JP5327783B2 - Water-resistant self-supporting film and method for producing the same - Google Patents
Water-resistant self-supporting film and method for producing the same Download PDFInfo
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
Description
本発明は、耐水性自立膜とその製造方法に関するものであり、更に詳しくは、ゼオライトとセラミックの混合粉体を用いて作製した、数十ナノメートルから数十ミクロン径の細孔径分布を有する耐水性自立膜、その製造方法及び用途に関するものである。 The present invention relates to a water-resistant self-supporting membrane and a method for producing the same, and more specifically, a water-resistant membrane having a pore size distribution of several tens of nanometers to several tens of microns produced using a mixed powder of zeolite and ceramic. The present invention relates to a self-supporting film, its manufacturing method and use.
ゼオライトは、規則的に配列したミクロ孔を有し、一般に、耐熱性が高く、化学的にも安定なものが数多く得られることから、様々な分野で利用されている。このゼオライトは、その骨格構造が、Ｓｉの一部がＡｌに置換したアルミノシリケートであり、分子オーダー（３〜１０Å程度）の細孔を有し、立体選択的な吸着作用を持つことより、モレキュラーシーブ（分子ふるい）としての機能を有する。数十種類の天然に産出するゼオライトの他に、これまでに、１５０種類以上のゼオライトが合成されており、固体酸触媒、分離吸着剤、及びイオン交換剤等の分野で幅広く用いられている。 Zeolites have regularly arranged micropores, and are generally used in various fields because many heat resistant and chemically stable materials can be obtained. This zeolite is an aluminosilicate whose skeleton structure is a part of Si substituted by Al, has pores of molecular order (about 3 to 10 cm), and has a stereoselective adsorption action, so that it is molecular. It functions as a sieve (molecular sieve). In addition to dozens of naturally occurring zeolites, more than 150 types of zeolites have been synthesized so far and are widely used in fields such as solid acid catalysts, separated adsorbents, and ion exchangers.
このゼオライトは、可塑性に乏しいため、膜状などに成形する場合、ほとんどの場合は水熱合成法により、基板上にゼオライト膜を合成している。すなわち、大量の水とアルミニウム源、シリカ源、アルカリ金属、アミン類などの有機結晶化調整剤を適宜目的の生成物のゼオライト組成になるように調合し、オートクレーブ等の圧力容器にそれらを封じ込めて、アルミナやムライトなどの多孔質基板やチューブを共存させて加熱することにより、それらの基板上にゼオライト膜を合成している。 Since this zeolite is poor in plasticity, when it is formed into a film or the like, in most cases, a zeolite film is synthesized on a substrate by a hydrothermal synthesis method. That is, a large amount of water and an organic crystallization regulator such as an aluminum source, a silica source, an alkali metal, and amines are appropriately formulated so as to have a desired zeolite composition, and they are sealed in a pressure vessel such as an autoclave. A zeolite membrane is synthesized on these substrates by heating in the presence of a porous substrate or tube such as alumina or mullite.
これまでに、例えば、ＭＦＩ、ＭＥＬ、ＬＴＡ、ＡＮＡ、ＣＨＡ、ＦＡＵ、ＳＯＤ、ＭＯＲ、ＥＲＩ、ＢＥＡ、ＬＴＬ、ＤＤＲ（以上はhttp://www.iza-structure.org/databases/のframework Typesに記載されているゼオライトの３次元構造の種類を表すコードである。）といったゼオライト膜が合成されており、それぞれのゼオライトの性質（例えば、細孔径・親和性）から、分離対象を適宜選択している。また、先行文献には、ゼオライト種結晶を塗布した後、更に、水熱合成することにより欠陥のないゼオライト膜を合成する方法が開示されている（特許文献１）。また、これらの手法で合成されたゼオライト膜は、気体又は液体混合物からの分離・濃縮などに利用されることが開示されている（特許文献２）。 Up to now, for example, MFI, MEL, LTA, ANA, CHA, FAU, SOD, MOR, ERI, BEA, LTL, DDR Zeolite membranes such as the three-dimensional structure types of zeolite described in the above are synthesized, and the separation target is appropriately selected from the properties (for example, pore diameter and affinity) of each zeolite. Yes. Further, the prior literature discloses a method of synthesizing a defect-free zeolite membrane by hydrothermal synthesis after applying a zeolite seed crystal (Patent Document 1). Further, it is disclosed that the zeolite membrane synthesized by these methods is used for separation / concentration from a gas or liquid mixture (Patent Document 2).
