KR101400356B1 - Manufacturing Method of Inorganic Membrane Filter For Selective Separation of Liquid and Gas By Ion Exchange Method - Google Patents

Abstract

The present invention relates to a method for manufacturing a semiconductor device, comprising: a first step of coating a gamma type alumina or silica having a large specific surface area as an intermediate material on a ceramic substrate made of an inorganic material;
A second step of coating NaA-type zeolite having a pore size of 4 Å on the gamma-type alumina or silica surface coated in the first step;
The NaA-type zeolite having a pore size of 4 angstroms coated in the second step process is ion-exchanged with salts of a metal having a larger or smaller radius of an atom than that of sodium, A third step;
A fourth step of washing with a solvent to remove impurities other than the ion-exchanged metal in the third step; And
And a fifth step of drying in order to remove the solvent used in the fourth step. The present invention also relates to a method for producing an inorganic film for selective separation of liquid and gas by an ion exchange method.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an inorganic membrane for selective separation of liquid and gas by an ion exchange method,

The present invention relates to a method for preparing inorganic membranes for selective separation of liquids and gases by ion exchange, and more particularly, to a method for producing inorganic membranes by a method of preparing a zeolite having a pore size of 4 Å by coating NaA zeolite on a ceramic substrate, Ion exchange with a salt of metal which is larger or smaller than the atomic radius of Na is possible to provide the function of the catalyst by the ion-exchanged metal, and the pore size of the inorganic membrane can be varied The present invention relates to a method for preparing inorganic membranes for selective separation of liquid and gas by an ion exchange method which can be selectively separated according to the size of a kinetic diameter of liquid and gas molecules.

In the 1980s, natural disasters around the world increased due to abnormal weather, and the debate about global warming became fierce. GHGs, known as the main contributors to global warming, are CO 2 (CO 2), methane (CH 4), nitrous oxide (N 2 O), hydrogen fluoride (HFCs), perfluorocarbons Conference of the parties. Of these, about 80% of the total greenhouse gas emissions are carbon dioxide. Climate change is inevitable because carbon dioxide remains in the atmosphere for about 50 to 200 years, even if the greenhouse gas concentration is maintained at the current level.

The greenhouse gases of methane gas generated during the digestion process of carbon dioxide and fertilizer, rice paddies, garbage, and herbivores generated by the use of fossil fuels can not radiate radiant heat from the surface of the earth which receives heat energy from the sun, The result is a rapid change of the future climate change, which can lead to the earth 's weather changes that can be worst for human society and natural ecosystem.

The most fundamental solution to prevent global warming is to develop alternative energy and new energy that does not generate carbon dioxide, and it is necessary to develop new and existing greenhouse gases in the atmosphere through immobilization technology and reforming It may be most desirable to produce the useful gas produced by the reforming reaction and to use it as a useful starting material for thermal energy and industrial products using highly concentrated individual gases separated by separation techniques, The need for hydrogen is on the rise in demand for hydrogen in the next few years due to the chemical industry and household heating and the demand for clean fuels in automobiles. Hydrogen produced by fossil fuels over the next decade is a chemical process Not only does it create products with superior derivatives, It is expected to be made by the reforming reaction of fossil fuels.

The separation membrane refers to a film in the form of a film capable of selectively separating a target gas or liquid to be separated. A film is a phase in which the total resistance of all transfer phenomena is concentrated, and the resistance is selectively different depending on the material. Therefore, depending on the material, the rate of movement through the membrane is different, which leads to the separation of the material.

The importance of Carbon Capture and Sequestration (CCS) technology to recover carbon dioxide, which is the main cause of global warming, is growing. For this reason, membrane manufacturing and process technologies have been extensively used in a wide range of applications ranging from simple laboratory scale to large-scale fixation in the industrial sector, depending on the social needs such as manufacturing of high purity, highly functional materials and protection of the global environment.

Since the membrane separation process is a physical and mechanical separation operation that does not require a phase change unlike a distillation process in which vaporization and condensation are repeated, the energy is reduced to about 70 to 80% or more as compared with the standard energy consumption type process It is reported that it can save. In addition, since the separation principle and process are relatively simple, the configuration and installation of the apparatus are simple and the space occupied by the apparatus is also small.

This membrane separation technology is based on the technology of membrane synthesis that develops high-tech membrane materials, membrane forming technology that makes membrane membranes easy to handle by assembling each membrane, membrane fouling resistance inevitably occurs in the vicinity of membranes due to filtration separation characteristics There are complex application technologies consisting of physics, chemistry, biology and fluid mechanics to minimize and large-scale process system design and operation. As the membrane separation technology is developed, the energy-saving separation process is needed, and the social need for clean environment process technology such as free circulation is increased, the membrane separation process is being carried out from petrochemical, waste treatment, domestic water purifier, It is extensively applied to the field of recovery and purification of foods, medicines, bio-related compounds, and gas separation including hydrogen and oxygen.

Membrane materials vary widely, but can be broadly divided into biomembranes and synthetic membranes. Biological membrane means a membrane existing in a living body, and the name of a living body part such as a cornea or a bladder membrane in a human eye is attached, and these are collectively referred to as a biomembrane. However, since the biomembrane is difficult to obtain in large quantities and it is difficult to modularize it, industrially almost all synthetic membranes are used.

The synthetic membrane can be divided into an organic membrane and an inorganic membrane. The organic membrane is mostly made of a polymer and is called a polymeric membrane. The inorganic membrane is made of ceramics, glass, and a metal material.

The principle of the gas separation membrane in the membrane is that the separation of the gas using the separation membrane proceeds according to the selective gas permeation principle for the separation membrane. When the gas mixture contacts the membrane surface, the gas component dissolves and diffuses into the membrane In this case, the solubility and permeability of each gas component are different depending on the separation foil material.

