KR101189757B1 - Preparation method of randomly assembled mesostructure constructed with hierarchically mesoporous and microporous MFI zeolite nanosheets of single-unit-cell thickness, using water glass as the silica source - Google Patents

Abstract

According to the present invention, a single unit crystal lattice-thick crystalline skeleton, synthesized by adding an organic surfactant to a synthetic composition of zeolite using water glass as a raw material of silica, is mesoporous. The present invention relates to an MFI zeolite molecular sieve material in which micropores coexist with a method for preparing the same. Furthermore, the present invention encompasses micro-mesoporous molecular sieve materials activated and functionalized by dealuminization, ion exchange, and other post-treatment and methods for their preparation, including the utilization of catalysts of the prepared molecular sieve materials. do. MFI zeolite molecular sieve material according to the present invention has dramatically increased the outer surface area due to the ultra fine thickness of the skeleton structure, thereby increasing the molecular diffusion to significantly increase the activity in the function of the catalyst and ion exchange resins seen in conventional zeolites It was.

Description

Manufacture method of MFP zeolite molecular sieve material in which mesopores and micropores coexist hierarchically by irregularly aligning a crystalline skeleton having a single unit crystal lattice thickness using water glass as a raw material for silica (Preparation method of randomly assembled mesostructure constructed with hierarchically mesoporous and microporous MFI zeolite nanosheets of single-unit-cell thickness, using water glass as the silica source}

The present invention provides an economic and economical method for the production of MFI zeolite molecular sieve materials based on the 3-letter code of the International Zeolite Association where mesopores and micropores coexist with irregularly aligned crystalline skeletons of single unit cell lattice thickness. And a manufacturing method which can be synthesized in a short time. More specifically, an economical silica raw material such as water glass is used, and a manufacturing method of MFI zeolite molecular sieve which can drastically shorten the production time in the presence of Na ⁺ ions, and the manufacturing method MFI zeolite molecular sieves produced using the present invention and catalyst applications of these MFI zeolite molecular sieves.

Zeolites are defined as crystalline aluminosilicate materials in which uniform micropores (0.3 <diameter <2 nm) in the molecular size region are regularly arranged. Since the micropores of zeolites have a diameter of a molecular size region, they have a molecular sieve function to selectively adsorb and diffuse molecules. These molecular sieve effect is enabled the molecule selective adsorption, ion exchange and catalytic processes (CS Cundy, et al, Chem. Rev. 2003, 103 , 663).

However, slow molecular diffusion into very small diameter zeolite micropores has caused reaction rate constraints in many applications. In order to solve this problem, attempts have been made in the past to improve the molecular diffusion into zeolite micropores by synthesizing zeolite having a larger outer surface area by thinning the skeleton.

As a strategy for enhancing the specific surface area, studies have been conducted to synthesize the zeolite into microcrystals having a nanometer thickness. Synthesis methods of zeolites having a colloidal state of nanometer size (10 nm or more) by controlling the synthesis composition and lowering the crystallization temperature have been published (L. Tosheva et al. , Chem. Mater . 2005, 17 , 2494). . However, these synthesis methods had a low crystallinity and synthesis yield of zeolites, and had a limitation of separation after centrifugation rather than filtration after synthesis.

As another strategy, attempts have been made to enhance the specific surface area of zeolites by generating mesopores (2 <diameter <50 nm) and macropores (50 nm <diameter) with larger diameters inside the zeolite crystals. Anderson and his colleagues synthesized zeolites with macropores by crystallizing diatomaceous earth treated with zeolite seed crystals (Anderson, MW et al . , Angew . Chem . Int . Ed . 2000, 39 , 2707). .

Recently, a method of preparing mesopores in zeolite crystals by synthesizing zeolite in the presence of various solid molds such as carbon nanoparticles, nanofibers, and spherical polymers has been published. Stein and his colleagues published a technique for synthesizing mesoporous molecular sieves using spherical polystyrene with a uniform size of about 100 microns (US Patent No. 6680013, B1), and Jacobson Mesoporous zeolite having a broad pore distribution of 10-100 nm was synthesized as a template (US Pat. No. 6,620,402, B2). Materials prepared using solids as a template have been reported to exhibit enhanced catalytic activity due to easy molecular diffusion through mesopores (Christensen, CH et al . , J. Am . Chem . Soc . 2003, 125 , 13370).

