of PST-2 could be found when compared to previously reported X-ray diffraction patterns of zeolites. This means that PST-2 has a new skeletal structure that has not been known at all. The results of the X-ray diffraction measurement test with the solid powder obtained in Example 1 are shown in Table 5 and FIG. 2.

2θ d 100×I/I _O 5.9 to 6.0 15.0 to 15.1 100 6.5 to 6.6 13.7 to 13.8 81 10.2 to 10.3 8.7 to 8.8 23 12.0 to 12.1 7.4 to 7.5 8 18.7 to 18.8 4.7 to 4.8 19 20.3 to 20.4 4.4 to 4.5 5 21.3 to 21.4 4.2 to 4.3 8 21.8 to 21.9 4.1 to 4.2 15 24.1 to 24.2 3.7 to 3.8 74 25.7 to 25.8 3.5 to 3.6 20 26.0 to 26.1 3.4 to 3.5 24 27.0 to 27.1 3.3 to 3.4 43 28.2 to 28.3 3.2 to 3.3 41 29.5 to 29.6 3.0 to 3.1 92 30.7 to 30.8 2.9 to 3.0 14 31.3 to 31.4 2.9 to 3.0 16 33.1 to 33.2 2.7 to 2.8 19 34.2 to 34.3 2.6 to 2.7 5 35.6 to 35.7 2.5 to 2.6 16 36.2 to 36.3 2.5 to 2.6 10 37.4 to 37.5 2.4 to 2.5 8 39.0 to 39.1 2.3 to 2.4 4 41.3 to 41.4 2.2 to 2.3 12 43.5 to 43.6 2.1 to 2.2 5 45.9 to 46.0 2.0 to 2.1 2 47.2 to 47.3 1.9 to 2.0 5 48.9 to 49.0 1.9 to 2.0 5

In Table 5, θ, d, and I mean the Bragg angle, the interlattice 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 sun tube was used. It was measured at a speed of 5 degrees (2θ) per minute from a powder sample compressed horizontally, and d and I were calculated from the 2θ value and peak height of the observed X-ray diffraction peak.

As a result of thermogravimetric analysis and elemental analysis of the solid powder obtained in Example 1, it was confirmed that it contained about 10.5% by weight of water and 8.0% by weight of TEA in PST-2 zeolite. In addition, it was confirmed that the Si / Al ratio of the zeolite produced using the Inductively Coupled Plasma (ICP) was about 3.1.

Referring to FIG. 3, in order to confirm that PST-2 is a pure material without impurities, as a result of scanning electron microscope (SEM) measurement, a very uniform coin-shaped plate-like layered crystal pattern was observed. and no other crystal morphology was observed.

Example 2: NaNO in the reaction mixture ₃ increase and CsNO ₃ decrease

Same as Example 1 except that 0.064 g of sodium nitrate (NaNO ₃ ) was used instead of 0.022 g and 0.049 g of cesium nitrate (CsNO ₃ ) was used instead of 0.15 g in Example 1. A solid powder was obtained by the method.

[Reaction mixture composition]

16.0 TEAOH : 0.76 NaNO ₃ : 0.26 Cs NO ₃ : 1.0 Al ₂ O ₃ : 16 SiO ₂ : 480 H ₂ O

Referring to FIG. 4, as a result of the X-ray diffraction measurement test with the solid powder obtained in Example 2, a small amount of PST-2 zeolite was crystallized and a product containing a large amount of zeolite Y impurities was formed. .

Example 3. NaNO in reaction mixture ₃ Instead of LiNO ₃ , KNO ₃ , RbNO ₃ use each

Example 3-1: NaNO ₃ Instead of LiNO ₃ use

In Example 1, a solid powder was obtained in the same manner as in Example 1, except that a reaction mixture having the following composition was prepared using 0.017 g of lithium nitrate (LiNO ₃ ) instead of 0.022 g of sodium nitrate (NaNO ₃ ). .

[Reaction mixture composition]

16.0 TEAOH : 0.26 Li,NO ₃ : 0.76 Cs NO ₃ : 1.0 Al ₂ O ₃ : 16 SiO ₂ : 480 H ₂ O

Referring to FIG. 5, as a result of an X-ray diffraction measurement test on the solid powder obtained in Example 3-1, pure PST-2 crystals were not obtained.

Example 3-2: NaNO ₃ instead of KNO ₃ use

A solid powder was obtained in the same manner as in Example 1 except that a reaction mixture having the following composition was prepared using 0.026 g of potassium nitrate (KNO ₃ ) instead of 0.022 g of sodium nitrate (NaNO ₃ ) in Example 1.