このように、ゼオライト膜の利用はナノサイズの細孔による成分分離膜が一般的である。近年問題とされるバラスト水のろ過処理においては、５，０００ｔから数万トンの水処理が必要となり、ナノメートルサイズの細菌類除去の他に数ミクロンサイズの微生物除去が重要となる。現状の水処理装置では、大型微生物の処理には５０μｍサイズのＳＵＳフィルターによるろ過や機械的殺滅が検討されている。ろ過による処理は主にアメリカやカナダで検討されている。処理量としては３，０００ｔ／ｈの処理が可能とされ、現状で４００ｔ／ｈ以上の規模の実船試験も行なわれている。
日本では装置のコンパクト化やメンテナンスの容易さから、パイプ式機械的殺滅法に着目しており、その処理能力は、現状最大で３００ｔ／ｈｒ程度となっており、５，０００ｔ量の処理には半日以上、５０，０００ｔクラスのバラスト水を搭載する大型船舶では１週間かかる。また、１０μｍサイズ以下の微生物に対しては殺傷効果が低く、年々厳しくなる排水基準や、処理量の増加に対して、船舶へのバラストポンプの増設や装置のパイプ性能の向上が必要になるなど、困難な点も抱えている。
いずれにせよ、１０μｍ以下の微生物の除去にはＵＶやオゾン処理、化学処理による殺菌が考えられているが、海水中に殺菌剤が流出することは許されないので、殺菌剤を流出しない形で担持でき、且つ数ミクロンサイズの微生物の除去もできる精密ろ過膜の利用はこれから有用であると考えられる。
このような精密ろ過分野で、ゼオライトをろ過補助材として使用する例は複数報告や特許があるが、これらはゼオライトを微生物等の吸着剤として用い、吸着媒のゼオライトを吸着質と一緒にろ過して処理するといった利用法である。例としては、銀担持ゼオライトを無機抗菌剤として、家庭用浄水器の中空糸フィルターの前段に用いる技術（特許文献３）がある。また清涼飲料水や酒類のプレフィルターとしてゼオライト担持膜を利用する特許出願がある（特許文献４）。また、船舶のバラスト水処理用のろ過フィルターとして金属製スリットを擁した円筒状中空フィルタエレメントが考案されており、珪藻土やゼオライトがそのろ過助剤とされている（特許文献５）。これらのフィルターは再利用のためのメンテナンスが必要で、バラスト水や食品製造用水の処理といった、微生物等を含んだ多量の水を短時間に処理しなければならない用途には、膜ごと使い捨て可能な自立膜がより便利であると考えられる。
ゼオライト粉体を利用して板状の成形体にする方法としては、ゼオライト粉体に加える水の量を２０〜４０質量％にコントロールして成形、焼成することによってバインダーなしに成形体が得られる方法が提案され、焼結温度が４００℃までなら陽イオン交換容量の１００質量％が、５００〜７００℃までならの７０〜８０質量％が保持されることが報告されている（特許文献６）。
しかしながら、この従来技術では、ゼオライトの強い親水性のため、５００〜６００℃焼結後もフィルター用途としては耐圧性、耐水性が乏しく、支持膜が無い状態では崩れ易い。また、細孔は小さくなり、減圧下でも非常に低い水透過性しか得られない。強度を上げるため、焼成温度を高くすると空隙率が下がり、イオン交換性も激減する。このようにゼオライトは、それだけで基材などを用いない自立膜として且つ高い空隙率とマクロポアを有する膜に作製するのは困難であった。
Thus, the use of a zeolite membrane is generally a component separation membrane with nano-sized pores. In the filtration treatment of ballast water, which has been a problem in recent years, water treatment of 5,000 to tens of thousands of tons is required, and in addition to removal of nanometer-sized bacteria, removal of microorganisms of several microns is important. In the current water treatment apparatus, filtration with a 50 μm size SUS filter and mechanical killing are being studied for the treatment of large microorganisms. Filtration treatment is mainly studied in the United States and Canada. The processing amount is 3,000 t / h, and an actual ship test with a scale of 400 t / h or more is currently performed.
In Japan, we are focusing on the pipe-type mechanical killing method because of the compactness of the equipment and ease of maintenance, and its processing capacity is currently about 300 t / hr at the maximum, and it can handle 5,000 t of processing. is half a day or more, in large vessels to mount the ballast water of 50,000t class takes one week. Also, for microbes of 10 μm size or less, the killing effect is low, and it becomes necessary to increase the ballast pump on the ship and improve the pipe performance of the equipment in response to the stricter drainage standards and the increase in throughput. There are also difficult points.
In any case, sterilization by UV treatment, ozone treatment, or chemical treatment is considered to remove microorganisms of 10 μm or less. However, it is not allowed for the germicide to flow into the seawater, so it is supported in a form that does not allow the germicide to flow out. The use of a microfiltration membrane that is capable of removing microorganisms having a size of several microns is considered useful from now on.
There are several reports and patents on the use of zeolite as a filter aid in such microfiltration field, but these use zeolite as an adsorbent for microorganisms and filter the adsorbent zeolite together with the adsorbate. This is a usage method. As an example, there is a technique (Patent Document 3) in which silver-supported zeolite is used as an inorganic antibacterial agent in the front stage of a hollow fiber filter of a domestic water purifier. There is also a patent application that uses a zeolite-supported membrane as a pre-filter for soft drinks and alcoholic beverages (Patent Document 4). Further, the cylindrical hollow filter element home to metallic slit as filtration filter for ballast water treatment vessels have been devised, diatomaceous earth, zeolite is its filter aid (Patent Document 5). These filters require maintenance for reuse, and can be disposable with membranes for applications where a large amount of water containing microorganisms must be treated in a short period of time, such as treatment of ballast water and food production water. Free-standing membranes are considered more convenient.
As a method of forming a plate-shaped molded body using zeolite powder, a molded body can be obtained without a binder by molding and firing by controlling the amount of water added to the zeolite powder to 20 to 40% by mass. A method has been proposed, and it has been reported that if the sintering temperature is up to 400 ° C., 100% by mass of the cation exchange capacity is maintained, and if it is from 500 to 700 ° C., 70 to 80% by mass is maintained (Patent Document 6). .
However, in this prior art, due to the strong hydrophilicity of zeolite, even after sintering at 500 to 600 ° C., the pressure resistance and water resistance are poor as a filter application, and it tends to collapse without a support membrane. In addition, the pores become small and only a very low water permeability can be obtained even under reduced pressure. To increase the strength, increasing the firing temperature decreases the porosity and drastically reduces ion exchange properties. Thus, it has been difficult to produce a zeolite as a self-supporting membrane that does not use a base material alone and that has a high porosity and macropores.
