KR101677253B1 - Zeolite core/silica zeolite shell composites, method of prefaring the same and catalystic use the same - Google Patents

Abstract

The present invention relates to a process for preparing a zeolite seed crystal by adding a zeolite seed crystal to a gel solution containing a silicon-source compound , a structure-directing agent and a fluorine anion-source compound, A method of making a zeolite core / silica zeolite shell composite comprising growing a silica zeolite shell, a zeolite core / silica zeolite shell composite prepared by the method, and a zeolite core / silica zeolite shell composite .

Description

ZEOLITE CORE / SILICA ZEOLITE SHELL COMPOSITES, METHOD OF PREPARATION THE SAME, AND CATALYST USE THE SAME Technical Field The present invention relates to a zeolite core / silica zeolite shell composite,

The present invention relates to a zeolite core / silica zeolite shell complex, a process for its preparation and its catalytic use.

Natural or synthetic crystalline microporous molecular sieves have been demonstrated to have catalytic properties for various types of hydrocarbon conversion processes. In addition, crystalline microporous molecular sieves have been used as adsorbents and catalyst supports for various types of hydrocarbon conversion processes and other applications. These molecular sieves are regular porous crystalline materials having a defined crystalline structure as measured by x-ray diffraction, in which there are a number of small cavities and these cavities can be interconnected by smaller channels or pores. The size of these channels or voids is such that they allow adsorption of molecules of a particular size while rejecting large molecules. The interstitial spaces or channels formed by the crystalline network structure can be used as molecular sieves, such as crystalline silicates, aluminosilicates, crystalline silicoaluminophosphates and crystalline aluminophosphates, in the separation process as a molecular sieve and in a wide variety of hydrocarbon conversion processes Catalyst and catalyst support.

Within the pores of the crystalline molecular sieve, the hydrocarbon conversion reactions, such as isomerization of paraffins, isomerization of olefinic skeleton or double bonds, disproportionation, alkylation, and alkylation of aromatic compounds, It is governed by the binding force granted. Product selectivity problems arise when the fraction of feedstock is too large to allow entry into the pore and unreacted, while product selectivity problems arise if some of the product can not leave the channel or subsequently not react. The product distribution may also be altered by the transition state selectivity because a particular reaction can not take place because the reaction transition state is too large to form in the pores. Also, if the size of the molecules is close to the size of the pore system, selectivity problems can also result from structural constraints on diffusion. This non-selective reaction at the molecular sieve surface, for example at the surface acidic site of the molecular sieve, is generally undesirable because this reaction is a form selective binding imparted to the reaction taking place in the channel of the molecular sieve .

Zeolites are crystalline microporous molecular sieves composed of lattice silica coupled with exchangeable cations (e.g., alkali metal or alkaline earth metal ions) and / or optionally alumina. Although the term "zeolite" includes silica and optionally materials containing alumina, it is recognized that some of the silica and alumina may be replaced entirely or partially with different oxides. For example, germanium oxide, titanium oxide, tin oxide, phosphorus oxide, and mixtures thereof may replace portions of silica. Boron oxide, iron oxide, gallium oxide, indium oxide, and mixtures thereof may replace some alumina. Thus, the terms "zeolite", "zeolites" and "zeolite material" as used herein refer to materials that contain silicon atoms and optionally aluminum atoms in its crystal lattice structure, as well as suitable substitution elements for such silicon and aluminum Also included are materials containing, for example, gallosilicates, borosilicates, silicoaluminophosphates (SAPO) and aluminophosphates (ALPO). As used herein, the term "aluminosilicate zeolite" refers to a zeolite material that essentially comprises a silicon atom and an aluminum atom in its crystal lattice structure.

In certain hydrocarbon conversion processes it is sometimes desirable to modify the catalyst used in this process to maximize its performance in a particular hydrocarbon conversion process (e.g., Korean Patent Laid-open No. 10-2002-0010143).

