KR20090119125A - Manufacturing methods of crystalline zeolite - Google Patents

Abstract

PURPOSE: A manufacturing method of crystalline zeolite is provided to produce zeolite particles of 100 nano size and sol effectively with a hydrothermal synthesis method. CONSTITUTION: A manufacturing method of crystalline zeolite comprises the following steps of: manufacturing zeolite powder of micron size by a hydrothermal synthesis method with a first zeolite precursor aqueous solution(S10); manufacturing zeolite nano powder and nano sol using ball milling or a pulverizer(S30); and manufacturing zeolite nano powder by the hydrothermal synthesis method by adding zeolite nano powder and nano sol(S40).

Description

Manufacturing method of crystalline zeolite {Manufacturing methods of Crystalline zeolite}

The present invention relates to a method for producing a crystalline zeolite from which a template material is excluded, and more particularly, a method for preparing a crystalline zeolite, which can produce crystalline zeolite particles of tens to hundreds of nanoscales using a low cost process. It is about.

Molecular sieves find numerous uses by physical, biochemical and chemical methods. Among the most notable are the use as selective adsorbents and catalysts to effect separation of components in mixtures. In this application, the crystallographically defined pore structure in the molecular sieve material is typically required to have voids, and all the structure-directing agents used in the manufacture of the molecular sieve are essential by sintering or the like. Should be removed. Numerous materials are known to act as the molecular sieve, among which zeolites are best known.

Zeolites are also known as 'stones', ie boiling stones, and generally refer to aluminum aluminum oxide (Al ₂ O ₃ · SiO ₂ , alumina silica). That is, the physical properties and the intended use vary greatly depending on the ratio of mixing alumina and silica. The more alumina, the stronger the acidity, and is also used as a solid acid. Zeolites have larger pores than other silicate crystals, and have excellent ion exchange properties, making them suitable for the concentrated water industry such as soil improvers, fertilizer mixes, pesticide extenders, wastewater treatment agents, desiccants, ceramic raw materials, crude economy, building and cracking catalysts, and synthesis. Fuel Products Widely used for petrochemical applications. In order to diversify the use of zeolites, it is necessary to be able to control the size, distribution and shape of the crystals of the zeolite as well as an economical synthesis method. Recently, as nanotechnology, the necessity for the application of various nanoparticles as a coating agent and an abrasive material in semiconductors, sensors, and the like has been expanded.

Such zeolites have a three-dimensional structure with uniform nanometer-sized pores, and a method of synthesizing in the presence of a template of tetrapropylammonium cation is disclosed in US Pat. No. 3,702,886.

Since then, methods have been developed using various organic directing agents.

The organic template material is included in a mixed aqueous solution of a silica source, an alkali metal source, or the like, which constitutes a zeolite precursor aqueous solution in the general manufacturing method, to induce the formation of a predetermined molecular sieve by a so-called 'templating effet'. It is a substance. The role of organic template materials in the synthesis of molecular sieves is described in Lok et al., Zeolites 1983, volume 3, p282-291. The effect of the organic template is that when the organic skeleton is formed, the organic compound grows as a template to induce crystallization of zeolite or to induce crystallization to form a specific crystal skeleton.

Examples of the organic template include tetramethylammonium (TMA), tetraethylammonium (TEA), triethylmethylammonium (TEMA), tetrapropylammonium (TPA), tetrabutylammonium (TBA), and tetrabutylphosphonium (TBP). composed of anions such as ^-), trimethylbenzylammonium (TMBA), trimethyl cetyl ammonium (TMCA), trimethyl neopentyl ammonium (TMNA), triphenyl benzyl phosphonium (TPBP) cation and OH, such as ^-, Br ^-, Cl do. However, according to this method, an expensive organic template material must be used for commercialization, and in order to obtain a desirable pore structure, the organic template material must be removed by firing or the like, which has a disadvantage in that the execution cost of the firing process is expensive. .