したがって、本発明は、ゼオライトの特性である吸着性やイオン交換性を有する新規な精密ろ過膜を作製できる新材料を提供することを目的とするものである。更に、本発明は、微生物を含有する海水ろ過と同時に、イオン交換や担持金属イオンによる殺菌を行える精密ろ過膜として使用できる自立膜（以下、ゼオライト−セラミック複合自立膜ということもある。）及びこれらに用いる新材料と複合自立膜の製造方法を提供することを目的とするものである。 Accordingly, an object of the present invention is to provide a new material capable of producing a novel microfiltration membrane having adsorptivity and ion exchange properties which are the characteristics of zeolite. Furthermore, the present invention is a self-supporting membrane (hereinafter sometimes referred to as a zeolite-ceramic composite self-supporting membrane ) that can be used as a microfiltration membrane that can be sterilized by ion exchange and supported metal ions simultaneously with filtration of seawater containing microorganisms . It aims at providing the manufacturing method of the new material used for a composite, and a composite self-supporting film | membrane.
本発明者らは、これまでに報告されていないゼオライトの精密ろ過用自立膜を作製できる新材料を開発すべく、鋭意検討を行った結果、低温固結性のセラミック系バインダーの混合により耐水性でイオン交換性も高い自立膜を得ることができることを見い出し、この知見に基づき本発明を完成するに至った。
本発明は、ゼオライトとセラミック系バインダーとの混合物の固結体からなる自立膜（本明細書において、ゼオライト−セラミック複合自立薄膜ということもある。）であって、耐熱性、耐水性及び調湿性の他に、イオン交換性、吸着性等ゼオライトの特性を有することを特徴とするゼオライト−セラミック複合自立薄膜であり、原料粉末中にセラミック系バインダーを混入することによって行う上記ゼオライト−セラミック複合自立薄膜の製造方法である。また、本発明は、上記のゼオライト−セラミック複合膜から成ることを特徴とする精密ろ過膜である。また、本発明は、精密ろ過とイオン交換もしくは殺菌を同時に行うことができるゼオライト−セラミック複合膜およびその製造方法である。
The present inventors, in order to develop a new material that can be fabricated so far unreported microfiltration for freestanding membrane of zeolite, extensive studies were carried out result, water resistance by mixing the low-temperature solidification of the ceramic binder Thus, it was found that a self-supporting membrane having a high ion exchange property can be obtained, and the present invention has been completed based on this finding.
The present invention is a self-supporting film ( sometimes referred to as a zeolite-ceramic composite self-supporting thin film in this specification) made of a solidified mixture of a zeolite and a ceramic binder, and has heat resistance, water resistance and humidity control. a ceramic composite self-standing thin film, said zeolite carried out by incorporating the ceramic binder in the raw material powder - - in addition to, ion exchange, zeolites characterized by having the properties of adsorption and the like zeolite ceramic composite self-standing film It is a manufacturing method. The present invention also provides a microfiltration membrane comprising the above-mentioned zeolite-ceramic composite membrane. The present invention is also a zeolite-ceramic composite membrane capable of performing microfiltration and ion exchange or sterilization at the same time, and a method for producing the same.
すなわち本発明は、
（１）ゼオライトと、アルミナ、ジルコニア、マグネシア及びシリカからなる群より選択されるセラミック系バインダーとの混合物の固結体からなる耐水性自立膜であって、数十ナノメートルから数十ミクロン径の細孔径分布を有し、水溶液の精密ろ過性と、吸着性及びイオン交換性とを有する耐水性自立膜
（２）ゼオライトが天然産のモルデナイトであることを特徴とする（１）記載の耐水性自立膜
（３）形状が平板状もしくは任意形状である（１）又は（２）に記載の耐水性自立膜
（４）厚さが０．８〜３ｍｍである（１）〜（３）のいずれか１項に記載の耐水性自立膜
（５）４〜５ミクロンサイズのビール酵母を分散液中から手動加圧ろ過できる（１）〜（４）のいずれか１項に記載の耐水性自立膜
（６）前記ゼオライトと前記セラミック系バインダーの混合比が、質量比で１：１から１：２である（１）〜（５）のいずれかに記載の耐水性自立膜、及び
（７）ゼオライト粉末と、アルミナ、ジルコニア、マグネシア及びシリカからなる群より選択されるセラミック系バインダーとを混合して成型した後、成型体を常温〜３００℃で固結させることを特徴とする（１）〜（６）のいずれか１項に記載の耐水性自立膜の製造方法
を提供するものである。
That is, the present invention
(1) and the zeolite, alumina, zirconia, a water-resistant self-supporting film ing from consolidated body of a mixture of a ceramic binder selected from the group consisting of magnesia and silica, tens of microns diameter from a few tens of nanometers Water-resistant self-supporting membrane having a fine pore size distribution and having an aqueous solution microfiltration property , adsorptivity and ion exchange property (2) The zeolite is a natural mordenite, and is water-resistant as described in (1) The self-supporting film (3) has a flat plate shape or an arbitrary shape. The water-resistant self-supporting film (4) according to (1) or (2) has a thickness of 0.8 to 3 mm (1) to (3) The water-resistant self-supporting membrane according to any one of the above items (5) The water-resistant self-supporting membrane according to any one of (1) to (4) , which can manually filter the brewer's yeast having a size of 4 to 5 microns from the dispersion. wherein the membrane (6) the zeolite Cerami The mixing ratio of the click-based binder is 1 mass ratio: 1 to 1: 2 (1) Water resistance free standing film according to any one of the - (5), and (7) a zeolite powder and alumina, zirconia, Any one of (1) to (6) , wherein the molded body is solidified at room temperature to 300 ° C. after being mixed with a ceramic binder selected from the group consisting of magnesia and silica. The manufacturing method of the water-resistant self-supporting film | membrane as described in 1 is provided.
