• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
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    • 专利摘要:
    zsm-5 zeolite preparation method using nanocrystalline zsm-5 seeds, discloses in the present patent application, a method of preparing zsm-5, including: providing a nanocrystalline zsm-5 seed with a size of 70 ~ 300nm ; adding the nanocrystalline zsm-5 seed to a stock solution including sodium silicate (water glass) as a silica source, alumina source, a neutralizer and water to form the reaction mixture; keeping the reaction mixture at 150 ~ 200 ° C to crystallize the reaction mixture. The method is advantageous, since zsm-5 having crystals of small and uniform sizes and without uniforms and without uniforms and without impurities, can be synthesized and a short period of time.
    公开号:BR112012009397B1
    申请号:R112012009397-5
    申请日:2010-10-18
    公开日:2020-10-13
    发明作者:Sun Choi；Deuk Soo Park；Suk Joon Kim；Dae Hyun Choo；Yong Ki Park；Chul Wee Lee；Hee Young Kim；Won Choon Choi；Na Young Kang；Bu Sub Song
    申请人:Sk Innovation Co., Ltd；
    IPC主号:
    专利说明:

    Application field
    [001] The present application refers to a method of preparing the ZSM-5 zeolite using ZSM-5 nanocrystalline seeds having a size of 70 ~ 300 nm. State of the art
    [002] Generally, zeolite is widely used as a catalyst, an adsorbent, a molecular sieve, an ion exchanger or similar due to a peculiar three-dimensional aluminosilicate crystal structure, and has a large pore and excellent ion exchange performance in comparison other aluminosilicate crystals. The use of natural zeolite is limited due to its structural restrictions, but the use of synthetic zeolite is gradually increasing. To expand the use of zeolite, arbitrary control of the size of the crystal, distribution of the particle size and shape of the zeolite is required, as well as efficient synthesis of the zeolite.
    [003] ZSM-5 zeolite forms three-dimensional pores defined by 10 tetrahedron rings, and its size is equal to that of zeolite A or is in the middle between zeolite X and zeolite Y.
    [004] Also, zeolite ZSM-5 is a type of pentasil zeolite that is a selective format catalyst exhibiting peculiar adsorption and diffusion characteristics, and generally has high thermal stability and hydrophobicity because it has a high SiO2 / A12O3 index.
    [005] Also, the ZSM-5 zeolite has resistant Lewis acid sites, but has weak Bronsted acid sites.
    [006] In particular, the ZSM-5 zeolite is used to directly obtain a fraction of gasoline having a high amount of octane from methanol by an MTG process, and is known to have excellent selectivity of the gasoline fraction.
    [007] After ZSM-5 having a high silica content, which was first developed by Mobil Corporation in the early 1970s, research on this material has been done in a variety of ways for peculiar catalytic activity and format selectivity, resulting in the effect molecular sieve of this material. Unlike aluminosilicate zeolite, several types of organic materials have been used as a structure inducing substances to form a structure to prepare ZSM-5.
    [008] Until now, among the organic materials known to act effectively in the formation of the structure of ZSM-5, ammonium tetrapropyl cations have been known to have the most excellent structure-inducing effect. Currently, most commercially available ZSM-5 is being synthesized using this material. However, although organic structures inducing materials, including ammonium tetrapropyl ions, exhibit excellent structure-inducing effects, attempts have been made not to use them because they are disadvantageous in economic and environmental aspects, and several processes for these purposes have been developed (Patent of the USA No. 4,257,885). The reason for not using organic structures to induce materials is that they are expensive and cause environmental pollution, since they have high toxicity. When ZSM-5 is synthesized using an organic structure inducing material, a secondary cost is required to treat a toxic unreacted organic structure inducing material included in the discarded water.
    [009] Therefore, in order to solve the above problems, Flanigen et al. (U.S. Patent No. 4,257,885) first reported a method for synthesizing ZSM-5 using crystalline seeds under the condition of excluding an inducing material from the organic structure or without using crystalline seeds. However, this method of synthesis is problematic, as it requires a long reaction time of 68 ~ 120 hours. In addition, when ZSM-5 is synthesized under the condition of excluding the material inducing the organic structure, this method is significantly influenced by the reaction conditions, thus requiring careful attention.
