JP2006111674A - Coating for forming zeolite membrane, manufacturing method of the zeolite membrane using the coating and the zeolite membrane - Google Patents
Coating for forming zeolite membrane, manufacturing method of the zeolite membrane using the coating and the zeolite membrane Download PDFInfo
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本発明は、水分吸脱着能を向上したゼオライト膜形成用塗料及び該塗料を用いたゼオライト膜の製造方法、ゼオライト膜に関するものである。 The present invention relates to a coating material for forming a zeolite membrane with improved moisture absorption / desorption ability, a method for producing a zeolite membrane using the coating material, and a zeolite membrane.
ゼオライトはその結晶中に空洞を有する多孔質媒体であり、その構造により様々な物質を取り込むことができるため、触媒や吸着剤、イオン交換剤、調湿剤として広く実用化されている。
調湿剤の用途としては、表面にゼオライト等からなる水分吸着材が配置された熱交換部材の一表面に被処理空気を通流させ、他の表面に熱媒流体を通流させることを特徴とする乾式除湿装置が開示されている（例えば、特許文献１参照。）。この特許文献１に示される乾式除湿装置では、熱交換管に複数のアルミニウムプレートフィンが嵌合され、この熱交換管の外周面及びフィンの表面の全面にアクリル粘着性バインダを塗布し、このアクリル粘着剤バインダ膜にゼオライト粒子を埋め込むようにして、添着することにより熱交換管やフィン表面に吸着材を形成している。また、ゼオライトの粉末を水ガラスとともに混練し、この混練物を銅管外周面及びフィン表面に押し出して塗布した後、水ガラス分を乾燥焼成し、ゼオライト粉末と水ガラスをフィン表面等に固着することにより吸着材を設けている。
The use of the humidity control agent is characterized in that the air to be treated is passed through one surface of a heat exchange member having a moisture adsorbent made of zeolite or the like on the surface and the heat transfer fluid is passed through the other surface. A dry dehumidifier is disclosed (for example, see Patent Document 1). In the dry dehumidifying device disclosed in Patent Document 1, a plurality of aluminum plate fins are fitted to a heat exchange tube, and an acrylic adhesive binder is applied to the entire outer peripheral surface of the heat exchange tube and the surface of the fin. Adsorbents are formed on the heat exchange tubes and fin surfaces by adhering zeolite particles in the adhesive binder membrane. Also, the zeolite powder is kneaded with water glass, and this kneaded product is extruded and applied to the outer peripheral surface of the copper tube and the fin surface, and then the water glass component is dried and fired to fix the zeolite powder and water glass to the fin surface and the like. Thus, an adsorbent is provided.
しかし、上記特許文献１に示される乾式除湿装置の吸着材では、ゼオライトをアクリル粘着剤バインダ膜に添着させているか、水ガラスを使用して固着しているだけであるため、十分な水分吸脱着能が発揮されていなかった。
本発明の目的は、水分吸脱着能を向上し得るゼオライト膜形成用塗料及び該塗料を用いたゼオライト膜の製造方法、ゼオライト膜を提供することにある。
However, in the adsorbent of the dry dehumidifying device shown in the above-mentioned Patent Document 1, since the zeolite is attached to the acrylic adhesive binder film or is fixed using water glass, sufficient moisture adsorption / desorption is achieved. Noh was not demonstrated.
An object of the present invention is to provide a coating material for forming a zeolite membrane capable of improving the moisture adsorption / desorption ability, a method for producing a zeolite membrane using the coating material, and a zeolite membrane.
請求項１に係る発明は、ゼオライト、バインダ組成物及び有機溶剤をそれぞれ含むゼオライト膜形成用塗料の改良である。その特徴ある構成は、添加剤としてメタクリル酸エステルモノマーを更に含むところにある。
請求項１に係る発明では、ゼオライト膜形成用塗料に添加剤としてメタクリル酸エステルモノマーを含むことで、この塗料を塗布した基材を焼成した際に、添加剤であるメタクリル酸エステルモノマーが塗膜内から焼飛んで、この焼飛んだ箇所が膜中に膜表層に連通する連通孔（ポア）として形成される。通常のゼオライト膜形成用塗料を塗布焼成したゼオライト膜では、表層近傍のみが水分吸脱着能を発揮するが、本発明のゼオライト膜形成用塗料を塗布焼成したゼオライト膜では、表層近傍だけでなく、メタクリル酸エステルモノマーが焼飛んで形成された連通孔近傍も水分吸脱着能を発揮するため、水分吸脱着能が向上した優れたゼオライト膜が得られる。
The invention according to claim 1 is an improvement of the coating material for forming a zeolite film containing a zeolite, a binder composition and an organic solvent. The characteristic structure is that it further contains a methacrylic acid ester monomer as an additive.
In the invention according to claim 1, by including a methacrylic ester monomer as an additive in the coating for forming a zeolite film, the methacrylic ester monomer as the additive is coated when the base material coated with the coating is baked. The burned-out portion is formed as a communication hole (pore) communicating with the membrane surface layer in the membrane. In the zeolite membrane coated and baked with a normal coating material for forming a zeolite film, only the vicinity of the surface layer exhibits moisture absorption / desorption ability, but in the zeolite membrane coated and baked with the coating material for forming a zeolite film of the present invention, not only in the vicinity of the surface layer, Since the vicinity of the communication hole formed by burning out the methacrylic acid ester monomer also exhibits the moisture adsorption / desorption capability, an excellent zeolite membrane with improved moisture adsorption / desorption capability can be obtained.
請求項２に係る発明は、請求項１に係る発明であって、バインダ組成物がシリカゾルを含む塗料である。
請求項３に係る発明は、請求項１又は２に係る発明であって、有機溶剤、ゼオライト、添加剤及びバインダ組成物の混合割合が重量比で５６〜８０：３〜９：３〜２４：１０〜３１である塗料である。
請求項４に係る発明は、請求項１ないし３いずれか１項に係る発明であって、ゼオライトの平均粒子径が０．５〜１０μｍであり、孔径が０．２〜１ｎｍである塗料である。
The invention according to claim 2 is the invention according to claim 1, wherein the binder composition is a paint containing silica sol.
The invention according to claim 3 is the invention according to claim 1 or 2, wherein the mixing ratio of the organic solvent, the zeolite, the additive and the binder composition is 56-80: 3-9: 3-24: 10 to 31 paint.