As described above, in the present method, it is difficult to manufacture tens of nanometer-sized zeolite particles at low cost in the absence of a template material, and thus, a low-cost process can produce a zeolite having a desired size and specific surface area. Development is requested.

The present invention is to solve the above problems, an object of the present invention is a crystallinity that can be prepared by removing the organic template material zeolite particles in the range of tens to hundreds of nano size It is to provide a method for preparing zeolite nanopowder and nanosol.

The present invention is to solve the above problems, the method for producing a crystalline zeolite according to the first embodiment of the present invention, by using a first zeolite precursor solution excluding a template material to prepare a micron-sized zeolite powder by hydrothermal synthesis Making; Preparing zeolite nanopowders and nanosols containing amorphous particles of several tens of nanometers in size by using either the milling or grinding mills of the zeolite powder or commercially available zeolite powder; And preparing a crystalline zeolite nanopowder by hydrothermal synthesis by adding the amorphous zeolite nanopowder and nanosol as seeds to a second aqueous solution of zeolite precursor without a template.

Here, the zeolite precursor solution excluding the template material is a silica source consisting of at least one of tetraortho silicate, colloidal silica, fumed silica, sodium silicate, aluminum nitrate (Al (NO ₃ ) ₃ ), aluminum chloride (AlCl ₃ ), Hydrogen consisting of at least one of an alumina source consisting of at least one of aluminum sulfate (Al (SO ₄ ) ₃ ), sodium aluminate (NaAlO ₂ ), aluminum hydroxide (Al (OH) ₃ ), sodium hydroxide, potassium hydroxide and lithium hydroxide It is preferred to include a roxyl ion source for carrying out the method of preparing zeolite excluding the template material.

In addition, the manufacturing method of the crystalline zeolite according to the second embodiment of the present invention, preparing a micron-sized zeolite powder by hydrothermal synthesis using an aqueous solution of zeolite precursor excluding the template material; Preparing zeolite nanopowders and nanosols containing amorphous particles of several tens of nanometers in size by using either the milling or grinding mills of the zeolite powder or commercially available zeolite powder; And adding a hydroxyl ion source to the zeolite nanopowder comprising the amorphous and the nanosol and rehydrothermally treating the zeolite nanopowder having a crystalline phase.

Here, the zeolite precursor solution excluding the template material is a silica source consisting of at least one of tetraorthosilicate, colloidal silica, fumed silica, and sodium silicate, aluminum nitrate (Al (NO ₃ ) ₃ ), aluminum chloride (AlCl ₃ ), Hydroxyl consisting of at least one of an alumina source consisting of at least one of aluminum sulfate (Al (SO ₄ ) ₃ ), sodium aluminate (NaAlO ₂ ), aluminum hydroxide (Al (OH) ₃ ), sodium hydroxide, potassium hydroxide and lithium hydroxide It is preferred to include an ion source for carrying out the method of preparing zeolite excluding the template material.

In addition, after preparing the zeolite nanopowder, further comprising the step of dispersing the aggregated zeolite nanopowder in water by ball milling using a zirconia ball of 1 to 100㎛ size to prepare a zeolite nanosol nanometer It is preferred to obtain zeolite nanosols of size.

In addition, the zeolite used in the present invention is A-zeolite, X-zeolite, Y-zeolite, zeolite L, and ZSM-5, mordenite, beta-zeolite, ZSM-8, ZSM-11 having a pentasil structure, Silicalite-1.

In addition, the first zeolite precursor aqueous solution and the second zeolite precursor aqueous solution excluding the template material include scandium (Sc), titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), It is preferable to further include a transition metal aqueous solution made of at least one of cobalt (Co), nickel (Ni), copper (Cu), and zinc (Zn) in order to serve as a molecular sieve which is equally substituted in silica to impart various functions.

In addition, it is preferable that the process temperature at the time of the hydrothermal synthesis and the rehydrothermal treatment is 50 to 250 ° C, and the synthesis time is 1 to 240 hours.