Polysulfones, which are polymeric materials, are used as general commercialization membrane materials. Polysulfone polymer materials are a basic reason for separating the mixed gas using the polymer membrane depending on the relative permeation rate to the gas. In the case of oxygen and nitrogen which occupies most of the air, the permeation rate of oxygen is faster than that of nitrogen, so that nitrogen can be separated and concentrated. Also, the performance of the gas permeation membrane, However, since the separator of the polymer material is composed of organic materials, the durability, the heat resistance, and the chemical stability are insufficient, which is applied only to the limited selective permeation separation. .

Therefore, among many porous ceramic materials having various structures, a ceramic thin film having a pore size of nano or less can be applied not only as a membrane for gas separation selectively permeating a desired molecule according to its size, but also as a material for heat resistance, Mechanical properties are superior to those of organic polymer membranes. Therefore, it is necessary to develop gas separation membranes of various inorganic materials for selective permeation in a corrosive atmosphere of high temperature and high pressure.

The prior art of the gas separation type inorganic membrane that has been studied and developed in connection with the present invention will now be described.

Korean Patent Laid-Open Publication No. 2008-0099632 discloses a method for producing a high-performance silicon carbide microtube having controlled pore size and porosity on the wall surface. In the cited invention, the fibers derived from the polycarbosilane are partially cured A hollow fiber is produced by dissolving and removing an unhardened portion, and a heat treatment is performed on the hollow fiber to manufacture a porous silicon carbide microtube having controlled pore size and porosity of the wall surface. A step of forming a large gamma type alumina or silica having a specific surface area between the ceramic support and the zeolite as a support without limiting the material of the inorganic film as a support, A step of coating a zeolite of NaA type having (Na) type zeolite having a pore size of 4 angstroms and then ion exchanged with salts of metal which is larger or smaller than the atomic radius of sodium (Na), provides not only the function of the catalyst but also the pore size of the inorganic membrane It can be seen that the composition of the separating zeolite, which can be selectively separated depending on the size of the kinetic diameter of the liquid and gas molecules, is completely different from that of the inorganic membrane production method.

U.S. Patent No. 8030399 discloses a crosslinked organic-inorganic hybrid membrane and a method for separating gas using the same. In the cited invention, similar to the present invention, the technical idea for gas separation is similar, but polyethylene oxide and cellulose acetate , And is crosslinked by a sol-gel reaction with a polymer composed of polyethylene oxide and organic silica under an acid catalyst. In the present invention, however, it is solely composed of an inorganic substance and the size of various pores Is completely different from the method of producing the inorganic film having the above-mentioned structure.

U.S. Patent No. 7,998,247 discloses a gas separation membrane composed of a layer coated with an inorganic oxide and a gas-selective material. In the cited invention, a hydrogen permeable material is used as an egg shell catalyst composed of a precious metal on the substrate, In this case, NaA zeolite is coated on a substrate made of ceramic to provide a zeolite having a pore size of 4 Å, and then ion exchange with a metal salt which is larger or smaller than the atomic radius of sodium results in ion- It can be seen that the inorganic film having various pore sizes is constituted and completely different from the present invention and the technical construction which can be selectively separated according to the size of the kinetic diameter of liquid and gas molecules have.

U.S. Patent No. 7938894 discloses a hybrid type organic-inorganic gas separation membrane. In the present invention, a chemical vapor deposition method is used to provide an organic-inorganic membrane on a porous alumina substrate. In the present invention, however, Type alumina or silica having a specific surface area between the ceramic support and the zeolite as the final inorganic separator, and a step of coating a NaA-type zeolite having pores of 4 Å coated on the substrate surface of the ceramic substrate with a coating And a method of manufacturing an inorganic film having various pore sizes through an ion exchange process by a metal salt which is larger or smaller than the atomic radius of sodium in a NaA type zeolite having pores of 4 Å coated on the substrate surface, And the technical configuration of the second embodiment is completely different from that of the second embodiment.

In this paper, we investigate the effect of cross-linking of side-by-side molecules between the substrate and neighboring microcrystals to form a covalent bond between the microcrystals of zeolite. In the present invention, in order to connect microcrystals of zeolite-A on a substrate for an inorganic film, an aminopropyl group or terephthaldicarboxaldehyde or 1,4- diisocyanatobutane to increase the bonding force between the ceramic substrate and the monolayer of zeolite by crosslinking. On the other hand, in the present invention, the ratio of the ratio between the ceramic support and the zeolite, which is the final inorganic separator, A step of forming a large-gamma-type alumina or silica having a surface area, A step of coating NaA type zeolite having a pore size of 4 Å coated on the substrate surface and a step of ion exchange process of NaA type zeolite having a pore size of 4 Å coated on the substrate surface with a metal salt having a size smaller than or smaller than the atomic radius of sodium The present invention proposes a method for producing an inorganic membrane having various pore sizes while providing the function of a catalyst, and thus the technical structure of the inorganic film can be completely different from that of a cited study.

The zeolite membranes can achieve gas separation under stable operation with membrane reactors and chemical detectors in XIAOBO CHEN, WEISHEN YANG, JIE LIU, XIAOCHUN XU, AISHENG HUANG, LIWU LIN, JOURNAL OF MATERIALS SCIENCE LETTERS 21, 2002, 1023-1025 Due to the potential for the reaction / separation device to be combined, it has been actively researched and proposed a method for providing a membrane of a zeolite having excellent components and performance for a zeolite membrane, , A surface modification of the substrate using an alpha type alumina substrate with a pore radius of 0.3 to 0.5 탆, a thickness of 3 mm, a seeding step for the zeolite crystal nucleus growth of NaA and a grain growth step for synthesis of the zeolite A zeolite-coated zeolite membrane was formed on the alpha-alumina surface, A process of forming large gamma type alumina or silica having a specific surface area between a ceramic support and a zeolite as a final inorganic separation membrane without limiting the material of any inorganic film and a step of forming a 4 Å pore coated on the substrate surface of the ceramic substrate And a step of coating a zeolite having a pore size of 4 Å coated on the substrate surface with an inorganic membrane having various pore sizes through an ion exchange process with a metal salt having a size smaller than or smaller than the atomic radius of sodium As a method of manufacturing, it can be seen that the technical composition is different from the cited study.