[Reaction mixture composition]

16.0 TEAOH : 0.26 KNO ₃ : 0.76 Cs NO ₃ : 1.0 Al ₂ O ₃ : 16 SiO ₂ : 480 H ₂ O

Referring to FIG. 5, as a result of an X-ray diffraction measurement test with the solid powder obtained in Example 3-2, pure PST-2 crystals were not obtained.

Example 3-3: NaNO ₃ Instead of RbNO ₃ use each

A solid powder was obtained in the same manner as in Example 1 except that a reaction mixture having the following composition was prepared using 0.037 g of rubidium nitrate (RbNO ₃ ) instead of 0.022 g of sodium nitrate (NaNO ₃ ) in Example 1. .

[Reaction mixture composition]

16.0 TEAOH : 0.26 RbNO ₃ : 0.76 Cs NO ₃ : 1.0 Al ₂ O ₃ : 16 SiO ₂ : 480 H ₂ O

Referring to FIG. 5, as a result of an X-ray diffraction measurement test with the solid powder obtained in Example 3-3, pure PST-2 crystals were not obtained.

Example 4: Increase in reaction temperature during synthesis

A solid powder was obtained in the same manner as in Example 1 except that the reaction mixture was heated at 150° C. for 7 days instead of stirring and heating the reaction mixture at 100 ^° C. for 14 days. Referring to FIG. 6, as a result of an X-ray diffraction measurement experiment with the solid powder obtained in Example 4, offretite zeolite was produced.

Example 5: NaNO ₃ and Cs NO ₃ : instead of Cs NO ₃ use

In a plastic beaker, 0.51 g of aluminum trisec butoxylate (Al[OCH(CH ₃ )C ₂ H ₅ ] ₃ ) and 6.73 g of TEAOH at 35% by weight were first added and stirred for 1 hour. Put in silica sol (Ludox AS-40) and 2.92 g of tertiary distilled water, stir for 1 hour, and then age at 80℃ for 18 hours. Finally, 0.20 g of cesium nitrate (CsNO ₃ ) was added and stirred for 24 hours to obtain a reaction mixture having the composition shown in Formula 6 below.

[Formula 6]

16.0 TEAOH : 1.0 Cs NO ₃ : 1.0 Al ₂ O ₃ : 16 SiO ₂ : 480 H ₂ O

Subsequently, the reaction mixture obtained above was transferred to a Teflon reactor, put into a stainless steel container, stirred and heated at 100 ° C. for 14 days, and the obtained solid product was repeatedly washed with water and dried at room temperature.

Referring to FIG. 7, as a result of an X-ray diffraction measurement test with the solid powder obtained in Example 5, the same X-ray diffraction pattern of pure PST-2 as in Example 1 was observed.

Example 6: Preparation of H-PST-2 zeolite

After calcining the PST-2 zeolite prepared in Example 1 under air at 550 ^o C for 8 hours, 1.0 g of zeolite was added to 50 mL of 1.0 M sodium ammonium (NH ₄ NO ₃ ) solution and heated at 80 ^o C for 6 hours. After repeating ion exchange four times, the solid product obtained was repeatedly washed with water, dried at room temperature, calcined for 4 hours in air at 550 ^° C, converted to H-PST-2 zeolite, and then the X-ray diffraction pattern was measured again. It was observed that the sample calcined when fired showed essentially the same X-ray pattern as that of Example 1, and the results are shown in Table 6 and FIG. 8.

As a result of thermogravimetric analysis and elemental analysis, it was confirmed that all of the organic structure-inducing substances (TEA) in the H-PST-2 zeolite were burned and only 20.2 wt% of water was contained.

In addition, as a result of the nitrogen adsorption experiment, the H-PST-2 zeolite was observed to have a BET surface area of about 820 m ² /g, which is shown in FIG. 9 .

2θ d 100×I/I _O 6.0 to 6.1 14.8 to 14.9 59 6.4 to 6.5 13.8 to 13.9 100 10.3 to 10.4 8.6 to 8.7 38 12.2 ~ 12.3 7.3 to 7.4 10 15.7 to 15.8 5.6 to 5.7 9 17.9 to 18.0 5.0 to 5.1 3 19.0 ~ 19.1 4.7 to 4.8 4 20.7 to 20.8 4.3 to 4.4 9 21.6 to 21.7 4.1 to 4.2 9 22.1 to 22.2 4.0 to 4.1 9 24.4 to 24.5 3.7 to 3.8 11 26.4 to 26.5 3.4 to 3.5 8 27.4 to 27.5 3.3 to 3.4 9 28.5 to 28.6 3.1 to 3.2 5 30.0 to 30.1 3.0 to 3.1 19 31.2 to 31.3 2.9 to 3.0 5 33.7 to 33.8 2.7 to 2.8 3 36.4 to 36.5 2.5 to 2.6 One 42.1 to 42.2 2.1 to 2.2 One

In Table 6, θ, d, and I mean the Bragg angle, the interlattice 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 sun tube was used. It was measured at a rate of 5 degrees (2θ) per minute from a powder sample compressed horizontally, and d and I were calculated from the 2θ value and peak height of the observed X-ray diffraction peak.