    [0010] Factors influencing the synthesis of ZSM-5 may include the type of a silica source, Si / Al ratio, concentration of an alkali solution, the sequence of mixing of the reagents, crystallization temperature, crystallization time, degree of aging, agitated or not, and the like. Among these factors, the type of a silica source is known as the most important factor.
    [0011] Sodium silicate, silica sol or the like is used as the source of silica. Sodium silicate, which is prepared by melting solid silicate with water, is the cheapest source of silica. However, it is difficult to control the composition of reagents because sodium silicate includes a large amount of alkaline components. Therefore, the concentration of alkaline components in the sodium silicate can be controlled by the addition of sulfuric acid or aluminum sulfate. However, this method of synthesis is problematic, since the ZSM-5 is not uniformly crystallized because the reaction conditions are complicated, and the cost for post-treatment, such as salt removal, is increased (German Patent related No. 207,185).
    [0012] Sol silica, which is another source of silica, has good reactivity and is easily treated. However, silica sol is more expensive than other sources of silica, and its silica components are dispersed in a large amount of colloidal water and react with the aluminum components to form hydrogel, so that the two components they must be brought into contact with each other in a diluted state in order to prevent hydrogel formation. In this case, there are problems where the solids content of the synthesized ZSM-5 is low based on the crystallized particles during the ZSM-5 synthesis process, and the crystalline ZSM-5 particles are finely dispersed in a state of separate particles, so that a high load occurs during a separation process and washing water remaining in the process, and in which the unreacted components are discharged from the remaining residues and the water washing solution, with the result that productivity of ZSM-5 becomes low, so this method of synthesis is not suitable for industrial production methods (related German Patent No. 207,186).
    [0013] In addition, Examined Korean Patent Application No. 10-2007-0020354 discloses a method of preparing a ZSM-5 molecular sieve catalyst having a small crystal size using diatomite or silica airgel as the main source silica by adding a guiding agent for the crystal seed, silica sol and sodium silicate to perform the kneading and molding and then carrying out a crystallization of the gas-solid phase of the silica source, using organic amine and steam to convert the source of crystallized silica to ZSM-5 with a small crystal size. However, this method is also problematic since the costs of the process are higher, as the nanometric seeds and organic amine are used in order to obtain the final ZSM-5.
    [0014] In addition, the Examined Korean Patent Application No. 1996-0002621, filed by Mobil Corporation, discloses a method of preparing small crystal ZSM-5 having a high absorption of mesitylene without adding any organic material. In this method, ZSM-5 is prepared using a reaction mixture, including a source of alumina, acid and seeds of ZSM-5 in addition to sodium silicate used as a source of silica under the condition that there is no material inducing the organic structure. This method is characterized by the fact that the size of the ZSM-5 crystal is controlled using the solids content of the reaction mixture and the molar ratio of OH- / SiO2, but it is problematic, since the degree of crystallization of ZSM-5 does not reaches 50 ~ 75%.
    [0015] Meanwhile, recently, as a method to reduce the time of hydrothermal synthesis, a microwave synthesis method is introduced. In the microwave synthesis method, the time required to form seeds and crystallize a sample can be reduced by directly supplying microwave energy to the sample, not by supplying energy from an external heat source to the sample using thermal conduction . That is, the ions are quickly vibrated and the water dipoles are quickly rotated by microwave, so that the temperature is quickly increased by the friction between the molecules in a solution, quickly crystallizing the sample.
    [0016] The US Mobil Corporation first introduced a method for preparing a porous molecular sieve material using microwave energy (U.S. Patent No. 4,778,666). In this method, the microwave energy used to synthesize the zeolite had a frequency range of 915 ~ 2450 MHz, and the zeolite ZSM-5 was synthesized using crystal seeds, in a container (glass, ceramic, PTF). Recently, nanometric silicalite-1 synthesis methods, ZSM-5, LTL, LTA and the like, dividing the reactions into two steps of a seed formation reaction and a crystallization reaction and then applying microwaves to them have been reported by Nan Ren and Yi Tang et al. (Microporous and Mesoporous Materials, 3,306 (2009)).