According to the present invention, the zeolite particles prepared by the hydrothermal synthesis method excluding the template material are subjected to milling and hydrothermal processes, thereby effectively producing zeolite particles and sol having a size of several tens to one hundred nanometers.

Hereinafter, the manufacturing method of the crystalline zeolite by this invention is demonstrated.

1 is a flow chart sequentially showing a method for producing a crystalline zeolite according to a first embodiment of the present invention.

As shown in Figure 1, the method for producing a crystalline zeolite according to the first embodiment of the present invention, the first zeolite powder manufacturing step (S10), the first milling step (S20), the second zeolite powder production Nanoparticles of crystalline zeolite are prepared through step S30, and nanosol of crystalline zeolite may be obtained by further performing a second milling step (nanosol preparation step) (S40).

The zeolite produced by the crystalline zeolite manufacturing method according to the present invention is A-zeolite, X-zeolite, Y-zeolite, zeolite L, and ZSM-5 having a pentasil structure, mordenite, beta-zeolite, ZSM- 8, ZSM-11, or silicalite-1.

The first zeolite powder manufacturing step (S10) is a step of preparing a micron-sized zeolite powder by hydrothermal synthesis by preparing a first zeolite precursor solution excluding a template material. However, in the present invention, the first milling step (S20) may be performed by using a commercially available zeolite powder without passing through the zeolite powder manufacturing step (S10).

In the present invention, as the first zeolite precursor aqueous solution, at least one of tetraorthosilicate (TEOS), colloidal silica, fumed silica, sodium silicate, or a silica source, aluminum nitrate (Al (NO _{3 3} ), an alumina source comprising at least one of aluminum sulfate (Al (SO ₄ ) ₃ ), aluminum chloride (AlCl ₃ ), sodium aluminate (NaAlO ₂ ), or aluminum hydroxide (Al (OH) ₃ ) At least one of sodium hydroxide (NaOH), potassium hydroxide (KOH), and lithium hydroxide (LiOH) is mixed or supplied with a hydroxyl ion source. Therefore, the crystalline zeolite can be obtained at low cost without the aforementioned organic template material.

In particular, the present invention is characterized by excluding organic template material. As described above, the mold material itself is expensive, and the cost of the firing process is also expensive, the present invention provides a method for preparing zeolite nanoparticles without this.

The silica source and the alumina source act as an aluminosilicate compound in a zeolite precursor aqueous solution, and the hydroxyl ion source hydrolyzes the aluminosilicate compound and then condenses again to form a zeolite structure as a charge balance material. It serves to facilitate the formation of the structure. In addition, it is effective to enter the zeolite structure and indirectly take the role of the template material.

Here, the molar ratio of H ₂ O to SiO ₂ in the mixture is in the range of 5 to 100, preferably 20 to 60. When the molar ratio is less than 5 and less H ₂ O is added, there is a problem such as gelation of the aqueous solution of nanoparticles during hydrothermal synthesis, and if it exceeds 100, it is uneconomical. In addition, the molar ratio of Si / Al in the mixture is preferably 1 or more, more preferably in the range of 1 to 80. In addition, for example, when preparing a ZSM-5 zeolite, the molar ratio of SiO ₂ and NaOH as a hydroxyl ion source is in the range of 0.5 to 20, preferably 1.5 to 5. In addition, for example, when preparing a zeolite L, a hydroxyl ion source and its content are used differently depending on what kind of zeolite product is desired, such as using KOH as a hydroxyl ion source. When the content of the hydroxyl ion source is too large (for example, when SiO ₂ : NaOH is 1:20 or more in the production of the ZSM-5), hydrothermal synthesis is incompletely performed, and the content thereof is too small. In the case of (eg, SiO ₂ : NaOH in the production of ZSM-5 is less than 1: 0.5), there is a disadvantage in that the effect as the hydroxyl ion source cannot be exerted.

