KR20220138306A - 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 the zeolite as a catalyst and adsorption/separation agent. More specifically, according to the present invention, a large-pore aluminosilicate PST-2 zeolite having a completely different structure from that of zeolites reported so far is manufactured, and provided is the possibility of using the PST-2 zeolite as an adsorbent in a carbon dioxide separation process and as a catalyst for fluid catalytic cracking of heavy oil.

Description

PST-2 zeolite and its manufacturing method

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

Zeolites and related nanoporous materials contain pores having a uniform shape and size due to their internal framework structure, thus exhibiting unique shape selectivity not found in amorphous oxides in general, as well as skeletal silicon charge and aluminum charge. It has acid catalytic properties due to the imbalance of Due to the above properties, zeolite is used in various places in the industry as a catalyst support as well as adsorption, separation and catalyst.

Large-pore (consisting of 12 rings of oxygen atoms) zeolites facilitate diffusion of relatively large reactants and products (0.9 ~ 1.0 nm) due to their large pore size 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, the cage-based FAU zeolite having a three-dimensional structure and large pores is widely used as an ion exchanger, a separator, a catalyst or a 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 ions is used as an adsorbent to separate nitrogen and oxygen in the air, and zeolite Y with increased structural safety through steam treatment ( USY, Si/Al ratio: 1.5 or more) is used as a commercial catalyst for catalytic cracking of heavy oil.

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

On the other hand, the SBS and SBT structures among the mentioned zeolites are described in Science 19 Dec 1997: Vol. 278, Issue 5346, pp. 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 the metal skeletons.

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 weak and 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 industrial fields is very limited.

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

However, an aluminosilicate zeolite having an SBS structure has not yet been synthesized, and an SBS/SBT symbiotic structure (SBS/SBT intergrowth) in which the SBS structure and the SBT structure grow alternately has not been revealed.

Accordingly, the present inventors repeated research for synthesizing zeolite having a new framework and composition, SBS/SBT symbiotic structure (SBS/SBT intergrowth) of aluminosilicate composition having high thermal stability and three-dimensionally 12-ring pores It has been found that zeolites with

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

Another object of the present invention is to prepare an aluminosilicate, PST-2 zeolite having SBS/SBT intergrowth of a new crystal structure to be used as an ion exchanger, catalyst or catalyst support, gas separation agent, in various industrial processes in the field of environment and energy, in particular, An object of the present invention is to provide a PST-2 zeolite that can be used as a catalyst for catalytic cracking of heavy oil and a method for producing the same.

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

The PST-2 zeolite may include an aluminosilicate represented by 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 may be represented by 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 an SBS/SBT intergrowth structure having the SBS backbone and the SBT backbone in one crystal.

In addition, the SBS/SBT symbiosis (SBS/SBT intergrowth) structure may be a structure in which the SBS skeleton and the SBT skeleton alternately grow with each other in one crystal.

In addition, the PST-2 zeolite may have three-dimensional nest-shaped micropores, and the micropores may include 12-ring-shaped microinlets 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 lattice spacing, and the intensity of the X-ray diffraction peak, respectively. Powder X-ray diffraction data were measured using standard X-ray diffraction methods, and copper Kα rays and an X-ray tube operating at 40 kV, 30 mA were used as radiation sources. It was measured at a rate of 5˚ (2θ) per minute from a horizontally compressed powder sample, 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).

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 grating spacing, and the intensity of the X-ray diffraction peak, respectively. Powder X-ray diffraction data were measured using standard X-ray diffraction methods, and copper Kα rays and an X-ray tube operating at 40 kV, 30 mA were used as radiation sources. Measurements were made at a rate of 5˚ (2θ) per minute 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 addition, M may include at least one selected from the group consisting of Na and Cs.

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

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

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

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 PST-2 zeolite of the present invention comprises the steps of (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) reacting the mixture to prepare PST-2 zeolite.

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

In addition, the step (a) comprises the steps of (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; may include.

In addition, the step (c) comprises the steps of (c-1) stirring the mixture at a temperature of 90 to 110 ℃; And (c-2) reacting the stirred mixture at a temperature of 90 to 110 ℃ for 1 to 30 days to prepare a PST-2 zeolite; may include.

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 a 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 comprises at least one alkylalkyl 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 may be represented by 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 comprises 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. An optional 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 the heavy oil by catalytic cracking reaction (Fluid Catalytic Cracking) using the catalyst containing the PST-2 zeolite.

