KR101555128B1 - The aluminophosphate PST-5 and PST-6 and their manufacturing process - Google Patents

Abstract

The invention in the aluminophosphate and as it relates to a process for the preparation, and more particularly, aluminophosphate having a novel structure containing an organic structure derived molecules and the hydroxyl groups pore PST-5 and this, 550 ^o C with the new structure Another novel structure of PST-6 produced by firing is described, and a method of manufacturing the same.
PST-5 and PST-6 according to the present invention are aluminophosphates having a specific X-ray diffraction pattern comprising oxide compositions in a molar ratio as shown in Formula 1 below and containing lattice intervals.
0.5-1.5 Al ₂ O ₃ : 1.0 P ₂ O ₅ (1)

Description

Aluminophosphate PST-5, PST-6 and a process for producing the same,

The invention in the aluminophosphate and as it relates to a process for the preparation, and more particularly, aluminophosphate having a novel structure containing an organic structure derived molecules and the hydroxyl groups pore PST-5 and this, 550 ^o C with the new structure Another novel structure of PST-6 produced by firing is described, and a method of manufacturing the same.

A representative material of the nanoporous material is aluminosilicate, which is a zeolite, and contains pores different in size and shape within an error range of 0.1 Å or less depending on the skeletal structure thereof. Therefore, a unique shape that is not observed in an amorphous oxide It is a representative molecular sieve with selectivity. As a result, it has been widely used as an ion exchanger, separating agent, catalyst, or catalyst support in various fields such as fine chemicals and petrochemicals, and has enabled the development of numerous new processes having significant commercial significance as well as dramatically improving existing chemical processes.

The commercial success of these nanoporous materials is to study the physicochemical and catalytic properties of aluminosilicates composed of silicon (Si) and aluminum (Al) as well as the synthesis of new molecular sieves. It is possible to apply them more effectively to the separation process.

In particular, the aluminophosphate synthesized by US UOP for the first time in the early 1980s is composed of aluminum (Al) and phosphorus (P) and is still used as a separating agent, adsorbent, catalyst or catalyst support. Thereafter, molecular sieves of various compositions such as silicoaluminophosphate and metalloalumino-phosphate substituted with silicon or various metal atoms instead of phosphorus and aluminum are synthesized in the skeleton and used for various reactions As a representative example, SAPO-34, which is a silicoaluminophosphate, exhibits a high selectivity to ethylene and propylene with a high conversion rate in a methanol-to-olefin (MTO) process for producing olefins from methanol, MTO process), and recently it has been reported as an excellent catalyst in NO SCR (Selective Catalytic Reduction) reaction.

Not only this composition change, but also the synthesis of nanoporous materials, which are fundamentally different from conventional materials in the size and shape of pores, have a tremendous ripple effect throughout industry and academia. The new skeletal nanoporous material, which has been continuously discovered over the past several decades, has served as a driving force in technological innovation by being widely applied to numerous petrochemical and fine chemical processes and will continue to overcome the limitations of existing technologies in the environment and energy fields. It can be said that it has an infinite possibility of application.

Thus, it is possible to produce aluminophosphates having skeletal structures quite different from the nanoporous materials known so far and to be used as separators, adsorbents, catalysts with unique shape selectivity or catalyst supports for specific molecules in the environment and energy fields. There is a continuing need for aluminophosphates having physical properties and a method for producing the same.

A problem to be solved by the present invention is to provide a novel structure of aluminophosphate.

Another object of the present invention is to provide a process for producing aluminophosphate having a novel structure.

In order to solve the above-mentioned problems, the aluminophosphate according to the present invention has a basic skeleton structure having an oxide composition in a molar ratio as shown in Formula 1 below, and has an X-ray diffraction pattern .

0.5-1.5 Al ₂ O ₃ : 1.0 P ₂ O ₅ (1)

2? d 100 x I / I _O 9.4 to 9.5 9.4 to 9.3 45 to 50 9.6 ~ 9.7 9.2 to 9.1 20-25 11.2 to 11.3 7.9-7.8 20-25 12.5 to 12.6 7.1 to 7.0 20-25 12.7 to 12.8 7.0 to 6.9 40 to 45 14.8 to 14.9 6.0 to 5.9 65 to 70 16.4 to 16.5 5.4 to 5.3 20-25 16.6 to 16.7 5.4 to 5.3 20-25 17.0 to 16.9 5.3 to 5.2 25 to 30 17.3 to 17.2 5.2 to 5.1 25 to 30 23.5 to 23.6 3.80 ~ 3.75 100 24.4 to 24.5 3.65 ~ 3.60 55 ~ 60 26.9-27.0 3.35 ~ 3.30 25 to 30 27.3 to 27.4 3.30 ~ 3.25 25 to 30 27.6 to 27.7 3.25 ~ 3.20 50 to 55 28.7 to 28.8 3.15-3.10 25 to 30

In Table 1, &thetas;, d, and I denote the Bragg angle, the lattice spacing, and the intensity of the X-ray diffraction peak, respectively. All the 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. As the radiation source, a copper Kα line and X Ray tubes were used. From the horizontally compacted powder samples, measured at a rate of 5 degrees per minute (2θ), d and I were calculated from the 2θ values and peak heights of the observed X-ray diffraction peaks.

