KR101631324B1 - UZM-12 zeolite and method for its synthesizing and a catalyst for conversion of methanol using it - Google Patents

Abstract

The present invention relates to a UZM-12 zeolite, a method for synthesizing the same and a methanol conversion catalyst using the same, and more particularly, to a UZM-12 zeolite capable of controlling the size of a crystal including a novel organic structure- And a methanol conversion catalyst using the same.
The UZM-12 zeolite according to the present invention can control the crystal size of the UZM-12 zeolite prepared according to the size and shape of the organic structure inducing molecule, and the size of the crystal of the UZM-12 zeolite can be easily controlled. The catalyst can be used as a more stable catalyst, and is particularly effective for the methanol conversion reaction.

Description

UZM-12 Zeolite, its Synthesis Method and Methanol Conversion Catalyst Using the same [UZM-12 zeolite and method for its synthesis and conversion of methanol using it]

The present invention relates to a UZM-12 zeolite, its synthesis method and its use as a catalyst, and more particularly to a novel UZM-12 zeolite which has an alkyl group of a different shape and size from the organic structure- The present invention relates to a process for preparing UZM-12 zeolite using organic structure-derived molecules and using UZM-12 zeolite prepared therefrom as a catalyst for methanol conversion reaction.

Zeolite is a typical nanoporous structure that exhibits unique shape selectivity that is not observed in amorphous oxides because it contains microscopic pores with different shapes and sizes in each structure. Therefore, these materials are widely used as ion exchangers, separating agents, catalysts or catalyst supports in various chemical industries such as fine chemicals and petrochemicals [Kirk Othmer Encyclo. Chem. Technol., 1996, Vol. 16, p. 888].

Since the hydrothermal synthesis method was developed by Barrer and Milton in the late 1940s, zeolite having a novel structure was synthesized in the past decades by using organic structure induction molecules such as amine and alkylammonium ions. In addition, An artificial synthesis of natural zeolite was also made possible.

Among the known synthetic zeolites, zeolite-T [US Pat. No. 2,950,952, 1960] and LZ-220 zeolite [US Pat. No. 4,503,023, 1985] have been reported to have an erionite structure, but another zeolite, opretite Offretite) is always crystallized as an impurity.

As a result of the studies on the synthesis of UZM-12 zeolite, the present inventors have found new organic structure-inducing molecules capable of crystallizing the zeolite in addition to the organic structure-derived molecules that have been used in the past. The size of UZM-12 zeolite crystals can be controlled, and UZM-12 zeolite, which can be used as a catalyst superior in the conversion of methanol to lower olefins, was synthesized, and their synthesis range was broadened.

Accordingly, an object of the present invention is to find a novel structure-inducing molecule of a novel structure for synthesizing UZM-12 zeolite whose crystal size can be controlled, and to provide a low olefin conversion catalyst of methanol containing the same.

In order to accomplish the above object, the present invention provides a UZM-12 zeolite comprising any one of organic structure-derived molecules represented by the following structural formulas 1 to 4:

[Structural formula 1]

, N, N'-디에틸-N,N, N' , N'-테트라메틸알칸디일디암모늄 (N, N'-Diethyl-N,N, N' , N'-tetramethylalkanediyldiammonium)

, N, N '- diethyl - N, N, N', N '- tetramethyl-alkanediyl ildi ammonium (N, N' -Diethyl- N, N, N ', N' -tetramethylalkanediyldiammonium)

(Wherein the notation is Me ₄ Et ₂ -diquat-n and n is 4 to 7).

[Structural formula 2]

, N,N, N' , N'-테트라에틸-N, N'-디메틸알칸디일디암모늄 (N,N, N' , N'-Tetraethyl-N, N'-dimethylalkanediyldiammonium)

, N, N, N ', N' - tetraethyl - N, N '- dimethyl alkanediyl ildi ammonium (N, N, N', N '-Tetraethyl- N, N' -dimethylalkanediyldiammonium)

(In the above formula, the notation is Et ₄ Me ₂ -diquat-n, and n is 4 to 7.)