Recently, a strategy for generating mesopores in zeolite crystals by adding an organosilane to the synthetic composition of the zeolite has been published (domestic patent, 10-0727288). In addition, Corma and his colleagues have published a synthesis method of delamination of layered FER and MWW structures into single zeolite films (A. Corma et al., Nature 1998, 396 , 353) (A. Corma et al., Spanish Patent No. 9502188 (1996) PCT-WO Patent 97/17290 (1997).

In addition, an MFI aluminosilicate in the form of a plate-like structure having a single unit lattice thickness (2 nm) has been reported using an organic surfactant capable of inducing a zeolite skeleton and simultaneously forming mesopores (M. Choi et al. , Nature , 2009, 461 , 246). Such a material has a very high external specific surface area and a large pore volume compared to the conventional zeolite due to the plate-like structure composed of a very small thickness of a single unit lattice size. Moreover, the use of this material as a solid acid catalyst resulted in significantly higher catalytic activity and longer catalyst life in the process of methanol to gasoline compared to conventional commercial zeolites.

MFI zeolite molecular sieve materials, which are hierarchically co-located with mesopores and micropores due to irregularly aligned crystalline skeletons of single unit cell thickness, have many advantages as catalysts due to their large specific surface area and large pore volume. Despite this, it is known to use silica raw materials with very high production costs because they can take a long time (more than 11 days at 150 ^° C.) or can be synthesized only in special cases without Na ⁺ ions. Therefore, in order to industrially use such zeolites, there is a demand for a new production method that can reduce the cost of synthesis and shorten the synthesis time.

The present invention uses an inexpensive silica raw material such as water glass and adjusts the synthesis environment, thereby significantly reducing the existing manufacturing cost and dramatically shortening the synthesis completion time, thereby industrially very economical and cost-effective MFI zeolite It is an object to provide a method for producing a molecular sieve.

It is also an object of the present invention to provide an MFI zeolite molecular sieve prepared using the above production method and a catalyst application method of the MFI zeolite molecular sieve.

The present invention is to solve the above-mentioned problems of the prior art, A) an organic surfactant comprising two or more ammonium functional groups, or an organic surfactant comprising one ammonium functional group and one amine functional group and water glass and Polymerizing together to form an organic-inorganic composite gel; B) converting the inorganic gel region of the organic-inorganic composite gel into zeolite through a crystallization process; And C) isolating the zeolite from the mixture obtained in step B).

As the organic surfactant, an organic surfactant represented by Formula 1 or an organic surfactant represented by Formula 2 may be used.

Formula (1)

Formula (2)

Wherein X is a halogen (Cl, Br, I) anion or a hydroxide (OH) anion, C1, C2 are each independently a substituted or unsubstituted alkyl group, and C3 is a substituted or unsubstituted alkyl group An alkenyl group or an alkyl group in which some carbon atoms are replaced with another atom or an alkenyl group.)

In the above formulas (1) and (2), the carbon chain length of C1 is 8 to 22 carbon atoms, the carbon chain length of C2 is 3 to 6 carbon atoms, and the carbon chain length of C3 is preferably 1 to 8 carbon atoms.

The inorganic shear body may further include an alumina raw material.

The alumina raw material may be, for example, sodium aluminate (NaAlO ₂ , sodium aluminate), aluminum sulfate (Al ₂ (SO ₄ ) _3, aluminum sulfate), aluminum hydroxide (Al (OH) _3, aluminum hydroxide) or aluminum chloride (AlCl _3, aluminum chloride) may be used.

In step A), an acid may be further added during the preparation of the organic-inorganic composite gel.

At this time, the acid is preferably added so that the pH of the organic-inorganic composite gel is 9 to 12. At pH in this range, silica and aluminum or other inorganic shears efficiently bind and form anions, which then effectively assemble by electrostatic interaction with the cationic organic surfactant.

The step B) may be performed using, for example, hydrothermal synthesis, microwave heating, or dry-gel synthesis.

Step C) may be performed using, for example, filtration or centrifugation.

The manufacturing method of the MFI zeolite molecular sieve may further comprise the step of selectively removing the organic material from the zeolite through firing or chemical treatment.

In addition, the zeolite may further comprise the step of activating or reforming by using a post-treatment reaction, such as dealuminization, base aqueous solution treatment, ion exchange, metal loading or organic functionalization.

