JP2000334250A - Gas separating filter and its production - Google Patents
Gas separating filter and its productionInfo
- Publication number
- JP2000334250A JP2000334250A JP11150976A JP15097699A JP2000334250A JP 2000334250 A JP2000334250 A JP 2000334250A JP 11150976 A JP11150976 A JP 11150976A JP 15097699 A JP15097699 A JP 15097699A JP 2000334250 A JP2000334250 A JP 2000334250A
- Authority
- JP
- Japan
- Prior art keywords
- gas
- support tube
- filter
- separation membrane
- gas separation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
- Degasification And Air Bubble Elimination (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、混合ガス中から特
定ガスを分離、回収するための特定ガス分離フィルタ
や、気体が溶解した液体中から該気体を除去する脱気フ
ィルタ等の被処理物から特定ガスを分離、回収するため
のガス分離フィルタに関するものであり、特に分離効率
の高い無機分離膜を有するガス分離フィルタおよびその
製造方法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an object to be treated such as a specific gas separation filter for separating and recovering a specific gas from a mixed gas and a degassing filter for removing the gas from a liquid in which the gas is dissolved. More particularly, the present invention relates to a gas separation filter having an inorganic separation membrane having high separation efficiency and a method for producing the same.
【０００２】[0002]
【従来技術】従来より、混合ガス中から特定ガスを分離
回収するための特定ガス分離フィルタや、気体が溶解し
た液体中から該気体を除去する脱気フィルタ等のガス分
離フィルタが知られている。2. Description of the Related Art Conventionally, gas separation filters such as a specific gas separation filter for separating and recovering a specific gas from a mixed gas and a degassing filter for removing the gas from a liquid in which the gas is dissolved are known. .
【０００３】例えば、各種装置に用いられる冷却水は、
装置の腐食防止ために脱酸素や脱炭酸ガスが求められて
おり、また、半導体洗浄用に使用される超純水は、生菌
の発生を抑えかつシリコンウエハの酸化を防ぐため、溶
存酸素濃度が１０ｐｐｂ以下に超脱気することが必要と
されている。[0003] For example, cooling water used for various devices is:
Deoxygenation and decarbonation gas are required to prevent equipment corrosion, and ultrapure water used for cleaning semiconductors uses dissolved oxygen concentration to suppress the generation of viable bacteria and prevent oxidation of silicon wafers. Is required to be super-degassed to 10 ppb or less.
【０００４】このような液体の脱気には、例えば加熱沸
騰法、減圧法、イオン交換樹脂法、不活性ガス置換法等
が良く知られている。しかしながら、前記加熱沸騰法は
高温操作のため危険性が高く、減圧法は脱気効率が悪
く、またイオン交換樹脂法は樹脂の再生処理が必要であ
り、さらに不活性ガス置換法はランニングコストがかさ
むものであった。[0004] For degassing such a liquid, for example, a heating boiling method, a decompression method, an ion exchange resin method, an inert gas replacement method and the like are well known. However, the heating and boiling method has a high risk due to high temperature operation, the decompression method has low degassing efficiency, the ion exchange resin method requires a resin regeneration treatment, and the inert gas replacement method has a low running cost. It was bulky.
【０００５】これに対して、装置が小型で処理工程が簡
便であること等の利点から分離膜を有するフィルタを用
いた脱気フィルタが多く採用されている。[0005] On the other hand, a deaeration filter using a filter having a separation membrane is often used because of its advantages such as a small apparatus and a simple processing step.
【０００６】かかる分離膜を有するフィルタとしては、
例えば、特定のガスを分離膜内部に吸収し、拡散により
ガスが膜内を透過する、いわゆる溶解拡散機構を用いた
高分子膜からなるものや、多孔質の高分子膜からなるも
のがすでに実用化されているが、いずれもガス分離効率
が低いものであった。[0006] As a filter having such a separation membrane,
For example, those made of a polymer membrane using a so-called dissolution-diffusion mechanism, in which a specific gas is absorbed inside the separation membrane and the gas permeates through the membrane by diffusion, and those made of a porous polymer membrane are already in practical use. However, in each case, the gas separation efficiency was low.