[Structural Formula 3]

, N, N'-(알칸디일)비스(1-메틸피롤리디늄) (N, N'-(Alkanediyl)bis(1-methylpyrrolidinium))

, N, N '- (alkanediyl) bis (1-methylpyrrolidin-pyridinium) (N, N' - ( Alkanediyl) bis (1-methylpyrrolidinium))

(Where MPr ₂ -diquat-n is the notation and n is 4 to 7).

[Structural Formula 4]

, N, N'-(알칸디일)비스(1-메틸피페리디늄) (N, N'-(Alkanediyl)bis(1-methylpiperidinium))

, N, N '- (alkanediyl) bis (1-methyl piperidinium) (N, N' - ( Alkanediyl) bis (1-methylpiperidinium))

(Wherein MPP ₂ -diquat-n is a notation and n is 4 to 7).

According to the present invention, the size of the resultant UZM-12 zeolite crystal varies in accordance with the size and shape of the organic structure-derived molecule used in the UZM-12 zeolite, and the change in the crystal size generally affects the catalytic reaction It is possible to find a more suitable crystal size when the catalyst is used as a catalyst for converting methanol into lower olefin.

Fig. 1 is a graph showing catalyst life as a result of the experiment of Experimental Example 1. Fig.
Fig. 2 is a graph showing conversion ratios as a result of the experiment of Experimental Example 1. Fig.

Hereinafter, the technical idea of the present invention will be described in more detail.

The present invention provides a UZM-12 zeolite containing a new type of organic structure-derived molecule different from the conventional ones, a method for synthesizing the same, and its use as a catalyst for producing a lower olefin.

The organic structure-derived molecule is included as a material forming the structure of UZM-12 zeolite during the synthesis of UZM-12 zeolite. The organic structure-derived molecules have the ability to induce unique zeolite structures under specific synthesis conditions and have the ability to change the physico-chemical properties of existing zeolites, even if they are not new structures. In particular, this study can change the physico-chemical properties of the crystal size of UZM-12 zeolite by using various organic structure-derived molecules.

In addition, the organic structure-derived molecules contained in the UZM-12 zeolite were fired during the synthesis of the H-UZM-12 zeolite catalyst and disappeared. Methanol was introduced into the site where the organic structure- appear. That is, the organic structure-derived molecules inducing the formation of the structure are present in the interior of the UZM-12 zeolite after the synthesis of the UZM-12 zeolite, but they disappear during the calcination of the catalyst after the synthesis of the H- Methanol enters the place where the molecule was present.

Thus, by controlling the crystal size of UZM-12 zeolite, the activity of H-UZM-12 zeolite catalyst is determined by securing the time required for methanol accessibility and conversion reaction. In other words, if the crystal size of the organic structure-derived molecule is small, the accessibility of methanol is improved but the reaction may be deteriorated due to the flow-out before the reaction occurs. On the other hand, However, if the crystal size of the organic structure-derived molecules is varied as in the case of the present invention, the reaction can be performed with a sufficient reaction time at the reaction point located outside the crystal, As shown in FIG.

In the above Structural Formulas 1 to 4, when n is 3 or less, the stability of the molecule itself is poor and decomposition occurs during synthesis, so that synthesis does not proceed. When n is 8 or more, the molecular size becomes too large to enter the structure of UZM-12 zeolite It was confirmed that the synthesis did not occur.

On the other hand, a preferred embodiment of the organic structure derived molecule that acts as described above, N, N of the formula 1 '- diethyl - N, N, N', N '- tetramethyl-alkanediyl ildi ammonium N, N '- diethyl - N, N, N', N '- tetramethyl-butane-di ildi ammonium or N, N' - diethyl - N, N, N ', N' - tetramethyl pentane di ildi ammonium or N, N '- diethyl - N, N, N', N '- tetramethyl-hexane-di ildi ammonium one can, in the structural formula 2 N, N, N', N '- tetraethyl - N, N' - dimethyl al alkanediyl ildi ammonium N, N, N ', N ' - tetraethyl - N, N '- dimethyl-butane-di ildi ammonium or N, N, N', N '- tetraethyl - N, N' - dimethyl-pentane-di ildi Ammonium or N, N, N ' , N' -tetraethyl- N, N' -dimethylhexanediyldiammonium.