As described above, the present invention relates to an aluminosilicate PST-2 zeolite having a new crystalline structure having a symbiotic structure with SBS and SBT, which is not known in the past, and a method for preparing the same, and its utility as a catalyst and adsorption/separating agent using PST-2 zeolite can provide

1 is a structure of the PST-2 zeolite of Example 1.
2 is an X-ray diffraction (XRD) result of an aluminosilicate PST-2 zeolite prepared according to Example 1. FIG.
3 is a scanning microscope (SEM) image of the aluminosilicate PST-2 prepared according to Example 1. FIG.
4 is an X-ray diffraction (XRD) result of a product containing a large amount of zeolite Y as an impurity prepared according to Example 2.
5 is an X-ray diffraction (XRD) result of impure PST-2 zeolites prepared according to Example 3. FIG.
6 is an X-ray diffraction (XRD) result of an offretite structure made according to Example 4. FIG.
7 is an X-ray diffraction (XRD) result of the aluminosilicate PST-2 made according to Example 5.
8 is an X-ray diffraction (XRD) result of aluminosilicate PST-2 made 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 resolution of 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 can have various embodiments, specific embodiments are illustrated and described in detail in the detailed description. However, this is not intended to limit the present invention to specific embodiments, and should be understood to include all modifications, 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 a related known technology may obscure the gist of the present invention, the detailed description thereof will be omitted.

In addition, terms including ordinal numbers such as first, second, etc. to be used hereinafter may be used to describe various elements, but the elements are not limited by the terms. The above terms are used only for the purpose of distinguishing one component from another. For example, without departing from the scope of the present invention, a first component may be referred to as a second component, and similarly, a second component may also be referred to as a first component.

Also, when it is stated that a component is "on another component", "formed on another component" or "stacked on another component," it is directly applied to the front surface or one surface on the surface of the other component. It may be attached and formed or stacked, but it will be understood that other components may be further present in the middle.

The singular expression includes the plural expression unless the context clearly dictates otherwise. In the present application, terms such as “comprise” or “have” are intended to designate that a feature, number, step, operation, component, part, or combination thereof described in the specification exists, but one or more other features It is to be understood that this does not preclude the possibility of the presence or addition of numbers, steps, operations, components, parts, or combinations thereof.

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

The PST-2 zeolite may have a composition represented by the following Chemical Formula 1.

[Formula 1]

(M ₂ O) _x (Al ₂ O ₃ ) _y (SiO ₂ ) _z

In Formula 1,

M includes at least one alkylalkyl 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 to be.

That is, the PST-2 zeolite may be represented by 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 skeletal 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 ~ 21.9 4.1 to 4.2 W 24.1 to 24.2 3.7 to 3.8 VS 25.7 ~ 25.8 3.5 to 3.6 M 26.0 to 26.1 3.4 to 3.5 M 27.0 ~ 27.1 3.3 to 3.4 S 28.2 to 28.3 3.2 to 3.3 S 29.5 ~ 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 ~ 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 ~ 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 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, the zeolite having the X-ray diffraction pattern including the lattice spacings given in Table 1 and having a framework structure having the same composition as in Formula 1 above is named PST-2 (POSTECH Number 2). According to the reported literature, there is still no zeolite having a framework structure similar to that of PST-2 (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 octahedral hexagonal columns (Double 6-ring) and 11-sided Cancrinite structural units, and they are classified into SBS and SBT zeolites according to their arrangement. However, at this time, a zeolite having the arrangement of these structural units at the same time in one crystal may exist, which is called a symbiotic structure, intergrowth. The symbiotic structure may or may not have certain rules, and preferably, there may be certain rules. However, to date, the synthesis of SBS/SBT intergrowth in aluminosilicate and metal phosphate compositions has not been revealed 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 three-dimensionally inside, but because it is not a simple physical mixture of SBS and SBT zeolite, SBS and SBT Another physicochemical property may be expressed from that of the zeolite of the structure.

If PST-2 zeolite, an 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 one of the most widely used zeolites in the industry. Like 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 12-ring pore openings that can be accessed three-dimensionally, and the size of this 12-ring pore opening is also similar to that of FAU zeolite, SBS/SBT of aluminosilicate composition The intergrowth zeolite has a very high utility value not only academically but also practically.

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 :2.0 ~ 200 SiO ₂ It can be expressed, more preferably 1.0: 2.0 ~ 50, the 2θ, d, 100×I/I ₀ of Table 1 may 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 to 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 ~ 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 ~ 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 ~ 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 ~ 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 ~ 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 ~ 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 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 present invention, the monovalent metal is preferably an alkali metal, and Li, Na, K, Rb, Cs, etc. 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 It is.