The present invention also provides an MFI zeolite molecular sieve prepared using the method for preparing the MFI zeolite molecular sieve.

The present invention also provides a method for modifying a hydrocarbon or a hydrocarbon derivative using the MFI zeolite molecular sieve as a catalyst.

Here, the hydrocarbons and hydrocarbon derivatives may be in a gas, liquid, solid, or mixed phase thereof.

The present invention also provides a method for reforming methanol using the MFI zeolite molecular sieve as a catalyst.

The present invention also provides a method of liquid condensing benzaldehyde and 2-hydroxyaceto-phenone using MFI zeolite molecular sieve as a catalyst.

The present invention also provides a method for synthesizing a hydrocarbon or a hydrocarbon derivative by decomposing waste plastic using MFI zeolite molecular sieve as a catalyst.

According to the present invention, although the expensive silica raw material used in the conventional manufacturing method uses water glass, which is a cheap silica raw material, and under conditions in which Na ⁺ ions are present, a wide synthetic environment, that is, the amount of organic surfactant, Despite wide variations in amounts, the crystalline backbone of the same single unit crystal lattice thickness can be irregularly aligned to produce MFI zeolite molecular sieve materials in which mesopores and micropores hierarchically coexist. In addition, it is possible to dramatically shorten the completion time of the synthesis through such a change in the synthetic composition.

The zeolitic material prepared by the present invention has a very high specific surface area and a very large pore volume at the same time as that of MFI zeolite having only micropores. In particular, by using a cheap silica raw material it is possible to reduce the manufacturing cost, and to control the synthesis environment to shorten the manufacturing time, as well as mass production. In addition, due to the much higher activity and enhanced catalyst life than conventional zeolites, it is expected that industrial utilization will be greatly increased because the process of catalyst replacement and regeneration can be reduced.

1 is a (a) low angle and (b, top) high angle X-ray diffraction pattern of a material prepared according to Example 1 and (b, bottom) a high angle X-ray diffraction pattern of ordinary MFI zeolite.
2 is (a) a scanning electron micrograph and (b) a transmission electron micrograph of a material prepared according to Example 1. FIG.
Figure 3 is a (a) nitrogen adsorption isotherm and (b) pore size distribution of the material prepared according to Example 1.
4 is (a) low angle and (b) high angle X-ray diffraction patterns of the material prepared according to Example 2. FIG.
5 is (a) a scanning electron micrograph and (b) a transmission electron micrograph of a material prepared according to Example 2. FIG.
6 is (a) nitrogen adsorption isotherms and (b) pore size distributions of materials prepared according to Example 2. FIG.
7 is (a) low angle and (b) high angle X-ray diffraction patterns of a material prepared according to Example 3. FIG.
8 is (a) a scanning electron micrograph and (b) a transmission electron micrograph of a material prepared according to Example 3. FIG.
9 is (a) a scanning electron micrograph and (b) a transmission electron micrograph of a material prepared according to Example 4. FIG.

Hereinafter, the present invention will be described in detail. In describing the present invention, detailed descriptions of related well-known configurations or functions are omitted.

The terms and words used in the present specification and claims should not be construed as limited to ordinary or dictionary meanings and should be construed in accordance with the technical meanings and concepts of the present invention.

The embodiments described in the specification and the configuration shown in the drawings are preferred embodiments of the present invention, and do not represent all of the technical idea of the present invention, various equivalents and modifications that can replace them at the time of the present application are There may be.

The present invention provides a nanoplatelet having a large specific surface area and a large pore volume using water glass, which is a cheap silica raw material, in the production of molecular sieve materials in which irregularly assembled nanoplate-shaped MFI zeolites with a single unit crystal lattice thickness are formed. It provides a method for producing a MFI zeolite molecular sieve that can synthesize zeolite and can significantly shorten the synthesis time.

Hereinafter, the method of preparing the MFI zeolite molecular sieve of the present invention will be described in more detail step by step.

<Step 1: Synthetic Gel Preparation Step>

As the inorganic shear, water glass, which is a silica raw material, is polymerized with other gel shears containing an organic surfactant to form an organic-inorganic composite gel. Here, the water glass refers to sodium silicate (sodium silicate, 29 wt% SiO ₂ , Si / Na = 1.75) composed of SiO ₂ , Na ₂ O, and H ₂ O.