For example, the catalyst used in the hydrocarbon conversion process is sometimes desired to be a multifunctional catalyst, for example a bifunctional catalyst or a bifunctional catalyst. Bifunctional catalysts include two separate catalysts, for example, two zeolites having different composition or structure types to induce individual reactions. The reaction product may be a separate one or two catalysts may be used together so that the reaction product of one catalyst is carried to the catalyst site of the second catalyst and reacted thereon. In addition, one of the advantages of using zeolite catalysts is that the catalysts are shape-selective, and since nonselective reactions at the zeolite surface are generally undesirable, the catalysts used in the hydrocarbon conversion process are not suitable for adsorption of undesirable molecules Has the ability to prevent or at least reduce undesirable reactions that may occur at the surface of a zeolite catalyst by selectively screening molecules in the feed stream based on their size or shape to prevent them from entering the zeolite catalyst bed and reacting with the catalyst Sometimes it is desirable. In addition, the performance of zeolite catalysts can sometimes be maximized when the catalysts selectively select the desired molecule based on its size or shape to prevent the molecules from escaping out of the catalyst bed of the catalyst.

However, when the conventional Al-containing zeolite is used as a catalyst for the hydrocarbon conversion reaction, there is a problem that Al is eluted from the zeolite in the course of the reaction to lower the hydrocarbon reaction, and development of a zeolite structure .

Accordingly, the present invention provides a process for preparing a zeolite seed crystal, comprising the steps of: preparing a gel solution containing a structure-directing agent, a silicon-source compound and a fluorine anion-source compound and a silica zeolite shell having a coherent crystal structure with the zeolite seed crystal ) Of the zeolite core / silica zeolite shell composite.

Also provided is a zeolite core / silica zeolite shell composite prepared by the process according to the present invention and its catalytic use.

However, the problems to be solved by the present invention are not limited to the problems described above, and other problems not described can be clearly understood by those skilled in the art from the following description.

One aspect of the present invention relates to a process for preparing a zeolite seed crystal by adding a zeolite seed crystal to a gel solution containing a structure-directing agent, a silicon-source compound and a fluorine anion-source compound, Silica zeolite shell complexes comprising growing a zeolite core / silica zeolite shell.

Another aspect of the invention is a zeolite core / silica zeolite composite prepared by the process according to the present invention, wherein the crystal structure of the silica zeolite shell is formed to match the crystal structure of the zeolite core. Shell complex.

Another aspect of the present invention is to provide a catalyst comprising the zeolite core / silica zeolite shell complex according to the present invention.

The present invention relates to a silica-zeolite shell having a coherent crystal structure with the zeolite seed crystals using a silicon-source compound , a gel solution containing a structural directing agent and a fluorine anion-source compound, shell zeolite core / silica zeolite shell composite prepared by the above method is used as a catalyst, the conventional Al-containing zeolite is converted into a hydrocarbon conversion , The problem that Al is eluted from the zeolite in the course of the reaction to lower the hydrocarbon reaction can be solved.

1 is a _{TEAOH / (NH 4) 2 SiF} 6 ] In one embodiment of the present (A) showing crystal morphology changes after secondary growth in the gel, and SL (a) and (b) in the TEAOH / (NH ₄ ) ₂ SiF ₆ gel along the three spindles a, (B) showing a plot of the shell thickness of the crystal versus the reaction time.
Figure 2 is a SEM photo of SL determined after TEAOH / (NH _{4) 2} SiF ₆ gel secondary growth in 165 ℃ according to the different response times in one embodiment of the present application.
Figure 3 is a SEM image of SL crystals after secondary growth at 165 ° C using TEAOH / (NH ₄ ) ₂ SiF ₆ gels with different seed concentrations in one embodiment of the invention.
FIG. 4 is a graphical representation of the results of a comparison of (NH ₄ ) ₂ SiF ₆ Of TEAOH / with different amounts of (NH _{4) 2} SiF ₆ is a SEM photograph of the silicalite-1 powder obtained by the secondary growth of the gel (temperature = 150 ℃, reaction was performed for 7 days).
FIG. 5 is a graphical representation of the results of a comparison of (NH ₄ ) ₂ SiF ₆ (Temperature = 165 ° C, reaction for 7 days) of a silicalite-1 powder prepared by secondary growth of a TEAOH / (NH ₄ ) ₂ SiF ₆ gel having a different amount of the silicalite-1 powder.
FIG. 6 is a SEM photograph of SL crystal after secondary growth in TEAOH / (NH ₄ ) ₂ SiF ₆ gel at 150 ° C. using fumed silica as a silica source in one embodiment of the present invention.