The invention according to claim 4 is the invention according to any one of claims 1 to 3, wherein the zeolite has an average particle diameter of 0.5 to 10 μm and a pore diameter of 0.2 to 1 nm. .
請求項５に係る発明は、請求項１ないし４いずれか１項に記載の塗料を基材に塗布する工程と、塗料を塗布した基材を２０℃〜５０℃で仮焼成する工程と、仮焼成した基材を塗料に含まれる添加剤の沸点以上基材の融点以下で本焼成する工程とを含むことを特徴とするゼオライト膜の製造方法である。
請求項６に係る発明は、基材を２０℃〜５０℃で仮焼成する工程と、請求項１ないし４いずれか１項に記載の塗料を仮焼成した基材に塗布する工程と、塗料を塗布した基材を塗料に含まれる添加剤の沸点以上基材の融点以下で本焼成する工程とを含むことを特徴とするゼオライト膜の製造方法である。
請求項５又は６に係る発明では、上記工程を経ることで、より水分吸脱着能を向上させたゼオライト膜を製造することができる。
The invention according to claim 5 includes a step of applying the paint according to any one of claims 1 to 4 to a base material, a step of pre-baking the base material coated with the paint at 20 ° C to 50 ° C, And a step of subjecting the fired base material to a main firing at a temperature not lower than the boiling point of the additive contained in the paint and not higher than the melting point of the base material.
The invention according to claim 6 includes a step of calcining the substrate at 20 ° C. to 50 ° C., a step of applying the paint according to any one of claims 1 to 4 to the calcined substrate, and a paint And a step of subjecting the applied base material to a main firing at a temperature not lower than the boiling point of the additive contained in the paint and not higher than the melting point of the base material.
In the invention which concerns on Claim 5 or 6, the zeolite membrane which improved the water absorption / desorption ability more can be manufactured by passing through the said process.
請求項７に係る発明は、請求項１ないし４いずれか１項に記載の塗料を基材表面に塗布焼成することにより形成されたゼオライト膜、或いは請求項５又は６記載の方法により製造されたゼオライト膜であって、膜中に含まれるゼオライトとシリカゾル由来のＳｉＯ2の重量比が６：４〜８：２であることを特徴とするゼオライト膜である。 The invention according to claim 7 is manufactured by a zeolite membrane formed by applying and baking the coating material according to any one of claims 1 to 4 on a substrate surface, or by the method according to claim 5 or 6. A zeolite membrane, wherein the weight ratio of zeolite contained in the membrane to silica sol-derived SiO 2 is 6: 4 to 8: 2.
本発明のゼオライト膜形成用塗料は、添加剤としてメタクリル酸エステルモノマーを含むことで、この塗料を塗布した基板を焼成した際に、添加剤であるメタクリル酸エステルモノマーが塗膜内から焼飛んで、この焼飛んだ箇所が膜中に膜表層に連通する連通孔（ポア）として形成される。その結果、通常のゼオライト膜形成用塗料を塗布焼成したゼオライト膜では、表層近傍のみが水分吸脱着能を発揮するが、本発明のゼオライト膜形成用塗料を塗布焼成したゼオライト膜では、表層近傍だけでなく、メタクリル酸エステルモノマーが焼飛んで形成された連通孔近傍も水分吸脱着能を発揮するため、水分吸脱着能が向上した優れたゼオライト膜が得られる。
本発明のゼオライト膜の製造方法は、前述した本発明のゼオライト膜形成用塗料を基材に塗布し、塗料を塗布した基材を仮焼成した後に、この仮焼成した基材を塗料に含まれる添加剤の沸点以上基材の融点以下で本焼成するか、基材を仮焼成した後に、前述した本発明のゼオライト膜形成用塗料を仮焼成した基材に塗布し、塗料を塗布した基材を塗料に含まれる添加剤の沸点以上基材の融点以下で本焼成することで、より水分吸脱着能を向上させたゼオライト膜を製造することができる。
The coating material for forming a zeolite film of the present invention contains a methacrylic acid ester monomer as an additive. When the substrate coated with the coating material is baked, the methacrylic acid ester monomer as an additive is burned out from the coating film. The burned-out portion is formed as a communication hole (pore) communicating with the film surface layer in the film. As a result, in the zeolite membrane coated and baked with the usual zeolite film-forming paint, only the vicinity of the surface layer exhibits moisture absorption / desorption ability, but in the zeolite membrane coated and baked with the zeolite film-forming paint of the present invention, only in the vicinity of the surface layer. In addition, the vicinity of the communication hole formed by burning out the methacrylic acid ester monomer also exhibits the moisture adsorption / desorption capability, so that an excellent zeolite membrane with improved moisture adsorption / desorption capability can be obtained.
In the method for producing a zeolite membrane of the present invention, the above-described coating material for forming a zeolite film of the present invention is applied to a base material, the base material coated with the paint is temporarily fired, and then the temporarily fired base material is included in the paint. After the main baking is performed at a temperature equal to or higher than the boiling point of the additive and not higher than the melting point of the base material, or the base material is temporarily fired, the above-described zeolite film-forming coating material of the present invention is applied to the temporarily fired base material. Can be produced at a temperature equal to or higher than the boiling point of the additive contained in the paint and equal to or lower than the melting point of the base material, whereby a zeolite membrane with improved moisture absorption / desorption ability can be produced.
次に本発明を実施するための最良の形態を説明する。
本発明のゼオライト膜形成用塗料は、ゼオライト、バインダ組成物及び有機溶剤をそれぞれ含むゼオライト膜形成用塗料の改良であり、その特徴ある構成は、添加剤としてメタクリル酸エステルモノマーを更に含むところにある。ゼオライト膜形成用塗料に添加剤としてメタクリル酸エステルモノマーを含むことで、この塗料を塗布した基材を焼成した際に、添加剤であるメタクリル酸エステルモノマーが塗膜内から焼飛んで、この焼飛んだ箇所が膜中に膜表層に連通する連通孔（ポア）として形成される。通常のゼオライト膜形成用塗料を塗布焼成したゼオライト膜では、表層近傍のみが水分吸脱着能を発揮するが、本発明のゼオライト膜形成用塗料を塗布焼成したゼオライト膜では、表層近傍だけでなく、メタクリル酸エステルモノマーが焼飛んで形成された連通孔近傍も水分吸脱着能を発揮するため、水分吸脱着能が向上した優れたゼオライト膜が得られる。
Next, the best mode for carrying out the present invention will be described.
