KR102224614B1 - Silicoaluminophosphate molecular sieves with CHA topology and their manufacturing method using inorganic structure-directing agent - Google Patents

Abstract

The present invention provides a novel CHA-type SAPO silicoaluminophosphate molecular sieve comprising an inorganic metal prepared using the preparation of a CHA-type SAPO silicoaluminophosphate molecular sieve using an inorganic structure-inducing substance and the same.

Description

CHA-type SAPO containing an inorganic metal component and its manufacturing method TECHNICAL FIELD [Silicoaluminophosphate molecular sieves with CHA topology and their manufacturing method using inorganic structure-directing agent}

The present invention relates to an SAPO and a method for producing the same, and more particularly, to a CHA-type SAPO containing an inorganic metal component and a method for producing the same.

Silicoaluminophosphate (SAPO) is a molecular sieve in which phosphorus atoms form a skeleton together with aluminum and silicon. CHA type SAPO-34 has a wide range of industrial applications, and various synthesis methods are being developed.

In Korean Patent Publication No. 10-2016-0077109, a silicon aluminophosphate molecular sieve (SAPO-34) using a first slurry containing a first organic structure-inducing material and a second slurry containing a second organic structure-inducing material. It provides a method of manufacturing.

Republic of Korea Patent Publication No. 10-2017-0044145 provides a method of preparing a high purity SAPO-34 molecular sieve using monoisopropanolamine.

The problem to be solved in the present invention is to provide a new CHA-type SAPO containing an inorganic metal component.

Another problem to be solved in the present invention is to provide a method for producing a new CHA-type SAPO containing an inorganic metal component.

In order to solve the above problems, the present invention provides a CHA structure silicoaluminophosphate molecular sieve having a molar ratio composition as shown in the following formula (1).

mM:(Si _x Al _y P _z )O ₂ (1)

Here, "M" is an inorganic metal component,

"m" is the number of moles of M per mole _{of (Si x} Al _y P _z )O _{2, 0.01≤m≤0.5,}

x , y , z are the mole fractions of Si, Al, and P, respectively , as 0.01≦x ≦0.98, 0.01≦ y ≦0.98, and 0.01≦ z ≦0.98, where x + y + z =1.00.

In the present invention, the inorganic metal component is at least one inorganic cation, and the inorganic cation may be an alkali metal cation, an alkaline earth metal cation, and a transition metal, and a combination of two or more metal cations is possible.

In the present invention, the alkali metal may be Li, Na, K, Rb, Cs, preferably Na or K.

In the present invention, the alkaline earth metal may be Be, Mg, Ca, Sr, Ba, preferably Ca or Sr.

In the present invention, the transition metal may be Ti, Mn, Fe, Co, Ni, Cu, Zn, Zr, Pd, Ag, and preferably Mn.

In the present invention, the inorganic metal component may be an inorganic structure-inducing material used to induce the CHA structure of the silicoaluminophosphate molecular sieve.

In the practice of the present invention, the K-SAPO-CHA belongs to the R 3 space group of the rhombohedral crystal system, and the crystal axis unit cell length a is approximately 10 Å (Angstrom), α= 95 ° (degree ) Can be.

In one embodiment of the present invention, the Na-SAPO-CHA belongs to the R -3 space group of the trigonal crystal system, and the crystal axis unit cell length a is approximately 10 Å (Angstrom), α= 95 It can be in degrees.

In the present invention, the number of moles "m" of the inorganic structure-inducing material is the number of moles of M per 1 mole _{of (Si x} Al _y P _z )O _{2, and preferably 0.2 to 0.4.}

In the present invention, the CHA structure silicoaluminophosphate molecular sieve SAPO including the inorganic structure-inducing material may further include an organic structure-inducing material.