As described above, since the gas separation type inorganic films studied and developed so far are composed of a hybrid type inorganic film composed of a single inorganic oxide or organic / inorganic substance on a ceramic substrate, it is possible to provide an inorganic film of fine pores uniformly, There are many difficulties in providing a membrane composed of an inorganic thin film. In addition, in the case of a hybrid type inorganic membrane composed of an oil and an inorganic material, a chemical reaction / gas separation is simultaneously carried out, It is not possible to provide a membrane of a gas separation type as well as a function of a catalyst at the same time due to the characteristic of being very weakened by the heat source. Therefore, there is a problem that the yield of the chemical reaction can not be increased, Among the liquids, the kinematic diameter In order to effectively separate the effective components in the mixed gas or liquid, the pore size of the inorganic membrane is larger than the kinematic diameter of the active ingredient mixed in the mixed gas or liquid, because the kinetic diameter is varied and varied. It is necessary to provide selectivity of various pores. However, in the case of inorganic membranes so far, it is not possible to provide inorganic membranes for simultaneously providing the functions of the catalyst while having various sizes of pores by a simple method as described herein. It is not only very poor but also low in yield.

Korean Patent Laid-Open Publication No. 2008-0099632 U.S. Patent No. 8030399 US Patent No. 7998247 US Patent No. 7938894

 Jin Seon Park, Yun Jo Lee and Kyung Byung Yoon, JACS comunications, Published on Web 01/29/2004.  XIAOBO CHEN, WEISHEN YANG, JIE LIU, XIAOCHUN XU, AISHENG HUANG, LIWU LIN, JOURNAL OF MATERIALS SCIENCE LETTERS 21, 2002, 1023-1025

As described above, the inorganic films of the gas and liquid separation type, which have been studied and developed so far, are composed of a hybrid type inorganic film composed of a single inorganic oxide or an organic / inorganic substance on a ceramic substrate, In addition to the difficulty in providing a membrane composed of an inorganic thin film having excellent bonding strength, in the case of a membrane of a mineral-inorganic composite membrane, in a field where a high temperature is required as the chemical reaction / gas separation proceeds at the same time, It is impossible to provide a gas and a liquid separating type membrane according to the characteristic of being very weakened by a heat source. Particularly, the inorganic films of the conventional gas and liquid separation type are simply formed of a gas or a liquid mobile phase suited to the pore size constituting the inorganic film Because of the separation function, the production of chemical reactions Catalytic role for the improvement was the problem can not be provided at all. SUMMARY OF THE INVENTION The present invention has been made to solve the problems of the prior art,

After the NaA type zeolite is formed on the ceramic upper layer, the pore size of the inorganic membrane is variously changed depending on the ion exchange with a metal having a larger or smaller radius of the atom than that of sodium to provide various pore sizes of the zeolite. And the kinetic diameter of the gas molecules. In addition, it is possible to simultaneously provide the separation and the catalytic reaction by providing the function of the catalyst, and at the same time, the efficiency of selective separation of gas and liquid And a method for producing an inorganic film for selective separation of liquid and gas by an ion exchange method capable of maximizing productivity improvement.

In order to achieve the above object,

The present invention relates to a method for manufacturing a semiconductor device, comprising: a first step of coating a gamma type alumina or silica having a large specific surface area as an intermediate material on a ceramic substrate made of an inorganic material; A second step of coating NaA-type zeolite having a pore size of 4 Å on the gamma-type alumina or silica surface coated in the first step; The NaA type zeolite having a pore size of 4 angstroms coated in the second step process is ion-exchanged with salts of a metal having a larger or smaller radius of an atom than that of sodium, so that the zeolite functions as a catalyst, A third step of varying the pore size of the zeolite; A fourth step of washing with a solvent to remove impurities other than the ion-exchanged metal in the third step; And a fifth step of drying in order to remove the solvent used in the fourth step. The present invention also provides a method for producing an inorganic film for selective separation of liquid and gas by an ion exchange method.

The present invention also provides an inorganic membrane for selective separation of liquid and gas by the ion exchange method, which is produced by the above-described production method.

The inorganic film for selective separation of liquid and gas by the ion exchange method according to the present invention is formed by coating a NaA type zeolite on the upper layer of a ceramic substrate having excellent heat resistance and then performing ion exchange with a metal having an atomic radius larger or smaller than sodium atom, Thereby providing an inorganic film capable of selectively separating the liquid and the gas. Therefore, it is possible not only to provide a high yield in the liquid phase and gas phase reaction, but also to carry out a chemical reaction / gas separation simultaneously with gas and liquid separation type inorganic films having selective pores by ion exchange, It is possible to completely overcome the problems of conventional polymer membranes which are very vulnerable to heat sources. In addition, since the pore size can be varied to form a heat resistant inorganic film, the pore size can be variously selected to maximize the separation efficiency selectively as well as to be used in various fields where high temperature is required in the long term , And the function of the catalyst can be provided at the same time.