The inorganic shear body may include an alumina raw material together with water glass, and the alumina raw material may be, for example, sodium aluminate (NaAlO ₂ , sodium aluminate), aluminum sulfate (Al ₂ (SO ₄ ) _3, aluminum sulfate), aluminum hydroxide ( Al (OH) _3, aluminum hydroxide) or aluminum chloride (AlCl _3, aluminum chloride) may be used.

Here, the hydrophobic organic domain is formed by self assembly between inorganic regions by non-covalent bonds between organic materials, that is, van der Waals forces, dipole-dipole interactions, ionic interactions, and the like. At this time, the gel areas are arranged in a regular or complete manner according to the structure or concentration of the organic material.

The organic surfactant used in this step is a pure organic molecular surfactant containing two ammonium functional groups or one ammonium functional group and one amine functional group at the same time. An organic surfactant represented by the following Chemical Formula 1 or Chemical Formula 2 may be used. have.

[Formula 1]

[Formula 2]

In Formulas 1 and 2, X is a halogen (Cl, Br, I) anion or a hydroxide (OH) anion, C1, C2 are each independently substituted or unsubstituted alkyl groups, and C3 is substituted or unsubstituted It is an alkyl group or an alkenyl group or an alkyl group in which some carbon atoms are substituted with other atoms or an alkenyl group. In addition, ammonium functional groups can be extended to two or more and can be used to conceptually expand to a variety of materials.

In the above formulas (1) and (2), the carbon chain length of C1 is 8 to 22 carbon atoms, the carbon chain length of C2 is 3 to 6 carbon atoms, and the carbon chain length of C3 is preferably 1 to 8 carbon atoms. In the present specification, the organic surfactant is represented by generalizing in order of C1-C2-C3 according to the length of C1, C2, C3 (for example, 16-6-6 is C1 having 16 carbon atoms and C2 is carbon atom). 6, C3 has 6 carbon atoms, and represents an organic surfactant composed of two ammonium functional groups, 16-6-0 shows C1 having 16 carbon atoms, C2 having 6 carbon atoms, one ammonium functional group and one Organic surfactants consisting of amine functional groups).

<Step 2: Crystallization Step>

Subsequently, the nano-sized inorganic gel region stabilized by the organic region is converted into MFI zeolite having a nanoplatelet structure having a single unit crystal lattice thickness depending on the structure of the organic surfactant or the number of ammonium functional groups contained therein through the crystallization process. . At this time, due to the stabilizing effect of the organic material surrounding each zeolite growth of the zeolite is suppressed in the b -axis, the crystal size is controlled to an extremely fine thickness of 30 nm or less. Furthermore, The final formation of the zeolite structure is determined by adjusting the C1 alkyl tail length of the organic surfactant used in the synthetic gel in the range of 8 to 22 carbon atoms, or by adjusting the pH of the synthetic gel using a common acid. The general acid includes sulfuric acid (H ₂ SO ₄ ), hydrochloric acid (HCl), bromic acid (HBr), acetic acid (CH ₃ CO ₂ H) and other inorganic and organic acids, and neutralized with base (OH ⁻ ) in aqueous solution. Any acid that can provide a cation (H ⁺ ) that can react.

The zeolite formed through such a crystallization process has a structure of MFI zeolite having a form in which a single plate-like structure is irregularly arranged.

The crystallization process of this step may be carried out through hydrothermal synthesis, dry-gel synthesis, microwave synthesis, and other conventional crystallization methods may be used.

<Step 3: recovery of the formed zeolite>

The crystallized zeolite can be obtained through conventional methods such as filtration or centrifugation, and the material thus obtained can be selectively or completely removed only organic matter through firing or other chemical reaction.

Furthermore, the prepared zeolite can be activated or modified by post-aluminization, base aqueous treatment, ion exchange, metal support or post-treatment reaction of organic functionalization.

The MFI zeolite molecular sieve of the present invention is a method of manufacturing a MFI zeolite molecular sieve material in which the crystalline skeleton of a single unit crystal lattice thickness is irregularly aligned so that mesopores and micropores hierarchically coexist with cheap silica raw materials such as water glass. Can be used and prepared in an environment where Na ⁺ ions are present.