Hereinafter, embodiments and examples of the present invention will be described in detail with reference to the accompanying drawings, so that those skilled in the art can easily carry out the present invention.

It should be understood, however, that the present invention may be embodied in many different forms and is not limited to the embodiments and examples described herein. In order to clearly illustrate the present invention, parts not related to the description are omitted, and similar parts are denoted by like reference characters throughout the specification.

Throughout this specification, when an element is referred to as "including " an element, it is understood that the element may include other elements as well, without departing from the other elements unless specifically stated otherwise.

As used herein, the terms "about," " substantially, "and the like are used herein to refer to or approximate the numerical value of manufacturing and material tolerances inherent in the stated sense, Accurate or absolute numbers are used to prevent unauthorized exploitation by unauthorized intruders of the mentioned disclosure. The word " step (or step) "or" step "used to the extent that it is used throughout the specification does not mean" step for.

As used throughout this specification, the term "alkyl ", when not otherwise defined, when used alone or in combination with other terms such as" alkoxy ", "arylalkyl "," alkanolamine ", and "alkoxyamine" Having from about 1 to about 20 carbon atoms, or from about 1 to about 20 carbon atoms, or from about 1 to about 12 carbon atoms, or from about 1 to about 10 carbon atoms, or from about 1 to about 6 carbon atoms Or branched alkyl groups. For example, the alkyl may be methyl, ethyl, propyl, isopropyl, n-butyl, t-butyl, isobutyl, pentyl, hexyl, isohexyl, heptyl, 4-trimethylpentyl, nonyl, decyl, undecyl, dodecyl and isomers thereof, but are not limited thereto.

Throughout this specification, the term "aralkyl ", alone or as part of another group, includes an aromatic ring, i.e., an aryl-substituted alkyl group, linked through an alkyl as described above. By way of non-limiting example, aralkyl is an aralkyl group having from about 1 to about 22 carbon atoms, or from about 1 to about 20 carbon atoms, or from about 1 to about 10 carbon atoms, or from about 1 to about 6 carbon atoms Or an arylalkyl group attached to a linear or branched alkyl group. Examples of such aralkyl include benzyl, phenylethyl, phenylpropyl, phenylbutyl, phenylpentyl, phenylhexyl, biphenylmethyl, biphenylethyl, biphenylpropyl, biphenylbutyl, biphenylpentyl, biphenylhexyl, naphthyl But are not limited thereto.

Throughout this specification, the term "aryl ", alone or as part of another group, refers to a monocyclic or acyclic aromatic ring such as phenyl, substituted phenyl, as well as a fused group such as naphthyl , Phenanthrenyl, indenyl, tetrahydronaphthyl, indanyl, and the like. Thus, an aryl group contains one or more rings having 6 or more atoms, and there may be 5 or fewer rings containing up to 22 atoms, and a double bond between adjacent carbon atoms or suitable heteroatoms may be alternately (Resonance) can exist. The aryl group may be optionally substituted with one or more substituents independently selected from halogen such as F, Br, Cl or I, alkyl such as methyl, ethyl, propyl, alkoxy such as methoxy or ethoxy, hydroxy, carboxy, carbamoyl, alkyloxycarbonyl, Substituted with one or more groups including, but not limited to, methyl, ethyl, hydroxy, trifluoromethyl, amino, cycloalkyl, aryl, heteroaryl, cyano, alkyl S (O) m (m = 0,1,2) .