Figure 1 is an electron micrograph of an untreated alumina substrate.
2 is an electron micrograph of an intermediate coated on a ceramic substrate of the present invention.
3 is an electron micrograph of a zeolite-coated top layer on a ceramic substrate of the present invention.
4 is a flow chart according to one embodiment of the present invention.

Hereinafter, a method for producing an inorganic film for selective separation of liquid and gas by the ion exchange method according to the present invention will be described in detail.

The method for preparing an inorganic film for selective separation of liquid and gas by the ion exchange method according to the present invention comprises the steps of: (a) mixing a gamma type alumina or silica having a large specific surface area as an intermediate material on a ceramic substrate made of an inorganic material; A first step of coating; (b) a second step of coating NaA-type zeolite having a pore size of 4 Å on the gamma-type alumina or silica surface coated in the first step; (c) NaA-type zeolite having a pore size of 4 Å coated in the second step process is ion-exchanged with salts of a metal having a larger or smaller radius of an atom than that of sodium, so that the zeolite functions as a catalyst A third step of varying the pore size of the zeolite; (d) a fourth step of washing with a solvent to remove impurities other than the metal ion-exchanged in the third step; And (e) a fifth step of drying to remove the solvent used in the fourth step.

In order to produce an inorganic film for selective separation of liquid and gas by the ion exchange method,

(a) First, alumina or silica is coated on a ceramic substrate through a first step of coating a gamma type alumina or silica having a large specific surface area as an intermediate material on a ceramic substrate made of an inorganic material.

Since most of the ceramic substrates constituted for the present invention are made of coarse particles, pores are very large and the smoothness of the surface is insufficient, so that a defective NaA type zeolite is formed on the upper layer of the substrate. , An intermediate material is formed on a ceramic substrate, and the intermediate material is coated with alumina or silica having a gamma crystal structure having a large specific surface area. The inorganic material constituting the ceramic substrate is not particularly limited as long as it can be used as a ceramic substrate in the art.

(Γ-Al ₂ O ₃ ) or silica (γ-SiO ₂ ) as an intermediate material on the ceramic substrate, it is preferable to use alumina sol or silica sol manufacturing method A spray coating, a spray coating, a roll coating (roll coating), or the like, which is made of alumina or silica sol having a solids content of 0.25 to 15 wt% coating is applied on the ceramic substrate by a coating method selected from among the coating method, and then the alumina or silica intermediate material having a gamma crystal structure having a large specific surface area is coated on the ceramic substrate by heating in the drying step and the calcination step.

The drying step may be carried out in a temperature range of 15 ° C to 185 ° C by any one of a near-infrared heating method, an infrared heating method, a microwave heating method, an oven heating method, a hot plate direct heating method, Heating method.

The calcination process is a process for providing a bonding force with a ceramic substrate while removing organic substances or organic by-products present in alumina or silica coated portions coated and heated on a ceramic substrate, At a temperature of 30 minutes to 12 hours, alumina or silica having a gamma crystal structure having a large specific surface area is coated on the ceramic substrate, wherein the specific surface area of the alumina or silica is 80 to 250 m ² / g Size.

As the alumina or silica sol solution of the gamma crystal structure, a sol solution of 0.10 wt.% To 15.0 wt.% Of alumina (Al ₂ O ₃ ) or silica (SiO ₂ ) solids may be used, By weight or 10.0% by weight of the sol solution, more preferably from 2.5% by weight to 7.5% by weight of the sol solution, most preferably from 3.5% by weight to 6.0% by weight of the alumina or silica sol solution Can be used. When the content of the alumina or silica is less than 0.10 wt%, the content of alumina or silica is insufficient on the ceramic substrate because the solid content is low, so that the coating process, the drying process, and the calcination process must be performed several times. And when the sol solution containing 15.0 wt% or more of solids is used, the concentration is too high to be chemically unstable and the probability of gelation is high. Therefore, a stable alumina or silica sol It is very difficult to maintain and manage state.

In the present invention, the ceramic substrate may be formed of a material selected from the group consisting of Alumina, Titania, Zirconia, Silica, Silicon carbide, Silicon nitride, Tungsten carbide, Tungsten nitride, zircon, petite, olivine, kaolin, diatomite, wollastonite, pyrophyllite, dolomite, lithium minerals, magnesite, Magnesite, Bauxite, Bentonite, Pumice, Borate, Serpentine, Acid clay, Iron Oxide, Garnet, Carbonate Minerals, Carbonate Minerals, Attapulgite, Sepiolite, Nephrite, Apatite, Illite-Mica, Feldspar, Perlite, Vermiculite, Barite, talc, diatomaceous earth, graphite, In the group consisting of Hectorite, Clay Minerals, Tourmaine, Fume silica, Aerogel, Fly ash and Furnace slag, And may be composed of any one or two or more kinds of ceramic components selected.

The substrate composed of the ceramic of the present invention preferably has a thickness of 0.1 to 10 mm. When the thickness of the substrate is less than 0.1 mm, the thickness of the ceramic is small. Therefore, it is possible that the mixed gas can penetrate without passing a large obstacle when passing through the inorganic film to separate a large amount of gas. However, There is a problem that a large processing cost is required for processing or installing a ceramic substrate for gas separation or a membrane may be broken in a gas separation process. When the thickness of the substrate exceeds 10 mm, the thickness of the ceramic is thick Not only the pressure of the gas is required but also the productivity is low due to a small amount of gas to be separated.

(b) Next, NaA-type zeolite having a pore size of 4 Å is coated on the surface of gamma-type alumina or silica coated in the first step.