    [0017] As described above, the aforementioned methods of synthesizing ZSM-5 are problematic in that, when ZSM-5 is synthesized using cheap sodium silicate as a source of silica, without an organically-inducing material, the range of synthesizable reagent compositions is narrow, and the synthesis time is long. In addition, the aforementioned methods of synthesizing ZSM-5 are problematic in that the particle size distribution is wide, and the degree of crystallinity of the synthesized zeolite is low. Disclosure of the Invention Technical problem
    [0018] Thus, the present inventors have done extensive research in solving the above problems. As a result, they found that in the synthesis of ZSM-5 using sodium silicate as a source of silica under the exclusion of an organic structure-inducing material, when the nanocrystalline ZSM-5 seeds are introduced, having the ZSM- 5 100% or more of relative Christianity, which has small crystals, is uniform and does not include impurities, and can be prepared. Based on this finding, the present invention has been completed.
    [0019] The present invention aims to provide a method of preparing fine and uniform ZSM-5 with a relative crystallinity of 100% or more by adding nanocrystalline ZSM-5 seeds with a particle size of 70 ~ 300 nm for the composition that does not contain an organic structure-inducing material. Solution of the problem
    [0020] One aspect of the present invention provides a method for preparing ZSM-5, including: providing nanocrystalline ZSM-5 seeds having a size of 70 ~ 300 nm; adding the nanocrystalline ZSM-5 seeds to a solution, including sodium silicate as a silica source, alumina source, neutralizer and water to form a reaction mixture; and keeping the reaction mixture at 150 ~ 200 ° C to crystallize the reaction mixture.
    [0021] Here, the solution can have a composition represented by [Na2θ] x [AI2O3] Y [SiO2] 100 [H2O] z where X is 10 ~ 26, Y is 0.2 ~ 5, and Z is 2500 ~ 4000.
    [0022] In addition, the amount of nanocrystalline mi ZSM-5 seeds added to the solution can be 0.1 to 6% in water based on the reaction mixture.
    [0023] In addition, the alumina source can be one or more of the elements selected from sodium aluminate, aluminum nitrate, aluminum chloride, aluminum acetate, aluminum sulfate, aluminum isopropoxide, and aluminum acetylacetonate.
    [0024] In addition, the neutralizer can be any element selected from hydrochloric acid, nitric acid, phosphoric acid, sulfuric acid, and aluminum sulfate.
    [0025] Also, crystallization of the reaction mixture can be carried out for 12 ~ 72 hours. Advantageous Effects of the Invention
    [0026] As described above, according to the present invention, ZSM-5 having uniform crystals of small size and still without impurities can be prepared in a short period of time by introducing nanocrystalline ZSM-5 seeds. In addition, the crystal size of the ZSM-5 can be adjusted by adjusting the size of the nanocrystalline ZSM-5 seeds. In addition, the ZSM-5 is ecological and can be prepared, as an organic structure induction material is not used. In addition, high-quality ZSM-5 can be more easily synthesized from a wide range of sodium silicate compositions. Brief Description of Drawings
    [0027] Objects, characteristics and advantages described above, and others, of the present invention will be more clearly understood from the following detailed description taken in conjunction with the attached drawings, in which: Figure 1 is a flow chart showing a process of synthesis of nanocrystalline ZSM-5 seeds according to the present invention; Figure 2 is a flow chart showing a process for synthesizing ZSM-5 according to the present invention; Figure 3 shows a graph and a photograph of X-ray diffraction analysis (XRD) and a scanning electron microscope (SEM) analysis of the ZSM-5 seeds synthesized in Preparation Examples 1 and 2, respectively; Figures 4A and 4B show a graph and a photograph of X-ray diffraction analysis (XRD) and a scanning electron microscope (SEM) analysis of ZSM-5 seeds synthesized in Comparative Examples 1 to 3, respectively; Figures 5A and 5B show a graph and a photograph of X-ray diffraction analysis (XRD) and a scanning electron microscope (SEM) analysis of ZSM-5 seeds synthesized in Comparative Examples 4 to 7, respectively; Figures 6A and 6B show a graph and photograph of X-ray diffraction analysis (XRD) and scanning electron microscope (SEM) analysis of ZSM-5 seeds synthesized in Examples 1 to 4, respectively, and A Figures 7A and 7B show a graph and a photograph of X-ray diffraction analysis (XRD) and a scanning electron microscope (SEM) analysis of ZSM-5 seeds synthesized in Examples 3, 5 and 6, respectively. Best Way to Carry Out the Invention
    [0028] Hereinafter, the present invention will be described in detail.