In addition, another specific embodiment of the organic structure derived molecule, of the formula 3 N, N '- (alkanediyl) bis (1-methylpyrrolidin-pyridinium) is N, N' - (butane-diyl) bis (1 -methylpyrrolidone pyridinium) or N, N '- (pentane-diyl) bis (1-methylpyrrolidin-pyridinium) or N, N' - (hexane-diyl) may be bis (1-methylpyrrolidin-pyridinium), the structural formula of 4 N, N '- (alkanediyl) bis (1-methyl piperidinium) is N, N' - (butane-diyl) bis (1-methyl piperidinium) or N, N '- (pentane-diyl) Bis (1-methylpiperidinium) or N, N ' - (hexanediyl) bis (1-methylpiperidinium).

The organic structure-deriving molecules are generally selected from the group consisting of dimethylethylamine or diethylmethylamine or 1-methylpyrrolidine, using ethanol and / or acetone and / or ether solution as a solvent, (1, n-Dibromoalkane; n = 1 or more natural number) in the presence of a base, such as 1-methylpiperidine, or 1-methylpiperidine.

The UZM-12 zeolite containing the organic structure-derived molecules as shown in the structural formulas 1 to 4 is synthesized as follows.

First, 10 to 15 mol of tetraethylammonium hydroxide (TEAOH) was added to a plastic beaker in an amount of 1 mole of aluminum tri-sec-butoxide, and the mixture was thoroughly stirred. Then, (Ludox AS-40) at a molar ratio of 300 to 500 in water at a molar ratio of 300 to 500 and thoroughly stirred to obtain 0.5 to 3.0 moles of the organic structure-derived molecule in an amount of 0.5 to 3.0 moles of an alkaline substance of potassium chloride or rubidium chloride And the mixture is further stirred at room temperature for about 24 hours.

In addition, the organic structure-derived molecule may be included in UZM-12 zeolite in the form of its precursor. Generally, in the synthesis of UZM-12 zeolite, an organic structure-derived molecule is firstly prepared and used for synthesis. In the form of a precursor, which is a state before preparation of the organic structure-derived molecule, an organic substance The UZM-12 zeolite is synthesized. This is an excellent method compared to the conventional method in which crystallization does not occur or other materials may be produced unless synthesized in the form of an organic structure-derived molecule in the synthesis of UZM-12 zeolite.

That is, the organic structure-deriving molecule may be selected from the group consisting of dimethylethylamine, diethylmethylamine, 1- (2-ethylhexyl) methylamine, (1-methylpyrrolidine), and 1-methylpiperidine in a mixed molar ratio of 1-5. Preferably, the mixing molar ratio may be synthesized by using the selected compound in a mixed molar ratio of 2 to 3 based on the dibromoalkane (1, n-dibromoalkane; n = 1 or more natural water). The composition of the reaction mixture thus synthesized is shown in the following chemical formula (1).

 [Chemical Formula 1]

12 - 20 SiO ₂ : 1 Al (OH) ₃ : 10-15 TEAOH: 0.5-3.0 KCl: 0.5-3.0 R: 300-500 H ₂ O

In the above formula (1), R is an organic structure-derived molecule, and the reaction mixture obtained is transferred to a Teflon reactor. The reaction mixture is placed in a container made of stainless steel again and reacted at a reaction temperature of 100 to 150 ° C. for 7 to 35 days When the reaction mixture is reacted, UZM-12 zeolite is synthesized.

The thus synthesized UZM-12 zeolite is represented by the following chemical formula 2 and has the X-ray diffraction diagram given in Table 1 below. In the following Table 1,?, D and I indicate the Bragg angle, the lattice spacing, and the intensity of the X-ray diffraction peak, respectively.

 (2)

100 XO ₂ : a Y ₂ O ₃ : b M ₂ O

Wherein M is at least one alkali metal cation (group 1A in the periodic table), ammonium, hydrogen, X is silicon or germanium, Y is aluminum or It is gallium.)