The coating material for forming a zeolite film of the present invention is an improvement of the coating material for forming a zeolite film containing a zeolite, a binder composition and an organic solvent, respectively, and its characteristic constitution is that it further contains a methacrylic ester monomer as an additive. . By including a methacrylic acid ester monomer as an additive in the zeolite film forming coating material, when the base material coated with this coating material is baked, the methacrylic acid ester monomer as an additive is burned out from within the coating film. The flying portion is formed as a communication hole (pore) communicating with the membrane surface layer in the membrane. In the zeolite membrane coated and baked with a normal coating material for forming a zeolite film, only the vicinity of the surface layer exhibits moisture absorption / desorption ability, but in the zeolite membrane coated and baked with the coating material for forming a zeolite film of the present invention, not only in the vicinity of the surface layer, Since the vicinity of the communication hole formed by burning out the methacrylic acid ester monomer also exhibits the moisture adsorption / desorption capability, an excellent zeolite membrane with improved moisture adsorption / desorption capability can be obtained.
本発明のゼオライト膜形成用塗料で添加剤として添加されるメタクリル酸エステルモノマーを例示すると、メタクリル酸メチルモノマー、メタクリル酸エチルモノマー、メタクリル酸ノルマルブチルモノマー、メタクリル酸セカンダリーブチルモノマー、メタクリル酸ターシャリーブチルモノマー、メタクリル酸イソブチルモノマー、メタクリル酸アリルモノマー、フェニルメタクリレートモノマー、ベンジルメタクリレートモノマー等が挙げられる。本発明で添加剤として使用されるメタクリル酸エステルモノマーの沸点を次の表１にそれぞれ示す。 Examples of the methacrylic acid ester monomer added as an additive in the zeolite film forming paint of the present invention include methyl methacrylate monomer, ethyl methacrylate monomer, normal butyl methacrylate monomer, secondary butyl methacrylate monomer, and tertiary butyl methacrylate. Monomers, isobutyl methacrylate monomers, allyl methacrylate monomers, phenyl methacrylate monomers, benzyl methacrylate monomers, and the like. The boiling points of methacrylic acid ester monomers used as additives in the present invention are shown in the following Table 1, respectively.
本発明のゼオライト膜形成用塗料におけるバインダ組成物には、シリカゾルが含まれる。バインダ組成物成分としてシリカゾルを用いた場合、シリカゾルにはアルキルシリケートの加水分解物又は部分加水分解物が使用される。シリカゾルを用いることにより、シリカゾルの均一混合作用により透明度を低下させることがなく、高い水分吸脱着能を得ることが出来、更にシリカゾルの作用で基材との密着性が一層向上する。バインダ組成物は、シリカゾルと任意の溶媒を所望の割合で混合して使用される。
また、本発明のゼオライト膜形成用塗料における有機溶剤は、塗布する基材等によっても異なるが、メタノール、エタノール、ｎ−プロピルアルコール、ｉｓｏ−プロピルアルコール、工業用の混合アルコールが挙げられる。
Silica sol is contained in the binder composition in the coating material for forming a zeolite film of the present invention. When silica sol is used as the binder composition component, hydrolyzate or partial hydrolyzate of alkyl silicate is used for silica sol. By using the silica sol, the transparency can not be lowered by the uniform mixing action of the silica sol, and a high moisture absorption / desorption ability can be obtained, and the adhesion to the substrate is further improved by the action of the silica sol. The binder composition is used by mixing silica sol and an arbitrary solvent in a desired ratio.
Moreover, although the organic solvent in the coating material for forming a zeolite film of the present invention varies depending on the base material to be applied, methanol, ethanol, n-propyl alcohol, iso-propyl alcohol, and industrial mixed alcohols may be mentioned.
本発明のゼオライト膜形成用塗料における有機溶剤、ゼオライト、添加剤及びバインダ組成物の混合割合は、重量比で５６〜８０：３〜９：３〜２４：１０〜３１の範囲内が好適である。特に好ましい混合割合は、重量比で６０〜７０：３〜７：７〜２０：１０〜２２である。メタクリル酸エステルモノマーの混合割合を上記範囲内に規定したのは、下限値未満であると、添加剤を混合した効果が得られないためであり、上限値を越えると、塗料を塗布した後に焼成して得られるゼオライト膜に形成される連通孔が多くなりすぎてしまい、膜の強度が低下する不具合を生じるからである。また、塗料を塗布した後に焼成したとしても、塗料中に含まれるメタクリル酸エステルモノマーの一部が膜中に残留してしまい、水分吸脱着能等のゼオライトが有する諸機能が低下してしまうおそれがある。
本発明のゼオライト膜形成用塗料に使用されるゼオライトは、塗布対象となる基材や、ゼオライト膜の使用環境等によっても異なるが、その平均粒子径が０．５〜１０μｍであり、孔径が０．２〜１ｎｍのゼオライトを用いることが好ましい。
The mixing ratio of the organic solvent, zeolite, additive, and binder composition in the coating for forming a zeolite film of the present invention is preferably in the range of 56 to 80: 3 to 9: 3 to 24:10 to 31 by weight ratio. . A particularly preferable mixing ratio is 60 to 70: 3 to 7: 7 to 20:10 to 22 by weight ratio. The mixing ratio of the methacrylic acid ester monomer is defined within the above range because if it is less than the lower limit value, the effect of mixing the additive cannot be obtained. If the upper limit value is exceeded, baking is performed after coating the paint. This is because too many communicating holes are formed in the resulting zeolite membrane, resulting in a problem that the strength of the membrane is reduced. In addition, even if the paint is baked after being applied, some of the methacrylic acid ester monomers contained in the paint may remain in the film, reducing the various functions of the zeolite such as the ability to absorb and desorb moisture. There is.
The zeolite used in the coating material for forming a zeolite membrane of the present invention varies depending on the base material to be coated, the use environment of the zeolite membrane, etc., but the average particle size is 0.5 to 10 μm and the pore size is 0. It is preferable to use zeolite of 2 to 1 nm.