In the practice of the present invention, SAPO having a CHA structure including an organic structure-inducing material and an inorganic structure-inducing material may be represented by the following formula (2).

mM:nR:(Si_xAl_yP_z) O₂ (2)

Here, "M" is an inorganic structure-inducing material, "R" is an organic structure-inducing material,

"m" is the number _{of moles of M per mole of (Si x} Al _y P _z )O ₂ , 0.01 ≤ m ≤ 0.5,

"n" is the number _{of moles of R per mole of (Si x} Al _y P _z )O ₂ , 0.01 ≤ n ≤ 0.3,

x , y , z are the mole fractions of Si, Al, and P, respectively, as 0.01 ≤ x ≤ 0.98, 0.01 ≤ y ≤ 0.98, 0.01 ≤ z ≤ 0.98, and x + y + z = 1.00.

In the practice of the present invention, the organic structure-inducing material (R) that can be used together with the inorganic structure-inducing material may be at least one organic amine, ammonium, or phosphonium compound.

In a preferred embodiment of the present invention, the organic amine may be, for example, diethylamine, triethylamine, and morpholine, the ammonium compound may be tetraethylammonium hydroxide, and the phosphonium compound may be tetraethylphosphonium.

In one aspect, the present invention provides a method for preparing SAPO, a CHA-type silicoaluminophosphate molecular body, using at least one material selected from alkali metal, alkaline earth metal, and transition metal cations as inorganic structure-inducing material (M). .

In the present invention, the preparation of the CHA-type SAPO may be performed by hydrothermal synthesis.

In the present invention, the hydrothermal synthesis method for preparing the CHA-type SAPO silicoaluminophosphate molecular sieve includes a silica source, an aluminum source, a phosphate source, an alkali metal, an alkaline earth metal, and a structure-derived material selected from transition metal cations. , And by reacting a mixture containing water to prepare a synthetic compound having the composition of the following formula (3), and if necessary, it may include heating the same together with the seed crystal.

aM ₂ O:(Si _x Al _y P _z )O ₂ :bH ₂ O (3)

Here, "M" is an inorganic structure-inducing material, and is at least one inorganic cation selected from the group consisting of an alkali metal cation, an alkaline earth metal cation, and a transition metal cation,

"a" is an amount required to act as a structure-inducing material of inorganic cation (M), and is at least 0 <a ≤ 3,

"b" is the amount of water required for the production of the silicoaluminophosphate molecular sieve, 0 ≤ a ≤ 500,

x , y , z are the mole fractions of Si, Al, and P that make up the silicoaluminophosphate composite mixture, and are 0.01 ≤ x ≤ 0.98, 0.01 ≤ y ≤ 0.98, and 0.01 ≤ z ≤ 0.98, respectively. This notation is normalized to (Si+Al+P)=( x + y + z ) = 1.0 mol, and the synthetic compound composition shown in the actual general example is normalized to 1.0 mol of Al ₂ O ₃ . It is expressed as the number of moles of _{M 2} O, P ₂ O ₅ , SiO ₂ and H _{2 O.}

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 ( aluminum isopropoxide), sodium aluminate, aluminum hydroxide, aluminum alkoxide, aluminum metal, aluminosilicate zeolite, aluminophosphate or silicoaluminophosphate zeolite, etc. Do.

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, alumina Nosilicate to silicoaluminophosphate zeolite and the like are possible.

In the practice of the present invention, the phosphorus (P) precursor compound may be phosphorus or a precursor compound containing phosphorus, and, for example, is preferably phosphoric acid.

In the present invention, the heating condition of the silicoaluminophosphate composite mixture having the composition of Formula 3 may be heated at 100 to 220 °C for 1 to 18 days.

In the present invention, the seed crystal may be used to induce the crystal structure to the CHA structure when SAPO having a different structure such as MER is generated in the absence of the seed crystal. In the practice of the present invention, the seed (seed) crystal source may be CHA type silicoaluminophosphate zeolite, and CHA and AFT, AFV, AFX, AVL, ERI, LEV, OFF type aluminosilicate, aluminophosphate, silica Aluminophosphate, metalloaluminophosphate zeolite, etc. are possible.