Example 7: Selective adsorption of carbon dioxide

100 mg of the H-PST-2 zeolite of Example 6 was filled in a fixed-bed microreactor of a quartz tube (0.64 cm inner diameter), and the temperature was raised to 250 °C at 10 ^° C per minute while reducing the pressure to 0.009 torr, and then maintained at 250 ^{° C} for 2 hours. kept for a period of time to completely dehydrate. After the material was cooled to room temperature in a vacuum state, the carbon dioxide adsorption amount was measured by continuously changing the carbon dioxide pressure while maintaining the temperature at 25° C. using a water circulator. The results are shown in FIG. 10, and it was confirmed that the carbon dioxide adsorption amount of 1.5 mmol/g at 0.1 bar and the carbon dioxide adsorption amount of 3.9 mmol/g at 1.0 bar were shown. In order to evaluate the adsorption amount of nitrogen and methane gas of the PST-2 zeolite prepared in Example 6, at 25 ^o C in the same way, while continuously changing the pressure of nitrogen and methane gas, nitrogen and methane gas of PST-2 zeolite The adsorption amount of methane was measured respectively. The results are shown in FIG. 10, and it was confirmed that nitrogen and methane adsorption amounts of 0.02 mmol/g and 0.05 mmol/g at 0.1 bar and nitrogen and methane adsorption amounts of 0.41 mmol/g and 0.64 mmol/g at 1.0 bar were shown. It became.

These results well show the selective adsorption and separation ability of PST-2 zeolite for carbon dioxide gas in a mixed gas of methane/carbon dioxide/nitrogen, and can be used as a very useful separator or adsorbent in the separation and recovery process of carbon dioxide. can be said to be

Example 8: Heavy oil catalytic cracking

The performance of the PST-2 catalyst prepared in Example 6 in the catalytic cracking reaction of heavy oil was confirmed using a fixed bed reactor. 100 mg of H-PST-2 zeolite was placed in a fixed-bed reactor and completely dehydrated by maintaining at 600 ^° C with 100 mL/min of nitrogen for 2 hours. Next, heavy oil was injected with 6 mL/min nitrogen at a rate of 1.6 g/h as a reactant, and the reaction temperature was 600 ^° C. for 10 minutes at 1.0 bar pressure. HY (Albemarle, Si / Al = 5) and H-beta (Zeolyst), which are large pore zeolites of the comparative group, were also subjected to heavy oil decomposition reactions in the same manner as above, and the results are shown in FIG. was

Referring to FIG. 11 , it was confirmed that the yield of ethylene and paraffin was higher than that of H-Y and H-beta of the other comparative groups, especially in the case of H-PST-2 zeolite. Therefore, it was confirmed that H-PST-2 zeolite can be used as a catalyst for the catalytic cracking reaction of heavy oil.

The scope of the present invention is indicated by the following claims rather than the detailed description above, and all changes or modifications derived from the meaning and scope of the claims and equivalent concepts should be interpreted as being included in the scope of the present invention. do.

Claims (20)

A PST-2 zeolite having an SBS framework and an SBT framework,
The PST-2 zeolite has three-dimensional nest-shaped micropores,
The PST-2 zeolite, wherein the micropores include 12-ring (12-ring) shaped microinlets made of oxygen atoms. According to claim 1,
PST-2 zeolite, characterized in that the PST-2 zeolite comprises an alumino silicate represented by Formula 1 below.
[Formula 1]
(M ₂ O) _x (Al ₂ O ₃ ) _y (SiO ₂ ) _z
In Formula 1,
M includes one or more alkali metals selected from the group consisting of Li, Na, K, Rb, Cs, and Fr;
x is 0.1≤x≤10,
y is 1;
z is 2.0≤z≤200. According to claim 1,
The PST-2 zeolite, characterized in that the PST-2 zeolite includes a SBS / SBT intergrowth structure having the SBS skeleton and the SBT skeleton at the same time in one crystal. According to claim 3,
PST-2 zeolite, characterized in that the SBS / SBT intergrowth structure is a structure in which the SBS framework and the SBT framework grow alternately with each other in one crystal. delete According to claim 1,
PST-2 zeolite, characterized in that the PST-2 zeolite comprises a skeleton according to the XRD pattern shown in Table 1 below.