本発明により、
（１）精密ろ過膜でありながら、ゼオライトのイオン交換性や吸着性を併せ持つゼオライト−セラミック複合体からなる耐水性材料が得られる。
（２）この耐水性材料から作製した複合膜はＭｇイオンなどの陽イオンを含有する水溶液の吸着、イオン交換作用を有し、かつ耐水性で自立複合膜とできる。
（３）本発明のゼオライト−セラミック複合膜は、例えば、食品工業用排水の処理剤として好適に使用することができる。
（４）耐水性、耐熱性、湿度調整機能を持ち合わせることから、高温高湿度環境における壁材としても使用することが可能である。また、ゼオライトが３次元細孔構造を有することから、ＶＯＣ等の有害ガスの吸着分離に使用することが可能である。また、銀その他の金属イオン等を担持することにより、抗菌性や触媒作用等の機能を付与することが可能である。
According to the present invention,
(1) A water-resistant material comprising a zeolite-ceramic composite having both ion exchange properties and adsorptivity of zeolite can be obtained while being a microfiltration membrane.
(2) A composite membrane produced from this water-resistant material has an adsorption and ion exchange action of an aqueous solution containing cations such as Mg ions, and is water-resistant and can be a self-supporting composite membrane.
(3) The zeolite-ceramic composite membrane of the present invention can be suitably used as, for example, a treatment agent for wastewater for food industry.
(4) Since it has water resistance, heat resistance, and humidity adjustment functions, it can also be used as a wall material in a high temperature and high humidity environment. Moreover, since zeolite has a three-dimensional pore structure, it can be used for adsorption separation of harmful gases such as VOC. Further, by carrying silver or other metal ions, it is possible to impart functions such as antibacterial properties and catalytic action.
次に、本発明の好適な実施の形態を説明する。なお、本発明において、数値範囲の記載は、両端値のみならず、その中に含まれる全ての任意の中間値を含むものである。
本発明において用いるゼオライトの種類について特に限定はしない。また、天然産ゼオライトであることや、結晶粒子が数ミクロンサイズと大きいのは一向に差し支えないが、ベントナイトのように水膨潤性の粘土成分を１０質量％以上含むものは８００℃以下の焼成では、焼成後も水膨潤性が残り、耐水性が得られないので好ましくない。本発明においてゼオライト結晶の結晶粒子径は好ましくは０．０５〜１００μｍ、より好ましくは０．０５〜２０μｍ程度であり、粉末として粒径は好ましくは≦０．７ｍｍ、より好ましくは≦０．２ｍｍである。
Next, a preferred embodiment of the present invention will be described. In the present invention, the description of the numerical range includes not only both end values but also all arbitrary intermediate values included therein.
There is no particular limitation on the type of zeolite used in the present invention. In addition, it is natural that the zeolite is a natural product or the crystal particles are as large as several microns, but those containing 10% by mass or more of a water-swelling clay component such as bentonite are calcined at 800 ° C. or lower. Water swellability remains after firing, and water resistance cannot be obtained, which is not preferable. In the present invention, the crystal particle diameter of the zeolite crystal is preferably 0.05 to 100 μm, more preferably about 0.05 to 20 μm, and the particle diameter of the powder is preferably ≦ 0.7 mm, more preferably ≦ 0.2 mm. is there.
本発明においてセラミックとバインダーと予め混合したセラミック系バインダーを用いるのが好ましい。このセラミック系バインダーとはゼオライト粉末を固めるためのつなぎであり、セラミックをベース成分とした低温固結性の接着剤（結合剤）のことである。このセラミック系バインダーは水溶性の粉末もしくはそれのスラリーで４００℃以下で固結し、固結後は耐水性が高いものが好ましい。具体的にはセラミック系バインダーのベース成分の種類としてはアルミナ、ジルコニア、マグネシア、シリカなどが挙げられこれらの粒径は特に制限するものではないが、好ましくは０．０２〜１００μｍ、より好ましくは０．０２〜２０μｍとして用いられる。セラミック系バインダー中の前記ベース成分の含有量は特に限定しないが、好ましくは９５〜１００質量％とする。ゼオライト粉末と混合してスラリーとする場合はこれらに水を添加してスラリー状に調製する。 Preferably a ceramic-based binder premixed with the ceramic and the binder in the present invention. This ceramic binder is a bond for solidifying the zeolite powder, and is a low-temperature-setting adhesive (binder) based on ceramic . The ceramic binder is consolidated at 400 ° C. The following water-soluble powder or its slurry, after consolidation is preferable that a high water resistance. Specifically alumina as the type of base component of the ceramic binder is zirconia, magnesia, but is not intended to these particle size particularly limited cited such as silica, preferably 0.02～100Myuemu, more preferably 0 Used as 02 to 20 μm. The content of the base component of the ceramic binder is not particularly limited, preferably 95 to 100 mass%. When mixed with zeolite powder to form a slurry, water is added to these to prepare a slurry.
