KR101912719B1 - Method for manufacturing alumina membranre modified with y zeolite having mesopores and micropores - Google Patents

Abstract

The present invention relates to a method for manufacturing alumina membranes modified with Y-zeolite having meso-pores and micro-pores. The method for manufacturing alumina membranes modified with Y zeolite having meso-pores and micro-pores includes the steps of: (1) mixing alumina membranes and NH_2 functional group compounds in a solvent at a weight ratio of 1:1 and stirring the mixture to manufacture the alumina membranes modified with NH_2; (2) preparing Y-zeolite sol substances by stirring a pore-forming substance and a precursor solution prepared by mixing Y-zeolite and sodium hydroxide; (3) preparing a synthetic mixture by using the reaction of the Y-zeolite sol substances and the alumina membranes modified with NH_2; (4) hydrothermally synthesizing the synthetic mixture to prepare a porous material; (5) washing the porous material with ethanol and drying the porous material; and (6) firing the porous material after step (5) to remove the pore forming substance. Steps (1) and (2) can be reversed in order while individual steps can be executed simultaneously.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a method for producing an alumina membrane modified with Y zeolite having mesopores and micropores,

The present invention relates to a process for preparing alumina membranes modified with Y zeolites having mesopores and micropores.

Zeolite is a microporous crystalline aluminosilicate having a structure in which a silicon atom and an aluminum atom are coordinated to tetrahedrons through an oxygen atom shared with each other to form a general skeleton. Due to the inherent porosity characteristics of zeolites, wide availability, low cost and high efficiency, they are used in many applications.

The main applications of zeolites are as catalysts in petrochemical cracking, as separation and removal of gases and solvents, and ion-exchange applications in water softening, purification, heavy metal removal and nuclear effluent treatment. This is because exchangeable ions (sodium, calcium and potassium ions) in the zeolite are relatively harmless. Furthermore, other applications are also used for filtration, odor removal and drying in aquaculture, agriculture and animal husbandry. For example, clinoptilolite zeolites (typical natural zeolites) have been extensively studied as ion exchangers and are also used commercially in the treatment of industrial and municipal wastewater to lower the ammonia concentration.

Zeolites are generally microporous materials, but in recent years, mesoporous zeolites have been studied, that is, zeolites having mesopores larger than 2 nm in pore size. The development of such mesoporous zeolite materials has led to the development of molecular sieves for adsorption and separation of molecules with a size larger than the pore size of the microporous material, The application of the material becomes possible.

The present inventors completed the "Method for producing FAU zeolite having both mesopores and micropores (Registration No. 10-1812598)" is the result of such studies.

In order to utilize the FAU zeolite having both mesopores and micropores simultaneously for water treatment, the present inventors completed the present invention after a long period of research and trial and error.

The present invention provides a method for manufacturing an aluminum membrane capable of removing various metals in contaminated water by applying an alumina membrane to water treatment, thereby improving the efficiency of removal.

And more particularly to a method for producing an alumina membrane modified with Y zeolite having mesopores and micropores.

On the other hand, other unspecified purposes of the present invention will be further considered within the scope of the following detailed description and easily deduced from the effects thereof.

(1) mixing an alumina membrane and an NH ₂ functional group compound in a solvent at a weight ratio of 1: 1 and stirring the mixture to prepare an alumina membrane modified with NH ₂ ;

(2) mixing a precursor solution prepared by mixing sodium hydroxide and Y zeolite with each other to produce a Y-zeolite sol;

(3) reacting the NH ₂ modified alumina membrane with the Y zeolite sol to prepare a synthesis mixture;

(4) hydrothermally synthesizing the synthesis mixture to produce a porous material;

(5) washing the porous material with ethanol and drying the porous material; And

The method of any one of claims 1 to 5, wherein the step (5) comprises firing the porous material to remove the pore forming material, wherein the steps (1) and (2) ≪ / RTI >

Mesopores and mesopores of a zeolite-modified alumina membrane.

The solvent in step (1) may be toluene, and the NH ₂ functional group compound may be 3-aminopropyltriethoxysilane.

The alumina membrane and the 3-aminopropyltriethoxysilane can be stirred at 110 ° C for 24 hours.

In the step (3), the alumina membrane modified with NH ₂ may be vertically disposed, and then the reaction solution may be prepared while injecting the Y zeolite sol.

Also provided is an alumina membrane modified with Y zeolite having mesopores and micropores prepared by one of the embodiments of the present invention.