The aluminophosphates disclosed in the present invention are hereinafter referred to as PST-5 (POSTECH Number 5). Nano-porous materials with the same skeletal structure as PST-5 have not yet been described in the literature [Atlas of Zeolite Structure Types, Butterworth 2007], [http://www.iza-structure.org/].

In the practice of the present invention, a typical X-ray diffraction pattern for the PST-5 is included within the range of the lattice intervals recorded in Table 2. [

2? d 100 x I / I _O 8.4 to 8.5 10.5 to 10.4 15-20 9.4 to 9.5 9.4 to 9.3 45 to 50 9.6 ~ 9.7 9.2 to 9.1 20-25 11.2 to 11.3 7.9-7.8 20-25 12.5 to 12.6 7.1 to 7.0 20-25 12.7 to 12.8 7.0 to 6.9 40 to 45 13.8 to 13.9 6.4 to 6.3 15-20 14.8 to 14.9 6.0 to 5.9 65 to 70 16.4 to 16.5 5.4 to 5.3 20-25 16.6 to 16.7 5.4 to 5.3 20-25 17.0 to 16.9 5.3 to 5.2 25 to 30 17.3 to 17.2 5.2 to 5.1 25 to 30 21.8 ~ 21.9 4.1 to 4.0 15-20 23.5 to 23.6 3.80 ~ 3.75 100 24.4 to 24.5 3.65 ~ 3.60 55 ~ 60 26.9-27.0 3.35 ~ 3.30 25 to 30 27.3 to 27.4 3.30 ~ 3.25 25 to 30 27.6 to 27.7 3.25 ~ 3.20 50 to 55 28.7 to 28.8 3.15-3.10 25 to 30 34.1 to 34.2 2.65 ~ 2.60 15-20

The PST-5 aluminophosphate according to the present invention can be prepared by using diethylamine (DEA), which is one of the simplest organic amines, as an organic structure-inducing molecule.

In the practice of the present invention, the synthesis of PST-5 can be carried out by hydrothermal crystallization by selecting an aluminum raw material and adjusting the content of DEA in the reaction mixture.

In a preferred embodiment of the present invention, the PST-5 beaker is slowly added to 1 to 3 moles of aluminum isopropoxide so as to have a ratio of 2 moles of o -phosphoric acid and mixed well, and then 1.5 to 3.5 moles DEA was added and the mixture was stirred at room temperature for 24 hours to obtain a composition of the reaction mixture as shown in the following formula 2. The reaction mixture was transferred to a Teflon reactor and then placed in a container made of stainless steel for 2-14 days at 150-250 ^° C Wherein the PST-5 aluminophosphate is produced by a method comprising the steps of:

1.5-3.5 DEA: 0.5-1.5 Al ₂ O ₃ : 1 P ₂ O ₅ : 20-200 H ₂ O (2)

In a preferred embodiment of the present invention, the reaction mixture has a composition represented by the following Chemical Formula 3, and pure PST-5 aluminophosphate can be easily synthesized by heating at 200 ^° C for 5 days.

2 DEA: 1 Al ₂ O ₃ : 1 P ₂ O ₅ : 40 H ₂ O (3)

In one aspect, the present invention provides a novel lattice structure of aluminophosphate obtained by firing the PST-5.

2? d 100 x I / I _O 8.2 to 8.3 10.8 to 10.7 25 to 30 8.8 to 8.9 10.0 to 9.9 15-20 10.3 to 10.4 8.6 to 8.5 30 to 35 15.5 to 15.6 5.7-5.6 15-20 16.0 ~ 16.1 5.6 to 5.5 15-20 19.5 to 19.6 4.6 to 4.5 30 to 35 21.2 to 21.3 4.20-4.15 100 21.6 to 21.7 4.15-4.10 15-20 22.3 to 22.4 4.00 ~ 3.95 45 to 50 22.6 to 22.7 3.95 to 3.90 25 to 30 23.0-23.1 3.90 ~ 3.85 15-20 23.8 to 23.9 3.75-3.70 35 to 40

According to the above results, the nanoporous material having an X-ray diffraction pattern, which has a skeletal structure of the formula 1 and at least the lattice intervals given in Table 3, is now defined as PST-6 aluminophosphate.