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

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

The 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 Silica sol or amorphous silica is added to the solution prepared by slowly adding TEAOH, an organic structure-inducing material in the hydroxyl form, in a ratio of 2 to 50 moles, preferably 4 to 20 moles, one by one, followed by stirring for 1 hour. It is added to the solution in a ratio of 2 to 200 moles, preferably 2 to 50 moles, and stirred for 1 hour, and the resulting solution is aged at 80 °C for 18 hours. Finally, +1 sodium nitrate (NaNO ₃ ) is added in a ratio of 0.1 to 10 moles, preferably 0.1 to 5 moles, and 0.1 to 10 moles, preferably 0.1 to 5 moles, of cesium nitrate (CsNO ₃ ). After addition to a ratio of , the mixture 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 procedure and reagents described above is transferred to a Teflon reactor, put again in a stainless steel container, 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 excessively elapsed, there is a risk that the structure of the heating furnace for a long time is deformed.

In order to increase the purity of PST-2, after adding TEA, a structure-inducing organic substance in the form of hydroxide, and before stirring at room temperature for 24 hours, PST-2 zeolite is used as much as 4% of the silicon content (seed method) Through this, the purity of PST-2 zeolite can be increased. In the case of seed synthesis, one of the methods commonly used among zeolite synthesis methods can induce rapid crystallization of the zeolite, increase the yield of the zeolite, and increase the purity of the material.

In one aspect, in order to apply the present invention to acid catalysis, a PST-2 (hereinafter, H-PST-2) zeolite in which the charge of Al in the skeleton is compensated with proton (H ⁺ ) can be prepared.

In the present invention, the H-PST-2 zeolite is a 1.0 M sodium ammonium (NH ₄ NO ₃ ) solution after calcining the PST-2 zeolite obtained using the reaction mixture of Chemical Formula 2 at 550° C. for 8 hours at 80° C. After four times of ion exchange, it can be obtained after calcination at 550 °C for 4 hours. Under the above conditions, 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 ~ 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 to 12.3 7.3 ~ 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 to 19.1 4.7 to 4.8 W 20.7 to 20.8 4.3 to 4.4 W 21.6 ~ 21.7 4.1 to 4.2 W 22.1 to 22.2 4.0 ~ 4.1 W 24.4 to 24.5 3.7 to 3.8 W 26.4 ~ 26.5 3.4 to 3.5 W 27.4 ~ 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 ~ 33.8 2.7 to 2.8 W 36.4 ~ 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 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).

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

2θ d 100 × I/I _O 6.0 ~ 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 to 12.3 7.3 ~ 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 to 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 ~ 21.7 4.1 to 4.2 5 to 10 22.1 to 22.2 4.0 ~ 4.1 5 to 10 24.4 to 24.5 3.7 to 3.8 10 to 15 26.4 ~ 26.5 3.4 to 3.5 5 to 10 27.4 ~ 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 ~ 33.8 2.7 to 2.8 0 to 5 36.4 ~ 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 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 ^- PST-2 zeolite, PST-2 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-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, a BET surface area of 700 to 900 m ² /g.

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

[Example]

Example 1: Preparation of PST-2 zeolite

First, in a plastic beaker, 0.51 g of aluminum trisec butoxide (Al[OCH(CH ₃ )C ₂ H ₅ ] ₃ ) 35 wt% 6.73 g of TEAOH was added and stirred for 1 hour. In the resulting aqueous solution, 2.40 g of colloidal silica It is put in sol (Ludox AS-40) and 2.92 g of tertiary distilled water, stirred for 1 hour, and then aged at 80°C 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

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

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

As a result of transmission electron microscopy testing with the solid powder obtained in Example 1, referring to the left drawing of FIG. 1, it can be seen that a uniformly arranged layered structure and a relatively bright circle can be seen at the same time, which is a large pore. (12-ring) and not physically mixed, it was confirmed that the SBS layered structure and the SBT layered structure existed simultaneously in one crystal. To express this more easily, the 12-ring pore is marked with a circle with each color, and the structure with the order of green, blue, orange, blue, and green circles means SBT, What you have means the SBS structure. Therefore, referring to the right drawing of FIG. 1 , it can be seen that the PST-2 zeolite is a zeolite containing both SBS and SBT structures.