次に、本発明の第１のゼオライト膜の製造方法を説明する。
先ず、前述した本発明のゼオライト膜形成用塗料を基材に塗布する。塗布方法としては、スピンコート法、ディッピング法、スプレー法等により施すことができるが、特に塗布方法は限定されない。本発明に使用される基材としては、建家や部屋の壁、エアコン等の熱交換器などが挙げられる。建家や部屋の壁にゼオライト膜を形成することで、建築物壁面の結露を防止するための壁面結露防止作用が得られる。また、エアコン等の熱交換器にゼオライト膜を形成することで、エアコンを設置した居住空間の調湿作用が得られる。
Next, the manufacturing method of the 1st zeolite membrane of this invention is demonstrated.
First, the above-described coating material for forming a zeolite film of the present invention is applied to a substrate. As the coating method, spin coating, dipping, spraying, etc. can be used, but the coating method is not particularly limited. As a base material used for this invention, heat exchangers, such as a building, a wall of a room, an air-conditioner, etc. are mentioned. By forming a zeolite membrane on the wall of a building or room, a wall surface condensation prevention action for preventing condensation on the wall surface of the building can be obtained. In addition, by forming a zeolite membrane on a heat exchanger such as an air conditioner, the humidity control effect of the living space where the air conditioner is installed can be obtained.
次に、本発明のゼオライト膜形成用塗料を塗布した基材を２０℃〜５０℃で仮焼成する。この仮焼成工程を施さないと、添加剤と有機溶剤が同時に蒸発してしまい、塗膜にポアを形成することができない。続いて、仮焼成した基材を塗料に含まれる添加剤の沸点以上基材の融点以下で本焼成する。本焼成の温度が添加剤の沸点未満では、添加剤が十分に焼飛ばないため、形成されるゼオライト膜に残留してしまう不具合を生じ、本焼成の温度が基材の融点を越えると、ゼオライト膜は形成されるが、成型加工した基材の形状を保持することができないため好ましくない。この本焼成を施すことで、ゼオライト膜が形成されるとともに、添加剤であるメタクリル酸エステルが塗膜内から焼飛んで、この焼飛んだ箇所が膜中に膜表層に連通する連通孔（ポア）として形成される。形成された連通孔により、膜の下側に埋もれて水分吸脱着に寄与していなかったゼオライトも水分吸脱着に利用することができるため、水分吸脱着能が大幅に増大する。このように上記工程を経ることで、水分吸脱着能に優れたゼオライト膜を製造することができる。なお、エアコン等の熱交換器などに使用されるアルミ基板にゼオライト膜を形成する際に、アルミ基板表面にアンダーコート層として水ガラス層を形成しておくことが好ましい。この水ガラス層をアンダーコート層として形成しておくことで、アルミ基板とゼオライト膜との密着性が向上する。具体的には、水ガラスを水で希釈した液を用意し、この水ガラス希釈液にアルミ基板を浸漬することにより基板表面に水ガラス希釈液を塗布した後、基板を焼成することで基板表面に水ガラス層を形成する。焼成後の基板は水洗しておく。この水ガラス層を形成したアルミ基板表面に前述した本発明の製造方法によりゼオライト膜を形成する。 Next, the base material to which the coating material for forming a zeolite film of the present invention is applied is temporarily fired at 20 ° C to 50 ° C. If this pre-baking step is not performed, the additive and the organic solvent are evaporated simultaneously, and pores cannot be formed in the coating film. Subsequently, the temporarily fired base material is finally fired at the boiling point of the additive contained in the paint or higher and below the melting point of the base material. If the temperature of the main calcination is lower than the boiling point of the additive, the additive will not be burned out sufficiently, resulting in a problem of remaining in the formed zeolite membrane, and if the temperature of the main calcination exceeds the melting point of the base material, Although a film is formed, it is not preferable because the shape of the molded base material cannot be maintained. By performing this main calcination, a zeolite membrane is formed, and the methacrylic acid ester as an additive is burned out from the inside of the coating film, and the burned-out portion communicates with the membrane surface layer in the membrane (pores). ). Due to the formed communication holes, zeolite that has been buried under the membrane and has not contributed to moisture adsorption / desorption can also be used for moisture adsorption / desorption, so that the moisture adsorption / desorption ability is greatly increased. Thus, a zeolite membrane excellent in moisture absorption / desorption ability can be produced through the above steps. In addition, when forming a zeolite membrane on an aluminum substrate used for a heat exchanger such as an air conditioner, it is preferable to form a water glass layer as an undercoat layer on the aluminum substrate surface. By forming this water glass layer as an undercoat layer, the adhesion between the aluminum substrate and the zeolite membrane is improved. Specifically, a solution obtained by diluting water glass with water is prepared, and the substrate surface is obtained by baking the substrate after applying the water glass dilution solution to the substrate surface by immersing the aluminum substrate in the water glass dilution solution. A water glass layer is formed. The substrate after firing is washed with water. A zeolite membrane is formed on the surface of the aluminum substrate on which the water glass layer is formed by the production method of the present invention described above.
また、本発明の第２のゼオライト膜の製造方法では、先ず、基材を２０℃〜５０℃で仮焼成する。次に、前述した本発明のゼオライト膜形成用塗料を仮焼成した基材に塗布する。この後に続く工程は、前述した本発明の第１のゼオライト膜の製造方法と同様である。 In the second method for producing a zeolite membrane of the present invention, first, the substrate is temporarily calcined at 20 ° C to 50 ° C. Next, the above-described coating material for forming a zeolite film of the present invention is applied to a temporarily fired substrate. The subsequent steps are the same as in the first method for producing a zeolite membrane of the present invention described above.
次に、本発明のゼオライト膜について説明する。
本発明のゼオライト膜は、前述した本発明のゼオライト膜形成用塗料を基材表面に塗布焼成することにより形成されるか、或いは前述したゼオライト膜の製造方法により製造されたゼオライト膜である。その特徴ある構成は、膜中に含まれるゼオライトとシリカゾル由来のＳｉＯ2の重量比が６：４〜８：２であるところにある。本発明のゼオライト膜中に含まれるゼオライトとシリカゲル由来のＳｉＯ2の重量比を上記重量比を規定したのは、膜中のゼオライト比率が６割未満になると、ゼオライトの水分吸着能が十分に発揮されず、膜中のゼオライト比率が８割を越えると、バインダであるＳｉＯ2比率が低くなり、膜の硬度及び密着性が悪くなるためである。特に好ましい重量比は、７：３〜８：２である。
Next, the zeolite membrane of the present invention will be described.