According to the method for producing MFI zeolite molecular sieve of the present invention, By appropriately adjusting the length of the C1 alkyl tail, the hydrophobic region, non-covalent bonds between organic domains around the nanoplatelet structure of single unit crystal lattice thickness, ie van der Waals forces, dipole-dipole interactions, ionic interactions It is possible to control the degree of self assembly caused by the action. Therefore, by adjusting the structure and concentration of the organic surfactant, it is possible to selectively control the skeletal arrangement of the nanoplatelet zeolite formed after the crystallization step in the complete or local region.

Furthermore, when the pH of the synthetic gel is lowered using an acid, even when an organic surfactant having a long C1 alkyl tail is used, the crystalline skeleton having a single unit crystal lattice thickness is irregularly aligned so that mesopores and micropores coexist hierarchically. MFI zeolite molecular sieve material can be prepared. In more detail, the number of basic nuclei crystals formed in the first step is determined according to the pH of the synthetic gel. If the pH of the synthetic gel is low, the number of nuclei crystals is distributed, and if the pH of the synthetic gel is high, the number of nuclei crystals is determined. Less distributed. As a result, a large number of nuclear crystals act as a center of crystal growth, increasing the rate of crystallization.

It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit or scope of the present invention. Such variations and modifications are intended to be within the scope of the appended claims.

Example  One : Water glass  Using a silica raw material and 22-6-6 organic surfactant as a structural derivative, the crystalline skeleton of single unit crystal lattice thickness is irregularly aligned. Mesoporation Division  Hierarchically coexisting micropores MFI Aluminosilicate ( aluminosilicate ) Method for preparing molecular sieve material

Organic surfactant of Formula 1 wherein C1 is 22 carbon atoms, C2 is 6 carbon atoms, C3 is 6 carbon atoms, and is composed of two ammonium functional groups and two halide anions (Br ⁻ ) (22-6-6 The organic surfactant) was mixed well with water glass, sodium aluminate (NaAlO ₂ ) _, sulfuric acid (H ₂ SO ₄ ) and distilled water. The molar composition ratio of the final synthetic gel is as follows.

7.5 22-6-6 Organic Surfactant: 100 SiO ₂ : 1 Al ₂ O ₃ : 30 Na ₂ O: 24 H ₂ SO ₄ : 4000 H ₂ O

After the mixed gel was stirred at 60 ^° C. for 6 hours, the final mixture was placed in a stainless autoclave and hydrothermally synthesized at 150 ^° C. for 3 days. After the reaction is completed, the autoclave is cooled to room temperature, the product is filtered and washed several times with distilled water. The product obtained was dried at 130 ^° C.

The material obtained according to Example 1 was confirmed by a low angle X-ray diffraction analysis (Fig. 1 (a)) to have an irregular arrangement without regularity of mesoregions. Elevated X-ray diffraction analysis (above FIG. 1 (b)) confirms that the synthesized material has a pattern (under FIG. 1 (b)) that matches the structure of a normal MFI zeolite). It has been shown that the material is zeolite with MFI backbone. The materials synthesized from the scanning electron micrographs (Fig. 2 (a)) and the transmission electron micrographs (Fig. 2 ( b )) are narrow plates with a single unit lattice thickness of very thin (2 nm) on the b -axis. The structures were irregularly stacked and had a size of 30-50 nm on the ac side of the crystal. Analysis of the pore structure of the product calcined through nitrogen adsorption isotherm (Fig. 3 (a)) and pore distribution diagram (Fig. 4 (b)) showed that the diameter was 5-6 nm and the pore volume was 1.0 cm ³ g ^{- 1} It was confirmed that it contains the mesopores. This zeolitic material exhibited a BET surface area of 660 m ² g ⁻¹ and was confirmed to be 47 by Si / Al in the product using ICP.

Example  2 : Water glass  As a raw material of silica and using a 16-6-6 organic surfactant as a structural derivative, the crystalline skeleton of single unit crystal lattice thickness is irregularly aligned. Mesoporation Division  Hierarchically coexisting micropores MFI Aluminosilicate  Method for preparing molecular sieve material

MFI aluminosilicate molecular sieves of the same type could be prepared by using 16-6-6 organic surfactant instead of 22-6-6 organic surfactant in the synthetic composition of Example 1. In this example, the molar composition ratio of the final synthetic gel was adjusted as follows.