本発明においてゼオライト粉末に低温固結性のセラミック系バインダー、水を加えて練り合わせたスラリーを成型し、さらにこれを低温、例えば常温〜３００℃で固結させることにより比較的簡単にゼオライト−セラミック複合膜を得る。
本発明における、ゼオライト−セラミック複合膜の製造方法についてさらに詳細に説明すると、上記ゼオライト粉末とセラミック系バインダー粉末を混合した後に、これにゼオライトと等量の水を混入してスラリーとする。このとき、セラミック系バインダーとゼオライト粉末の混合比は混合するバインダーの種類に影響されるが、質量比で２：１から１：１が好ましい。少なすぎると、耐水性が低下するため、より高温での焼成が必要となり、結果としてゼオライトのイオン交換性、空隙率、透水性の低下が起きる。多すぎてもゼオライトの性質が反映されにくくなり、イオン交換性や空隙率が低下する。また、成型時の水添加量については、全重量の２５〜３５ｗｔ％が好ましい。少なすぎると成型時に崩れ易く、また、細孔容積や、細孔径が小さくなる。多すぎると成型が困難であり、乾燥、焼成、通水時にも亀裂や崩れが生じ易い。成型の手法には特に制限はなく好きな形に成型してよい。一軸性成型機による加圧成型の際には、特に強く加圧する必要はなく、成型機での加圧は１００ＭＰａ以下が好ましい。加圧の圧力が高すぎると、細孔が潰れ、空隙率の低下を引き起こすので好ましくない。本発明のゼオライト−セラミック複合体の乾燥・固結後の空隙率は水銀ポロシメーター（島津製作所社製、オートポアIII９４００型）で測定した値で、好ましくは３０％〜７０％であり、より好ましくは３０％〜６５％である。
Low caking of ceramic binder to the zeolite powder in the present invention, water is added by molding kneaded slurry, further low temperature this example relatively easily zeolite by consolidation at room temperature to 300 ° C. - ceramic composite Get a membrane.
The method for producing a zeolite-ceramic composite membrane in the present invention will be described in more detail. After mixing the zeolite powder and the ceramic binder powder, an equivalent amount of water is mixed with the zeolite powder to form a slurry. At this time, although the mixing ratio of the ceramic binder and the zeolite powder is affected by the kind of the binder to be mixed, the mass ratio is preferably 2: 1 to 1: 1. If the amount is too small, the water resistance is lowered, so that firing at a higher temperature is necessary, and as a result, the ion exchange property, porosity, and water permeability of the zeolite are lowered. If the amount is too large, the properties of the zeolite are hardly reflected, and the ion exchange property and porosity are lowered. Moreover, about the water addition amount at the time of shaping | molding, 25-35 wt% of the total weight is preferable. If the amount is too small, it tends to collapse during molding, and the pore volume and pore diameter become small. If the amount is too large, molding is difficult, and cracks and collapse are likely to occur during drying, firing, and water flow. There is no particular limitation on the molding method, and it may be molded into a desired shape. In the case of pressure molding by a uniaxial molding machine, it is not necessary to press particularly strongly, and the pressure by the molding machine is preferably 100 MPa or less. An excessively high pressure is not preferable because the pores are crushed and the porosity is reduced. The porosity of the zeolite- ceramic composite of the present invention after drying and consolidation is a value measured with a mercury porosimeter (manufactured by Shimadzu Corporation, Autopore III 9400 type), preferably 30% to 70%, more preferably 30 % To 65%.
本発明において、複合膜成形後の乾燥・固結処理を行うが、この際、乾燥方法としては室温乾燥、凍結乾燥他のいずれの乾燥方法を用いても差し支えないが、急激な加熱脱水処理は膜が割れ易いので、好ましくない。固結処理を行う場合も同様に急激な加熱・冷却を避けることが望ましい。
本発明のゼオライト−セラミック複合体からなる前記の微細な細孔径を有する、水溶液の精密ろ過が可能な材料は、基材を用いずにそれ自体で適当な膜状に成形し使用可能である。
とりわけ本発明の複合膜は、それ自体、厚くなくても、また基材がなくても、自立して薄い膜状を保ち、適当な強度を有する。
この自立膜とできる場合の膜厚は特に制限するものではないが好ましくは０．８ｍｍ以上、より好ましくは１〜３ｍｍである。
In the present invention, after the composite film is formed, drying / consolidation treatment is performed. At this time, any drying method such as room temperature drying, freeze drying, or the like may be used, but rapid heating and dehydration treatment is performed. Since the film is easily broken, it is not preferable. Similarly, when performing the consolidation process, it is desirable to avoid rapid heating and cooling.
The material having the fine pore diameter and made of the zeolite- ceramic composite of the present invention and capable of microfiltration of an aqueous solution can be used by forming it into a suitable film by itself without using a substrate.
In particular, the composite membrane of the present invention itself has a suitable strength even when it is not thick or without a substrate, and maintains a thin membrane shape.
The thickness of the self-supporting film is not particularly limited, but is preferably 0.8 mm or more, more preferably 1 to 3 mm.
次に、実施例に基づいて本発明をさらに詳細に説明するが、本発明は以下の実施例等によって何ら限定されるものではない。 EXAMPLES Next, although this invention is demonstrated further in detail based on an Example, this invention is not limited at all by the following Examples etc.