In the second step, the silicon dioxide (SiO ₂ ) stoichiometrically stoichiometrically, the aluminum oxide (Al ₂ O ₃ ) corresponding to 1 mole and the sodium oxide corresponding to 5 moles (Na ₂ O); Contacting a slurry solution of amorphous sodium aluminosilicate produced in the mixing step with a gamma-type alumina or silica-coated ceramic substrate having a large specific surface area; And a crystal growth step for growing the amorphous sodium aluminosilicate particles provided on the ceramic substrate by heating the amorphous sodium aluminosilicate at a temperature of 75 to 130 DEG C and a pressure of 30 kg / cm < 2 > or less.

In the mixing step, silicon dioxide (SiO ₂ ) corresponding to two molar equivalents, aluminum oxide (Al ₂ O ₃ ) corresponding to one mole and sodium oxide (Na ₂ O ₃ ) corresponding to 5 mol ₂ O) are mixed to produce a slurry of amorphous sodium aluminosilicate.

Thereafter, the amorphous slurry of sodium aluminosilicate produced in the contacting step is brought into contact with the alumina or silica-coated ceramic substrate coated with the gamma crystal.

In the crystal growing step, the amorphous sodium aluminosilicate is heated to grow particles to produce a 4NaA type zeolite. The crystal growth step crystallizes amorphous sodium aluminosilicate that is in contact with the surface of alumina or silica having a gamma structure having a large specific surface area coated on a ceramic substrate to form sodium (Na) while having pores of 4 angstroms at grain boundaries of the ceramic substrate, And is provided so that other elements are ion-exchanged. The amount of amorphous sodium aluminosilicate in contact with the upper layer of the ceramic substrate of the present invention may be varied depending on the size of the particles, and the reaction time, reaction temperature, and reaction conditions may vary depending on the particle size. kg / cm < ² > or less to grow amorphous particles of sodium aluminosilicate provided on the ceramic substrate. Crystalline zeolite having a pore size of 4 Å is formed through the above-mentioned crystalline clustering step and can be used for separating a liquid or a gas suitable for the pore size. Depending on pores formed by ion exchange of other metal elements, It can be used as an inorganic film capable of simultaneously providing a role of a catalyst as well as a gas separation.

The sodium silicate for producing the amorphous sodium aluminosilicate may be one selected from the group consisting of sodium metasilicate (Na2SiO3), sodium orthosilicate (Na4SiO4), and sodium diacylate (Na2Si2O5) Silicates can be used. More preferably, the sodium silicate may be any one or a mixture of two or more selected from 1 to 4 kinds of liquid sodium silicate of Korean Industrial Standard KSM 1415.

The liquid sodium silicate is preferably used in a molten state or in a state in which the powder is dissolved in water.

The sodium aluminate (NaAlO2) is not particularly limited, but sodium aluminate is preferably used in a molten state or in a state in which the powder is dissolved in water.

(c) The NaA-type zeolite having a pore size of 4 angstroms coated in the second step process is ion-exchanged with salts of a metal having a larger or smaller radius than that of sodium, Function and makes the pore size of the zeolite vary.

By ion-exchanging salts of a metal having a larger or smaller radius of an atom than that of sodium to provide various sizes of pores of the zeolite so as to selectively separate the liquid and the gas, NaA type zeolite having a pore size of 4 Å is contacted with a metal salt having a larger or smaller atomic radius than that of sodium (atomic radius: 186 picom) to be ion-exchanged to be located in the zeolite crystal structure The pores of the zeolite may be larger or different than the size of 4 Å and may be selectively separated by the kinetic diameter of the gas and liquid phase.

The ion exchange is performed by ion-exchanging an aqueous solution in which a molar number of moles of the metal salt is dissolved in an amount larger than the molar number of sodium constituted in the NaA type zeolite structure with NaA type zeolite coated on the upper layer of the ceramic substrate,

The metal salt to be ion-exchanged for this purpose is lithium (Li, atomic radius: 152 picom), magnesium (Mg, atomic radius: 160 picom), aluminum (Al, atomic radius: 143 picom) (Atomic radius: 162 picometers), titanium (Ti, atomic radius: 147 picometers), vanadium (V, atomic radius: 134 picometers), chromium (Cr, atomic radius: 128 picometers), manganese (Mn, atomic radius: 127 picometers), iron (Fe, atomic radii: 126 picometers), cobalt (Atomic radius: 128 picometers), zinc (Zn, atomic radius: 134 picometers), gallium (Ga, atomic radius: 135 picometers) (Sr, atomic radius: 215 picometers), germanium (Ge, atomic radius: 132 picometers), arsenic (As, atomic radius: 119 picometers), selenium (Y, circle) : 180 picometers), zirconium (Zr, atomic radius: 160 picometers), niobium (Nb, atomic radius: 146 picometers), molybdenum (Mo, atomic radius: 139 picometers), technetium (Atomic radius: 144 picometers), cadmium (Cd, atomic radius: 151 picometers), indium (In, atomic radius: 167 picoseconds) (Atomic radius: 140 picometers), barium (Ba, atomic radius: 222 picometers), tungsten (W, atomic radius: 139 picometers) , Gold (Au, atomic radius: 144 picometers), lead (Pb, atomic radius: 175 picometers), bismuth (Bi, atomic radius: 156 picometers), platinum (S) selected from the group consisting of sulfuric acid, nitrate, chloride, fluoride or carboxylate of one or more metals selected from the group It is.

(d) In the fourth step of washing with a solvent to remove impurities other than the ion-exchanged metal in the third step, the fourth step is not particularly limited, and the ion- It is preferable to remove impurities other than the constituent materials constituting the ceramic substrate so as to provide a separable inorganic film of gas and liquid having selective pores while providing a role of a catalyst. For this purpose, it is preferable to wash the water (water) several times by using distilled water as much as possible. In order to improve the workability during the washing process, it is preferable to wash under the underwater condition of the ultrasonic wave.