    [0029] As described above, the present invention provides a method of preparing ZSM-5, including: • providing a nanocrystalline ZSM-5 seed having a size of 70 ~ 300 nm; • add the nanocrystalline ZSM-5 seed to a solution including sodium silicate as a source of silica, a source of alumina, a neutralizer and water to form a reaction mixture; • and keep the reaction mixture between 150 and 200 ° C to crystallize the reaction mixture.
    [0030] In the present invention, firstly, a nanocrystalline ZSM-5 seed is provided. The seeds of ZSM-5 nanocrystalline serve to increase the speed of crystallization, and have a size of 70 ~ 300 nm, preferably 70 ~ 150 nm. In addition, nanocrystalline ZSM-5 seeds can have a relative crystallinity of 100% or more, which does not include impurities.
    [0031] Here, the term "relative crystallinity" used in this specification is represented by the following equation (in this specification, ACZeo - Z NOaO (SiO2 / AI2O3 molar ratio = 30), manufactured by Albemarle Corporation, was used as an example of commercially available ZSM-5): • Relative crystallinity (%) = (peak area of 22-25 obtained after DXR analysis of the synthesized product) x 100 • Peak area of 22-25 obtained after DXR analysis of ZSM- 5 commercially available
    [0032] Meanwhile, nanocrystalline ZSM-5 seeds can be synthesized using any of the generally known synthesis methods (for example, a synthesis method proposed by Nan Ren and Yi Tang (Microporous and Mesoporous Materials) ], 3., 306, (2009))), as long as it has a constant nanometric size and does not include impurities. Therefore, in the process of synthesis of nanocrystalline ZSM-5 seeds, whether they are or not, an organic structure induction material, type of silica source or aluminum source, and type of crystallization method (for example, hydrothermal synthesis or microwave synthesis) does not act as factors that limit the scope of the ZSM-5 nano crystaline seed of the present invention.
    [0033] In addition, the solution used to prepare the nanocrystalline ZSM-5 seed has a composition represented by [TPA +] 25 [SiO2] 100 [AI2O3] x [H2O] 1 600 (here, X is 0.5 ~ 10 ).
    [0034] The source of silica that constitutes the solution can be selected from tetraethyl orthosilicate (TEOS), diatomite, sodium silica, colloidal silicate, and solid powder silica (smoked silica). Preferably, the source of silica can be tetraethyl orthosilicate (TEOS). In addition, the alumina source can be selected from sodium isopropoxide, sodium aluminate, and aluminum oxide. Preferably, the source of alumina is sodium isopropoxide. If an organic structure inducing material is used, such as the organic structure inducing material, several types of amines, such as propylamine, dipropylamine, tripropylamine, ethylenediamine, diaminopropane, diaminobutane, diaminopentane, di-aminoethanol, tetrapropylammonium hydroxide (TPAOH), tetrapropyl ammonium bromide (TPABr) and the like can be used. Preferably, the organic structure-inducing material can be tetrapropylammonium hydroxide (TPAOH) or tetrapropyl ammonium bromide (TPABr).
    [0035] The composition is stirred and aged at room temperature, and the aged composition can be crystallized using a commonly known method, for example, hydrothermal synthesis or microwave synthesis. When the aged composition is crystallized by microwave synthesis, mainly, the aged composition is irradiated by microwave at a temperature of 60 ~ 100 ° C for 60 ~ 120 minutes, and, secondarily, irradiated with microwave at a temperature of 110 to 170 ° C for 30 ~ 240 minutes.
    [0036] The nanocrystalline ZSM-5 seeds obtained in this way have a relative crystallinity of 100% or more, which is assessed by X-ray diffraction analysis (CXR), and has a particle size of 70 ~ 300 nm .
    [0037] The synthesized nanocrystalline ZSM-5 seed can be used to increase the rate of crystallization and crystallinity and to adjust the size of the crystal during the preparation of ZSM-5 of the present invention. In addition, the amount of nanocrystalline ZSM-5 seeds used can be adjusted depending on the crystal size of the final ZSM-5. Generally, the crystal size of ZSM-5 decreases when the amount of nanocrystalline ZSM-5 seeds increases. Therefore, in order to obtain a fine and uniform ZSM-5, the amount of nanocrystalline ZSM-5 seeds is added to the solution in an amount of 0.1 ~ 6% in water, preferably 0.1 ~ 4% in water based on the reaction mixture.