In addition, a transition metal aqueous solution may be mixed with the first zeolite precursor aqueous solution. The alkali metal means an element belonging to Groups 3 to 12 of the periodic table, preferably 4 cycles of scandium (Sc), titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn) and iron. One selected from (Fe), cobalt (Co), nickel (Ni), copper (Cu), and zinc (Zn) may be used alone or in admixture of two or more. Since the transition metal can be homomorphized during the synthesis of zeolite, the transition metal is uniformly dispersed in silica and serves as a molecular sieve to impart various functions such as acid point of the catalyst and physicochemical adsorption.

When the mixing of the zeolite precursor aqueous solution is finished, the zeolite precursor aqueous solution or the commercialized zeolite aqueous solution is reacted by hydrothermal synthesis.

Hydrothermal synthesis is used to accelerate the growth of crystals by applying heat to a mixture containing water. The hydrothermal synthesis is carried out by placing the mixture in an airtight container and then reacting it under pressure generated by raising the temperature.

The reaction apparatus used for the hydrothermal synthesis reaction is not particularly limited, but in some cases, it is preferable to perform in a stainless steel autoclave or the like. The treatment temperature at the time of hydrothermal synthesis is 50 to 250 ° C, preferably 90 to 200 ° C, depending on the desired crystalline zeolite. In addition, the synthesis time is 1 to 240 hours, preferably 10 to 48 hours. The synthesis time may vary depending on the temperature of the hydrothermal reaction, and can be controlled with a short synthesis time under high synthesis temperature.

Upon completion of hydrothermal synthesis, the obtained crystals are filtered, washed and dried in a conventional manner to obtain micron-sized zeolite particles or nanosols containing crystalline. The washing technique used herein is not particularly limited, but may also be subjected to sonication in water, pentane, acetone or methanol.

The first milling step (S20) is The micron-sized zeolite particles or commercially available crystalline zeolite particles are milled by ball milling or attrition milling to obtain zeolite nanopowders containing amorphous particles of 100 nm or less.

By carrying out the first milling step (S20), it is possible to obtain a zeolite nanopowder comprising primarily amorphous nanometer size, the nanopowder is used as a seed in a post-process, finally the crystallinity Zeolite nano powder is obtained. At this time, the specific surface area of the obtained nanoparticles is 100-300 m ² / g, preferably 150-250 m ² / g. The particle size is also in the range of 5 to 500 nm, preferably 20 to 150 nm.

The secondary zeolite powder manufacturing step (S30) is a step of preparing the crystalline zeolite nanopowder by hydrothermal synthesis by adding the zeolite nanopowder and the sol containing the amorphous to the second aqueous solution of the zeolite precursor excluding the template material as a seed. The second zeolite precursor is mixed by the same method as the first zeolite precursor, and hydrothermal synthesis is performed by the same method as the hydrothermal synthesis. At this time, for example, in the case of ZSM-5, the addition amount of the zeolite nanoparticles (seed) containing the amorphous is 0.001 to 30% by weight, preferably 0.1 to 10% by weight. If the amount of the zeolite seed containing the amorphous is less than 0.001% by weight, it is not easy to control the size of the nanoparticles below the submicron, and if it exceeds 30% by weight, it is disadvantageous compared to the effect. . The specific surface area of the prepared crystalline zeolite is 300 m ² / g or more, preferably 350 m ² / g or more. In addition, the particle size of the prepared crystalline zeolite is 50nm to 1㎛.

The zeolite produced by the crystalline zeolite manufacturing method is A-zeolite, X-zeolite, Y-zeolite, zeolite L, and ZSM-5 having a pentasil structure, mordenite, beta-zeolite, ZSM-8, ZSM-11 or any one of silicalite-1 (Silicalite-1), preferably ZSM-5 having a three-dimensional structure of pentasil shape.