7.5 16-6-6 Organic Surfactant: 100 SiO ₂ : 1 Al ₂ O ₃ : 30 Na ₂ O: 24 H ₂ SO ₄ : 4000 H ₂ O

4 shows the X-ray diffraction of the material finally obtained after the synthetic gel was prepared in the same manner as in Example 1, and the final mixture was placed in a stainless autoclave for 3 days after hydrothermal synthesis at 150 ^° C. Pattern. The low angle (FIG. 4 (a)) and high angle (FIG. 4 (B)) X-ray diffraction patterns confirmed that there was no regular mesoregion alignment, and the material produced was a zeolite with an MFI backbone. It can be seen that the crystals of the zeolite synthesized through the scanning electron micrograph (FIG. 5 (A)) and the transmission electron micrograph (FIG. 5 (B)) are irregularly assembled with plate-shaped zeolites having a single unit lattice thickness. It was confirmed that the zeolite crystals had a single unit lattice size (2.0 nm) on the b -crystal axis and were also suppressed by a very narrow platelet structure (20 nm or less) on the ac side of the crystal. The pore structure of the fired product was analyzed by nitrogen adsorption isotherm (Fig. 6 (a)) and pore size distribution (Fig. 6 (b)), and the specific surface area was 610 m ² g ^{- 1} and the total pore volume was 0.7 cm ³ g ^{- 1} , the pore diameter was confirmed to be 5 ~ 6 nm. ICP was used to confirm that the Si / Al ratio of the product was 45.

Example  3: Water glass  Using a silica raw material and 22-6-6 organic surfactant as a structural derivative, the crystalline skeleton of single unit crystal lattice thickness is irregularly aligned. Mesoporation Division  Hierarchically coexisting micropores MFI  pure Silicate ( silicate ) Method for preparing molecular sieve material

By using the 16-6-6 organic surfactant in the synthetic composition of Example 2 and by adjusting the synthetic composition could be prepared MFI pure silicate molecular sieve having the same form as in Example 2. In this example, the molar composition ratio of the final synthetic gel was adjusted as follows.

7.5 16-6-6 Organic Surfactant: 100 SiO ₂ : 28.6 Na ₂ O: 16.6 H ₂ SO ₄ : 4000 H ₂ O

7 is a synthetic gel prepared in the same manner as in Example 2, and the final mixture is placed in a stainless steel autoclave X-ray diffraction of the material finally obtained after hydrothermal synthesis for 5 days at 150 ^° C. Pattern. The low angle X-ray diffraction pattern (FIG. 7 (A)) confirmed that there was no regular mesoregion alignment as in Example 2, and the material prepared through the high angle X-ray diffraction pattern (FIG. 7 (B)). It was confirmed that it was a zeolite having the same MFI skeleton as in Example 2. However, since the zeolite material had a single unit crystal lattice length along the b -crystal axis, only the diffraction pattern corresponding to h0l diffraction appeared clearly. Scanning electron micrograph (Fig. 8 (a)) through were synthesized zeolite is confirmed determined hayeoteum growth of a single plate-like structural form, a transmission electron micrograph (Fig. 8 (b)) the zeolite crystals synthesized by the b - It was confirmed that the crystal axis had a single unit lattice size (2.0 nm) and also a very narrow plate-like structure (20 nm or less) in the ac plane of the crystal. The pore structure of the product calcined through the nitrogen adsorption isotherm showed that the specific surface area was 580 m ² g ^{- 1} and the total pore volume was 0.75 cm ³ g ^{- 1} . ICP was used to confirm that the Si / Al ratio of the product consisted of pure silicate.

Example  4:  The crystalline skeleton of a single unit lattice thickness of high aluminum content is irregularly aligned Mesoporation Division  Hierarchically coexisting micropores MFI Aluminosilicate  Method for preparing molecular sieve material

A high aluminum content MFI alumino having the same form as the material obtained in Examples 1 and 2 by using 22-6-6 or 16-6-6 organic surfactant in the synthetic compositions of Examples 1 and 2 and adjusting the synthetic composition Silicate molecular sieves could be prepared. In this example, the molar composition ratio of the final synthetic gel was adjusted as follows.