In a preferred embodiment of the present invention, the synthetic mixture having the composition of formula (3) _{is mixed with 0-500 mol of water (H 2} O) and 0.01-0.98 mol of aluminum source in a plastic beaker, and 0.01-0.98 mol of phosphorus source and After adding 0.01-0.98 moles of silica source, it is sufficiently stirred. 0.01-3.00 mol of at least one alkali metal hydroxide, alkaline earth hydroxide metal, or transition metal hydroxide is added to the mixture as an inorganic structure-inducing material (M _{2 O), followed by sufficiently stirring and mixing.}

In the present invention, the silicoaluminophosphate molecular sieve may be prepared using an organic structure-inducing material together with an inorganic structure-inducing material. If necessary, 0.0-3.0 moles of at least one organic amine, ammonium compound, and phosphonium compound are added to the mixture as an organic structure-inducing material (R _{2 O), followed by sufficiently stirring and mixing.}

In the present invention, when the inorganic inducing material and the organic inducing material are used together, the silicoaluminophosphate molecular sieve comprises a silica source, an aluminum source, a phosphate source, an inorganic structure inducing material, an organic structure inducing material, and a mixture containing water. By reacting, a synthetic compound having the composition of the following formula (4) is prepared, and if necessary, seed crystals are added, and then it can be prepared by heating.

aM ₂ O:bR ₂ O:(Si _x Al _y P _z )O ₂ :cH ₂ O (4)

Here, "M" is an inorganic structure-inducing material, and is at least one inorganic cation selected from the group consisting of an alkali metal cation, an alkaline earth metal cation, and a transition metal cation,

"R" is an organic structure-inducing material, and is at least one material selected from the group consisting of organic amine, ammonium, and phosphonium compounds,

"a" is an amount required to act as a structure-inducing material of inorganic cation (M), and is at least 0<a≤3,

"b" is an amount of an organic structure-inducing material that can be selectively used together with an inorganic structure-inducing material, and is at least 0≦b≦3,

"c" is the amount of water required for hydrothermal synthesis of the silicoaluminophosphate molecular sieve, 0≤c≤500,

x , y , z are the mole fractions of Si, Al, and P that make up the silicoaluminophosphate composite mixture, and are 0.01 ≤ x ≤ 0.98, 0.01 ≤ y ≤ 0.98, and 0.01 ≤ z ≤ 0.98, respectively. This notation is normalized to (Si+Al+P)=( x + y + z ) = 1.0 mol, and the synthetic compound composition shown in the actual general example is normalized to 1.0 mol of Al ₂ O ₃ . It is expressed as the number of moles of _{M 2} O, R ₂ O, P ₂ O ₅ , SiO ₂ , and H _{2 O.}

Through the present invention, a method of preparing SAPO having a CHA structure using an inorganic structure-derived material was provided.

SAPO-CHA manufactured according to the present invention is a new SAPO containing inorganic structure-inducing material in the pores, and it is more economical and eco-friendly than CHA-type SAPO (SAPO-34) synthesized using an existing organic structure-inducing material. .

In addition, the present invention provides a way to form the SAPO of the CHA structure under the condition that the SAPO of another type is formed instead of the SAPO of the CHA structure.

The present invention also provides a new CHA-type SAPO containing an inorganic cation derived from an inorganic structure-inducing substance.

1 is an X-ray diffraction (XRD) result of silicoaluminophosphate K-SAPO-CHA prepared according to Example 1 of the present invention.
2 is a scanning microscope (SEM) image of a silicoaluminophosphate K-SAPO-CHA prepared according to Example 1 of the present invention.
3 is an X-ray diffraction (XRD) result of silicoaluminophosphate K-SAPO-CHA prepared according to Example 2 of the present invention.
4 is a scanning microscope (SEM) image of a silicoaluminophosphate K-SAPO-CHA prepared according to Example 2 of the present invention.
5 is an X-ray diffraction (XRD) result of the silicoaluminophosphate Na-SAPO-CHA prepared according to Example 3 of the present invention.
6 is a silicoaluminophosphate prepared according to Example 3 of the present invention.
This is a scanning microscope (SEM) image of Na-SAPO-CHA.