2? d 100 x I / I ₀ 7.7-7.8 11.4 to 11.3 100 9.6 ~ 9.7 9.15 ~ 9.10 5 to 10 11.7 to 11.8 7.60 ~ 7.55 15-20 13.4 to 13.5 6.60 ~ 6.65 30 to 35 14.0 to 14.1 6.30 ~ 6.25 5 to 10 15.5 to 15.6 5.70-5.65 35 to 40 16.6 to 16.7 5.35 ~ 5.30 5 to 10 17.8 to 17.9 5.00 ~ 4.95 10 to 15 19.5 to 19.6 5.50 to 5.45 55 ~ 60 20.6 to 20.7 4.35 ~ 4.30 65 to 70 21.4 to 21.5 4.15-4.10 10 to 15 23.4 to 23.5 3.80 ~ 3.75 65 to 70 23.7-23.8 3.75-3.70 90 ~ 95 24.8 to 24.9 3.60 ~ 3.55 90 ~ 95 27.1-27.2 3.30 ~ 3.25 25 to 30 28.3 to 28.4 3.15-3.20 30 to 35 30.6 to 30.7 2.95 to 2.90 5 to 10 31.4 to 31.5 2.85 ~ 2.80 80 ~ 85 31.9 to 32.0 2.85 ~ 2.80 5 to 10 33.6 to 33.7 2.70 ~ 2.65 10 to 15 35.5 to 35.6 2.55 to 2.50 0-5 36.1 to 36.2 2.50 to 2.45 10 to 15 36.3 to 36.4 2.50 to 2.45 10 to 15 39.5 to 39.6 2.30 ~ 2.25 0-5 41.1 to 41.2 2.20-2.15 0-5 43.0 to 43.1 2.15 to 2.10 5 to 10 43.6 to 43.7 2.10 to 2.05 0-5 45.9 to 46.0 2.00 ~ 1.95 0-5 46.5 to 46.6 2.00 ~ 1.95 0-5 48.1 to 48.2 1.90 to 1.85 10 to 15 48.8 ~ 48.9 1.90 to 1.85 0-5

Further, in the above formula (2), crystallization does not easily occur if the range of 15? A? 25 and 4? B? 8 is outside the range. In some cases, other zeolites other than UZM-12 may be synthesized. It is more preferable that UZM-12 zeolite is such that X is silicon and Y is aluminum.

The UZM-12 zeolite is preferably used for the crystallization of UZM-12 zeolite in addition to the organic structure-derived molecules and further containing an alkali substance such as potassium chloride or rubidium chloride. In other words, it is possible to synthesize UZM-12 zeolite with rubidium chloride in place of the previously used potassium chloride. Potassium or rubidium is exchanged with ammonium ions during the reaction of the catalyst, and ammonium is released into ammonia during the temperature calcination and remains in the form of H ⁺ , which eventually acts as a catalyst, It is because of the ability of induction. However, UZM-12 zeolite can not be synthesized when lithium or sodium, which is another cation, is used.

Meanwhile, in a preferred embodiment of the present invention, the H-UZM-12 zeolite catalyst using UZM-12 zeolite is prepared by the following method.

First, a reaction mixture composed of K ₂ O or Rb ₂ O, Al ₂ O ₃ , SiO ₂ , and H ₂ O is prepared by using the organic structure-derived molecules represented by Structural Formulas 1 to 4 or a precursor thereof, To produce a UZM-12 zeolite. The resulting UZM-12 zeolite is calcined, ammonium ion exchanged, and re-calcined to prepare an H-UZM-12 zeolite catalyst.

The H-UZM-12 zeolite catalyst prepared by the above method is used for the reaction of converting methanol into a lower olefin. The H-SAPO-34 catalyst, which is one of the conventionally used methanol conversion catalysts, has a strong acid point and shows a high conversion rate at the beginning of the reaction. However, H-UZM-12 catalyst Lt; RTI ID = 0.0 > ethylene < / RTI > selectivity.

On the other hand, the H-SPAO-34 and H-UZM-12 catalysts are zeolites with nodular acid sites, which react in the form of a hydrocarbon pool mechanism. That is, the reaction proceeds in the form of methanol -> dimethyl ether -> lower olefins (ethylene, propylene). If the size of the crystal is too large, methanol can diffuse only to the acid sites outside the catalyst crystals. Efforts have been made to reduce the size of crystals in order to use the acid sites in the. However, if the size of the crystal is too small, it is escaped to the intermediate form of dimethyl ether before reaching the lower olefin. In the case of H-UZM-12 zeolite, generally, a crystal size of about 900 to 1100 nm .