【０００７】そこで、最近では、直線状の多孔質セラミ
ック支持管の表面にＳｉＯ2 等の無機分離膜を被着形成
したフィルタを用いることが検討され、これにより、ガ
ス分離効率が向上することが報告されている（特開平１
０−５５５７号公報等参照）。Therefore, recently, it has been studied to use a filter in which an inorganic separation membrane such as SiO 2 is formed on the surface of a linear porous ceramic support tube, thereby improving the gas separation efficiency. It has been reported (Japanese Unexamined Patent Publication
No. 0-5557).
【０００８】[0008]
【発明が解決しようとする課題】しかしながら、特開平
１０−５５５７号公報等に開示されているガス分離フィ
ルタでは、被処理物を支持管内に供給すると、被処理物
の支持管内の流れは層流状態となり、被処理物中の特定
ガスが支持管の壁面と接触する割合が減ずるため、ガス
分離効率には限界があった。However, in the gas separation filter disclosed in Japanese Patent Application Laid-Open No. H10-5557, when the object to be processed is supplied into the support tube, the flow of the object to be processed in the support tube becomes laminar. As a result, the rate at which the specific gas in the object to be treated comes into contact with the wall surface of the support tube is reduced, so that the gas separation efficiency is limited.
【０００９】そこで、被処理物をらせん状の管内に供給
することによって、被処理液体の乱流を促進し、脱気効
率を高めることが特開平３−１６９３０４号公報に提案
されているが、特開平３−１６９３０４号公報は高分子
膜に適用するのみであって、セラミック支持体の表面に
無機分離膜を有するセラミック系の無機分離膜フィルタ
について、具体的な構成について記載がなく、また、特
開平１０−５５５７号公報においては、らせん状のセラ
ミック支持管を押出し成形によって直線状の成形体を作
製することが記載されるのみで、らせん状の支持管を作
製する具体的な方法については記載されないものであっ
た。Japanese Patent Application Laid-Open No. 3-169304 proposes that a turbulent flow of a liquid to be treated is promoted by supplying a substance to be treated into a helical tube to enhance degassing efficiency. Japanese Patent Application Laid-Open No. 3-169304 only applies to a polymer membrane, and does not describe a specific configuration of a ceramic inorganic separation membrane filter having an inorganic separation membrane on the surface of a ceramic support. Japanese Patent Application Laid-Open No. H10-5557 only discloses that a spiral shaped ceramic support tube is extruded to form a linear molded body, and a specific method for manufacturing a spiral shaped support tube is described. It was not described.
【００１０】本発明は前記課題を解決するためになされ
たもので、その目的は、ガス分離効率が高く、耐熱性お
よび耐薬品性に優れるセラミック支持管の内面または外
面に無機分離膜を被着形成したフィルタを用いることに
よって、被処理物の乱流を促進してガス分離効率を高め
ることができるガス分離フィルタおよびその製造方法を
提供することにある。SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems, and an object of the present invention is to attach an inorganic separation membrane to the inner or outer surface of a ceramic support tube having high gas separation efficiency and excellent heat resistance and chemical resistance. It is an object of the present invention to provide a gas separation filter capable of enhancing the gas separation efficiency by promoting turbulence of an object to be processed by using the formed filter, and a method for manufacturing the same.
【００１１】[0011]
【課題を解決するための手段】本発明者は、前記課題に
対しフィルタの構造について研究を重ねた結果、押出し
成形法を改良することによりらせん状の多孔質セラミッ
ク支持管を作製し、これに無機分離膜を被着形成したフ
ィルタを用いることによって、該フィルタのガス分離効
率を高めることができることを知見した。Means for Solving the Problems As a result of repeated studies on the structure of the filter for the above-mentioned problems, the present inventor has produced a helical porous ceramic support tube by improving the extrusion method. It has been found that by using a filter on which an inorganic separation membrane is formed, the gas separation efficiency of the filter can be increased.