Also, a typical X-ray diffraction pattern for all PST-6 aluminophosphate materials is defined to fall within the range of the lattice spacings recorded in Table 4. [

2? d 100 x I / I _O 8.2 to 8.3 10.8 to 10.7 25 to 30 8.8 to 8.9 10.0 to 9.9 15-20 9.0 to 9.1 9.8 to 9.7 10 to 15 10.3 to 10.4 8.6 to 8.5 30 to 35 15.5 to 15.6 5.7-5.6 15-20 16.0 ~ 16.1 5.6 to 5.5 15-20 16.4 to 16.5 5.4 to 5.3 10 to 15 19.5 to 19.6 4.6 to 4.5 30 to 35 21.2 to 21.3 4.20-4.15 100 21.6 to 21.7 4.15-4.10 15-20 22.3 to 22.4 4.00 ~ 3.95 45 to 50 22.6 to 22.7 3.95 to 3.90 25 to 30 23.0-23.1 3.90 ~ 3.85 15-20 23.8 to 23.9 3.75-3.70 35 to 40 31.5 to 31.6 2.85 ~ 2.80 10 to 15

According to the present invention, aluminophosphates PST-5 and PST-6, which are nanoporous materials having a novel skeletal structure, which have not been known hitherto, and a process for producing the same are provided. PST-5 according to the present invention can be used as a catalyst or catalyst support having a separator, an adsorbent, a unique shape selectivity for a specific molecule in the field of environment and energy.

The aluminophosphate PST-5 according to the present invention has a different skeletal structure through further processing, for example, high-temperature calcination, and has a separator, an adsorbent for a specific molecule in the environment and energy fields, a catalyst having a unique shape selectivity Or aluminophosphate PST-6, which can be used as a catalyst support.

1 is an X-ray diffraction (XRD) result of aluminophosphates PST-5 and PST-6 prepared according to Example 1 of the present invention.
2 is a scanning electron microscope (SEM) image of aluminophosphate PST-5 and PST-6 prepared according to Example 1 of the present invention.

Hereinafter, the present invention will be described in order to provide a detailed understanding of the method for producing aluminophosphate PST-5 according to a representative embodiment, but the present invention is not intended to limit the scope of the present invention.

Example 1 Preparation of Aluminophosphate PST-5

To the plastic beaker, 3.84 g of 85 wt% o -phosphoric acid ( o- H ₃ PO ₄ ) was added to 5.63 g of water to prepare aqueous solution A, and then 6.95 g of aluminum isopropoxide was added to 5.63 g And the mixture was stirred for 5 minutes. 2.45 g of DEA was added thereto to obtain a reaction mixture shown in Chemical Formula 4. Then, the reaction mixture obtained above was transferred to a Teflon reactor, and then, a stainless steel And heated at 200 ^° C for 5 days. The obtained solid product was repeatedly washed with water and dried at room temperature.

2 DEA: 1 Al ₂ O ₃ : 1 P ₂ O ₅ : 40 H ₂ O (4)

The solid powder obtained in Example 1 was subjected to an X-ray diffraction measurement test, and the results are shown in Table 5.

2? D 100 x I / I _O 8.4 10.5 15 9.4 9.4 49 9.6 9.2 22 11.2 7.9 21 12.5 7.0 21 12.7 6.9 44 13.8 6.4 17 14.8 6.0 65 16.4 5.4 23 16.6 5.3 24 17.0 5.2 30 17.3 5.1 26 21.8 4.1 17 23.5 3.78 100 24.4 3.64 57 26.9 3.30 26 27.3 3.26 29 27.6 3.22 54 28.7 3.11 30 34.1 2.62 18

The PST-5 thus prepared was compared with the X-ray diffraction patterns of the previously reported zeolites, and it was confirmed that the PST-5 was a completely new pattern of aluminophosphate which was not previously known. [Collection of Simulated XRD Patterns for Zeolites, Elsevier, 2007], [http://www.iza-structure.org/].

Also, as a result of measurement of a scanning electron microscope (SEM in abbreviation, SEM) (FIG. 2), a plate-like highly pure single crystal was shown. This indicates that PST-5 is a pure substance that does not mix with various substances (Physical Mixture).

In order to clarify the composition of this sample, elemental analysis was carried out by inductively coupled plasma (ICP) method to confirm that the Al / P ratio was 1.0.

Comparative Example.