The zeolite membrane of the present invention is formed by applying the above-described coating material for forming a zeolite film of the present invention to the surface of a base material and firing it, or is a zeolite membrane manufactured by the above-described method for manufacturing a zeolite membrane. The characteristic configuration is that the weight ratio of the zeolite contained in the membrane to the silica sol-derived SiO 2 is 6: 4 to 8: 2. The weight ratio of the zeolite contained in the zeolite membrane of the present invention to the silica gel-derived SiO 2 is defined as the above weight ratio. When the zeolite ratio in the membrane is less than 60%, the water adsorption ability of the zeolite is sufficiently exhibited. If the zeolite ratio in the film exceeds 80%, the ratio of SiO 2 as the binder decreases, and the hardness and adhesion of the film deteriorate. A particularly preferred weight ratio is 7: 3 to 8: 2.
次に本発明の実施例を比較例とともに詳しく説明する。
＜実施例１＞
エタノール９２５ｇに平均粒子径４μｍ、細孔径０．３ｎｍのゼオライト７５ｇを混合し、超音波洗浄機により１０分間分散して分散液を調製した。この分散液にメタクリル酸エチルモノマー２５０ｇと１０重量％のエチルシリケート系シリカゾル２５０ｇをよく混合して、本発明のゼオライト膜形成用塗料を調製した。調製したゼオライト膜形成用塗料中の有機溶剤、ゼオライト、添加剤及びバインダ組成物の混合割合は重量比で６２：５：１７：１７であった。このゼオライト膜形成用塗料に０．５ｍ2のアルミ基板を浸漬することにより、アルミ基板表面に塗料を塗布し、４０℃で０．２５時間仮焼成した。続いて１４０℃で０．５時間本焼成した。アルミ基板０．５ｍ2あたりのゼオライトの担持量が６０ｇとなるまで、塗料への浸漬、仮焼成及び本焼成を繰返して、アルミ基板上にゼオライト膜を形成した。
＜実施例２＞
イソプロピルアルコール６７５ｇに平均粒子径２μｍ、細孔径０．４５ｎｍのゼオライト７５ｇを混合し、ジルコニアビーズ１００ｇにより１時間ペイントシェーカーにて分散させて分散液を調製した。この分散液にメタクリル酸ターシャリーブチルモノマー９４ｇと１０重量％のメチルシリケート系シリカゾル１８８ｇをよく混合して、本発明のゼオライト膜形成用塗料を調製した。調製したゼオライト膜形成用塗料中の有機溶剤、ゼオライト、添加剤及びバインダ組成物の混合割合は重量比で６５：７．３：９．１：１８．２であった。このゼオライト膜形成用塗料に０．５ｍ2のアルミ基板を浸漬することにより、アルミ基板表面に塗料を塗布し、２０℃で０．５時間仮焼成した。続いて１５０℃で０．５時間本焼成した。アルミ基板０．５ｍ2あたりのゼオライトの担持量が６０ｇとなるまで、塗料への浸漬、仮焼成及び本焼成を繰返して、アルミ基板上にゼオライト膜を形成した。
＜実施例３＞
工業用として使用される混合アルコール６７５ｇに平均粒子径１μｍ、細孔径０．７ｎｍのゼオライト７５ｇを混合し、超音波洗浄機により１０分間分散して分散液を調製した。この分散液にメタクリル酸メチルモノマー８０ｇと１０重量％のエチルシリケート系シリカゾル２５２ｇをよく混合して、本発明のゼオライト膜形成用塗料を調製した。調製したゼオライト膜形成用塗料中の有機溶剤、ゼオライト、添加剤及びバインダ組成物の混合割合は重量比で６２：７：７：２３であった。このゼオライト膜形成用塗料に０．５ｍ2のアルミ基板を浸漬することにより、アルミ基板表面に塗料を塗布し、５０℃で０．５時間仮焼成した。続いて１１０℃で０．５時間本焼成した。アルミ基板０．５ｍ2あたりのゼオライトの担持量が６０ｇとなるまで、塗料への浸漬、仮焼成及び本焼成を繰返して、アルミ基板上にゼオライト膜を形成した。
＜実施例４＞
メタノール１４２５ｇに平均粒子径８μｍ、細孔径０．９ｎｍのゼオライト７５ｇを混合し、ジルコニアビーズ１００ｇにより１時間ペイントシェーカーにて分散させて分散液を調製した。この分散液にメタクリル酸セカンダリーブチルモノマー５２５ｇと１０重量％のメチルシリケート系シリカゾル２５０ｇをよく混合して、本発明のゼオライト膜形成用塗料を調製した。調製したゼオライト膜形成用塗料中の有機溶剤、ゼオライト、添加剤及びバインダ組成物の混合割合は重量比で６３：３．３：２３：１１であった。このゼオライト膜形成用塗料に０．５ｍ2のアルミ基板を浸漬することにより、アルミ基板表面に塗料を塗布し、３０℃で０．５時間仮焼成した。続いて１６５℃で０．５時間本焼成した。アルミ基板０．５ｍ2あたりのゼオライトの担持量が６０ｇとなるまで、塗料への浸漬、仮焼成及び本焼成を繰返して、アルミ基板上にゼオライト膜を形成した。
Next, examples of the present invention will be described in detail together with comparative examples.
<Example 1>
A dispersion was prepared by mixing 925 g of ethanol with 75 g of zeolite having an average particle size of 4 μm and a pore size of 0.3 nm and dispersing for 10 minutes with an ultrasonic cleaner. To this dispersion, 250 g of ethyl methacrylate monomer and 250 g of 10 wt% ethyl silicate-based silica sol were mixed well to prepare the coating material for forming a zeolite film of the present invention. The mixing ratio of the organic solvent, zeolite, additive, and binder composition in the prepared coating for forming a zeolite film was 62: 5: 17: 17 by weight ratio. By immersing a 0.5 m 2 aluminum substrate in this zeolite film-forming coating material, the coating material was applied to the surface of the aluminum substrate and pre-baked at 40 ° C. for 0.25 hour. Subsequently, main baking was performed at 140 ° C. for 0.5 hour. The zeolite film was formed on the aluminum substrate by repeating the dipping in the paint, temporary firing and main firing until the amount of zeolite supported per 0.5 m 2 of the aluminum substrate reached 60 g.