Hereinafter, the present invention will be described in detail with reference to examples and comparative examples. It is to be understood that the scope of the present invention is not limited by the description of the present invention.

Example  One

Synthesis of UZM-12 zeolite using MPr ₂ -diquat-4 bromide

First, 36.46 g of 35 wt% tetraethylammonium hydroxide (TEAOH) and 1.69 g of aluminum tri-sec-butoxide were added to the plastic beaker and stirred for 2 hours. 16.0 g of colloidal silica Silica sol (Ludox AS-40) and 14.89 g of water are added to the above solution and stirred for another 1 hour. Finally, 5.25 g of MPr ₂ -diquat-4 bromide and 0.75 g of potassium chloride (KCl) were added to obtain the composition of the reaction mixture shown in Formula 3 below. The reaction mixture obtained above was transferred into a Teflon reactor, , Heated at 100 ° C for 14 days, heated, and the resulting solid product is repeatedly washed and dried at room temperature. This product was observed with a scanning electron microscope to confirm that it consisted of 800 x 350 nm crystals of rice-grains.

The solid powder obtained through the above synthesis was subjected to an X-ray diffraction measurement test, and the results are shown in Table 2. All of the powder X-ray diffraction data of the present invention including the powder X-ray diffraction pattern were measured using a standard X-ray diffraction method. As the radiation source, a copper Kα line and an X-ray tube operating at 40 kV, 30 mA 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.

(3)

16 SiO ₂ : 1 Al (OH) ₃ : 13 TEAOH: 1.5 KCl: 2 MPr _2- diquat-4: 400 H ₂ O

2? D 100 x I / I ₀ 7.9 11.2 92.7 9.9 8.9 14.6 11.9 7.4 11.5 13.6 6.5 21.2 14.2 6.2 3.8 15.7 5.6 38.3 16.7 5.3 18.8 18.1 4.9 12.2 19.7 4.5 64.4 20.8 4.3 69.2 21.6 4.1 30.3 23.6 3.8 58.6 24.0 3.7 76.0 25.1 3.6 100.0 27.3 3.3 28.8 27.5 3.2 25.2 28.6 3.1 31.2 30.9 2.9 11.1 31.7 2.8 68.8 32.1 2.8 17.9 33.8 2.7 17.0 36.3 2.5 10.4 36.5 2.5 12.1 39.8 2.3 2.9 41.3 2.2 4.1 43.0 2.1 5.3 43.9 2.1 3.3 46.1 2.0 2.9 48.5 1.9 13.0 49.2 1.9 3.9

When a part of the sample obtained in this example was calcined at 550 ° C for 8 hours and then the X-ray diffraction pattern was measured again, the calcined sample exhibited essentially the same X-ray pattern as in Example 1 . In order to identify the composition of this sample, elemental analysis was carried out, and the obtained result was UZM-12 zeolite having the following chemical formula (4).

[Chemical Formula 4]

0.45 K ₂ O: 1.0 Al ₂ O ₃ : 12 SiO ₂

Example  2 to 6

Synthesis of UZM-12 Zeolite Using Structural Formulas 1 to 4

Elemental analysis of UZM-12 zeolite synthesized by heating at 100 ° C. for 14 days using organic structure-derived molecules of Structural Formulas 1 to 4 as follows in the course of preparing UZM-12 zeolite by the same method as in Example 1 The SiO ₂ / Al ₂ O ₃ molar ratio and the size of the crystal irradiated by scanning electron microscope are shown in Table 3 below.

Example Organic structure-inducing molecule Crystal size (nm) SiO ₂ / Al ₂ O ₃ mole ratio 2 Me ₄ Et ₂ -diquat-4 Rice-grains, 400 x 150 13.1 3 Me ₄ Et ₂ -diquat-5 Rice-grains, 1100 x 600 13.0 4 Et ₄ Me ₂ -diquat-4 Needles, 2500 x 650 10.9 5 MPr _2- diquat-5 Rice-grains, 1200 x 650 11.1 6 MPp ₂ -diquat-4 Needles, 2000 x 500 11.1

From the above table, it can be seen that the crystal size of UZM-12 zeolite synthesized in the present invention varies depending on the length of the central methylene chain in the ammonium ion used and the type of the alkyl group connected to the nitrogen atom. This is because the conventional method for controlling the crystal size has a slight change in the crystal size due to the change in the content of the cations, but the effect of not showing a definite change and showing a constant size distribution (Stud. Surf. Sci. ) Is a clear and significant change.