Hereinafter, the present invention will be described in detail through examples. It should be noted that the following examples are intended to illustrate the present invention, and in no case are described to limit the present invention.

Example 1.

Preparation of K-SAPO-CHA silicoaluminophosphate molecular sieve

In a plastic beaker, 3.87 g of tertiary distilled water and 0.54 g of aluminum chloride were first mixed and stirred for 30 minutes. 0.23 g of phosphoric acid (85%) aqueous solution was added to the mixture and stirred for 1 hour. The reaction compound obtained by adding an aqueous potassium hydroxide (KOH) solution and stirring the mixture so that the pH of the mixed solution is 7-8 is dried, and then added to a mixture of 3.82 g of tertiary distilled water and 0.12 g of dry silica and stirred. 0.25 g of potassium hydroxide aqueous solution (45%) was added to the above mixture and stirred to obtain the composition of the reaction mixture shown in the following formula (5), and then 0.002 g of SAPO-34 seed crystals were added and sufficiently stirred, and the obtained reaction mixture was transferred to a Teflon reactor. After putting it in, it was put in a stainless steel container and heated at 180° C. for 5 days, and the solid product obtained by heating was repeatedly washed and dried at room temperature.

The K-SAPO-MER silicoaluminophosphate molecular sieve according to the present invention has a basic skeletal structure in a dehydrated state consisting of an oxide composition in a molar ratio as shown in Formula 6 below, and X-ray diffraction with the solid powder obtained through the above synthesis. The measurement test was performed and the results are shown in Table 1.

[Formula 5]

0.5 K ₂ O: 1.0 Al ₂ O ₃ : 0.5 P ₂ O ₅ : 1.0 SiO ₂ : 110 H ₂ O

[Formula 6]

0.23K:(Si _0.28 Al _0.50 P _0.22 )O ₂

2θ D 100 x I/I ₀ 9.4 9.38 85.1(VS) 12.8 6.92 21.4 (M) 15.9 5.58 17.5 (W) 17.6 5.04 25.8 (M) 18.9 4.70 10.5 (W) 20.4 4.34 75.5 (VS) 22.2 4.00 6.4 (W) 22.8 3.89 44.7(S) 24.7 3.61 24.4 (M) 25.7 3.47 13.3 (W) 27.4 3.25 8.0 (W) 27.9 3.20 12.2 (W) 28.4 3.14 5.5 (W) 29.3 3.05 3.9 (W) 30.3 2.95 100.0 (VS) 30.8 2.91 51.2 (S) 32.0 2.79 6.2 (W) 33.1 2.70 6.2 (W) 34.2 2.62 17.4 (W) 34.6 2.59 7.1 (W) 35.6 2.52 13.4 (W)

In Table 1, θ, d, and I denote the Bragg angle, the grating interval, 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 a standard X-ray diffraction method, and as a radiation source, a copper Kα ray and an X-ray tube operating at 40 kV and 30 mA were used. Was used. It was measured at a speed of 5 degrees per minute (2θ) from the horizontally compressed powder sample, and d and I were calculated from the 2θ value and the peak height of the observed X-ray diffraction peak. Depending on the value of the relative intensity 100I/I _{0, it} is expressed as W (weak: 0-20), M (medium: 20-40), S (strong: 40-60), and VS (very strong: 60-100). As a result of comparing the prepared K-SAPO-CHA with the previously reported X-ray diffraction patterns of aluminosilicate and silicoaluminophosphate molecular sieves, it was confirmed that it was a chabazite structure pattern (FIG. 1). [Collection of Simulated XRD Patterns for Zeolites, Elsevier, 2007], [http://www.iza-structure.org/].