Nanosol manufacturing step (second secondary milling step) (S40) is a step of preparing a zeolite nanosol by dispersing the crystalline zeolite nanopowder in an aqueous system using ball milling, thereby obtaining the nanopowder in the form of nanosol Can be.

As a preferred embodiment of the ball milling, in order to disperse the agglomerated crystalline zeolite nanopowder into monodispersed nanoparticles in an aqueous system, a size of 100 μm (1Φ) or less, more preferably 3 to 20 μm (0.03 to 0.2Φ) Ball milling is performed using a zirconia ball.

 2 is a flow chart sequentially showing a method for producing a crystalline zeolite according to a second embodiment of the present invention.

As shown in Figure 2, the method for producing a crystalline zeolite according to the second embodiment of the present invention, through the zeolite powder manufacturing step (S100), milling step (S200), rehydrothermal treatment step (S300) of the crystalline zeolite The nanopowder is prepared, and nanosol of crystalline zeolite may be obtained by further performing a nanosol preparation step (second milling step) (S400).

The second embodiment of the present invention is the same process as the above-described first embodiment, the zeolite nanopowder including the amorphous first obtained in the second zeolite powder manufacturing step (S30) in the first embodiment and While using the sol as a seed, the rehydrothermal treatment step (S300) in the second embodiment is to add a hydroxyl ion source to the zeolite nanopowder containing the amorphous and rehydrothermal treatment. That is, in the first embodiment, the zeolite particles containing the amorphous obtained first were used as seeds in a later process and mixed with a separate second zeolite precursor aqueous solution. In the second embodiment, only the zeolite particles containing the amorphous material were used. The point of continuous injection into the post process is different.

Hereinafter, the physical properties of the crystalline zeolite obtained by the present invention will be described with reference to the drawings.

FIG. 3 is an SEM image of micron-sized crystalline ZSM-5 particles prepared by hydrothermal treatment of a zeolite precursor solution containing colloidal silica, sodium aluminate, and sodium hydroxide at 170 ^° C. for 12 hours without a template material, and FIG. 4. Is a FE-SEM picture of the micron-sized NaA zeolite particles prepared by hydrothermal treatment of the zeolite precursor aqueous solution at 100 ^o C for 12 hours without a template material, Figure 5 is a zeolite precursor aqueous solution for 12 hours at 150 ^o C without a template material FE-SEM photograph of micron-sized NaY zeolite particles prepared by hydrothermal treatment. As shown in the figure, no matter what zeolite particles are formed, the crystalline form is irregular after the first hydrothermal synthesis process, the crystal size is 1 to 10 ㎛.

FIG. 6 is a view showing a TEM image of amorphous ZSM-5 nano-sized particles obtained by ball milling the ZSM-5 particles of FIG. 3. As shown in the figure, it can be seen that due to the ball milling nanoparticles of 5 to 100nm are produced.

FIG. 7A is a diagram illustrating an XRD pattern of ZSM-5 micron powders obtained in FIG. 3, and FIG. 7B is a diagram illustrating an XRD pattern of ZSM-5 nanopowders including milled amorphous particles obtained in FIG. 6. As shown in the figure, it can be seen that the intensity of XSM diffraction pattern peculiar to ZSM-5 is smaller than the previous one after ball milling, and the value of 2θ is a wide distribution peak at 20 to 30 degrees. It can be seen that the crystallinity of ZSM-5 is changed to amorphous.

FIG. 8 is a SEM photograph of nanoparticles prepared by adding the amorphous particles obtained in FIG. 6 as a seed to a precursor solution for preparing ZSM-5 of FIG. 3. Based on the drawings, it can be seen that nanoparticles having a size of 100 to 200 nm were obtained.