Example  7

Synthesis of UZM-12 zeolite using Me ₆ -diquat-6 bromide and rubidium chloride

The reaction mixture was prepared in the same manner as in Example 1 except that 4.9 g of Me ₆ -diquat-6 bromide and 0.75 g of rubidium chloride (RbCl) were added instead of MPr ₂ -diquat-4 bromide and potassium chloride (KCl) And the composition of the reaction mixture was shown in the following formula (5). The X-ray diffraction measurement experiment was carried out with the solid powder obtained in Comparative Example 1, and the results are shown in Table 4.

[Chemical Formula 5]

16 SiO ₂ : 1 Al (OH) ₃ : 13 TEAOH: 1.5 RbCl: 2 Me ₆ -diquat-6: 400 H ₂ O

2? d 100 x I / I ₀ 3.1 28.9 32.0 7.8 11.3 100.0 9.7 9.1 3.2 11.6 7.6 13.1 13.5 6.5 9.6 15.6 5.7 14.8 16.6 5.3 5.3 19.5 4.6 64.4 20.7 4.3 28.3 21.5 4.1 11.1 23.5 3.8 66.9 23.8 3.7 85.3 24.6 3.6 44.1 27.1 3.3 21.5 28.2 3.2 35.1 31.4 2.8 60.1 31.5 2.8 41.2 33.7 2.7 6.3 35.3 2.5 2.7 36.2 2.5 13.1 41.3 2.2 4.2 43.0 2.1 3.6 43.8 2.1 3.4 46.0 2.0 4.9 47.7 1.9 6.5

Example  8

Synthesis of UZM-12 zeolite using precursor of MPr ₂ -diquat-4 bromide

In Example 1, 2 molar ratio of 1,4-dibromobutane and 4 to 6 molar ratio of 1-methylpyrrolidine were added instead of 2 molar ratio of MPr ₂ -diquat-4 bromide to obtain a reaction mixture , The reaction mixture obtained above is transferred into a Teflon reactor and then placed in a container made of stainless steel again, heated at 100 ° C. for 14 days, and then the solid product obtained by heating is repeatedly washed and dried at room temperature. As a result of X-ray diffraction measurement test with the solid powder obtained through the above synthesis, it was observed that the X-ray pattern essentially shows the same as that in Example 1. [ It is confirmed that UZM-12 zeolite can be synthesized even in the form of precursor before the formation of the organic structure-derived molecule, when the kind or form of the organic structure-inducing molecule is changed.

[Chemical Formula 6]

16 SiO ₂ : 1 Al (OH) ₃ : 13 TEAOH: 1.5 KCl: 2 1,4-dibromobutane: 4 -6 1-methylpyrrolidine: 400 H ₂ O

Example  9

Preparation of H-UZM-12 catalyst

A portion of the UZM-12 zeolite sample prepared in Example 1 was added to 1.0 molar ammonium nitrate aqueous solution at a weight ratio of 1: 100, and the mixture was ion-exchanged twice at 80 DEG C, followed by filtration, washing and drying at room temperature. Then, the resultant was calcined at a temperature of 550 ° C for 2 hours in air to perform nitrogen adsorption test, and H-UZM-12 zeolite was prepared. It was observed to have a BET surface area of about 640 m ² / g. The X-ray diffraction measurement test was carried out with the solid blend thus obtained, and the results are shown in Table 5.