In addition, as a result of performing an X-ray diffraction measurement test with the solid powder obtained in Example 1, the same pattern as that of PST-2 was not found at all when compared with the previously reported X-ray diffraction patterns of zeolites. This means that PST-2 has a new skeletal structure that has been completely unknown until now. The results of the X-ray diffraction measurement test using 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 ~ 21.9 4.1 to 4.2 15 24.1 to 24.2 3.7 to 3.8 74 25.7 ~ 25.8 3.5 to 3.6 20 26.0 to 26.1 3.4 to 3.5 24 27.0 ~ 27.1 3.3 to 3.4 43 28.2 to 28.3 3.2 to 3.3 41 29.5 ~ 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 ~ 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 ~ 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 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 a result of thermogravimetric analysis and elemental analysis of the solid powder obtained in Example 1, it was confirmed that the PST-2 zeolite contained about 10.5% by weight of water and 8.0% by weight of TEA. In addition, it was confirmed that the Si/Al ratio of the produced zeolite was about 3.1 using Inductive Coupled Plasma (ICP).

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

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

In Example 1, the sodium nitrate (NaNO ₃ ) amount was used instead of 0.022 g, and 0.064 g was used, and the cesium nitrate (CsNO ₃ ) amount was 0.15 g instead of 0.049 g, except that 0.049 g was used. 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 performing an 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 the 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, 0.017 g of lithium nitrate (LiNO ₃ ) instead of 0.022 g of sodium nitrate (NaNO ₃ ) was used to prepare a reaction mixture having the following composition, except that a solid powder was obtained in the same manner as in Example 1. .

[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 performing an X-ray diffraction measurement test with 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

In Example 1, 0.022 g of sodium nitrate (NaNO ₃ ) Instead of potassium nitrate (KNO ₃ ) 0.026 g was used to prepare a reaction mixture of the following composition to obtain a solid powder in the same manner as 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 performing 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 in Example 1, 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 ). .

[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 performing 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 in Example 1, 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 performing an X-ray diffraction measurement experiment with the solid powder obtained in Example 4, an offretite zeolite was produced.

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

In a plastic beaker, 0.51 g of aluminum trisecbutoxite (Al[OCH(CH ₃ )C ₂ H ₅ ] ₃ ), 35 wt% 6.73 g of TEAOH were first added and stirred for 1 hour. In the resulting aqueous solution, 2.40 g of colloidal It was put in silica sol (Ludox AS-40) and 2.92 g of tertiary distilled water, stirred for 1 hour, and then aged at 80°C 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 Chemical 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

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

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

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 the zeolite was placed in 50 mL of 1.0 M sodium ammonium (NH ₄ NO ₃ ) solution at 80 ^o C for 6 hours. After repeating the ion exchange four times, the solid product obtained was repeatedly washed with water and dried at ^room temperature. It was observed that the calcined sample exhibited essentially the same X-ray pattern as in 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 material (TEA) in the H-PST-2 zeolite was burned and only contained 20.2% by weight of water.

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

2θ d 100×I/I _O 6.0 ~ 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 to 12.3 7.3 ~ 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 to 19.1 4.7 to 4.8 4 20.7 to 20.8 4.3 to 4.4 9 21.6 ~ 21.7 4.1 to 4.2 9 22.1 to 22.2 4.0 ~ 4.1 9 24.4 to 24.5 3.7 to 3.8 11 26.4 ~ 26.5 3.4 to 3.5 8 27.4 ~ 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 ~ 33.8 2.7 to 2.8 3 36.4 ~ 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 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 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 while the pressure was reduced to 0.009 torr, the temperature was raised to 250 ^o C at 10 ^o C per minute and 250 ^o C for 2 hours It was kept for a while to completely dehydrate. After the material was cooled to room temperature in a vacuum state, the amount of carbon dioxide adsorption was measured by continuously changing the carbon dioxide pressure while maintaining 25 °C using a water circulator. The results are shown in FIG. 10, and it was confirmed that a carbon dioxide adsorption amount of 1.5 mmol/g at 0.1 bar and a carbon dioxide adsorption amount of 3.9 mmol/g at 1.0 bar were exhibited. To evaluate the adsorption amount of nitrogen and methane gas of the PST-2 zeolite prepared in Example 6, the nitrogen and methane gas pressures of PST-2 zeolite were continuously changed at 25 ^o C in the same manner. Methane adsorption amount 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 exhibited. became

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

Example 8: Heavy Oil Catalytic Cracking

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

Referring to FIG. 11 , in particular, in the case of H-PST-2 zeolite, it was confirmed that the yields of ethylene and paraffin were superior to those of H-Y and H-beta of other comparative groups. Therefore, it was confirmed that H-PST-2 zeolite can be used as a catalyst for catalytic cracking of heavy oil.