(e) a fifth step of drying to remove the solvent used in the fourth step, wherein the fifth step is a step of drying a solvent used for removing impurities other than the constituent material constituting the ceramic substrate Infrared heating method, an infrared heating method, a microwave heating method, a hot air heating method by an oven, a hot plate direct heating method, a hot-air heating method at room temperature The solvent present on the ceramic substrate is removed by any one of the heating methods selected from among the above methods.

In particular, the method of heating by microwave has the merit of rapidly removing the water contained in the object at a very high speed because the temperature of the polarized water molecule is increased by the vibration heat of the microwave when the microwave of 2,450 MHz is applied It is advantageous to use a heating method using a microwave (aka microwave) when drying an inorganic film having a relatively large thickness and a large size.

Hereinafter, embodiments of the present invention for realizing the technical idea of the present invention will be described, and the following embodiments are intended to illustrate one application example for implementing the technical idea of the present invention. And it is to be understood that the scope of protection of the present invention should be interpreted equivalently in terms of meaning and concept consistent with the technical idea of the present invention and that various equivalents and modifications may be substituted at the time of the present application .

Example

Example  One

An alumina substrate (thickness: 0.5 mm, φ 47 mm) of an alpha type processed by Ceramic First Co., Ltd. was purchased, and an alumina sol solution of 2.5 wt% of solid content was coated by a spin coating method. The mixture was completely dried and then calcined at a temperature of 550 ° C for 2 hours to prepare an intermediate. The surface of the alumina substrate coated with the intermediate is shown in Fig. Then, 32.9 g of liquid sodium silicate (Watery 3, Eskemec Co., Ltd.) was added to a sodium silicate solution diluted with 100 ml of water and a solution of sodium aluminate 16.4 g of sodium aluminate (NaAlO2), JUNSEI Co., Ltd.) and 24.5 g of sodium hydroxide were mixed while dropwise adding an aqueous solution of sodium aluminate diluted with 100 ml of water, and a solution of the resulting amorphous sodium aluminosilicate slurry The alumina substrate coated with the intermediate was immersed and heat treated at 95 ° C for 24 hours under atmospheric pressure to coat NaA type zeolite on the ceramic substrate. The surface of the alumina substrate coated with zeolite is shown in Fig.

Example  2

(Cu (NO ₃ ) ₂ .3H ₂ O) solution dissolved in 2.5 wt% on the zeolite coating of the NaA type zeolite-coated substrate of Example 1, and then immersed in a solution of 1 The NaA zeolite coated on the alumina substrate was ion-exchanged with copper (Cu) by ion-exchange for a period of time followed by washing and heating steps.

Example  3

(Zn (NO ₃ ) ₂ .3H ₂ O) solution of zinc chloride (ZnCl ₂ .2H ₂ O) dissolved in 2.5 wt% on the zeolite coating of the NaA type zeolite coated substrate of Example 1 And ion-exchanged with zinc (Zn) for 1 hour under the condition of an aqueous solution at 65 캜 for 1 hour, followed by washing and heating to coat the NaA zeolite coated on the alumina substrate.

Example  4

(SnCl ₂ .2H ₂ O) solution dissolved at 2.5 wt% on the zeolite coating of the NaA-type zeolite-coated substrate of Example 1 and subjected to ion-exchange for 1 hour in an aqueous solution at 65 ° C Then, the NaA zeolite coated on the alumina substrate was ion-exchanged with tin (Sn) by performing washing and heating steps.

Example  5

NaA type zeolite was coated on the silicon carbide substrate in the same manner as in Example 1, except that silicon carbide was used as the ceramic substrate, and then the zeolite-coated substrate of the NaA type zeolite- (Pb (NO ₃ ) ₂ ), ion exchanged in an aqueous solution at 65 ° C for 1 hour, and then washed and heated to prepare NaA zeolite coated on the silicon carbide substrate as lead (Pb) Ion exchange.

Example  6

NaA type zeolite was coated on the silicon carbide substrate in the same manner as in Example 1, except that silicon carbide was used as the ceramic substrate, and then the zeolite-coated substrate of the NaA type zeolite- (Y (NO ₃ ) ₃ .6H ₂ O) solution, ion-exchanged in an aqueous solution at 65 ° C for 1 hour, and then subjected to washing and heating steps to remove NaA zeolite coated on the silicon carbide substrate Ion exchanged with yttrium (Y).

Example  7

NaA type zeolite was coated on a zirconia substrate in the same manner as in Example 1, except that zirconia was used as a ceramic substrate. Then, on a zeolite coating of a substrate coated with NaA type zeolite, potassium nitrate (KNO ₃ ) solution, ion-exchanged for 1 hour under an aqueous solution of 65 ° C., and then washed and heated to ion-exchange the NaA zeolite coated on the zirconia substrate with potassium (K).

Example  8

(Co (NO ₃ ) ₂ .6H ₂ O and potassium nitrate (KNO ₃ ) dissolved in 2.5 wt% on the zeolite coating of the NaA type zeolite-coated substrate of Example 1, Ion exchanged for 1 hour under the condition of an aqueous solution at 65 캜 and then subjected to washing and heating steps to ion exchange the NaA zeolite coated on the alumina substrate with potassium (ionic radius: 227 pm) and cobalt (ionic radius: 125 pm) .

Example  9

Cobalt nitrate _{(Co (NO 3) 2 ·} 6H 2 O with potassium nitrate (nitrate, ruthenium, instead of a mixture of _{KNO 3) (Ru (NO)} · (NO 3) 3 and with a mixture of potassium nitrate (KNO ₃₎ Was carried out in the same manner as in Example 8. < tb >< TABLE >

Comparative Example  One

An alumina substrate (thickness: 0.5 mm,? 47 mm) purchased from Ceramic First Co. was used without any treatment. The surface of the alumina substrate of Comparative Example 1 is shown in Fig.