In the process of preparing aluminophosphate PST-5 in the same manner as in Example 1, the type of aluminum raw material and the amount of DEA in the reaction mixture were adjusted as shown in Table 4, followed by heating at 200 ^° C for 5 days The results of the solid products prepared are shown in Table 4. Here, x is a value in the reaction mixture composition represented by the following formula (5).

x DEA: 1 Al ₂ O ₃ : 1 P ₂ O ₅ : 40 H ₂ O (6)

Comparative Example Al raw material ^a X product One PB 0.5 tridymite 2 PB 1.0 AlPO ₄ -41 3 PB 2.0 AlPO ₄ -21 4 PB 4.0 AlPO ₄ -21 5 AiP 0.5 AlPO ₄ -11 6 AiP 1.0 AlPO ₄ -11 Example 1 AiP 2.0 PST-5 7 AiP 4.0 amorphous ^a PB means pseudoboehmite, and AiP means aluminum isopropoxide, respectively.

In Table 4, it was observed that the phase of the synthesized solid product changes easily depending on the kind of the aluminum raw material and the DEA mole ratio. Accordingly, in order to crystallize the aluminophosphate PST-5 of the present invention in a very narrow range, it is essential to precisely control the synthesis conditions in order to obtain pure aluminophosphate PST-5, which is the object of the present invention Able to know.

Example 2. Preparation of new aluminophosphate (PST-6) using PST-5

1.00 g of pure PST-5 sample synthesized beforehand in the crucible was placed and calcined at 550 ^° C for 8 hours. The X-ray diffraction measurement test was carried out with the solid powder obtained in Example 2, and the results are shown in Table 7.

2? D 100 x I / I _O 8.2 10.8 25 8.8 9.9 16 9.0 9.8 13 10.3 8.6 32 15.5 5.7 19 16.0 5.5 18 16.4 5.4 14 19.5 4.5 31 21.2 4.18 100 21.6 4.10 17 22.3 3.97 46 22.6 3.92 26 23.0 3.85 15 23.8 3.72 38 31.5 2.83 12

When the calcined material was compared with the X-ray diffraction patterns of previously reported zeolites, no pattern identical to the aluminophosphate obtained was found at all (FIG. 1). This proves that the resulting material has a new skeletal structure that is unknown until now (Collection of Simulated XRD Patterns for Zeolites, Elsevier, 2007).

Based on the results of X-ray diffraction, we performed Rietveld refinement. PST-6 has a space group of Pba2. Unit cell parameters are a = 39.5785 Å and b = 22.2843 Å. c = 8.32737 Å, and α = β = γ = 90 ^° . Compared to the unit cell parameter values of existing zeolites, we have found a completely different one, which also shows that PST-6 is a new skeletal structure that has not been known until now.

In order to confirm that PST-6 is a pure substance without mixing the physical mixture, SEM (FIG. 2) was measured and showed very pure single crystals of a plate-like shape, and no other crystals could be observed. In order to clarify the composition of this sample, elemental analysis was carried out by ICP to confirm that the Al / P ratio was 1.0. The nitrogen adsorption experiments of PST-6 showed that it had a BET surface area of about 152 m ² / g.

Claims (10)

The aluminophosphate PST-5, which has an oxide composition in the same molar ratio as shown in Formula 1, and has an X-ray diffraction pattern including the lattice intervals shown in Table 8 below.
0.5-1.5 Al ₂ O ₃ : 1.0 P ₂ O ₅ (1)
[Table 8]

The aluminophosphate PST-5 according to claim 1, wherein the PST-5 has an X-ray diffraction pattern comprising lattice intervals of Table 9 below.
[Table 9]

The aluminophosphate PST-5 according to any one of claims 1 to 5, which forms a plate-like crystal. 2 mol of o -phosphoric acid was slowly added to 1 to 3 mol of aluminum isopropoxide, mixed well, 1.5 to 3.5 mol of DEA was added, and the mixture was stirred at room temperature for 24 hours to prepare a reaction mixture of the following formula (2) , And the mixture is placed in a container and heated to produce the PST-5 of the first or second aspect.
1.5-3.5 DEA: 0.5-1.5 Al ₂ O ₃ : 1 P ₂ O ₅ : 20-200 H ₂ O (2) 5. The process according to claim 4, characterized in that it is placed in a container and heated at 150-250 ^° C for 2-14 days. 6. The method according to claim 4 or 5, wherein the PST-5 aluminophosphate is fired to change the lattice structure. The method according to claim 6, wherein the calcination is carried out at 200 to 1,000 ^° C for 2 to 24 hours. Wherein the aluminophosphate PST-6 has an oxide composition in a molar ratio as shown in Formula 1 below and has an X-ray diffraction pattern including lattice intervals shown in Table 10 below.
0.5-1.5 Al ₂ O ₃ : 1.0 P ₂ O ₅ (1)
[Table 10]

9. The aluminophosphate PST-6 according to claim 8, wherein the PST-6 has an X-ray diffraction pattern comprising lattice intervals of Table 11 below.
[Table 11]

The aluminophosphate PST-6 according to claim 8 or 9, wherein the aluminophosphate PST-6 forms a plate-like crystal.

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