［実施例１］
天然モルデナイトＣＰ（＜０．１５ｍｍφ、（株）新東北化学工業）１ｇに２ｇのアルミナ系セラミック系バインダー（粒径＜５μｍ、東亜合成 アロンセラミックＤ（バインダー成分、東亜合成社製） アルミナ含有量９４質量％）を混合し、これに１ｇの蒸留水を添加して練り合わせた。このモルデナイトスラリーをＳＵＳ製のディスク成型機に入れて１００ＭＰａで加圧成型した後、室温にて一晩乾燥を行った。その後、さらに固結させるため、オートクレーブ内部で１５０℃、２４時間加熱処理を行った。こうして得られた天然モルデナイト−セラミック複合膜を削って２ｍｍ厚とし、これをプラスティックのリング状ホルダーに装着し、１００ＭＰａの減圧下で水透過速度を測定したところ、１０ｍＬの通水では１．０ｃｍ／ｍｉｎで一定であった。続けて水の代わりに５ｍｍｏｌ／ＬのＭｇＣｌ２溶液を１０ｍＬ減圧下で透過させたところ、透過速度は０．６０ｃｍ／ｍｉｎで一定であった。また、ＭｇＣｌ２供給液中のＭｇ濃度は１２０ｐｐｍであったが、透過液中では１３ｐｐｍに低下した。同じ手法で作製した膜を水銀ポロシメーターで測定すると空隙率が３２％前後であり、細孔径分布曲線には０．０６，０．１，０．２，０．４および１μｍにピークが得られた（図１参照）。
[Example 1]
Natural mordenite CP (<0.15 mm, (Inc.) New Tohoku Kagaku Kogyo) 1 g to 2g of alumina ceramic binder (particle size <5 [mu] m, Toagosei Aron Ceramic D (binder component, manufactured by Toagosei Co., Ltd.) alumina content 94 1% by weight of distilled water was added and kneaded. This mordenite slurry was put in a SUS disk molding machine and pressure molded at 100 MPa, and then dried at room temperature overnight. Thereafter, in order to further solidify, heat treatment was performed at 150 ° C. for 24 hours inside the autoclave. The natural mordenite - ceramic composite membrane thus obtained was cut to a thickness of 2 mm, and this was mounted on a plastic ring holder, and the water permeation rate was measured under a reduced pressure of 100 MPa. It was constant at min. When the MgCl 2 solution 5 mmol / L instead of water were transmitted in 10mL vacuo continues, the permeation rate was constant at 0.60 cm / min. Further, the Mg concentration in the MgCl 2 supply liquid was 120 ppm, but it decreased to 13 ppm in the permeate. When the film produced by the same method was measured with a mercury porosimeter, the porosity was about 32%, and peaks were obtained at 0.06, 0.1, 0.2, 0.4 and 1 μm in the pore size distribution curve. (See FIG. 1).
［実施例２］
実施例１と同様の成型機で成型したディスクを、液体窒素で凍結し、一晩真空乾燥を行なった。そののちオートクレーブ内部で１５０℃、２４時間加熱処理を行った。こうして得られた天然モルデナイト−セラミック複合膜を削って２ｍｍ厚とし、これをプラスティックのリング状ホルダーに装着し、１００ＭＰａの減圧下で水透過速度を測定したところ、０．８ｃｍ／ｍｉｎであった。続けてＭｇＣｌ２溶液の減圧ろ過試験を行なった。減圧ろ過時のろ過速度は水透過速度と殆ど変わらず、およそ１ｃｍ／ｍｉｎであった。供給液及びろ液中のＭｇ濃度をＩＣＰにて測定したところ、供給液中６０ｐｐｍのＭｇ濃度が、減圧ろ過のろ液では検出されなかった。また、１％濃度のビール酵母（４−５μｍ径サイズ）サスペンジョンの手動加圧ろ過を行なったところ、ろ液中に確認される酵母はおよそ１％以下となった（図２参照）。図中（ａ）はろ過前の分散液を、（ｂ）はろ過液をそれぞれカーボンテープ上に等量滴下乾燥した状態の走査型電子顕微鏡（ＳＥＭ）像である。（ｂ）において白い点がないのでビール酵母が濾過されていることが分かる。同じ手法で作製した膜について、水銀ポロシメーターで細孔径分布を測定したところ、空隙率が４０％前後であり、細孔径分布曲線には０．０６，０．１，０．２，０．４，１および２μｍにピークが得られた（図１参照）。
[Example 2]
The disk molded by the same molding machine as in Example 1 was frozen with liquid nitrogen and vacuum dried overnight. After that, heat treatment was performed at 150 ° C. for 24 hours inside the autoclave. The natural mordenite - ceramic composite membrane thus obtained was shaved to a thickness of 2 mm, mounted on a plastic ring holder, and the water permeation rate was measured under a reduced pressure of 100 MPa. As a result, it was 0.8 cm / min. Subsequently, a vacuum filtration test of the MgCl 2 solution was performed. The filtration rate during vacuum filtration was almost the same as the water permeation rate, and was about 1 cm / min. When the Mg concentration in the supply liquid and the filtrate was measured by ICP, the Mg concentration of 60 ppm in the supply liquid was not detected in the filtrate of the vacuum filtration. Moreover, when manual pressure filtration of 1% concentration brewer's yeast (4-5 μm size) suspension was performed, the yeast confirmed in the filtrate was about 1% or less (see FIG. 2). In the figure, ( a ) is a dispersion before the filtration, and ( b ) is a scanning electron microscope (SEM) image in a state where an equal amount of the filtrate is dropped on a carbon tape and dried. Since there is no white point in ( b ), it turns out that brewer's yeast is filtered. When the pore size distribution was measured with a mercury porosimeter for the membrane produced by the same method, the porosity was about 40%, and the pore size distribution curve was 0.06, 0.1, 0.2, 0.4, Peaks were obtained at 1 and 2 μm (see FIG. 1).