Comparative Example  2

A silicon carbide substrate (thickness: 0.5 mm,? 47 mm) purchased from Ceramic First Co. was used without any treatment.

Comparative Example  3

A zirconia substrate (thickness: 0.5 mm,? 47 mm) purchased from Ceramic First Co. was used without any treatment.

Comparative Example  4

After purchasing an alumina substrate (t: 0.5 mm,? 47 mm) of an alpha type processed by Ceramic First Co., an alumina sol solution of 2.5 wt% of solid content was coated by a spin coating method, Dried and then calcined at a temperature of 550 ° C for 2 hours to coat pure gamma-type alumina sol.

Experimental Example  1: Selectivity for gas separation

The ceramic substrates prepared in Comparative Examples 1 to 3 and Examples 1 to 7 were injected into a thermostatable stainless steel gas separation apparatus and the experimental apparatus was heated to a temperature of 450 ° C. to confirm gas separation selectivity. Were experiments are present in order to check the selectivity for gas separation using the membrane tester as shown in FIG. 4, and 50% helium (He), a 25% hydrogen (H ₂₎ and 25% carbon dioxide (CO ₂₎ gas is The gas mixture was fed to a gas separation apparatus at a flow rate of 50 ml / min. The pressure of the gas separated by the separator was adjusted to atmospheric pressure, and gas chromatography (GC, DONAM INSTRUMENTS INC, Model DS 6200), and the separation selectivity of hydrogen, carbon dioxide and propene gas for gas separation was confirmed by the following Equation 1 to Equation 3 after quantitatively analyzing the gas. Table 1 shows the results.

[Formula 1]

[Formula 2]

[Formula 3]

Separation selectivity of gas (%) H ₂ CO ₂ Propene Example 1 44.5 42.9 12.6 Example 2 34.8 32.8 32.4 Example 3 35.0 33.2 31.8 Example 4 35.2 33.4 31.4 Example 5 35.6 34.8 29.6 Example 6 38.2 37.4 24.4 Example 7 94.2 4.26 1.54 Comparative Example 1 33.3 33.2 33.5 Comparative Example 2 33.3 33.3 33.4 Comparative Example 3 33.4 33.2 33.4

As shown in Table 1, in the case of Comparative Examples 1 to 3 which are substrates of ceramics itself made of alumina, silicon carbide, and zirconia, the ratio of hydrogen, carbon dioxide, and propene gas after mounting in a gas- 1: 1: 1 mixed gas composition, the ceramic substrate itself, which had not been subjected to any treatment, had no gas separation function.

On the contrary, when inorganic films were formed on ceramic substrates regardless of the substrate made of ceramics as in Examples 1 to 7, selectivity by separation was high.

Specifically, in Example 1, NaA-type zeolite has a porosity of 4 angstroms between crystal grain boundaries, so that zeolite having a porosity of 4 angstroms formed inside the ceramics substrate-shaped body of the present invention has a larger dynamic diameter In the case of pentane gas (0.46 nm (4.6 Å) in dynamic diameter), most of the gas was filtered and the selectivity by gas separation was very low. Hydrogen (0.28 Å) 0.36 nm (3.6 Å)), the pore size is smaller than that of 4A-zeolite having 4 Å pores formed on the ceramic substrate.

Also, as in Examples 2 to 6, when metals having a smaller atomic radius than sodium are ion-exchanged, it is possible to provide a porosity higher than that of a NaA-type zeolite having a pore size of 4 angstroms, It was confirmed that it can be selectively separated according to the diameter.

Experimental Example  2: Determination of the role and separability of catalyst

In order to confirm the role of the catalyst in the ion-exchanged substrate and the possibility of separation, the substrate of Example 8 (ion exchange with cobalt and potassium), Example 9 (ion exchange with ruthenium and potassium) and Comparative Example 4 were made of stainless And the mixture is heated to a temperature of 700 ° C, and a mixed gas of carbon dioxide and methane gas is sent to the ion-exchanged substrate. At this time, a synthesis gas containing hydrogen and carbon monoxide, which serves as an intermediate for producing a high-value-added hydrocarbon compound, is produced by the cobalt (Example 8) and ruthenium (Example 9) components. When the synthesis gas is passed through the separation membrane, , And the content of the separated gas was quantitatively analyzed by gas chromatography (GC, DONAM INSTRUMENTS INC, Model DS 6200).

Experimental results in Examples 8 and 9 and Comparative Example 4 show the contents of hydrogen and carbon monoxide produced by a gas mixture of carbon dioxide and methane with the ion-exchanged metal component of the present invention. Table 2 shows the contents of hydrogen and carbon monoxide Separation selectivity is shown in Table 3.

division Conversion rate of the generated gas (%) Carbon monoxide (CO) Hydrogen (H ₂ ) Example 8 98.1 96.4 Example 9 98.4 97.2 Comparative Example 4 0 0

division Separation selectivity of gas (%) Carbon monoxide (CO) Hydrogen (H ₂ ) Example 8 5.70 94.3 Example 9 5.90 94.1 Comparative Example 4 - -

As shown in Table 2, in the case of the substrate coated with the gamma-type alumina sol on the alumina substrate of the alpha type as in Comparative Example 4, no amount of carbon monoxide and hydrogen was produced, whereas in Examples 8 and 9, It can be seen that when the mixed gas of carbon dioxide and methane is passed through the inorganic film of the present invention, the reaction rate of the following reaction formula 1 shows that the formation rate of carbon monoxide and hydrogen is 95% or more, the effect of the catalyst can be sufficiently exhibited .