<Example 2>
To 675 g of isopropyl alcohol, 75 g of zeolite having an average particle size of 2 μm and a pore size of 0.45 nm was mixed, and dispersed with 100 g of zirconia beads in a paint shaker for 1 hour to prepare a dispersion. To this dispersion, 94 g of tertiary butyl methacrylate monomer and 188 g of 10 wt% methyl silicate-based silica sol were mixed well to prepare the coating material for forming a zeolite film of the present invention. The mixing ratio of the organic solvent, zeolite, additive, and binder composition in the prepared coating for forming a zeolite film was 65: 7.3: 9.1: 18.2 by weight. A 0.5 m 2 aluminum substrate was immersed in this zeolite film-forming coating material, whereby the coating material was applied to the surface of the aluminum substrate and pre-baked at 20 ° C. for 0.5 hour. Subsequently, main baking was performed at 150 ° C. for 0.5 hour. The zeolite film was formed on the aluminum substrate by repeating the dipping in the paint, temporary firing and main firing until the amount of zeolite supported per 0.5 m 2 of the aluminum substrate reached 60 g.
<Example 3>
A dispersion liquid was prepared by mixing 75 g of zeolite having an average particle diameter of 1 μm and a pore diameter of 0.7 nm with 675 g of mixed alcohol used for industrial use and dispersing for 10 minutes with an ultrasonic cleaner. To this dispersion, 80 g of methyl methacrylate monomer and 252 g of 10 wt% ethyl silicate-based silica sol were mixed well to prepare a coating material for forming a zeolite film of the present invention. The mixing ratio of the organic solvent, zeolite, additive, and binder composition in the prepared coating for forming a zeolite film was 62: 7: 7: 23 by weight. A 0.5 m 2 aluminum substrate was immersed in this zeolite film-forming coating material, whereby the coating material was applied to the surface of the aluminum substrate and pre-baked at 50 ° C. for 0.5 hour. Subsequently, main baking was performed at 110 ° C. for 0.5 hour. The zeolite film was formed on the aluminum substrate by repeating the dipping in the paint, temporary firing and main firing until the amount of zeolite supported per 0.5 m 2 of the aluminum substrate reached 60 g.
<Example 4>
1425 g of methanol was mixed with 75 g of zeolite having an average particle diameter of 8 μm and a pore diameter of 0.9 nm, and dispersed with a paint shaker for 1 hour using 100 g of zirconia beads to prepare a dispersion. To this dispersion, 525 g of secondary butyl methacrylate monomer and 250 g of 10 wt% methyl silicate-based silica sol were mixed well to prepare the coating material for forming a zeolite film of the present invention. The mixing ratio of the organic solvent, the zeolite, the additive, and the binder composition in the prepared coating for forming a zeolite film was 63: 3.3: 23: 11 by weight. A 0.5 m 2 aluminum substrate was immersed in this zeolite film-forming coating material, whereby the coating material was applied to the surface of the aluminum substrate and pre-baked at 30 ° C. for 0.5 hour. Subsequently, main baking was performed at 165 ° C. for 0.5 hour. The zeolite film was formed on the aluminum substrate by repeating the dipping in the paint, temporary firing and main firing until the amount of zeolite supported per 0.5 m 2 of the aluminum substrate reached 60 g.
＜実施例５＞
エタノール５２５ｇに平均粒子径４μｍ、細孔径０．３ｎｍのゼオライト７５ｇを混合し、超音波洗浄機により１０分間分散して分散液を調製した。この分散液にメタクリル酸ノルマルブチルモノマー７９ｇと１０重量％のエチルシリケート系シリカゾル１８８ｇをよく混合して、本発明のゼオライト膜形成用塗料を調製した。調製したゼオライト膜形成用塗料中の有機溶剤、ゼオライト、添加剤及びバインダ組成物の混合割合は重量比で６０．６：８．７：９．１：２１．６であった。このゼオライト膜形成用塗料に０．５ｍ2のアルミ基板を浸漬することにより、アルミ基板表面に塗料を塗布し、４０℃で０．２５時間仮焼成した。続いて１８５℃で０．５時間本焼成した。アルミ基板０．５ｍ2あたりのゼオライトの担持量が６０ｇとなるまで、塗料への浸漬、仮焼成及び本焼成を繰返して、アルミ基板上にゼオライト膜を形成した。
＜実施例６＞
イソプロピルアルコール９２５ｇに平均粒子径２μｍ、細孔径０．４５ｎｍのゼオライト７５ｇを混合し、ジルコニアビーズ１００ｇにより１時間ペイントシェーカーにて分散させて分散液を調製した。この分散液にメタクリル酸イソブチルモノマー１５０ｇと１０重量％のメチルシリケート系シリカゾル５００ｇをよく混合して、本発明のゼオライト膜形成用塗料を調製した。調製したゼオライト膜形成用塗料中の有機溶剤、ゼオライト、添加剤及びバインダ組成物の混合割合は重量比で５６．１：４．５：９．１：３０．３であった。このゼオライト膜形成用塗料に０．５ｍ2のアルミ基板を浸漬することにより、アルミ基板表面に塗料を塗布し、２０℃で０．５時間仮焼成した。続いて１６０℃で０．５時間本焼成した。アルミ基板０．５ｍ2あたりのゼオライトの担持量が６０ｇとなるまで、塗料への浸漬、仮焼成及び本焼成を繰返して、アルミ基板上にゼオライト膜を形成した。
＜実施例７＞
工業用として使用される混合アルコール９２５ｇに平均粒子径１μｍ、細孔径０．７ｎｍのゼオライト７５ｇを混合し、超音波洗浄機により１０分間分散して分散液を調製した。この分散液にフェニルメタクリレートモノマー１００ｇと１０重量％のエチルシリケート系シリカゾル２５０ｇをよく混合して、本発明のゼオライト膜形成用塗料を調製した。調製したゼオライト膜形成用塗料中の有機溶剤、ゼオライト、添加剤及びバインダ組成物の混合割合は重量比で６８．５：５．６：７．４：１８．５であった。このゼオライト膜形成用塗料に０．５ｍ2のアルミ基板を浸漬することにより、アルミ基板表面に塗料を塗布し、５０℃で０．５時間仮焼成した。続いて２３５℃で０．５時間本焼成した。アルミ基板０．５ｍ2あたりのゼオライトの担持量が６０ｇとなるまで、塗料への浸漬、仮焼成及び本焼成を繰返して、アルミ基板上にゼオライト膜を形成した。
＜実施例８＞