In addition, as a result of measuring a scanning microscope (Scanning Electron Microscope, SEM for abbreviation) (FIG. 2), pure crystals of agglomerated grains were shown. This indicates that K-SAPO-CHA is a pure substance that does not contain several substances (Physical Mixture).

In addition, to determine the composition of this sample, elemental analysis was performed through Inductive Coupled Plasma (ICP) to determine the composition of Si/(Si+Al+P) and (Al-P)/(Si+Al+). It was confirmed that the ratio of P) was 0.28 and 0.28, respectively.

Example 2

Preparation of K-SAPO-CHA silicoaluminophosphate molecular sieve

In a plastic beaker, 4.47 g of tertiary distilled water and 0.46 g of water boehmite were first mixed and stirred for 30 minutes. To the mixture was added 0.75 g of silica sol (Ludox AS-40) and 0.46 g of an aqueous solution of phosphoric acid (85%) and stirred for 1 hour. 1.12 g of 45% potassium hydroxide (KOH) aqueous solution was again added to the solution and sufficiently stirred to obtain the composition of the reaction mixture shown in the following formula (7), and then 0.009 g of SAPO-57 seed crystals were added and sufficiently stirred, and the obtained reaction mixture was Teflon. After being transferred to the reactor, it was placed in a stainless steel container and heated at 200° C. for 5 days, and the solid product obtained by heating was repeatedly washed and dried at room temperature.

The K-SAPO-CHA silicoaluminophosphate molecular sieve according to the present invention has a basic skeletal structure in a dehydrated state consisting of an oxide composition in a molar ratio as shown in Formula 6 below, and X-ray diffraction with the solid powder obtained through the above synthesis. The measurement test was performed and the results are shown in Table 2.

[Formula 5]

1.3 K ₂ O: 1.0 Al ₂ O ₃ : 0.5 P ₂ O ₅ : 1.25 SiO ₂ : 80 H ₂ O

[Formula 6]

0.25K:(Si _0.33 Al _0.46 P _0.21 )O ₂

2θ D 100 x I/I ₀ 9.5 9.36 41.7 (S) 12.9 6.87 18.2 (W) 15.9 5.56 9.0 (W) 17.4 5.10 23.1 (M) 18.9 4.70 6.7 (W) 20.5 4.33 48.2 (S) 21.7 4.10 2.3 (W) 22.3 3.98 7.7 (W) 22.9 3.89 33.0 (M) 24.4 3.65 22.5 (M) 25.8 3.45 7.1 (W) 27.5 3.24 7.7 (W) 28.4 3.14 9.1 (W) 30.4 2.94 100.0 (VS) 32.1 2.78 5.2 (W) 32.8 2.73 4.1 (W) 33.2 2.70 3.5 (W) 34.3 2.61 15.9 (W) 34.7 2.59 4.5 (W) 35.4 2.54 16.3 (W)

In Table 1, θ, d, and I denote the Bragg angle, the grating interval, 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 a standard X-ray diffraction method, and as a radiation source, a copper Kα ray and an X-ray tube operating at 40 kV and 30 mA were used. Was used. It was measured at a speed of 5 degrees per minute (2θ) from the horizontally compressed powder sample, and d and I were calculated from the 2θ value and the peak height of the observed X-ray diffraction peak. Depending on the value of the relative intensity 100I/I _{0, it} is expressed as W (weak: 0-20), M (medium: 20-40), S (strong: 40-60), and VS (very strong: 60-100). As a result of comparing the prepared K-SAPO-CHA with the previously reported X-ray diffraction patterns of aluminosilicate and silicoaluminophosphate molecular sieves, it was confirmed that it was a chabazite structure pattern (FIG. 3). [Collection of Simulated XRD Patterns for Zeolites, Elsevier, 2007], [http://www.iza-structure.org/].

In addition, as a result of measuring a scanning microscope (Scanning Electron Microscope, abbreviated SEM) (FIG. 4), pure crystals of aggregated grains were shown. This indicates that K-SAPO-CHA is a pure substance that does not contain several substances (Physical Mixture).