9 is a TEM photograph of a crystalline ZSM-5 nanopowder prepared by rehydrothermal treatment at 170 ^° C. for 12 hours using the particles obtained in FIG. 6, and shows that nanoparticles having a particle size of 30 to 70 nm were produced. have. 10 is an XRD photograph of the ZSM-5 nanopowder prepared in FIG. 9. This indicates that the value of 2θ in B of FIG. 7 represents an amorphous phase having a wide distribution peak at 20 to 30 degrees, whereas in FIG. 10, the amorphous phase disappears and shows a crystalline ZSM-5 diffraction pattern.

11 is a NaA nanoparticles prepared according to the method for preparing NaA zeolite nanopowder by rehydrothermal treatment of amorphous NaA particles pulverized into nano-size particles by ball milling the particles obtained in FIG. 4 at 100 ^° C. for 12 hours. FE-SEM picture of the powder. As shown in the figure, it can be seen that the nanopowder having a size of 50 to 100 nm is formed by the rehydrothermal treatment according to the second embodiment of the present invention.

FIG. 12 is a ball milling of the particles shown in FIG. 5 to obtain amorphous NaY particles pulverized into nano-sized particles, and the particles are prepared according to the method for producing NaY zeolite nanopowder by rehydrothermal treatment at 150 ^° C. for 12 hours. It is FE-SEM photograph of NaY nanopowder. It can be seen that the nano powder of 50 to 100nm is formed.

13 shows the present invention According to the dispersion method included in Examples 1 and 2, the particle size of ZSM-5 nanosol prepared by dispersing in aqueous solution within 3 hours by ball milling using the particles obtained in FIG. 9 was measured. It is a figure which shows. As shown in the figure, the particle size of the nanosol has an average particle diameter based on weight percent. D10 = 37 nm, D50 = 50.8 nm, D90 = 90 nm (based on Wt.%) You can check it.

Although the preferred embodiment of the present invention has been described above, the present invention may use various changes, modifications, and equivalents. It is clear that the present invention can be applied in the same manner by appropriately modifying the above embodiments. Accordingly, the above description does not limit the scope of the invention as defined by the limitations of the following claims.

1 is a flow chart sequentially showing a method for producing a crystalline zeolite according to a first embodiment of the present invention

2 is a flowchart sequentially showing a method for preparing a crystalline zeolite according to a second embodiment of the present invention.

3 is a SEM photograph of micron-sized ZSM-5 particles prepared by hydrothermal treatment at 170 ^° C. for 12 hours without template material.

Figure 4 is a view showing the FE-SEM picture of the micron-sized NaA zeolite particles prepared by hydrothermal treatment for 12 hours at 100 ^o C without a template material

FIG. 5 shows FE-SEM photographs of micron-sized NaY zeolite particles prepared by hydrothermal treatment at 150 ^° C. for 12 hours without a template material.

FIG. 6 is a TEM photograph of amorphous ZSM-5 nano-sized particles obtained by ball milling the ZSM-5 particles of FIG. 3. FIG.

7 is a view showing an XRD pattern of ZSM-5 micron powder and nanopowder obtained in FIGS. 3 and 6

FIG. 8 is a view showing an SEM photograph of nanoparticles prepared using the amorphous particles obtained in FIG. 6 as seeds.

9 is a TEM photograph of a crystalline ZSM-5 nanopowder prepared by rehydrothermal treatment at 170 ^° C. for 12 hours using the amorphous particles obtained in FIG. 6.

10 is an XRD photograph of the ZSM-5 nanopowder of FIG. 9.

FIG. 11 is a FE-SEM photograph of NaA nanopowder prepared by reheating amorphous NaA particles pulverized into nano-sized particles by ball milling the particles obtained in FIG. 4 at 100 ^° C. for 12 hours.

FIG. 12 is an FE-SEM photograph of NaY nanopowder prepared by rehydrothermal treatment of amorphous NaY particles pulverized into nanosize particles by ball milling the particles obtained in FIG. 5 at 150 ^° C. for 12 hours.

FIG. 13 is a view showing data for measuring particle sizes of ZSM-5 nanosols prepared by dispersing the particles obtained in FIG. 9 under aqueous conditions within 3 hours by ball milling.