メタノール１４２５ｇに平均粒子径８μｍ、細孔径０．９ｎｍのゼオライト７５ｇを混合し、ジルコニアビーズ１００ｇにより１時間ペイントシェーカーにて分散させて分散液を調製した。この分散液にベンジルメタクリレートモノマー７０ｇと１０重量％のメチルシリケート系シリカゾル２５０ｇをよく混合して、本発明のゼオライト膜形成用塗料を調製した。調製したゼオライト膜形成用塗料中の有機溶剤、ゼオライト、添加剤及びバインダ組成物の混合割合は重量比で７９：４：３．５：１３．５であった。このゼオライト膜形成用塗料に０．５ｍ2のアルミ基板を浸漬することにより、アルミ基板表面に塗料を塗布し、３０℃で０．５時間仮焼成した。続いて２７０℃で０．５時間本焼成した。アルミ基板０．５ｍ2あたりのゼオライトの担持量が６０ｇとなるまで、塗料への浸漬、仮焼成及び本焼成を繰返して、アルミ基板上にゼオライト膜を形成した。
<Example 5>
A dispersion liquid was prepared by mixing 525 g of ethanol with 75 g of zeolite having an average particle diameter of 4 μm and a pore diameter of 0.3 nm and dispersing for 10 minutes with an ultrasonic cleaner. To this dispersion, 79 g of normal butyl methacrylate monomer and 188 g of 10 wt% ethyl silicate-based silica sol were mixed well to prepare the coating material for forming a zeolite film of the present invention. The mixing ratio of the organic solvent, the zeolite, the additive, and the binder composition in the prepared coating for forming a zeolite film was 60.6: 8.7: 9.1: 21.6 by weight. By immersing a 0.5 m 2 aluminum substrate in this zeolite film-forming coating material, the coating material was applied to the surface of the aluminum substrate and pre-baked at 40 ° C. for 0.25 hour. Subsequently, main baking was performed at 185 ° C. for 0.5 hour. The zeolite film was formed on the aluminum substrate by repeating the dipping in the paint, temporary firing and main firing until the amount of zeolite supported per 0.5 m 2 of the aluminum substrate reached 60 g.
<Example 6>
A dispersion liquid was prepared by mixing 925 g of isopropyl alcohol with 75 g of zeolite having an average particle diameter of 2 μm and a pore diameter of 0.45 nm, and dispersing the mixture with 100 g of zirconia beads for 1 hour using a paint shaker. To this dispersion, 150 g of isobutyl methacrylate monomer and 500 g of 10 wt% methyl silicate-based silica sol were mixed well to prepare the coating material for forming a zeolite film of the present invention. The mixing ratio of the organic solvent, zeolite, additive, and binder composition in the prepared coating for forming a zeolite film was 56.1: 4.5: 9.1: 30.3 by weight. A 0.5 m 2 aluminum substrate was immersed in this zeolite film-forming coating material, whereby the coating material was applied to the surface of the aluminum substrate and pre-baked at 20 ° C. for 0.5 hour. Subsequently, main baking was performed at 160 ° C. for 0.5 hour. The zeolite film was formed on the aluminum substrate by repeating the dipping in the paint, temporary firing and main firing until the amount of zeolite supported per 0.5 m 2 of the aluminum substrate reached 60 g.
<Example 7>
A dispersion liquid was prepared by mixing 925 g of mixed alcohol used for industrial use with 75 g of zeolite having an average particle diameter of 1 μm and a pore diameter of 0.7 nm and dispersing for 10 minutes with an ultrasonic cleaner. To this dispersion, 100 g of phenyl methacrylate monomer and 250 g of 10 wt% ethyl silicate-based silica sol were mixed well to prepare the coating material for forming a zeolite film of the present invention. The mixing ratio of the organic solvent, zeolite, additive, and binder composition in the prepared coating for forming a zeolite film was 68.5: 5.6: 7.4: 18.5 in terms of a weight ratio. A 0.5 m 2 aluminum substrate was immersed in this zeolite film-forming coating material, whereby the coating material was applied to the surface of the aluminum substrate and pre-baked at 50 ° C. for 0.5 hour. Subsequently, main baking was performed at 235 ° C. for 0.5 hour. The zeolite film was formed on the aluminum substrate by repeating the dipping in the paint, temporary firing and main firing until the amount of zeolite supported per 0.5 m 2 of the aluminum substrate reached 60 g.
<Example 8>
1425 g of methanol was mixed with 75 g of zeolite having an average particle diameter of 8 μm and a pore diameter of 0.9 nm, and dispersed with a paint shaker for 1 hour using 100 g of zirconia beads to prepare a dispersion. To this dispersion, 70 g of benzyl methacrylate monomer and 250 g of 10 wt% methyl silicate-based silica sol were mixed well to prepare the coating material for forming a zeolite film of the present invention. The mixing ratio of the organic solvent, zeolite, additive, and binder composition in the prepared coating for forming a zeolite film was 79: 4: 3.5: 13.5 in weight ratio. A 0.5 m 2 aluminum substrate was immersed in this zeolite film-forming coating material, whereby the coating material was applied to the surface of the aluminum substrate and pre-baked at 30 ° C. for 0.5 hour. Subsequently, main baking was performed at 270 ° C. for 0.5 hour. The zeolite film was formed on the aluminum substrate by repeating the dipping in the paint, temporary firing and main firing until the amount of zeolite supported per 0.5 m 2 of the aluminum substrate reached 60 g.