Throughout this specification, the term " halogen "or" halo " means chlorine, bromine, fluorine or iodine.

One aspect of the present invention relates to a process for preparing a zeolite seed crystal by crystallizing zeolite seed crystals after adding a silicon-source compound, a structure-directing agent and a fluorine anion-source compound to a gel solution, Structure of a zeolite core / silica zeolite shell complex, comprising growing a silica zeolite shell having a structure.

In one embodiment, the fluorine anion source compound is _{HF, NH 4 F, (NH} 4) 2 SiF 6 But are not limited to, those selected from the group including < RTI ID = 0.0 > and combinations thereof. ≪ / RTI >

In one embodiment, the silicon-source compound may include but is not limited to those selected from the group including TEOS, fumed silica, and combinations thereof.

In one embodiment, the gels of the silicon (silicon) contained in the solution-to-source compound: the structure directing agent: the fluoride anion source compounds: water molar ratio is from about 2 to about 5: about 1.5 to about 2.5: about 0.1 To about 1.5: about 50 to about 100, but is not limited thereto.

In one embodiment, the crystal of the silica zeolite shell is characterized in that the growth rate along the c-axis direction of the zeolite seed crystal is faster than the growth rate along the a- and b-axis directions of the zeolite seed crystal Growth may be, but is not limited to.

In one embodiment, the crystal growth rate of the silica zeolite shell may be controlled by the molar ratio of the structure directing agent and the fluorine anion-source compound, but is not limited thereto.

In one embodiment, the crystal growth of the silica zeolite shell may be performed at a temperature of from about 100 ° C to about 250 ° C, but is not limited thereto. For example, the crystal growth of the silica zeolite shell may be performed at a temperature of from about 100 캜 to about 250 캜, or from about 120 캜 to about 250 캜, or from about 140 캜 to about 250 캜, or from about 100 캜 to about 2300 캜, Deg.] C to about 200 [deg.] C, or from about 100 [deg.] C to about 180 [deg.] C, or from about 120 [deg.] C to about 180 [deg.] C, or from about 140 [deg.] C to about 180 [deg.] C.

In one embodiment, the reaction time can be from about 6 hours to about 5 days, but is not limited thereto.

In one embodiment, the seed may be from about 0.1% to about 10%, based on the molar ratio of the silicon source in the gel, but is not limited thereto.

In one embodiment, the zeolite seed crystals may comprise, but are not limited to, zeolites containing Al. For example, the zeolite seed crystals are selected from the group consisting of ZSM-5, beta-zeolite, MFI, BEA, MOR, FER, FAU, LTL, MFS, MTW, OFF, GME, LTA, MAZ, MEI and MEL But are not limited to, silica zeolite shells.

In one embodiment, the silica zeolite shell is selected from the group consisting of silicalite-1 shell, silica BEA shell, silica MOR shell, silica FER shell, silica FAU shell, silica LTL shell, silica MFS shell, silica MTW shell, silica OFF shell, But are not limited to, crystals of zeolite selected from the group consisting of silica GME shells, silica LTA shells, silica MAZ shells, silica MEI shells and silica MEL shells.

In one embodiment, the zeolite core / silica zeolite shell composite comprises ZSM-5 core / silicalite-1 shell, beta-zeolite / silicalite-1 shell, aluminosilicate BEA core / silica BEA shell, aluminosilicate MOR core / silica MOR shell, aluminosilicate FER core / silica FER shell, aluminosilicate FAU core / silica FAU shell, aluminosilicate LTL core / silica LTL shell, aluminosilicate MFS core / silica MFS shell, aluminosilicate MTW core / silica MTW shell, aluminosilicate OFF core / silica OFF shell, aluminosilicate GME core / silica GME shell, aluminosilicate LTA core / silica LTA shell, aluminosilicate MAZ core / silica MAZ shell, MEI core / silica MEI shell, and aluminosilicate MEL core / silica MEL shell. It is to hereinafter, but is not limited to this.