    [0038] In order to prepare the ZSM-5 of the present invention, the synthesized crystalline ZSM-5 seed, a silica source, an alumina source, a neutralizer and water are used without the use of a structure-inducing material organic. As the source of silica, silica sol, sodium silicate or sodium silicate can be used, but in the present invention, it is preferred that sodium silicate is used.
    [0039] When the organic structure-inducing material is not used, alumina is a very important material in the preparation of ZSM-5. The source of alumina is selected from sodium aluminate, aluminum nitrate, aluminum sulfate, aluminum chloride, aluminum acetate, aluminum isopropoxide, aluminum acetylacetonate, and mixtures thereof. Preferably, the alumina source is selected from sodium aluminate, aluminum nitrate, aluminum sulfate, and mixtures thereof.
    [0040] As is well known, the water used in the reaction mixture of the present invention is an essential material for hydrothermal synthesis, and can be distilled water. The amount of water in the reaction mixture greatly influences the crystallization reaction. In the present invention, the amount of water in the reaction mixture is adjusted such that the H20 / SiO2 molar ratio is 25 ~ 40, preferably 25 - 30. When the amount of water in the reaction mixture is excessively high , the crystallization rate decreases, so that the crystallization reaction time is excessively increased and the ZSM-5 yield is decreased. Therefore, it is necessary that the amount of water in the reaction mixture is properly adjusted.
    [0041] In addition, the neutralizer used in the present invention is a material added to overcome the difficulty of controlling the composition of reagents. This difficulty is attributable to the fact that the source of silica and alumina includes the source of a large amount of alkaline components. The neutralizer may be hydrochloric acid, nitric acid, phosphoric acid or sulfuric acid, and preferably sulfuric acid.
    [0042] According to a preferred embodiment of the present invention, the solution including sodium silicate as a source of silica, a source of alumina, a neutralizer and water has a composition represented by [Na2O] X [AI2O3] Y [ SiO2] 100 [H2O] Z where X is 10 ~ 26, Y is 0.2-5, and Z is 2500 - 4000. The temperature condition in preparing the solution is not particularly limited, but the solution is usually prepared at room temperature.
    [0043] The solution can be prepared in one step or a plurality of steps. If the solution is prepared in one step, the order of mixing the components of the raw material is not particularly limited. Therefore, the raw material components can be mixed in the order of sodium silicate as a source of silica, water, a neutralizer and an alumina source or in the order of a source of alumina, water, a neutralizing cup and sodium silicate as a source of silica.
    [0044] However, in the solution, if the sodium silicate as a source of silica or the source of alumina is present in a state of aqueous gel solution, it greatly influences the synthesis of the uniform and fine ZSM-5. Therefore, it is preferable that the solution is prepared in a plurality of steps, rather than a single step.
    [0045] Therefore, the reaction mixture of the present invention is prepared as follows. First, a source of silica and water is mixed and then stirred for 20 to 40 minutes to form a first aqueous solution. Meanwhile, an alumina source, a neutralizer and water are mixed and then stirred for 15-30 minutes, and then the synthesized nanocrystalline ZSM-5 seed is added to form a second aqueous solution. Subsequently, the first aqueous solution and the second aqueous solution are mixed with each other to prepare the reaction mixture. In this case, when the molar ratio between H2O / SiO2 in the reaction mixture is less than 25, water can still be added as a balance component, selectively.
    [0046] According to a preferred embodiment of the present invention, the hydrothermal crystallization of the reaction mixture can be carried out at a temperature of 150 ~ 200 ° C for 12 ~ 48 hours, preferably 18 ~ 30 hours. Therefore, in the present invention, the time required to synthesize the ZSM-5 can be greatly reduced compared to conventional technologies.
    [0047] In the preparation of ZSM-5, when hydrothermal synthesis is performed using only the reaction mixture without adding the nanocrystalline ZSM-5 seeds, mordenite, as well as ZSM-5, are obtained simultaneously.