In addition, to determine the composition of this sample, elemental analysis was performed through Inductive Coupled Plasma (ICP) to determine the composition of Si/(Si+Al+P) and (Al-P)/(Si+Al+). It was confirmed that the P) ratio was 0.33 and 0.25, respectively.

<Example 3>

Preparation of Na-SAPO-CHA silicoaluminophosphate molecular sieve

In a plastic beaker, 189.76 g of tertiary distilled water and 26.94 g of aluminum chloride were first mixed and stirred for 30 minutes. 20.75 g of phosphoric acid (85%) aqueous solution was added to the mixture and stirred for 1 hour. 1.28 g of the reaction compound obtained by adding an aqueous sodium hydroxide (NaOH) solution and stirring so that the pH of the solution solution is 7-8 was added to a mixture of 6.70 g of tertiary distilled water and 1.27 g of silica sol (Ludox AS-40) and stirred. do. 0.77 g of sodium hydroxide aqueous solution (50%) was added to the above mixture and stirred to obtain the composition of the reaction mixture shown in the following formula (7), and then transferred to a Teflon reactor and then put into a stainless steel container and heated at 150°C for 7 days. Thereafter, the solid product obtained by heating is repeatedly washed and dried at room temperature.

The Na-SAPO-CHA silicoaluminophosphate molecular sieve according to the present invention has a basic skeleton structure of an oxide composition in a molar ratio as shown in Chemical Formula 8 below in a dehydrated state, and X-ray diffraction with the solid powder obtained through the above synthesis. The measurement test was performed and the results are shown in Table 3.

[Formula 7]

1.2 Na ₂ O: 1.0 Al ₂ O ₃ : 0.9 P ₂ O ₅ : 1.8 SiO ₂ : 110 H ₂ O

[Formula 8]

0.27 Na:(Si _0.34 Al _0.48 P _0.18 )O ₂

2θ D 100 x I/I ₀ 9.4 9.43 56.7 (VS) 12.8 6.94 30.8 (M) 13.7 6.46 2.3 (W) 15.9 5.58 15.4 (W) 17.5 5.07 34.5 (M) 18.8 4.71 5.1 (W) 20.4 4.35 82.0 (VS) 22.2 4.00 7.0 (W) 22.8 3.90 23.3 (M) 24.5 3.63 26.1 (M) 25.8 3.46 24.0 (M) 27.6 3.23 7.2 (W) 30.4 2.94 100.0 (VS) 32.0 2.80 7.3 (W) 33.0 2.71 6.6 (W) 34.3 2.62 15.2 (W) 35.5 2.53 10.1 (W)

In Table 1, θ, d, and I denote the Bragg angle, the grating interval, 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 a standard X-ray diffraction method, and as a radiation source, a copper Kα ray and an X-ray tube operating at 40 kV and 30 mA were used. Was used. It was measured at a speed of 5 degrees per minute (2θ) from the horizontally compressed powder sample, and d and I were calculated from the 2θ value and the peak height of the observed X-ray diffraction peak. Depending on the value of the relative intensity 100I/I _{0, it} is expressed as W (weak: 0-20), M (medium: 20-40), S (strong: 40-60), and VS (very strong: 60-100). As a result of comparing the prepared Na-SAPO-CHA with the previously reported X-ray diffraction patterns of aluminosilicate and silicoaluminophosphate molecular sieves, it was confirmed that it was a chabazite structure pattern (FIG. 5). [Collection of Simulated XRD Patterns for Zeolites, Elsevier, 2007], [http://www.iza-structure.org/].

In addition, as a result of measuring a scanning microscope (Scanning Electron Microscope, SEM for abbreviation) (FIG. 6), pure crystals of agglomerated grains were shown. This indicates that Na-SAPO-CHA is a pure substance that does not contain several substances (Physical Mixture).