In one embodiment, the structurally-directing agent is one that is commonly used in the art and can be used without any particular limitation. For example, the structurally-directing agent may be an organic structure-directing agent, and generally a compound containing a nitrogen-containing organic cation may be used. In an exemplary embodiment, the structure directing agent may be selected from the group consisting of alkylamines, alkanolamines, alkoxyamines, ammonium salts represented by the following formula (1), and combinations thereof. It is not:

R ₁ to R ₄ independently represent hydrogen, a halogen group element, a C ₁ to C ₂₂ alkyl group or a C ₁ to C ₂₂ alkoxy group, an aralkyl or an aryl group, and R ₁ to R ₄ represent One or more oxygen, nitrogen, sulfur or metal atoms;

X ^- represents a counter anion.

Non-limiting examples of the X ^- mating anion include, but are not limited to, a halide anion, a hydroxide anion, a sulfate anion, an acetate anion, or a carboxylate anion.

In one embodiment, the alkylamine can comprise a primary alkylamine, a secondary alkylamine, or a tertiary alkylamine, wherein the alkyl group comprised in the alkylamine has from about 1 to about 20 carbon atoms, or from about 1 to about 12 But is not limited thereto. In one embodiment, the alkanolamine comprises a primary alkanolamine, a secondary alkanolamine, or a tertiary alkanolamine, wherein the alkoxyamine is selected from the group consisting of a primary alkoxyamine, a secondary alkoxyamine, or a tertiary alkoxyamine But is not limited thereto. In other embodiments, the alkanolamine and the alkyl or alkylene group contained in the alkoxyamine may be a linear or branched alkyl or alkylene group having from about 1 to about 20 carbon atoms, or from about 1 to about 12 carbon atoms, It is not.

Non-limiting examples of such structuring agents include aliphatic or cycloaliphatic amines containing up to 8 carbon atoms, and specific examples include propylamine, isopropylamine, isobutylamine, n-butylamine, Pyridine, 4-methylpiperidine, cyclopentylamine, cyclohexylamine, 1,1,3,3-tetramethyl-butylamine, and cyclopentylamine. For example, diisobutylamine, trimethylamine, diisopropylamine, sec-butylamine, 2,5-dimethylpyrrolidine, 2,6-dimethylpiperidine, and the like, no.

In one embodiment, the structuring agent is selected from the group consisting of tetramethylammonium hydroxide (TMAOH), tetraethylammonium hydroxide (TEAOH), tetrapropylammonium hydroxide (TPAOH), tetrabutylammonium hydroxide (TBAOH ), And combinations thereof. However, the present invention is not limited thereto.

Another aspect of the invention is a zeolite core / silica zeolite shell composite produced by the process according to the present invention, wherein the crystal structure of the silica zeolite shell is formed to match the crystal structure of the zeolite core. Zeolite shell composite.

In one embodiment, the zeolite core / silica zeolite shell composite comprises an aluminosilicate BEA core / silica BEA shell, an aluminosilicate MOR core / silica MOR shell, an aluminosilicate FER core / silica FER shell, an aluminosilicate FAU Alumina silicate LTF core / silica LTL shell, aluminosilicate MFS core / silica MFS shell, aluminosilicate MTW core / silica MTW shell, aluminosilicate OFF core / silica OFF shell, aluminosilicate GME A core / silica GME shell, an aluminosilicate LTA core / silica LTA shell, an aluminosilicate MAZ core / silica MAZ shell, an aluminosilicate MEI core / silica MEI shell, and an aluminosilicate MEL core / silica MEL shell , But is not limited thereto.

Another aspect of the present invention is to provide a catalyst comprising the zeolite core / silica zeolite shell complex according to the present invention.

In one embodiment, the catalyst may additionally comprise a catalytically active metal, but is not limited thereto.

In one embodiment, the catalyst may be used for hydrocarbon conversion reactions, but is not limited thereto.