    [0048] However, when hydrothermal synthesis is performed using the reaction mixture including the seeds of nanocrystalline ZSM-5, only pure ZSM-5 with a uniform particle size is obtained. In addition, due to the addition of the nanocrystalline ZSM-5 seeds, ZSM-5 with high crystallinity can be obtained even without the addition of sulfuric acid, and the ZSM-5 crystal obtained is fine and uniform.
    [0049] The post-treatment of the obtained ZSM-5, not including impurities is performed as shown in FIG. 2. That is, the. Crystallized ZSM-5 is filtered and washed, and then dried at a temperature of 100 to 120 ° C for 10 to 15 hours. Subsequently, the dried ZSM-5 is ionically exchanged with NH4NO3 and then calcined at a temperature of 500 to 600 ° C for 5 to 8 hours to obtain a final product.
    The ZSM-5 synthesized according to the present invention has a narrow particle size distribution such that its average particle size is controlled within the range of 0.2 to 2.0 / pm.
    [0051] Meanwhile, the phase and relative crystallinity of the product obtained by the method described above can be calculated by collecting data of 2θ 7 ~ 9 0 and 22 ~ 25 0 corresponding to the characteristic peaks of ZSM-5, using ray diffraction -X (DRX) of the analyzer (for example, Model Rigaku D / Max III).
    [0052] The shape of the product can be observed by a scanning electron microscope (SEM) (for example, Akasi Alpha 25A), and its crystal size distribution can be measured by a particle size distribution analyzer ( PSD) (for example, ELS-Z2, Otsuka). Mode for invention
    [0053] Hereinafter, the present invention will be described in more detail with reference to the following examples. However, these examples are presented to illustrate the present invention, the scope of the present invention is not limited to them. Examples
    [0054] Preparation Examples 1 and 2: Synthesis of nanocrystalline ZSM-5 seeds 13, 6 g (Preparation Example 1) or 36.1 g (Preparation Example 2) of TPAOH serving as an organic structure induction material which was mixed with 0.1 g (Preparation Example 1) or 0.4 g (Preparation Example 2) of aluminum isopropoxide serving as a source alumina, and then the mixture was stirred uniformly for 30 minutes. After that, 13.6 g (Preparation Example 1) or 36.0 g (Preparation Example 2) of TEOS and 72.7 g (Preparation Example 1) or 27.5 g (Preparation Example 2) of water distilled mixture was added to the stirred mixture, and then it was stirred for 2 hours to form a reaction mixture.
    [0055] Subsequently, the reaction mixture was placed in a microwave synthesis reactor (manufactured by CEM Corp.), and then it was irradiated with microwave at 80 ° C for 90 minutes in the first step and then irradiated with microwave at 130 ° C for 180 minutes in the second step to synthesize a nanocrystalline ZSM-5 seed. After that, XRD analysis and SEM analysis of the samples obtained by centrifugation of solution separation, including the synthesized seed of ZSM-5 nanocrystalline were conducted. The results of it are shown in Table 1 and FIG. 3. Table 1
    Comparative Examples 1 to 3: Synthesis of ZSM-5 without the use of nanocrystalline ZSM-5 seed
    [0056] 26.1 g of sodium silicate which serves as a source of silica was mixed with 33.4 g of distilled water, and then stirred for 30 minutes to provide solution 1. In addition, 3.1 g of salt of aluminum, 4.0 g (Comparative Example 1), 3.2 g (Comparative Example 2) or 2.2 g (Comparative Example 3) of sulfuric acid, and 33.3 g of distilled water were mixed and then , stirred for 30 minutes to provide solution 2. Subsequently, solution 1 and solution 2 were mixed together, stirred, placed in a teflon vessel, hydrothermally synthesized at 170 ° C for 24 hours and then cooled to room temperature to obtain a synthesized solution. Subsequently, the synthesized solution was dried at 120 ° C for 12 hours, and then X-ray diffraction (DRX) analysis and scanning electron microscope (SEM) analysis of the synthesized dry solution was conducted. The results of it are shown in Table 1, FIG. 2 and FIGs. 4A and 4B. Comparative Examples 4 to 7: Synthesis of ZSM-5, using ZSM-5 nanocrystalline seed from Preparation Example 1