7.5 22-6-6 (or 16-6-6) Organic Surfactant: 100 SiO ₂ : 1.67 Al ₂ O ₃ : 30 Na ₂ O: 12 H ₂ SO ₄ : 4000 H ₂ O

Synthetic gel was prepared in the same manner as in Example 1, and the final mixture was placed in a stainless autoclave, and the low angle X-ray electron diffraction pattern of the material finally obtained after hydrothermal synthesis at 150 ^° C. for 7 days. It was confirmed that there is no regular meso-region alignment, and through the high-angle X-ray electron diffraction pattern it was confirmed that the material produced is a zeolite having an MFI skeleton. Transmission electron micrographs (FIG. 9) confirmed that the synthesized zeolite crystals were grown in an irregular arrangement, and the synthesized zeolite crystals had a single unit lattice size (2.0 nm) at the b -crystal axis and at the same time ac side of the crystal. It was also confirmed that it was suppressed by a very narrow plate structure (20 nm or less). The synthesized zeolite was calcined and analyzed using nitrogen adsorption isotherm. As a result, the specific surface area of the synthesized material was 580 m ³ g ^{- 1} and the total pore volume was 0.79 cm ³ g ^{- 1} . The synthesized material was analyzed using ICP, and found that the Si / Al molar ratio was 27.

Example  5 : The crystalline skeleton of single unit crystal lattice thickness is irregularly aligned Mesoporation Division  Hierarchically coexisting micropores MFI Of aluminosilicates  Catalytic reaction process

Three types of catalytic reactions included in this example show that water glass can be applied to various catalytic processes using MFI zeolite materials with nano-platelet shape with single unit crystal lattice thickness using silica as a raw material. Was carried out.

A. As a reforming catalyst for gaseous methanol, the crystalline backbones with a single unit crystal lattice thickness are irregularly aligned. Mesoporation Division  Hierarchically coexisting micropores MFI Of aluminosilicates  Applications

MFI aluminosilicate in the form of a nano-platelet with a single unit crystal lattice thickness prepared according to Example 1 was exchanged with H ⁺ ions, the powder was compacted without binder, and the pellets were ground to 14-20 mesh. Molecular sieve particles of size were obtained. In addition, to compare the zeolite catalyst performance, MFI zeolite (ZSM-5) containing only micropores was prepared. The methanol reforming reaction was carried out using a self-made fluidized stainless steel reactor (inner diameter = 10 mm, outer diameter = 11 mm, length = 45 cm), and the reaction result was obtained by on-line gas chromatography connected to the stainless steel reactor. And analyzed. In the reaction process, first, 100 mg of catalyst was mixed with 500 mg of 20 mesh quartz sand in order to assist in the heat of reaction and placed in a catalyst device (1/2 filter GSKT-5u) of a stainless steel reactor. After activating the catalyst under nitrogen flow at 550 ^° C. for 8 hours and lowering the reactor to the reaction temperature of 325 ^° C., methanol was introduced via a injection pump at a flow rate of 0.02 mL / m. At this time, the flow rate of nitrogen gas was maintained at 20 mL / m, and the product was analyzed using on-line gas chromatography periodically. The distribution results of the products are shown in Table 1. The nanoplatelet MFI aluminosilicate material synthesized in the present invention showed a significantly different product distribution from the general MFI zeolite catalyst including only micropores.

Product distribution Nano plate type MFI  Zeolite (%) Normal MFI  Zeolite (%) C ₂ H ₄ 12.0 40.5 C ₃ H ₆ 52.7 0 C ₄ H ₈ 8.8 13.0 Other fatty compounds 3.0 12.5 benzene 0.8 3.1 toluene 0.9 1.9 Xylene 2.5 9.5 Trimethylbenzene 5.9 8.2 C _{10 +} 12.8 10.5 Etc 0.6 0.8 total 100 100 % Selectivity to olefins 73.5 53.5 % Selectivity for gasoline 22.9 33.2

B. Benzaldehyde and  2 - Hydroxyl Aceto Of phenone (2-hydroxyaceto-phenone)  Liquid condensation reaction

The same material as used in Example 5A was catalyzed in a Pyrex reactor equipped with a reflux condenser. 0.1 g of catalyst powder was activated at 180 ^° C. for 2 hours and added to a reactor containing 20 mmol anhydrous 2-hydroxyacetophenone and 20 mmol benzaldehyde. The reaction proceeded with stirring under 140 ^° C. helium atmosphere. The reaction product was analyzed using gas chromatography periodically. The distribution results of the products are shown in Table 2.

catalyst Response time (time) 2- Hydroxyl aceto
Phenon  Conversion Rate (%) % Product distribution 2- Hydroxychalcon
(2- hydroxychalcone ) Plebanon
( flavanone ) Nano plate type  MFI Zeolite 5 19.0 20.0 81.2 24 51.0 15.2 84.5 Normal MFI  Zeolite 5 4.4 7.0 94.2 24 36.2 15.1 85.2