2? d 100 x I / I ₀ 7.9 11.2 84.1 9.8 9.0 30.7 11.8 7.5 31.5 13.6 6.5 96.5 14.2 6.2 51.5 15.7 5.6 14.2 16.8 5.3 12.6 19.4 4.6 30.9 20.9 4.3 38.1 21.7 4.1 30.7 23.7 3.8 58.5 24.0 3.7 62.0 25.0 3.6 100.0 27.4 3.2 43.1 28.6 3.1 37.2 31.8 2.8 58.8 33.9 2.6 12.4 36.6 2.5 8.7 43.3 2.1 2.4 48.5 1.9 7.2

Comparative Example  1-3

Synthesis of UZM-12 zeolite using various organic structure-derived molecules

In the process of synthesizing UZM-12 zeolite in the same manner as in Example 1, the following organic structure-derived molecules were used and SiO ₂ / Al ₂ O ₃ molar ratio and the size of the crystal irradiated with a scanning electron microscope are shown in Table 6 below.

Comparative Example Organic structure-inducing molecule Crystal size (nm) SiO ₂ / Al ₂ O ₃ mole ratio One Me _6- diquat-4 Needles, 100 x 30 12.6 2 Me _6- diquat-5 Rice-grains, 400 x 100 11.6 3 Me _6- diquat-6 Rice-grains, 1000 x 600 9.5

Comparative Example  4 to 6

Preparation of UZM-12 zeolite using various cations

The following organic structure-inducing molecules were used in the process of preparing UZM-12 zeolite in the same manner as in Example 7, lithium chloride, sodium chloride or cesium chloride was added instead of 1.5 molar rubidium chloride, The final produced materials by heating are shown in Table 7 below.

Comparative Example Organic structure-inducing molecule Alkali metal product 4 Me _6- diquat-6 Lithium chloride (LiCl) Dense phase (dense phase) 5 Me _6- diquat-6 Sodium chloride (NaCl) Amorphous / amorphous material 6 Me _6- diquat-6 Cesium chloride (CsCl) Analcime

When the above results were compared with those of Example 7 and Comparative Example 3, even when the same synthesis conditions and organic structure-derived molecules were used, when other cations were used instead of potassium chloride, which was used previously, UZM-12 zeolite was synthesized It was not. That is, it was confirmed that UZM-12 zeolite was synthesized only when potassium chloride and rubidium chloride were used.

Experimental Example  One

Olefin Conversion of Methanol under H-UZM-12 Catalyst

The UZM-12 zeolite prepared in Example 3 was converted into H-UZM-12 by the method described in Example 9 above. 0.1 g of H-UZM-12 zeolite was used to perform methanol conversion at 350 ° C, WHSV of 0.67 h ^{- 1} , and nitrogen-to-methanol molar ratio of 38.3 at atmospheric pressure, and the reaction characteristics were examined for 24 hours. In addition, H-SAPO-34 (2.0-6.0 mu m, Si / (Si + Al + P) = 0.08) which is currently used as a main catalyst for the conversion of lower olefins into methanol is compared with Comparative Examples 1, The prepared UZM-12 zeolite was subjected to a methanol conversion reaction under the same conditions as in Example 3, until the conversion was 10% or less. Experimental results show that the H-UZM-12 zeolite of the present invention has a longer catalyst life with higher ethylene selectivity (FIG. 2) than H-SAPO-34 and previously reported H-UZM-12 zeolite catalysts of similar crystal size (Fig. 1), especially at a size of about 1000 nm.

Claims (12)

UZM-12 zeolite comprising any one of the organic structure-derived molecules of Structural Formula 1, Structural Formula 2, and Structural Formula 4.
[Structural formula 1]

, N, N '- diethyl - N, N, N', N '- tetramethyl-alkanediyl ildi ammonium (N, N' -Diethyl- N, N, N ', N' -tetramethylalkanediyldiammonium)
(Wherein the notation is Me ₄ Et ₂ -diquat-n and n is 4 to 7).
[Structural formula 2]

, N, N, N ', N' - tetraethyl - N, N '- dimethyl alkanediyl ildi ammonium (N, N, N', N '-Tetraethyl- N, N' -dimethylalkanediyldiammonium)
(In the above formula, the notation is Et ₄ Me ₂ -diquat-n, and n is 4 to 7.)
[Structural Formula 4]