［実施例３］
実施例２においてゼオライトとアルミナ系セラミック系バインダーの混合比を質量比で１：１とした以外は、実施例２と同様にして作製した天然モルデナイト−セラミック複合膜を０．９ｍｍ厚まで削り、プラスティックのリング状ホルダーに装着してＭｇＣｌ２溶液の減圧、手動加圧、自然ろ過試験を行なった。ＩＣＰにて供給液は１７ｐｐｍ、減圧ろ過ではろ液中のＭｇ濃度が３．８ｐｐｍ，手動ろ過では１．５ｐｐｍ，自然ろ過で０．４ｐｐｍであった。同様にして作製した膜について水銀ポロシメーターで細孔径分布を測定したところ、空隙率が５０％前後、細孔径分布曲線には０．０５，０．１，０．２，０．５，１，２，１５，３７および６８μｍであった。
[Example 3]
A natural mordenite - ceramic composite membrane produced in the same manner as in Example 2 except that the mixing ratio of zeolite and alumina-based ceramic binder in Example 2 was 1: 1 by mass, and was cut to a thickness of 0.9 mm. Were attached to a ring-shaped holder, and the MgCl 2 solution was subjected to reduced pressure, manual pressure, and natural filtration tests. The supply liquid was 17 ppm by ICP, the Mg concentration in the filtrate was 3.8 ppm by vacuum filtration, 1.5 ppm by manual filtration, and 0.4 ppm by natural filtration. When the pore size distribution of the membrane prepared in the same manner was measured with a mercury porosimeter, the porosity was about 50%, and the pore size distribution curve was 0.05, 0.1, 0.2, 0.5, 1, 2. 15, 37 and 68 μm.
［実施例４］
天然モルデナイト６０Ｐ（＜０．２ｍｍφ、（株）新東北化学工業）１ｇに２ｇの粉末状シリカ系セラミック接着剤（粒径１〜５０μｍ（水分散によって、より細かくなる）、太陽金網 Ｔｈｅｒｍｅｅｚ ７０３０）を混合し、これに１．５ｇの蒸留水を添加して練り合わせた。このモルデナイトスラリーを実施例１と同様のＳＵＳ製の成型機に入れて１００ＭＰａで加圧成型した後、室温にて一晩乾燥を行った。その後、さらに固結させるため、オートクレーブ内部で６５℃で一晩、１５０℃で２時間追加加熱処理を行った。こうして得られた天然モルデナイト−セラミック複合膜を削って２ｍｍ厚とし、これをプラスティックのリング状ホルダーに装着し、１００ＭＰａの減圧下で水透過速度を測定したところ、０．２ｃｍ／ｍｉｎであった。また、手動加圧にてＭｇＣｌ２溶液を透過させたところ、供給液中１２０ｐｐｍであったＭｇ濃度が、透過液では９０ｐｐｍに減少した。同様にして手動加圧ろ過にてビール酵母分散液のろ過を行なったところ、ろ過液中の４−５μｍサイズの酵母数は１％以下に減少した。別途この方法で作製した膜について水銀ポロシメーターで細孔径分布を測定したところ、空隙率が３２％前後、細孔径は０．１，０．２，０．５，１，１０，３７および６８μｍであった。
[Example 4]
1 g of natural mordenite 60P (<0.2 mmφ, Shintohoku Chemical Co., Ltd.) 2 g of powdered silica-based ceramic adhesive (particle size 1 to 50 μm (becomes finer by water dispersion), solar wire mesh Thermez 7030) The mixture was mixed, and 1.5 g of distilled water was added and kneaded. This mordenite slurry was put into a SUS molding machine similar to that in Example 1 and subjected to pressure molding at 100 MPa, and then dried overnight at room temperature. Thereafter, additional heat treatment was performed at 65 ° C. overnight and at 150 ° C. for 2 hours in the autoclave for further consolidation. The natural mordenite - ceramic composite membrane thus obtained was shaved to a thickness of 2 mm, mounted on a plastic ring holder, and the water permeation rate was measured under a reduced pressure of 100 MPa. The result was 0.2 cm / min. Further, when the MgCl 2 solution was permeated by manual pressurization, the Mg concentration that was 120 ppm in the supply liquid was reduced to 90 ppm in the permeated liquid. Similarly, when the beer yeast dispersion was filtered by manual pressure filtration, the number of 4-5 μm sized yeast in the filtrate decreased to 1% or less. When the pore size distribution was measured with a mercury porosimeter for the membrane prepared separately by this method, the porosity was about 32%, and the pore sizes were 0.1, 0.2, 0.5, 1, 10, 37 and 68 μm. It was.