By preparing the alumina membrane modified with Y zeolite having mesopores and micropores according to the present invention, such a membrane can be used as a water treatment adsorbent, thereby greatly improving the diversity of adsorbed materials and the efficiency of adsorption.

The alumina membrane prepared according to the method of producing alumina membrane modified with Y zeolite having mesopores and micropores according to the present invention can greatly improve manganese and iron removal performance.

On the other hand, even if the effects are not explicitly mentioned here, the effect described in the following specification, which is expected by the technical features of the present invention, and its potential effects are treated as described in the specification of the present invention.

BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a diagram of a method for preparing an alumina membrane modified with Y zeolite having mesopores and micropores according to an embodiment of the present invention.
2 is a schematic diagram illustrating the fabrication of an alumina membrane modified with NH ₂ in accordance with one embodiment of the present invention.
3 is a schematic diagram illustrating the preparation of an alumina membrane modified with Y zeolite having mesopores and micropores according to one embodiment of the present invention.
4 is a graph showing the amount of Y zeolite having mesopores and micropores modified on an alumina membrane according to a weight ratio of an alumina membrane and an NH ₂ functional group compound.
5 is a graph showing manganese and iron removal rates of an alumina membrane and an alumina membrane modified with Y zeolite having mesopores and micropores prepared according to an embodiment of the present invention.
It is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Reference will now be made in detail to the embodiments of the present invention, examples of which are illustrated in the accompanying drawings, wherein like reference numerals refer to the like elements throughout.

The terminology used in this application is used only to describe a specific embodiment and is not intended to limit the invention. The singular expressions include plural expressions unless the context clearly dictates otherwise. In the present application, the terms "comprises" or "having" and the like are used to specify that there is a feature, a number, a step, an operation, an element, a component or a combination thereof described in the specification, But do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, or combinations thereof.

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, embodiments of a method for producing an alumina membrane modified with Y zeolite having mesopores and micropores according to the present invention will be described in detail with reference to the accompanying drawings.

The present invention provides a method for producing an alumina membrane capable of improving the treatment efficiency and selective metal removal rate of metals and the like in contaminated water by modifying an alumina membrane.

The alumina membrane produced according to the embodiment of the present invention is treated with Y zeolite on the surface of the alumina membrane. In this case, Y zeolite has zeolite with both fine and mesopores, which makes it very efficient to remove various pollutants.

Zeolite is a crystalline mineral that is rich in silica (the main component of sand) and aluminum, and is regularly pierced by innumerable nanopores that can enter small molecules inside the crystal. There are innumerable catalytic sites on the surface of the nanoporous pores and catalysis when the molecules are reacted. Because of this property, zeolite is the most widely used catalytic material worldwide in gasoline production and various petrochemical industries, and in fact accounts for 40% of the solid catalyst material in the chemical industry as a whole.

If such a zeolite acts as a catalyst for the reaction material, it can be used for removing various pollutants during water treatment if it is equipped with both the micropores and the mesopores.

BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a diagram of a method for preparing an alumina membrane modified with Y zeolite having mesopores and micropores according to an embodiment of the present invention.

Referring to FIG. 1, the method for preparing alumina membrane modified with Y zeolite having mesopores and micropores according to the present invention comprises the steps of modifying an alumina membrane with NH ₂ , preparing a Y zeolite sol containing a pore- Preparing a synthesis mixture by reacting an alumina membrane modified with NH ₂ with a Y zeolite sol, preparing a porous material by hydrothermal synthesis of the synthesis mixture, washing and drying the porous material, removing the pore forming material .

More specifically, (1) mixing an alumina membrane and an NH ₂ functional group compound in a solvent at a weight ratio of 1: 1 and stirring to prepare an alumina membrane modified with NH ₂ ; (2) mixing a precursor solution prepared by mixing sodium hydroxide and Y zeolite with each other to produce a Y-zeolite sol; (3) reacting the NH ₂ modified alumina membrane with the Y zeolite sol to prepare a synthesis mixture; (4) hydrothermally synthesizing the synthesis mixture to produce a porous material; (5) washing the porous material with ethanol and drying the porous material; And firing the porous material having been subjected to the step (5) to remove the pore forming material. The steps (1) and (2) may be reversed in order, and the steps may be changed or the steps may be simultaneously performed.

2 is a schematic diagram illustrating the fabrication of an alumina membrane modified with NH ₂ in accordance with one embodiment of the present invention.