＜比較例１〜８＞
添加剤であるメタクリル酸エステルモノマーを添加混合しない以外は実施例１〜８と同様にしてアルミ基板上にゼオライト膜を形成した。
＜比較試験１＞
先ず実施例１〜８及び比較例１〜８でそれぞれ得られたゼオライト膜が形成されたアルミ基板を２５０℃に維持された乾燥機内に入れて、３時間保持した。乾燥後は各アルミ基板をデシケーター内で放冷した。放冷後、空気中の水分が基板に吸着されないように注意しながら、各アルミ基板の重量を計測した。次いで、ゼオライト膜が形成されたアルミ基板を２５℃、相対湿度９０％に維持された恒温恒湿槽内に入れて１２時間保持し、ゼオライト膜に水分を吸着させた。保持後はゼオライト膜が形成されたアルミ基板を恒温恒湿槽内から取出し、直ちに各アルミ基板の重量を再び測定した。次に、水分吸着前後の重量の差を求め、単位面積あたりの吸着割合を算出した。実施例１〜８及び比較例１〜８で使用したゼオライト膜形成用塗料及びゼオライト膜が形成されたアルミ基板について測定した結果を表２及び表３に示す。
<Comparative Examples 1-8>
A zeolite membrane was formed on an aluminum substrate in the same manner as in Examples 1 to 8, except that the methacrylic acid ester monomer as an additive was not added and mixed.
<Comparison test 1>
First, the aluminum substrates on which the zeolite membranes obtained in Examples 1 to 8 and Comparative Examples 1 to 8 were formed were placed in a dryer maintained at 250 ° C. and held for 3 hours. After drying, each aluminum substrate was allowed to cool in a desiccator. After cooling, the weight of each aluminum substrate was measured while taking care not to adsorb moisture in the air to the substrate. Next, the aluminum substrate on which the zeolite membrane was formed was placed in a constant temperature and humidity chamber maintained at 25 ° C. and a relative humidity of 90% and held for 12 hours to adsorb moisture to the zeolite membrane. After the holding, the aluminum substrate on which the zeolite film was formed was taken out from the constant temperature and humidity chamber, and the weight of each aluminum substrate was immediately measured again. Next, the difference in weight before and after moisture adsorption was determined, and the adsorption ratio per unit area was calculated. Tables 2 and 3 show the measurement results of the coatings for forming a zeolite film used in Examples 1 to 8 and Comparative Examples 1 to 8 and the aluminum substrate on which the zeolite film was formed.
表２及び表３より明らかなように、ゼオライト膜形成用塗料に添加剤であるメタクリル酸エステルモノマーが含まれていない比較例１〜８で形成したゼオライト膜に比べて本発明のゼオライト膜形成用塗料を用いた実施例１〜８で形成したゼオライト膜は、同量のゼオライト担持量でも水分吸着割合が高い結果が得られていることが判る。
As is apparent from Tables 2 and 3, the zeolite membrane-forming coating material of the present invention is compared with the zeolite membranes formed in Comparative Examples 1 to 8 in which the methacrylic acid ester monomer as an additive is not contained in the zeolite membrane-forming coating material. It can be seen that the zeolite membranes formed in Examples 1 to 8 using paints have a high moisture adsorption ratio even with the same amount of zeolite supported.
Claims (7)
添加剤としてメタクリル酸エステルモノマーを更に含むことを特徴とするゼオライト膜形成用塗料。 In the zeolite film-forming paint containing each of the zeolite, the binder composition and the organic solvent,
A paint for forming a zeolite film, further comprising a methacrylic acid ester monomer as an additive.
前記塗料を塗布した基材を２０℃〜５０℃で仮焼成する工程と、
前記仮焼成した基材を塗料に含まれる添加剤の沸点以上前記基材の融点以下で本焼成する工程と
を含むことを特徴とするゼオライト膜の製造方法。 Applying the paint according to any one of claims 1 to 4 to a substrate;
A step of pre-baking the substrate coated with the paint at 20 ° C. to 50 ° C .;
And a step of subjecting the temporarily fired base material to a final firing temperature not lower than the boiling point of the additive contained in the paint and not higher than the melting point of the base material.
請求項１ないし４いずれか１項に記載の塗料を前記仮焼成した基材に塗布する工程と、
前記塗料を塗布した基材を塗料に含まれる添加剤の沸点以上前記基材の融点以下で本焼成する工程と
を含むことを特徴とするゼオライト膜の製造方法。 A step of calcining the substrate at 20 ° C. to 50 ° C .;
Applying the paint according to any one of claims 1 to 4 to the temporarily fired substrate;
And a step of subjecting the base material coated with the paint to a main firing at not less than the boiling point of the additive contained in the paint and not more than the melting point of the base material.
前記膜中に含まれるゼオライトとシリカゾル由来のＳｉＯ2の重量比が６：４〜８：２であることを特徴とするゼオライト膜。
A zeolite membrane formed by applying and baking the coating material according to any one of claims 1 to 4 on a substrate surface, or a zeolite membrane produced by the method according to claim 5 or 6,
A zeolite membrane characterized in that the weight ratio of zeolite contained in the membrane and SiO 2 derived from silica sol is 6: 4 to 8: 2.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008528263A (en) * | 2005-01-26 | 2008-07-31 | クリンゲンブルク ゲゼルシャフト ミット ベシュレンクテル ハフツング | Moisture and / or heat exchange device |
| CN102336566A (en) * | 2010-07-28 | 2012-02-01 | 鸿富锦精密工业（深圳）有限公司 | Composite target and preparation method thereof |
| CN112870992A (en) * | 2021-01-13 | 2021-06-01 | 同济大学 | Zeolite membrane and preparation method thereof |
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2004
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008528263A (en) * | 2005-01-26 | 2008-07-31 | クリンゲンブルク ゲゼルシャフト ミット ベシュレンクテル ハフツング | Moisture and / or heat exchange device |
| CN102336566A (en) * | 2010-07-28 | 2012-02-01 | 鸿富锦精密工业（深圳）有限公司 | Composite target and preparation method thereof |
| US20120024699A1 (en) * | 2010-07-28 | 2012-02-02 | Hon Hai Precision Industry Co., Ltd. | Composite target material and method for producing the same |
| US8535601B2 (en) * | 2010-07-28 | 2013-09-17 | Hong Fu Jin Precision Industry (Shenzhen) Co., Ltd. | Composite target material and method for producing the same |
| CN112870992A (en) * | 2021-01-13 | 2021-06-01 | 同济大学 | Zeolite membrane and preparation method thereof |
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