In addition, to determine the composition of this sample, elemental analysis was performed through Inductive Coupled Plasma (ICP) to determine the composition of Si/(Si+Al+P) and (Al-P)/(Si+Al+). It was confirmed that the ratio of P) was 0.34 and 0.30, respectively.

Claims (12)

CHA type silicoaluminophosphate SAPO molecular sieve having a molar ratio composition as shown in the following formula (1).
mM:(Si _x Al _y P _z )O ₂ (1)
Here, "M" is an inorganic structure inducing material, and includes K and/or Na,
"m" is the number of moles of M per mole _{of (Si x} Al _y P _z )O _{2, and 0.2≤m≤0.4,}
x , y , z are the mole fractions of Si, Al, and P, respectively, as 0.01≤ x ≤0.98, 0.01≤ y ≤0.98, 0.01≤ z ≤0.98, x + y + z =1.00,
Here, y is the largest in x , y , and z , and x > z . The method of claim 1,
The x is 0.28 ~ 0.34, characterized in that the CHA type silicoaluminophosphate SAPO molecular sieve. delete delete CHA-type silicoaluminophosphate, characterized in that the CHA-type silicoaluminophosphate SAPO molecular sieve according to claim 1 is prepared by hydrothermal synthesis using a metal containing K and/or Na as an inorganic structure-inducing material (M). SAPO molecular sieve manufacturing method. delete The method of claim 5,
The hydrothermal synthesis method is characterized in that by reacting a mixture containing a silica precursor compound, an aluminum precursor compound, a phosphate precursor compound, an inorganic structure-inducing material, and water to prepare a synthetic compound having the composition of the following formula (3), and heating it CHA type silicoaluminophosphate SAPO molecular sieve manufacturing method.
aM ₂ O:(Si _x Al _y P _z )O ₂ :bH ₂ O (3)
Here, "M" is an inorganic structure-inducing material, "a" is an amount necessary for the inorganic structure-inducing material to act as a structure-inducing material, 0<a≤3, and "b" is for the manufacture of a silicoaluminophosphate molecular sieve. It is the amount of water required, 0≤b≤500, x , y , z are the mole fractions of Si, Al, and P forming the silicoaluminophosphate composite mixture, respectively 0.01 ≤ x ≤ 0.98, 0.01 ≤ y ≤ 0.98, 0.01 ≤ z Is ≤ 0.98. The method of claim 7,
Aluminum (Al) precursor compounds include pseudoboehmite, aluminum chloride, aluminum isopropoxide, sodium aluminate, aluminum hydroxide, and aluminum alkoxide. aluminum alkoxide), aluminum metal, aluminosilicate zeolite, aluminophosphate to silicoaluminophosphate zeolite,
The silicon (Si) source is one or more selected from fumed silica, silica sol, organosilane, aluminosilicate to silicoaluminophosphate zeolite,
Phosphorus (P) source is phosphoric acid (phosphoric acid), aluminophosphate, CHA type silicoaluminophosphate SAPO molecular sieve production method, characterized in that one or more selected from the silica-aluminophosphate zeolite. The method of claim 5, further comprising seed crystals. The method of claim 9, wherein the seed crystal is one from the group consisting of CHA, AFT, AFV, AFX, AVL, ERI, LEV, OFF type aluminosilicate, aluminophosphate, silicoaluminophosphate, metalloaluminophosphate zeolite. CHA type silicoaluminophosphate SAPO molecular sieve production method, characterized in that selected above. The method of claim 7, wherein the synthetic mixture having the composition of Formula (3) _{comprises 0-500 moles of water (H 2} O), 0.01-0.98 moles of an aluminum precursor, 0.01-0.98 moles of a phosphorus precursor, and 0.01-0.98 moles of a silica precursor. CHA type silicoaluminophosphate SAPO molecular sieve manufacturing method, characterized in that it is formed by adding 0.01-3.00 mol of alkali metal hydroxide, alkaline earth hydroxide or transition metal hydroxide to the mixture The method of claim 5, further comprising an organic structure-inducing substance.

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