[Reaction Scheme 1]

In addition, as shown in Table 3, in Comparative Example 4, when the alumina sol was coated on the ceramic substrate, since the carbon monoxide and hydrogen were not present due to the failure to provide a catalyst, separation selectivity of the gas was measured , And in Examples 8 and 9, gas separation selectivity of hydrogen was very high. The selectivity of gas separation of hydrogen of high hydrogen is such that NaA type zeolite having a porosity of 4 Å is ion exchanged with potassium having a larger ion radius than sodium, thereby providing an inorganic film having a pore size of 3 Å provided in the zeolite lattice, It is judged that this is due to the clear separation between hydrogen having a radius of 3 Å or less and carbon monoxide having a Å of 3 Å or more.

Therefore, the inorganic film according to the present invention can provide both the role of the catalyst and the separation at the same time through Examples 8 and 9, which can greatly contribute to the field where the gas and liquid-phase telephone technology and separation technology can be performed at the same time Can be expected.

Claims (11)

(a) a first step of coating gamma-type alumina or silica having a large specific surface area as an intermediate material on a ceramic substrate made of an inorganic material;
(b) a second step of coating NaA-type zeolite having a pore size of 4 Å on the gamma-type alumina or silica surface coated in the first step;
(c) NaA-type zeolite having a pore size of 4 Å coated in the second step process is ion-exchanged with salts of a metal having a larger or smaller radius of an atom than that of sodium, so that the zeolite functions as a catalyst A third step of varying the pore size of the zeolite;
(d) a fourth step of washing with a solvent to remove impurities other than the metal ion-exchanged in the third step; And
(e) a fifth step of drying in order to remove the solvent used in the step (4). The method for producing an inorganic film for selective separation of liquid and gas according to claim 1, The method according to claim 1,
The ceramic substrate may be formed of a material selected from the group consisting of Alumina, Titania, Zirconia, Silica, Silicon carbide, Silicon nitride, Tungsten carbide, Tungsten nitride ), Zircon, olivine, kaolin, diatomite, wollastonite, pyrophyllite, dolomite, lithium minerals, magnesite, bauxite, Bentonite, Pumice, Borate, Serpentine, Acid clay, Iron Oxide, Garnet, Carbonate Minerals, Carbonate Minerals, It is also possible to use other materials such as Attapulgite, Sepiolite, Nephrite, Apatite, Illite-Mica, Feldspar, Perlite, Vermiculite, Barite Talc, diatomaceous earth, graphite, hectorite, One or two selected from the group consisting of Clay Minerals, Tourmaine, Fume silica, Aerogel, Fly ash and Furnace slag. Wherein the inorganic component is composed of at least one kind of ceramic component. The method according to claim 1,
In the first step, an alumina or silica sol solution having a solid content of alumina or silica of 0.10 wt% to 15.0 wt% is coated on a ceramic substrate, and then the ceramic substrate is dried and calcined to form an intermediate Wherein the alumina is coated with a gamma crystal structure having a large specific surface area. The method according to claim 1,
In the second step, the silicon dioxide (SiO ₂ ) stoichiometrically at a pH of 10 or more, the aluminum oxide (Al ₂ O ₃ ) corresponding to 1 mole and the sodium oxide (Na ₂ O) are mixed together;
Contacting a slurry solution of amorphous sodium aluminosilicate produced in the mixing step with a gamma-type alumina or silica-coated ceramic substrate having a large specific surface area; And
And a crystal growth step for growing amorphous sodium aluminosilicate particles provided on the ceramic substrate by heating the amorphous sodium aluminosilicate at a temperature of 75 to 130 DEG C and a pressure of 30 kg / cm < ² > Wherein the inorganic film is formed by the ion exchange method. The method according to claim 1,
In the third step, an aqueous solution in which a molar number of moles of metal is dissolved in an amount greater than the molar number of sodium constituted in the NaA type zeolite structure is ion-exchanged with NaA type zeolite coated on the upper layer of the ceramic substrate,
The metal salt may be at least one selected from the group consisting of Li, Mg, Al, K, Ca, Sc, Ti, V, Cr, (Mn), Fe (Fe), Co, Ni, Cu, Zn, Ga, Ge, As, (Sr), yttrium (Y), zirconium (Zr), niobium (Nb), molybdenum (Mo), technetium (Tc), palladium (Pd), silver (Ag), cadmium ), Tin (Sn), antimony (Sb), barium (Ba), tungsten (W), platinum (Pt), gold (Au), lead (Pb) and bismuth Characterized in that it is a metal salt of at least two kinds of metals selected from the group consisting of sulfates, nitrates, chlorides, fluorides and carboxylates. A method for producing an inorganic film for selective separation of a liquid and a gas. The method according to claim 1,
Wherein the fourth step is a step of washing by immersion, vortexing, or ultrasonic waves under water conditions. The method of claim 3,
The drying step may be carried out in a temperature range of 15 ° C to 185 ° C by any one of a near-infrared heating method, an infrared heating method, a microwave heating method, an oven heating method, a hot plate direct heating method, Wherein the inorganic film is formed by a heating method. The method of claim 3,
Wherein the calcination step is carried out at a temperature of 400 ° C to 850 ° C for 30 minutes to 12 hours. The method of claim 3,
Wherein the alumina has a specific surface area of 80 to 250 m < ² > / g. The method of claim 3,
The alumina sol solution is coated on a ceramic substrate by a coating method selected from spin coating, dip coating, spray coating and roll coating. (EN) METHOD FOR PRODUCING INORGANIC FILM FOR SELECTIVE SEPARATION OF LIQUID AND GAS by ion exchange. An inorganic membrane for selective separation of liquid and gas by the ion exchange method, which is produced by the production method of claim 1.

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