Claims (9)

Preparing a micron-sized zeolite powder by hydrothermal synthesis using an aqueous solution of a first zeolite precursor excluding a template material; Preparing zeolite nanopowders and nanosols containing amorphous particles of several tens of nanometers in size by using either the milling or grinding mills of the zeolite powder or commercially available zeolite powder; A method for producing a crystalline zeolite comprising preparing a crystalline zeolite nanopowder by hydrothermal synthesis by adding the amorphous zeolite nanopowder and the nanosol as seeds to an aqueous solution of the second zeolite precursor excluding a template. The method of claim 1, The first zeolite precursor aqueous solution and the second zeolite precursor aqueous solution, excluding the template material, A silica source consisting of at least one of tetraortho silicate, colloidal silica, fumed silica, sodium silicate, aluminum nitrate (Al (NO ₃ ) ₃ ), aluminum sulfate (Al (SO ₄ ) ₃ ), aluminum chloride (AlCl ₃ ), sodium A crystalline material comprising a source of alumina consisting of at least one of aluminate (NaAlO ₂ ) and aluminum hydroxide (Al (OH) ₃ ), a hydroxyl ion source comprising at least one of sodium hydroxide, potassium hydroxide and lithium hydroxide Method of preparing zeolites. Preparing a micron-sized zeolite powder by hydrothermal synthesis using an aqueous solution of zeolite precursor without a template; Preparing zeolite nanopowders and nanosols containing amorphous particles of several tens of nanometers in size by using either the milling or grinding mills of the zeolite powder or commercially available zeolite powder; The method of preparing a crystalline zeolite comprising the step of adding a hydroxyl ion source to the zeolite nanopowder comprising the amorphous and nanosol and rehydrothermal treatment to prepare a zeolite nanopowder having a crystalline. The method of claim 3, Zeolite precursor aqueous solution excluding the template material, A silica source consisting of at least one of tetraortho silicate, colloidal silica, fumed silica, sodium silicate, aluminum nitrate (Al (NO ₃ ) ₃ ), aluminum sulfate (Al (SO ₄ ) ₃ ), aluminum chloride (AlCl ₃ ), sodium A crystalline zeolite comprising a source of alumina consisting of at least one of aluminate (NaAlO ₂ ) and aluminum hydroxide (Al (OH) ₃ ), and a hydroxyl ion source consisting of at least one of sodium hydroxide, potassium hydroxide and lithium hydroxide. Manufacturing method. The method according to any one of claims 1 to 4, After preparing the zeolite nano powder, Dispersing the aggregated zeolite nano powder in water by ball milling using a zirconia ball having a size of 1 to 100 μm to prepare a zeolite nanosol. The method according to any one of claims 1 to 4, The zeolite may be A-zeolite, X-zeolite, Y-zeolite, zeolite L, and ZSM-5 having a pentasil structure, mordenite, beta-zeolite, ZSM-8, ZSM-11, silicalite-1 (Silicalite- It is any one of 1) The manufacturing method of crystalline zeolite characterized by the above-mentioned. The method according to any one of claims 1 to 4, The first zeolite precursor aqueous solution and the second zeolite precursor aqueous solution, excluding the template material, Among scandium (Sc), titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn) Method for producing a crystalline zeolite, characterized in that it further comprises at least one aqueous transition metal. The method of claim 6, The first zeolite precursor aqueous solution and the second zeolite precursor aqueous solution, excluding the template material, Among scandium (Sc), titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn) Method for producing a crystalline zeolite, characterized in that it further comprises at least one aqueous transition metal. The method according to any one of claims 1 to 4, The process temperature at the time of the hydrothermal synthesis and rehydrothermal treatment is 50 to 250 ℃, the synthesis time is 1 to 240 hours, characterized in that the manufacturing method of crystalline zeolite.

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