【００１２】すなわち、本発明のガス分離フィルタは、
多孔質セラミックスからなるらせん状支持管の内面また
は外面に無機分離膜を被着形成し、前記らせん状支持管
の内面に特定ガスが混合または溶解した被処理物を供給
して前記無機分離膜に接触させ、該被処理物中の特定ガ
スのみを前記無機分離膜を介して前記らせん状支持管の
外表面に透過させて前記特定ガスを分離、回収すること
を特徴とするものである。That is, the gas separation filter of the present invention comprises:
An inorganic separation membrane is formed on the inner or outer surface of the spiral support tube made of porous ceramics, and a specific gas mixed or dissolved material is supplied to the inner surface of the spiral support tube to supply an inorganic separation membrane to the inorganic separation membrane. The method is characterized in that the specific gas in the object is passed through the inorganic separation membrane to the outer surface of the helical support tube through the inorganic separation membrane to separate and collect the specific gas.
【００１３】ここで、前記らせん状支持管の内径が１．
５ｍｍ以下であること、また、前記らせん状支持管のら
せんの内径が３０〜１００ｍｍであることが望ましい。
また、本発明のガス分離フィルタの製造方法は、セラ
ミック粉末に有機バインダと溶剤を添加しスラリーを作
製する工程と、該スラリーをノズルを有する押出し成型
用容器内に充填し、前記ノズル内におけるスラリーの押
出し量に偏りをつけることによってらせん状の管成形体
を作製する工程と、該管成形体を焼成して多孔質支持管
を作製する工程と、該多孔質支持管の表面に無機分離膜
を形成するためのゾル溶液を成膜し、ゲル化した後、酸
化性雰囲気中で焼成して無機分離膜を被着形成する工程
と、を具備することを特徴とするものである。Here, the inner diameter of the helical support tube is 1.
It is preferable that the diameter is 5 mm or less, and the inner diameter of the spiral of the spiral supporting tube is 30 to 100 mm.
In addition, the method for producing a gas separation filter of the present invention includes a step of preparing a slurry by adding an organic binder and a solvent to a ceramic powder, and filling the slurry into an extrusion molding container having a nozzle, and forming a slurry in the nozzle. Producing a helical tubular molded body by imparting a bias to the amount of extrusion, baking the tubular molded body to produce a porous support tube, and an inorganic separation membrane on the surface of the porous support tube. Forming a film of a sol solution for forming a film, gelling, and firing in an oxidizing atmosphere to deposit and form an inorganic separation membrane.
【００１４】[0014]
【発明の実施の形態】本発明のガス分離フィルタの一例
について、その一部切り欠き斜視図を図１に示す。図１
のガス分離フィルタ１は、多孔質セラミックスからなる
らせん状支持管（以下、支持管と略す。）２の内面に、
無機分離膜（以下、分離膜と略す。）３が被着形成され
たものである。なお、分離膜３は支持管２の外面に形成
されていてもよいが、ガス分離フィルタ１を特定ガスが
溶解した液体から該特定ガスを分離するいわゆる脱気フ
ィルタとして用いる場合には、前記液体がフィルタ１の
他方の面に漏れガス分離性能が低下することを防止する
点で、支持管２の内面に分離膜３が形成されることが望
ましい。DESCRIPTION OF THE PREFERRED EMBODIMENTS FIG. 1 is a partially cutaway perspective view of an example of a gas separation filter of the present invention. FIG.
The gas separation filter 1 is provided with an inner surface of a helical support tube (hereinafter, abbreviated as a support tube) 2 made of porous ceramics.