    [0057] 25.8 g of sodium silicate serving as a source of silica were mixed with 33.2 g of distilled water, and then stirred for 30 minutes to provide a solution 1. In addition, 3.1 g of sodium sulfate aluminum, 4.0 g (Comparative Example 4), 3.0 g (Comparative Example 5), 2.0 g (Comparative Example 6) or 1.1 g (Comparative Example 7) of sulfuric acid, and 33.2 g distilled water was mixed and then stirred for 20 minutes and then 0.7 g of the ZSM-5 nanocrist a1 seed synthesized in Preparation Example 1 was added to it and then stirred for 20 minutes to provide solution 2. Subsequently, solution 1 and solution 2 were mixed with each other, stirred, placed in a teflon vessel, hydrothermally synthesized at 170 ° C for 24 hours and then cooled to room temperature to obtain a synthesized solution. Subsequently, the synthesized solution was dried at 120 ° C for 12 hours, and then X-ray diffraction analysis (XRD) and scanning electron microscope (SEM) analysis of the synthesized dry solution were conducted. The results of it are shown in Table 1, FIG. 2 and FIGs. 5A and 5B. Examples 1 to 4: Synthesis of ZSM-5, using ZSM-5 nanocrystalline seed from Preparation Example 2
    [0058] 25.8 g of sodium silicate serving as a source of silica was mixed with 33.2 g of distilled water, and then it was stirred for 30 minutes to provide solution 1. In addition, 3.1 g of sulfate aluminum, 4.0 g (Example 1), 3.0 g (Example 2), 2.0 g (Example 3) or 1.1 g (Example 4) of sulfuric acid, and 33.2 g of distilled water were mixed and then stirred for 20 minutes, then 0.7 g of the ZSM-5 nanocrystalline seed synthesized in Preparation Example 2 was added and then stirred for 20 minutes to provide solution 2 .
    [0059] Subsequently, solution 1 and solution 2 were mixed together, stirred, placed in a teflon vessel, hydrothermally synthesized at 170 ° C for 24 hours and then cooled to room temperature to obtain a synthesized solution. Subsequently, the synthesized solution was dried at 120 ° C for 12 hours, and then X-ray diffraction (DRX) analysis and scanning electron microscope (SEM) analysis of the synthesized dry solution was conducted. The results of it are shown in Table 1, Figure 2 and Figures 6A and 6B. Examples 5 and 6: Synthesis of ZSM-5, depending on the added amount of ZSM-5 nanocrystalline seed
    [0060] 25.6 g of glass water that serves as the silica source was mixed with 33.9 g of distilled water, and then stirred for 30 minutes to provide solution 1. In addition, 3.2 g (Example 5) or 3.1 g (Example 6) of aluminum salt, 1.9 g of sulfuric acid, and 33.9 g of distilled water were mixed and then stirred for 20 minutes, then 1.4 g (Example 5) or 2.9 g (Example 6) of ZSM-5 nanocrystalline seed synthesized in the Preparation Examples were added to it and then stirred for 20 minutes to provide solution 2.
    [0061] Subsequently, solution 1 and solution 2 were mixed together, stirred, placed in a teflon vessel, hydrothermally synthesized at 170 ° C for 24 hours and then cooled to room temperature to obtain a synthesized solution. Subsequently, the synthesized solution was dried at 120 ° C for 12 hours and then X-ray diffraction analysis (XRD) and scanning electron microscope (SEM) analysis of the synthesized dry solution were conducted. The results of it are shown in Table 1, figure 2 and Figures 7A and 7B. Table 2

    [0062] As shown in Table 2, it can be seen that the stability of the ZSM-5 obtained was improved and its size was uniform because the seed of ZSM-5 nanocrystalline was used to synthesize the ZSM-5. According to the effect attributable to the addition of nanocrystalline ZSM-5 seeds, when nanocrystalline ZSM-5 seeds that have a particle size of 20 ~ 60 nm were used, ZSM-5 was obtained over a wide range , but the ZSM-5 obtained had a low crystallinity and a wide particle size distribution.