［比較例１］
特許文献６（又は実施例１の図１）に記載の方法に従い、天然モルデナイトＣＰ（（株）新東北化学工業）３ｇに蒸留水を添加して練り合わせ、このモルデナイトスラリーの含水率が２７質量％になるまで室温放置した後、スラリーを実施例１と同様のＳＵＳ製の成型機に入れて２００ＭＰａで加圧成型し、室温乾燥を行い、さらにオートクレーブ内部で５００℃、１時間固結させるための加熱処理を行いディスク状のモルデナイト膜を得た。加熱処理後、水銀ポロシメーターで細孔径分布を測定したところ、空隙率が３７％前後、細孔径は０．０６，０．１，０．２および０．４μｍであった。このディスクをリング状ホルダーに装着して水透過率を測定したところ、空隙率が実施例１や４と比較して高いにもかかわらず、減圧方式で０．０３ｃｍ／ｍｉｎ程度の水透過量しか得られず、精密ろ過試験ができなかった。
[Comparative Example 1]
In accordance with the method described in Patent Document 6 (or FIG. 1 of Example 1), 3 g of natural mordenite CP (Shintohoku Chemical Co., Ltd.) was added with distilled water and kneaded. The water content of this mordenite slurry was 27% by mass. After being allowed to stand at room temperature until it becomes, the slurry is put into a SUS molding machine similar to that in Example 1 and pressure molded at 200 MPa, dried at room temperature, and further solidified at 500 ° C. for 1 hour inside the autoclave. Heat treatment was performed to obtain a disk-shaped mordenite film. When the pore size distribution was measured with a mercury porosimeter after the heat treatment, the porosity was about 37% and the pore sizes were 0.06, 0.1, 0.2 and 0.4 μm. When this disk was mounted on a ring-shaped holder and the water permeability was measured, the water permeation amount was only about 0.03 cm / min by the reduced pressure method even though the porosity was higher than in Examples 1 and 4. No microfiltration test was possible.
［比較例２］
モルデナイトスラリーの成型時の含水率を３５質量％にする他は、比較例１と同様の処理を行いディスク状のモルデナイト膜を得た。加熱処理後、水銀ポロシメーターで細孔径分布を測定したところ、細孔径は比較例１と同様であったが、空隙率が４９％前後に増加した（図１参照）。このディスクを実施例１と同様に２ｍｍ厚に削り、リング状プラスティックホルダーに装着し、１００ＭＰａの減圧下で水透過速度を測定した。その結果、通水１０ｍＬで膜が崩れ、測定が不可能になった。
[Comparative Example 2]
A disc-shaped mordenite film was obtained by performing the same treatment as in Comparative Example 1 except that the moisture content during molding of the mordenite slurry was 35% by mass. When the pore size distribution was measured with a mercury porosimeter after the heat treatment, the pore size was the same as in Comparative Example 1, but the porosity increased to around 49% (see FIG. 1). The disc was cut to a thickness of 2 mm in the same manner as in Example 1 and mounted on a ring-shaped plastic holder, and the water permeation rate was measured under a reduced pressure of 100 MPa. As a result, the membrane collapsed after 10 mL of water flow, making measurement impossible.
［比較例３］
モルデナイトスラリーの成型時の含水率を３４％とし、成型時の加圧圧力を１００ＭＰａ、焼成温度を７００℃とする以外は比較例１と同様の処理を行いディスク状のモルデナイト膜を得た。このディスクを実施例１と同様に２ｍｍ厚に削り、リング状プラスティックホルダーに装着し、水透過速度を測定したが、減圧方式で０．０３ｃｍ／ｍｉｎ程度の水透過量しか得られず、精密ろ過試験ができなかった。
[Comparative Example 3]
A disc-shaped mordenite film was obtained by performing the same treatment as in Comparative Example 1 except that the moisture content during molding of the mordenite slurry was 34%, the pressure applied during molding was 100 MPa, and the firing temperature was 700 ° C. The disc was cut to a thickness of 2 mm in the same manner as in Example 1 and mounted on a ring-shaped plastic holder, and the water permeation rate was measured. However, only a water permeation amount of about 0.03 cm / min was obtained by the decompression method, and microfiltration The test was not possible.
以上詳述したように、本発明は、ゼオライト−セラミック複合膜及びその製造方法に係るものであり、本発明により、現在までに報告されていない精密ろ過膜でありながら、ゼオライトのイオン交換性や吸着性を併せ持つゼオライト−セラミック複合膜を提供できる。本発明によれば、例えばバラスト水や食品工業用排水の処理膜として好適に使用することができる。耐水性、耐熱性、湿度調整機能を持ち合わせることから、高温高湿度環境における壁材としても使用することが可能である。また、ゼオライトが３次元細孔構造を有することから、ＶＯＣ等の有害ガスの吸着分離に使用することが可能である。また、銀その他の金属イオン等を担持することにより、抗菌性や触媒作用等の機能を付与することが可能である。 As described above in detail, the present invention relates to a zeolite-ceramic composite membrane and a method for producing the same, and according to the present invention, although it is a microfiltration membrane that has not been reported so far, A zeolite-ceramic composite membrane having both adsorptivity can be provided. According to the present invention, for example, it can be suitably used as a treatment film for ballast water or food industry wastewater. Since it has water resistance, heat resistance, and humidity adjustment functions, it can be used as a wall material in a high temperature and high humidity environment. Moreover, since zeolite has a three-dimensional pore structure, it can be used for adsorption separation of harmful gases such as VOC. Further, by carrying silver or other metal ions, it is possible to impart functions such as antibacterial properties and catalytic action.
Claims (7)
数十ナノメートルから数十ミクロン径の細孔径分布を有し、水溶液の精密ろ過性と、吸着性及びイオン交換性とを有する耐水性自立膜。 Zeolite, alumina, zirconia, a water-resistant self-supporting film ing from consolidated body of a mixture of a ceramic binder selected from the group consisting of magnesia and silica,
A water-resistant self-supporting membrane having a pore size distribution of several tens of nanometers to several tens of microns in diameter, and having microfiltration properties , adsorption properties, and ion exchange properties of aqueous solutions.
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