C. Waste plastic Reforming  Synthesis of Hydrocarbons Through

The same material as used in Example 5A was used for the decomposition of waste plastics. In this example, a solid powder of unstabilized linear low-density polyethylene was used as the standard reactant. A mixture of 10 g polyethylene and 0.1 g catalyst was placed in a semi-batch Pyrex reactor followed by physical stirring. At this time, the temperature of the reactor was increased at a rate of 6 ^o C / m from room temperature to 340 ^o C and maintained for 2 hours. Volatile products during the reaction were removed from the reactor using a nitrogen flow (flow rate = 35 mL / m), and these products were collected in liquid and gas phase respectively using ice traps and gas bags attached to the side of the reactor. After the reaction, the liquid and gaseous products were analyzed by gas chromatography. The distribution results of the products are shown in Table 3. In this reaction, the nanoplatelet MFI zeolite material of the present invention showed significantly enhanced catalytic activity compared to general MFI zeolite having only micro pores.

catalyst Conversion Rate (%) Reaction selectivity (mass%) C _One - C ₅ C ₆ - C ₁₂ > C ₁₃ Nano plate type MFI  Zeolite 83.1 92 8 0 Normal MFI

Zeolite 50.2 88 12 0

Claims (17)

A) polymerizing an organic surfactant comprising at least two ammonium functional groups or comprising one ammonium functional group and one amine functional group together with an inorganic shear comprising water glass to form an organic-inorganic composite gel;
B) converting the inorganic gel region of the organic-inorganic composite gel into zeolite through a crystallization process; And
C) separating the zeolite from the mixture obtained in step B),
The organic surfactant is a method for producing MFI zeolite molecular sieve, characterized in that represented by the formula (1) or (2).
Formula (1)

(2)

Wherein X is a halogen (Cl, Br, I) anion or a hydroxide (OH) anion, C1, C2 are each independently a substituted or unsubstituted alkyl group, and C3 is a substituted or unsubstituted alkyl group An alkenyl group or an alkyl group in which some carbon atoms are replaced with another atom or an alkenyl group.)
delete The method of claim 1,
The carbon chain length of the C1 is 8 to 22 carbon atoms, the carbon chain length of the C2 is 3 to 6 carbon atoms, the carbon chain length of the C3 is 1 to 8 carbon atoms manufacturing method of the molecular sieve.
The method of claim 1,
The inorganic shear sieve further comprises alumina raw material manufacturing method of MFI zeolite molecular sieve.
The method of claim 4, wherein
The alumina raw material is sodium aluminate (NaAlO ₂ , sodium aluminate), aluminum sulfate (Al ₂ (SO ₄ ) _3, aluminum sulfate), aluminum hydroxide (Al (OH) _3, aluminum hydroxide) and aluminum chloride (AlCl _{3 ,} aluminum chloride) method for producing MFI zeolite molecular sieve, characterized in that selected from the group consisting of.
The method of claim 1,
The step A) is a method for producing MFI zeolite molecular sieve, characterized in that further adding an acid when preparing the organic-inorganic composite gel.
The method according to claim 6,
The acid is a method of producing an MFI zeolite molecular sieve, characterized in that the addition of the pH of the organic-inorganic composite gel is 9 to 12.
The method of claim 1,
The step B) is a method of producing an MFI zeolite molecular sieve, characterized in that the hydrothermal synthesis (microwave heating), microwave heating (microwave heating) or dry-gel synthesis (dry-gel synthesis) characterized in that it is carried out.
The method of claim 1,
The step C) is a method for producing MFI zeolite molecular sieve, characterized in that it is made by filtration or centrifugation.
The method of claim 1,
And optionally removing the organics from the zeolite through calcining or chemical treatment.
The method of claim 10,
The method of manufacturing an MFI zeolite molecular sieve further comprising the step of activating or modifying the zeolite using a post-treatment reaction of dealuminization, base aqueous solution treatment, ion exchange, metal loading or organic functionalization.
delete delete delete A method of reforming methanol using a MFI zeolite molecular sieve prepared using the method for producing an MFI zeolite molecular sieve according to any one of claims 1 and 3 to 11 as a catalyst.
delete delete

Images