, N, N '- (alkanediyl) bis (1-methyl piperidinium) (N, N' - ( Alkanediyl) bis (1-methylpiperidinium))
(Wherein MPP ₂ -diquat-n is a notation and n is 4 to 7). The UZM-12 zeolite according to claim 1, wherein the UZM-12 zeolite is represented by the following formula (2).
(2)
100 XO ₂ : a Y ₂ O ₃ : b M ₂ O
Wherein M is at least one alkali metal cation (group 1A in the periodic table), ammonium, hydrogen, X is silicon or germanium, Y is aluminum or It is gallium.) The method according to claim 1, of the formula 1, N, N '- diethyl - N, N, N', N '- tetramethyl-alkanediyl ildi ammonium N, N' - diethyl - N, N, N ', N '- tetramethyl-butane-di ildi ammonium or N, N' - diethyl - N, N, N ', N' - tetramethyl pentane di ildi ammonium or N, N '- diethyl - N, N, N', N & Apos; -tetramethylhexanedioldiammonium < / RTI > zeolite. The method according to claim 1, of the formula 2 N, N, N ', N' - tetraethyl - N, N '- dimethyl alkanediyl ildi ammonium N, N, N', N '- tetraethyl - N, N' - dimethyl-butane-di ildi ammonium or N, N, N ', N ' - tetraethyl - N, N '- dimethyl-pentane-di ildi ammonium or N, N, N', N '- tetraethyl - N, N' - dimethyl UZM-12 zeolite, which is hexandiyldiammonium. delete The method according to claim 1, of the formula 4 N, N '- (alkanediyl) bis (1-methyl piperidinium) is N, N' - (butane-diyl) bis (1-methyl piperidinium) or N, UZM-12 zeolite with N ' - (pentanediyl) bis (1-methylpiperidinium) or N, N' - (hexanediyl) bis (1-methylpiperidinium). The UZM-12 zeolite according to claim 1, wherein the UZM-12 zeolite further comprises an alkaline substance which is potassium chloride or rubidium chloride. An H-UZM-12 zeolite catalyst comprising UZM-12 zeolite according to any of claims 1 to 4, 6 and 7. As a synthesis method of UZM-12 zeolite,
(a) 10 to 15 molar equivalents of tetraethylammonium hydroxide per mole of aluminum trihexobutoxide is added and stirred, and then added to the above solution at a rate of 300 to 500 mol of water to 12 to 20 mol of silica sol Stirring;
(b) adding 0.5 to 3 moles of organic structure-derived molecules to the solution to form a reaction mixture; And
(c) reacting the reaction mixture at a temperature of 100 to 150 DEG C for a period of 7 to 35 days,
The organic structure-derived molecule of the step (b) is any one of the organic structure-derived molecules of the following structural formulas 1, 2 and 4, a method of synthesizing UZM-12 zeolite,
[Structural formula 1]

, N, N '- diethyl - N, N, N', N '- tetramethyl-alkanediyl ildi ammonium (N, N' -Diethyl- N, N, N ', N' -tetramethylalkanediyldiammonium)
(Wherein the notation is Me ₄ Et ₂ -diquat-n and n is 4 to 7).
[Structural formula 2]

, N, N, N ', N' - tetraethyl - N, N '- dimethyl alkanediyl ildi ammonium (N, N, N', N '-Tetraethyl- N, N' -dimethylalkanediyldiammonium)
(In the above formula, the notation is Et ₄ Me ₂ -diquat-n, and n is 4 to 7.)
[Structural Formula 4]

, N, N '- (alkanediyl) bis (1-methyl piperidinium) (N, N' - ( Alkanediyl) bis (1-methylpiperidinium))
(Wherein MPP ₂ -diquat-n is a notation and n is 4 to 7). [12] The method according to claim 9, wherein the step (b) further comprises adding 0.5 to 3 moles of an alkali material such as potassium chloride or rubidium chloride to the UZM-12 zeolite. [12] The organic structure-derived molecule according to claim 9, wherein the organic structure-derived molecule is selected from the group consisting of dimethylethylamine, diethylmethylamine, 1-methylpiperazine, n-butyllithium, 12. A method for synthesizing UZM-12 zeolite comprising a compound selected from the group consisting of 1-methylpyrrolidine and 1-methylpiperidine in a mixing ratio of 1: 1 to 5: 1. The method according to claim 11, wherein the mixing molar ratio is 1: 2 to 3.

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