    [0063] However, when the seed of ZSM-5 nanocrystalline which has a particle size of 70 ~ 150 nm was used, the ZSM-5 with high crystallinity can be synthesized in a greater range compared to when the seed of ZSM- 5 nanocrystalline having a particle size of 20 ~ 60 nm was used, and high quality ZSM-5 can be obtained with fine and uniform crystals. In addition, as seen from the results of Examples 3, 5 and 6, finer ZSM-5 can be obtained by increasing the amount of seed added with nanocrystalline ZSM-5, although the compositions of the reaction mixtures are the same. Leqenda das Figuras Figure 1 Tl) (1) TPAOH + AIP T2) (2) TEOS + H2O T3) Mixture: (1) + (2) T4) Hydrothermal crystallization in a microwave oven Figure 2 T5) (1) Sodium silicate + H2O T6) (2) Aluminum salt + H2SO2 + H2O + (Salt) T7) Mixture (1) + (2) T8) Hydrothermal crystallization at 170 ° C, 200 rpm in T9 convection oven) Filtration and washing T10) Drying at 120 ° C for 12 hours T11) Tonic exchange with NH4NO2 T12) Calcination at 550 ° C for 6 hours.
    权利要求:
    Claims (4)
    [0001]
    1. "ZSM-5 PREPARATION METHOD", characterized by comprising: providing a nanocrystalline ZSM-5 seed, having an average size of 70 to 150 nm, as measured by SEM, from a material including an organic structure, a source of silica, a source of alumina and water; preparing a solution, including sodium silicate as a source of silica, a source of alumina, a neutralizer and water by stirring; adding the nanocrystalline ZSM-5 seed to the solution to form a reaction mixture; the nanocrystalline ZSM-5 seed is included in an amount of 0.1 to 6% by weight based on the reaction mixture; and maintaining the reaction mixture at 150 to 200 ° C to crystallize the reaction mixture; where the neutralizer is a material added to overcome the difficulty of controlling the composition of the solution, being a material added to reduce the alkali of the solution which is induced by the silica source and the alumina source "; and the ZSM-5 seed has a relative crystallinity of 100% or more, as measured by equation (1) :( 1) ACZeo - Z NO3O (SiO2 / A12O3 molar ratio = 30); the solution has a composition represented by [Na2Ü] X [AI2O3] Y [SiO2] 100 [H2O] Z, where X is 10 to 26 (moles), Y is 0.2 to 5 (moles) and Z is 2500 to 4000 (moles).
    [0002]
    2. "METHOD OF PREPARING ZSM-5", according to claim 1, characterized in that the alumina source is one or more selected (s) of sodium aluminate, aluminum nitrate, aluminum chloride, aluminum acetate, sulfate of aluminum, aluminum isopropoxide and aluminum acetylacetonate.
    [0003]
    3. "METHOD OF PREPARING ZSM-5", according to claim 1, characterized in that the neutralizer is any one selected from hydrochloric acid, nitric acid, phosphoric acid and sulfuric acid.
    [0004]
    4. "ZSM-5 PREPARATION METHOD", according to claim 1, characterized by the crystallization of the reaction mixture to be carried out from 12 to 72 hours.
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    同族专利:
    公开号 | 公开日
    CA2778370C|2017-04-25|
    EP2490985A2|2012-08-29|
    BR112012009397A2|2016-06-14|
    WO2011049333A2|2011-04-28|
    TW201114685A|2011-05-01|
    CA2778370A1|2011-04-28|
    TWI490167B|2015-07-01|
    US8840864B2|2014-09-23|
    RU2012115971A|2013-11-27|
    KR101614544B1|2016-04-22|
    KR20110042740A|2011-04-27|
    US20120230910A1|2012-09-13|
    EP2490985A4|2013-06-26|
    JP2013508253A|2013-03-07|
    JP5689890B2|2015-03-25|
    EP2490985B1|2018-12-05|
    RU2540550C2|2015-02-10|
    CN102666385A|2012-09-12|
    WO2011049333A3|2011-08-25|
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    法律状态:
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    优先权:
    申请号 | 申请日 | 专利标题
    KR1020090099550A|KR101614544B1|2009-10-20|2009-10-20|Method of Preparation Using Crystalline Nano-sized Seed|
    KR10-2009-0099550|2009-10-20|
    PCT/KR2010/007116|WO2011049333A2|2009-10-20|2010-10-18|Method of preparing zsm-5 zeolite using nanocrystalline zsm-5 seeds|
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