In one embodiment, the hydrocarbon conversion reaction is carried out in the presence of a hydrocarbon decomposition reaction, an isomerization reaction of an alkylaromatic compound, a disproportionation reaction of toluene, an alkylation reaction of an aromatic compound, an alkylation reaction of an aromatic compound, But are not limited to, reforming, conversion of paraffins and / or olefins into aromatic compounds, decomposition of naphtha into lower olefins, and de-waxing of hydrocarbons.

Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited thereto.

[Example]

_{TEOS, TEAOH, (NH 4)} 2 SiF 6, and the gel was prepared containing the DDW, wherein in said _{gel, TEOS: TEAOH: (NH 4} ) 2 SiF 6: H 2 O molar ratio of 4.00: 1.92: 0.36 : 78.40. The gel was prepared as follows.

(I) Preparation of TEOS / TEAOH solution (solution I)

TEAOH (35% - Alfa aesar, 20.2 g) and DDW (22.2 g) were added sequentially to a plastic beaker containing TEOS (98% - Acros, 31.8 g). The beaker containing the solution was tightly covered with a plastic wrap and stirred magnetically for about 30 minutes until the solution became clear.

(II) TEAOH / (NH ₄ ) ₂ SiF ₆ Preparation of solution (solution II):

TEAOH (35% - Alfa aesar, 10.1 g), (NH 4) 2 SiF 6 (98% - Aldrich, 2.45 g), and DDW (11.1 g) has been injected into a plastic beaker, all the (NH _{4) 2} SiF ₆ Lt; / RTI > until dissolved. The solution II was quickly poured into the solution I under vigorous stirring. The mixture immediately solidified. The solidified mixture was agitated for an additional 2 minutes using a plastic rod and aged under a static atmosphere for 6 hours. After the aging, 0.36 g of MFI powder was added. The semi-solid gel with the MFI seed was pulverized using a food mixer and transferred to a Teflon-connected autoclave. The sealed autoclave was placed in a preheated oven to the desired temperature. After the desired time, the autoclave was removed from the oven and rapidly cooled to room temperature by flowing tap water over them. The solid product was removed from the autoclave and washed with DDW by centrifugation until neutral. The washed solid powder was dried in a conventional oven at 12O < 0 > C for 12 hours. The product was calcined in air at 550 < 0 > C for 20 hours to remove the template.

 The characteristics of the obtained product were analyzed and shown in FIG. 1 to FIG. 6.

1 is a _{TEAOH / (NH 4) 2 SiF} 6 in the embodiment (A) showing the crystal morphology change after the second growth in the gel and SL in the TEAOH / (NH ₄ ) ₂ SiF ₆ gel along the three main axes a, b, and c in the present example (B) showing a plot of the shell thickness of the crystal versus the reaction time.

FIG. 2 is a SEM photograph of SL crystals after secondary growth in TEAOH / (NH ₄ ) ₂ SiF ₆ gel at 165 ° C. according to different reaction times in this example.

Figure 3 is a TEAOH / (NH _{4) 2} SiF ₆ using the gel at 165 ℃ after the second crystal growth SL SEM pictures having different seed concentrations in the present embodiment.

Figure 4 is a SEM photograph showing in _{(NH 4) 2 TEAOH / (} NH 4) The silicalite-1 powder obtained by the secondary growth of ₂ SiF ₆ gel with different amounts of SiF ₆ in the present embodiment (at a temperature of = 150 < 0 > C, 7 days).

5 is in _{(NH 4) 2 TEAOH / (} NH 4) SEM photograph of a silicalite-1 powder obtained by the secondary growth of ₂ SiF ₆ gel with different amounts of SiF ₆ in the embodiment (temperature: 165 [deg.] C for 7 days).

6 is an SEM photograph of SL crystal after secondary growth in TEAOH / (NH ₄ ) ₂ SiF ₆ gel at 150 ° C. using fumed silica as a silica source in this embodiment.