In Table 1, θ, d, and I are the Bragg angle, the interlattice spacing, and the intensity of the X-ray diffraction peak, respectively. Powder X-ray diffraction data were measured using a standard X-ray diffraction method, and copper Kα rays and an X-ray tube operating at 40 kV and 30 mA were used as radiation sources. It was measured at a rate of 5˚(2θ) per minute from a powder sample compressed horizontally, and d and I were calculated from the 2θ value and peak height of the observed X-ray diffraction peak, where 100×I/I ₀ is W (weak: 0-20), M (medium: 20-40), S (strong: 40-60), and VS (very strong: 60-100). According to claim 2,
PST-2 zeolite, characterized in that z is 2.0≤z≤50. According to claim 7,
PST-2 zeolite, characterized in that the PST-2 zeolite includes a skeleton according to the XRD pattern shown in Table 2 below.

In Table 2, θ, d, and I are the Bragg angle, the interlattice spacing, and the intensity of the X-ray diffraction peak, respectively. Powder X-ray diffraction data were measured using a standard X-ray diffraction method, and copper Kα rays and an X-ray tube operating at 40 kV and 30 mA were used as radiation sources. It was measured at a speed of 5˚(2θ) per minute from a powder sample compressed horizontally, and d and I were calculated from the 2θ value and peak height of the observed X-ray diffraction peak. According to claim 2,
PST-2 zeolite, characterized in that M comprises at least one selected from the group consisting of Na and Cs. According to claim 2,
PST-2 zeolite, characterized in that the PST-2 zeolite further comprises a proton (H ⁺ ), and the proton compensates for the charge amount of aluminum (Al) in the framework. According to claim 1,
PST-2 zeolite, characterized in that the PST-2 zeolite is used as an ion exchanger, catalyst, acid catalyst, base catalyst, catalyst support, heavy oil catalytic cracking catalyst, or gas separator. A catalyst comprising the PST-2 zeolite according to claim 1 . (a) preparing a mixed aqueous solution containing a structure-inducing organic material, an alumina precursor, and a silica precursor;
(b) preparing a mixture by mixing one or more alkali metal salts with the mixed aqueous solution; and
(c) preparing a PST-2 zeolite having an SBS framework and an SBT framework by reacting the mixture;
The PST-2 zeolite has three-dimensional nest-shaped micropores,
The method for producing a PST-2 zeolite, wherein the micropores include a 12-ring (12-ring) shaped microinlet made of oxygen atoms. According to claim 13,
the mixture
With respect to 1 mole of the alumina precursor
2.0 to 20.0 mol of the structure-derived organic matter.
0.01 to 1.0 mol of the alkali metal salt, and
Method for producing a PST-2 zeolite, characterized in that it comprises in a ratio of 10 to 600 moles of the silica precursor. According to claim 13,
The step (a)
(a-1) preparing a first aqueous solution containing the structure-inducing organic material and the alumina precursor;
(a-2) preparing a mixed aqueous solution containing the first aqueous solution and the silica precursor; and
(a-3) maintaining the mixed aqueous solution at a temperature of 70 to 90 ° C. for 12 to 24 hours to prepare an aged mixed aqueous solution; Method for producing PST-2 zeolite, characterized in that it comprises a. According to claim 13,
The step (c)
(c-1) stirring the mixture at a temperature of 90 to 110 °C; and
(c-2) preparing PST-2 zeolite by reacting the stirred mixture at a temperature of 90 to 110 ° C. for 1 to 30 days. According to claim 13,
The structure-inducing organic material includes tetraethylammonium hydroxide (TEAOH), the structure-inducing organic material includes aluminum tri-sec butoxide, and the silica precursor includes colloidal silica sol. Method for producing PST-2 zeolite. According to claim 13
A method for producing PST-2 zeolite, characterized in that the PST-2 zeolite is represented by Formula 1 below.
[Formula 1]
(M ₂ O) _x (Al ₂ O ₃ ) _y (SiO ₂ ) _z
In Formula 1,
M includes one or more alkali metals selected from the group consisting of Li, Na, K, Rb, Cs, and Fr;
x is 0.1≤x≤10,
y is 1;
z is 2.0≤z≤200. A method for selectively separating carbon dioxide, comprising the step of selectively adsorbing carbon dioxide to the PST-2 zeolite by contacting a mixed gas containing carbon dioxide with the PST-2 zeolite according to claim 1. A heavy oil reforming method comprising the step of reforming heavy oil by subjecting it to a catalytic cracking reaction (Fluid Catalytic Cracking) using a catalyst containing the PST-2 zeolite according to claim 1.

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