Referring to FIG. 2, an alumina membrane is prepared and modified with an NH ₂ functional group compound. The NH ₂ functional group compound may be 3-aminopropyltriethoxysilane (hereinafter, 3-APTES). The solvent in step (1) may be toluene. That is, the alumina membrane and 3-APTES are mixed with the toluene solvent at a weight ratio of 1: 1.

At this time, the alumina membrane modified with NH ₂ functional groups can be prepared by stirring at 110 ° C and 100 rpm for 24 hours.

The Y zeolite sol is prepared by mixing sodium hydroxide and Y zeolite with each other at a weight ratio of 0.02 to 0.23: 1 to prepare a precursor solution and stirring it with a pore forming material.

Sodium hydroxide dissolves a portion of the pores of the Y zeolite to expand the pore structure. The precursor solution of the Y zeolite formed by enlarging the pore structure and the pore forming material are then stirred and reacted with each other.

The pore-forming material can improve the Y zeolite specific surface area and pore volume characteristics by about 5 times as a surfactant.

The reason why the weight ratio of sodium hydroxide and Y zeolite is set to 0.02 to 0.23: 1 is as follows. If the weight ratio of sodium hydroxide to Y-zeolite is less than 0.02, the destruction of Y-zeolite does not occur sufficiently, so that the synthesis is not properly performed in the subsequent synthesis step. When the weight ratio of sodium hydroxide to Y zeolite is more than 0.23, the Y zeolite structure is completely destroyed by the reaction between sodium hydroxide and Y zeolite, which makes it difficult to produce a material having micropores and mesopores simultaneously.

Therefore, in the present invention, the weight ratio of sodium hydroxide and Y zeolite is set to 0.02 to 0.23: 1, and the production reaction is carried out thereafter.

The precursor solution thus prepared and the pore-forming material are stirred to prepare a Y zeolite sol. The pore forming material may be cetyltrimethyl-ammonium bromide (CTAB). The CTAB is prepared by dissolving in distilled water for 30 minutes at 40 to 60 ° C and then mixing it with the precursor solution.

That is, the preparation of the precursor solution and the dissolution of the pore forming material into the distilled water may be carried out separately or sequentially.

The pore-forming material (CTAB) according to the present invention is characterized in that 0.06 to 0.18 M is used. When the CTAB is less than 0.06 or exceeds 0.18M, the disassembled zeolite unit cell and the CTAB do not recombine, resulting in the eventual meso pore formation.

In the present invention, the weight ratio of the pore forming material to the Y zeolite may be 2.2. If the weight ratio of pore forming material to Y zeolite is less than 2.2, the pore forming material concentration is too low to properly react with Si in the zeolite precursor, and if the pore forming material is too large, the structure of Y zeolite may be destroyed.

The precursor solution and the pore-forming material can be stirred at a speed of 300 rpm at 40 ° C. If the precursor solution and the pore-forming material are stirred at a very high speed, the Y zeolite structure may not be maintained well, and the economical efficiency of the reaction time is lowered at a too slow rate, and the silica dissolved from the Y- Formation of micelles through self-assembly in solution may not be achieved well. Accordingly, the present invention is to stir the precursor solution and the pore-forming material at a speed of 300 rpm.

3 is a schematic diagram illustrating the preparation of an alumina membrane modified with Y zeolite having mesopores and micropores according to one embodiment of the present invention.

Referring to FIG. 3, a synthesis mixture is prepared by reacting an alumina membrane modified with NH ₂ and a Y zeolite sol, followed by hydrothermal synthesis, washing and drying, and removal of pore forming materials. Finally, mesopores and micropores To prepare an alumina membrane modified with Y-zeolite having the above-mentioned structure.

The Y zeolite is formed mainly in the portion modified with NH2 in the alumina membrane. The Y zeolite can be treated on the alumina membrane surface by interaction of particles of Y zeolite containing NH 2 functional group and hydroxyl group (-OH) produced by 3-APTES on alumina membrane surface.

As a result, in order to modify the Y zeolite to an alumina membrane, the modification of NH ₂ should precede the alumina membrane.

Then, the synthesis mixture is hydrothermally synthesized to prepare a porous material, which can be hydrothermally synthesized at 145 ° C for 24 hours. Then, the hydrothermally synthesized porous material is washed with ethanol and dried.

That is, the porous material is washed with distilled water having a temperature of 80 ° C or higher and ethanol, filtered, and then dried at 105 ° C for 24 hours. First, the prepared porous material is filtered through a filtration apparatus, washed with distilled water and ethanol 2-3 times, and then washed again with ethanol.