Claims (8)

A zeolite seed crystal is added to a gel solution containing a silicon-source compound, a structure-directing agent and a fluorine anion-source compound, followed by crystallization to form a silica zeolite shell having a coherent crystal structure with the zeolite seed crystal and growing a shell,
The crystal growth rate of the zeolite seed crystal along the c-axis direction grows faster than the growth rate along the a-axis direction and the b-axis direction of the zeolite seed crystal,
The crystal growth rate of the silica zeolite shell is controlled by the molar ratio of the structure directing agent and the fluorine anion-source compound,
Wherein the zeolite seed crystal comprises a zeolite containing Al,
The silicon-source compound contained in the gel solution : Wherein the molar ratio of the structure directing agent: fluorine anion-source compound: water is 2 to 5: 1.5 to 2.5: 0.1 to 1.5: 50 to 100;
Zeolite core / silica zeolite shell composite.
The method according to claim 1,
The fluorine anion source compound is _{HF, NH 4 F, (NH} 4) 2 SiF 6 And combinations thereof. ≪ RTI ID = 0.0 > 11. < / RTI >
The method according to claim 1,
Wherein the crystal growth of the silica zeolite shell is carried out at a temperature of 100 ° C to 250 ° C.
The method according to claim 1,
Wherein the zeolite seed crystals comprise zeolite crystals selected from the group consisting of MFI, BEA, MOR, FER, FAU, LTL, MFS, MTW, OFF, GME, LTA, MAZ, MEI and MEL. Lt; RTI ID = 0.0 > zeolite < / RTI >
The method according to claim 1,
The silica zeolite shell may be selected from the group consisting of silicalite-1 shell, silica BEA shell, silica MOR shell, silica FER shell, silica FAU shell, silica LTL shell, silica MFS shell, silica MTW shell, silica OFF shell, silica GME shell, silica LTA Wherein the silica zeolite shell comprises a silica zeolite shell selected from the group consisting of silica, silica MAZ shell, silica MEI shell, and silica MEL shell.
The method according to claim 1,
The zeolite core / silica zeolite shell composite may be a ZSM-5 core / silicalite-1 shell, an aluminosilicate BEA core / silica BEA shell, an aluminosilicate MOR core / silica MOR shell, an aluminosilicate FER core / silica FER shell , Alumino silicate FAU core / silica FAU shell, aluminosilicate LTL core / silica LTL shell, aluminosilicate MFS core / silica MFS shell, aluminosilicate MTW core / silica MTW shell, aluminosilicate OFF core / silica OFF shell , Alumino silicate GME core / silica GME shell, aluminosilicate LTA core / silica LTA shell, aluminosilicate MAZ core / silica MAZ shell, aluminosilicate MEI core / silica MEI shell, and aluminosilicate MEL core / silica MEL Zeolite core / silica zeolite shell < RTI ID = 0.0 > Method of producing a body.
The method according to claim 1,
Wherein the structure-directing agent comprises a compound selected from the group consisting of an alkylamine, an alkanolamine, an alkoxyamine, an ammonium salt represented by the following formula (1), and a combination thereof:
[Chemical Formula 1]

R ₁ to R ₄ each independently represent hydrogen, a halogen group element, a C ₁ to C ₂₂ alkyl group or a C ₁ to C ₂₂ alkoxy group, an aralkyl or aryl group, and R ₁ to R ₄ represent One or more oxygen, nitrogen, sulfur or metal atoms;
X ^- represents a counter anion.
8. The method of claim 7,
Wherein the alkylamine comprises a primary alkylamine, a secondary alkylamine or a tertiary alkylamine, wherein the alkanolamine comprises a primary alkanolamine, a secondary alkanolamine or a tertiary alkanolamine, wherein the alkoxy Wherein the amine comprises a primary alkoxyamine, a secondary alkoxyamine or a tertiary alkoxyamine, wherein the alkylamine, the alkanolamine and the alkyl or alkylene contained in each of the alkoxyamine are linear or branched having from 1 to 20 carbon atoms, Zeolite core / silica zeolite shell composite.

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