An inorganic separation membrane (hereinafter, abbreviated as a separation membrane) 3 is formed by adhesion. The separation membrane 3 may be formed on the outer surface of the support tube 2. However, when the gas separation filter 1 is used as a so-called degassing filter for separating a specific gas from a liquid in which the specific gas is dissolved, However, it is desirable that the separation membrane 3 be formed on the inner surface of the support tube 2 in order to prevent the leakage gas separation performance from being reduced on the other surface of the filter 1.
【００１５】支持管２は、気孔率が２０〜４０％、平均
細孔径０．１〜２μｍの多数の細孔を有し、α−アルミ
ナ、コージェライト等からなるものであって、望ましく
は、内径１．５ｍｍ以下、特に１．０ｍｍ以下であるこ
とが被処理物中の特定ガスがフィルタ表面に拡散する距
離が短く、ガス分離効率が向上する点、また、被処理物
の支持管２内の流れを乱流状態に促す点で望ましい。The support tube 2 has a large number of pores having a porosity of 20 to 40% and an average pore diameter of 0.1 to 2 μm, and is made of α-alumina, cordierite or the like. When the inner diameter is 1.5 mm or less, particularly 1.0 mm or less, the distance over which the specific gas in the object is diffused to the filter surface is short, and the gas separation efficiency is improved. It is desirable in that it promotes the turbulent flow.
【００１６】他方、分離膜３は平均細孔径０．２〜５ｎ
ｍ、特に平均細孔経０．５〜１．０ｎｍの細孔径を有す
るアルミナ、チタニア、ジルコニア、シリカ等、特に容
易に製造できる点で非晶質のアルミナやシリカからな
り、膜厚０．１〜２μｍであることが望ましいものであ
る。上記態様の無機分離フィルタは、ガス分離性能が高
く、かつ安定な無機物からなることから耐熱性および耐
薬品性に優れたものである。On the other hand, the separation membrane 3 has an average pore diameter of 0.2 to 5 n.
m, particularly alumina, titania, zirconia, silica having a pore diameter of 0.5 to 1.0 nm in average pore diameter, made of amorphous alumina or silica because it can be easily produced, and has a film thickness of 0.1 It is desirable that the thickness be about 2 μm. The inorganic separation filter of the above embodiment has high gas separation performance and is made of a stable inorganic substance, and thus has excellent heat resistance and chemical resistance.
【００１７】本発明によれば、らせん状の支持管２の表
面に分離膜３が被着形成されていることが大きな特徴で
あり、これにより、フィルタ１の管内に被処理物である
特定ガスを含有した混合ガスや特定ガスが溶解した液体
を供給する場合に、該被処理物の流れに乱流を促進して
該被処理物中の特定ガスがフィルタ１の内壁面に接触す
る頻度を高めることができる結果、該特定ガスの分離効
率を高めることができる。According to the present invention, a major feature is that the separation membrane 3 is formed on the surface of the helical support tube 2, whereby the specific gas to be processed is contained in the tube of the filter 1. When supplying a mixed gas or a liquid in which a specific gas is dissolved, a turbulent flow is promoted in the flow of the processing object, and the frequency at which the specific gas in the processing object contacts the inner wall surface of the filter 1 is increased. As a result, the efficiency of separating the specific gas can be increased.
【００１８】なお、前記らせん形状における隣接する支
持管は接触してもよく、または所定間隔で離間していて
もよい。また、らせんの内径Ｌが３０〜１００ｍｍであ
ることが製造の容易性および乱流促進効果の点で望まし
いものである。The adjacent support tubes in the spiral shape may be in contact with each other, or may be separated at a predetermined interval. Further, it is desirable that the inner diameter L of the helix is 30 to 100 mm in view of easiness of production and a turbulence promoting effect.
【００１９】さらに、支持管２と分離膜３との間には分
離膜３の成膜性を向上させる点で中間層が介在してもよ
い。Further, an intermediate layer may be interposed between the support tube 2 and the separation membrane 3 in order to improve the film forming property of the separation membrane 3.