The porous material is then fired at 550 ° C for 2 hours. And the pore forming material contained in the porous material is removed through the sintering process.

If the calcination temperature is too high, the Y zeolite structure may be destroyed by the structural deformation of Y zeolite itself at a temperature of 550 ° C or higher. If the calcination temperature is too low, the efficiency of the calcination process itself may deteriorate and the desired amount of Y zeolite may not be obtained.

After the step of removing the pore forming material, the alumina membrane modified with Y zeolite having mesopores and micropores shown in FIG. 3 can be obtained.

4 is a graph showing the amount of Y zeolite having mesopores and micropores modified on an alumina membrane according to a weight ratio of an alumina membrane and an NH ₂ functional group compound. That is, it is a photograph of Y zeolite having modified mesopores and micropores observed by scanning electron microscope (EDAX).

4 (a) shows the observation of the alumina membrane modified with Y zeolite by EDAX when the weight ratio of alumina membrane and 3-APTES was 1: 0.5.

As a result of EDAX analysis of the surface of the alumina membrane, the distribution of silicon representing Y zeolite can not be confirmed. That is, when the weight ratio of alumina membrane to 3-APTES is 1: 0.5, the amount of functionalized -NH 2 functional group is very small, so that the amount of zeolite Y to be treated is insufficient.

4 (b) shows the observation of the alumina membrane modified with Y zeolite by EDAX when the weight ratio of alumina membrane and 3-APTES was 1: 1. As a result of EDAX analysis of the surface of the alumina membrane, it can be seen that many silicones representing Y zeolite were formed.

FIG. 4 (c) shows the observation of the alumina membrane modified with Y zeolite by EDAX when the weight ratio of alumina membrane and 3-APTES was 1: 2. The distribution of silicon representing Y zeolite can not be confirmed as in the case of Fig. 4 (a). That is, it can be confirmed that Y zeolite is not treated well due to polymerization of functionalized -NH 2 functional group when the weight ratio of alumina membrane and 3-APTES is 1: 0.5.

It can be seen that when the weight ratio of alumina membrane to 3-APTES is 1: 1, Y zeolite is well treated on the surface of the alumina membrane.

5 is a graph showing manganese and iron removal rates of an alumina membrane and an alumina membrane modified with Y zeolite having mesopores and micropores prepared according to an embodiment of the present invention.

5 (a) shows a comparison of manganese removal rates of alumina membrane modified with Y zeolite having mesopores and micropores and general alumina membrane, and FIG. 5 (b) shows a comparison between manganese removal rates of Y zeolite modified with Y zeolite having mesopores and micropores A comparison of iron removal rates of alumina membrane and general alumina membrane is shown.

As can be seen from FIG. 5, the removal efficiency of manganese and iron of the alumina membrane modified with Y zeolite having mesopores and micropores was significantly improved compared with that of the general alumina membrane.

The scope of protection of the present invention is not limited to the description and the expression of the embodiments explicitly described in the foregoing. It is again to be understood that the scope of protection of the present invention can not be limited by obvious alterations or permutations of the present invention.

Claims (5)

(1) mixing an alumina membrane and an NH ₂ functional group compound in a solvent at a weight ratio of 1: 1 and stirring to prepare an alumina membrane modified with NH ₂ ;
(2) mixing the precursor solution prepared by mixing sodium hydroxide and Y zeolite with each other and the pore-forming material at a speed of 300 rpm at 40 ° C to prepare a Y zeolite sol;
(3) reacting the NH ₂ modified alumina membrane with the Y zeolite sol to prepare a synthesis mixture;
(4) hydrothermally synthesizing the synthetic mixture at 145 ° C for 24 hours to prepare a porous material;
(5) washing the porous material with distilled water and ethanol at 80 ° C or higher, filtering and drying at 105 ° C for 24 hours; And
(2), the porous material having been subjected to the step (5) is fired at 550 ° C for 2 hours to remove the pore forming material, wherein the steps (1) and Or each step can proceed at the same time,
Wherein the solvent in step (1) is toluene, the NH ₂ functional group compound is 3-aminopropyltriethoxysilane,
The alumina membrane and the 3-aminopropyltriethoxysilane were stirred at 110 ° C for 24 hours,
Wherein the step (3) comprises vertically arranging the alumina membrane modified with the NH _2, and then preparing the reaction solution while injecting the Y zeolite sol.
A process for preparing an alumina membrane modified with Y zeolite having mesopores and micropores.
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