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

Claims (20)

PST-2 zeolite with SBS framework and SBT framework. According to claim 1,
PST-2 zeolite, characterized in that the PST-2 zeolite comprises an aluminosilicate represented by Formula 1 below.
[Formula 1]
(M ₂ O) _x (Al ₂ O ₃ ) _y (SiO ₂ ) _z
In Formula 1,
M comprises at least one alkylalkyl metal 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,
PST-2 zeolite, characterized in that the PST-2 zeolite comprises an SBS/SBT intergrowth structure having the SBS backbone and the SBT backbone in one crystal. 4. The method of 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 alternately grow with each other in one crystal. According to claim 1,
The PST-2 zeolite has three-dimensional nest-shaped micropores,
PST-2 zeolite, characterized in that the micropores include a 12-ring (12-ring) shape fine inlet made of oxygen atoms. 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.

In Table 1, θ, d, and I are the Bragg angle, the lattice spacing, and the intensity of the X-ray diffraction peak, respectively. Powder X-ray diffraction data were measured using standard X-ray diffraction methods, and copper Kα rays and an X-ray tube operating at 40 kV, 30 mA were used as radiation sources. It was measured at a rate of 5˚ (2θ) per minute from a horizontally compressed powder sample, 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). 3. The method of claim 2,
z is 2.0≤z≤50 PST-2 zeolite, characterized in that. 8. The method of claim 7,
PST-2 zeolite, characterized in that the PST-2 zeolite comprises a skeleton according to the XRD pattern shown in Table 2 below.

In Table 2, θ, d, and I are the Bragg angle, the grating spacing, and the intensity of the X-ray diffraction peak, respectively. Powder X-ray diffraction data were measured using standard X-ray diffraction methods, and copper Kα rays and an X-ray tube operating at 40 kV, 30 mA were used as radiation sources. Measurements were made at a rate of 5˚ (2θ) per minute 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. 3. The method of claim 2,
PST-2 zeolite, characterized in that M comprises at least one selected from the group consisting of Na and Cs. 3. The method of claim 2,
PST-2 zeolite, characterized in that the PST-2 zeolite further comprises a proton (H ⁺ ), and the proton is for compensating for the charge amount of aluminum (Al) in the framework. According to claim 1,
The PST-2 zeolite is PST-2 zeolite, characterized in that it is used as an ion exchanger, a catalyst, an acid catalyst, a base catalyst, a catalyst support, a fluid catalytic cracking catalyst, or a gas separator. A catalyst comprising the PST-2 zeolite according to claim 1 . (a) preparing a mixed aqueous solution containing a structure-derived 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) reacting the mixture to prepare PST-2 zeolite;
Method for producing PST-2 zeolite comprising. 14. The method of claim 13,
the mixture
with respect to 1 mole of the alumina precursor
2.0 to 20.0 moles of the structure-derived organic matter.
0.01 to 1.0 mole of the alkali metal salt, and
The method for producing PST-2 zeolite, characterized in that it contains the silica precursor in a ratio of 10 to 600 moles. 14. The method of claim 13,
The step (a) is
(a-1) preparing a first aqueous solution containing the structure-derived 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) preparing an aged mixed aqueous solution by maintaining the mixed aqueous solution at a temperature of 70 to 90° C. for 12 to 24 hours; A method for producing a PST-2 zeolite comprising a. 14. The method of claim 13,
The step (c) is
(c-1) stirring the mixture at a temperature of 90 to 110 °C; and
(c-2) reacting the stirred mixture at a temperature of 90 to 110° C. for 1 to 30 days to prepare a PST-2 zeolite; 14. The method of claim 13,
The structure-inducing organic material comprises Tetraethylammonium hydroxide (TEAOH), the structure-inducing organic material comprises aluminum tri-sec butoxide, and the silica precursor comprises a colloidal silica sol. A method for producing a PST-2 zeolite. 14. The method of claim 13
The method for producing PST-2 zeolite, characterized in that the PST-2 zeolite has an SBS framework and an SBT framework, and is represented by Formula 1 below.
[Formula 1]
(M ₂ O) _x (Al ₂ O ₃ ) _y (SiO ₂ ) _z
In Formula 1,
M comprises at least one alkylalkyl metal 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 selective separation method of carbon dioxide 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 method for reforming heavy oil comprising the step of reforming the heavy oil by catalytic cracking using a catalyst comprising the PST-2 zeolite according to claim 1 .

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