【００２０】なお、本発明のガス分離フィルタは、混合
ガス中から特定ガスを分離回収するためのガス分離フィ
ルタや気体が溶解した液体中から該気体を除去する脱気
フィルタ等として使用される。The gas separation filter of the present invention is used as a gas separation filter for separating and recovering a specific gas from a mixed gas and a degassing filter for removing the gas from a liquid in which the gas is dissolved.
【００２１】次に、本発明のガス分離フィルタを製造す
る方法について説明する。まず、例えば、平均粒径０．
１〜２μｍのアルミナ原料に所定量の有機バインダ、潤
滑剤、可塑剤、水等を加え混合してスラリーを作製した
後、該スラリーを押出し成形により成形する。Next, a method of manufacturing the gas separation filter of the present invention will be described. First, for example, an average particle size of 0.1.
After a predetermined amount of an organic binder, a lubricant, a plasticizer, water, and the like are added to and mixed with an alumina raw material of 1 to 2 μm to prepare a slurry, the slurry is formed by extrusion molding.
【００２２】この時、押出し成形のノズル内におけるス
ラリーの押出し量に偏りをつけることによってらせん形
状の管成形体を作製することができる。すなわち、前記
ノズル内におけるスラリーの押出し量に偏りをつける方
法としては、図２に示すように、（ａ）前記ノズルの向
きを前記スラリーを押し出す方向に対して角度θをつけ
る方法、（ｂ）前記ノズルの開口端面に角度αをつける
方法、（ｃ）前記ノズルに屈曲部をつける方法等が挙げ
られる。At this time, a helical tube molded body can be manufactured by biasing the amount of slurry extruded in the extrusion nozzle. That is, as a method for biasing the amount of slurry extruded in the nozzle, as shown in FIG. 2, (a) a method in which the direction of the nozzle is set to an angle θ with respect to a direction in which the slurry is extruded, and (b) A method of forming an angle α on the opening end face of the nozzle, and (c) a method of forming a bent portion on the nozzle.
【００２３】その後、前記らせん状の管成形体を酸化性
雰囲気にて所定の温度で焼成することによりらせん状の
多孔質支持管を作製することができる。Thereafter, the helical tubular molded body is fired at a predetermined temperature in an oxidizing atmosphere to produce a helical porous support tube.
【００２４】一方、無機分離膜を作製するには、例え
ば、アルミニウムセカンダリーブトキシド等のアルミニ
ウムアルコキシドを加水分解することによってベーマイ
トゾルを作製し、上記の多孔質支持管の表面に前記ベー
マイトゾルを被着形成する。On the other hand, in order to prepare an inorganic separation membrane, for example, a boehmite sol is prepared by hydrolyzing an aluminum alkoxide such as aluminum secondary butoxide, and the boehmite sol is adhered to the surface of the porous support tube. Form.
【００２５】前記多孔質支持管内面に前記ベーマイトゾ
ルを被着形成する方法としては、前記ベーマイトゾルを
送液ポンプや注射器（シリンジ）等を用いて注入する方
法が適用でき、また、前記多孔質支持管外面に前記ベー
マイトゾルを被着形成する方法としては、前記ベーマイ
トゾルを塗布または前記ベーマイトゾル溶液中に前記多
孔質支持管を含浸して引き上げる方法が適用できる。As a method for forming the boehmite sol on the inner surface of the porous support tube, a method of injecting the boehmite sol using a liquid sending pump or a syringe (syringe) can be applied. The boehmite sol can be applied to the outer surface of the support tube by applying the boehmite sol or impregnating the porous support tube with the boehmite sol solution and pulling up.
【００２６】その後、前記被着形成したベーマイトゾル
を乾燥、ゲル化し、これを大気中、４００〜９００℃、
特に４００〜６００℃で熱処理することによって支持管
表面に無機分離膜を被着形成したフィルタを作製するこ
とができる。ここで、熱処理温度が４００℃より低いと
分離膜の支持管への結合力が弱く、所望の細孔径を有す
る細孔を得ることができず、また、９００℃より高いと
分離膜の焼結が進行しすぎて細孔が消失する。Thereafter, the boehmite sol thus formed is dried and gelled, and is dried at 400 to 900 ° C. in the air.
In particular, by performing a heat treatment at 400 to 600 ° C., a filter in which an inorganic separation membrane is formed on the surface of the support tube can be manufactured. Here, if the heat treatment temperature is lower than 400 ° C., the bonding force of the separation membrane to the support tube is weak, and it is impossible to obtain pores having a desired pore diameter. Progresses too much and pores disappear.
【００２７】また、本発明のガス分離フィルタを具備す
るガス分離装置の一例について、その概略断面図を示す
図３を基に説明する。ガス分離装置１０は、上述したよ
うなガス分離フィルタ１１がハウジング１２内に収納さ
れ、また、フィルタ１１は固定用治具１３を介してハウ
ジング１２の内壁に支持固定されている。An example of a gas separation device provided with the gas separation filter of the present invention will be described with reference to FIG. In the gas separation device 10, the above-described gas separation filter 11 is housed in a housing 12, and the filter 11 is supported and fixed to an inner wall of the housing 12 via a fixing jig 13.
【００２８】また、図３によれば、フィルタ１１の両端
部は、それぞれ特定ガスが混合または溶解した被処理物
を装置内へ導入するための被処理物導入口１５と、処理
済物を排出するための処理済物排出口１６とを形成し、
ハウジング１２の壁面を貫通して外部へ露出している。Further, according to FIG. 3, both ends of the filter 11 are provided with a processing object inlet 15 for introducing the processing object into which the specific gas is mixed or dissolved, and a processing object discharge port. And a processed material discharge port 16 for
It penetrates the wall surface of the housing 12 and is exposed to the outside.
【００２９】さらに、ハウジング１２の被処理物導入口
１５が配設される面には前記被処理物のうち特定ガスを
分離、回収するための特定ガス回収口１７が形成されて
いる。なお、被処理物導入口１５と処理済物排出口１６
は、ハウジング１２の側面に形成されてもよい。Further, a specific gas recovery port 17 for separating and recovering a specific gas from the workpiece is formed on the surface of the housing 12 where the workpiece introduction port 15 is provided. In addition, the processing object introduction port 15 and the processed substance discharge port 16
May be formed on the side surface of the housing 12.
【００３０】また、フィルタ１１の両端部である被処理
物導入口１５および処理済物排出口１６はハウジング１
２の壁面に樹脂、半田等の金属、ガラス等を介して接続
されるかＯリング等の封止部材１８を介在させることに
よりハウジング１２内が気密に封止されている。さら
に、ハウジング１２にはガスケット１９を設けることに
よってフィルタ１１の脱着が可能となる。The workpiece inlet 15 and the treated outlet 16 at both ends of the filter 11 are connected to the housing 1.
The inside of the housing 12 is hermetically sealed by being connected to the wall surface of the second through a metal such as resin or solder, glass or the like, or by interposing a sealing member 18 such as an O-ring. Further, by providing a gasket 19 on the housing 12, the filter 11 can be attached and detached.
【００３１】ガス分離フィルタ１１におけるガス分離方
法は、例えば、被処理物導入口１５から導入され特定ガ
スが溶解した液体を供給し、フィルタ１１の管内を通過
するとともにハウジング１２内を減圧して前記特定ガス
が溶解した液体から該特定ガスのみがフィルタ１１の壁
面を透過しハウジング１２内から特定ガス回収口１７か
ら系外へ排出される。一方、フィルタ１１を通過した液
体は処理済物排出口１６から系外へ排出される。The gas separation method in the gas separation filter 11 is, for example, a method in which a liquid in which a specific gas is dissolved introduced through the processing object introduction port 15 is supplied, passes through the pipe of the filter 11, and decompresses the inside of the housing 12. From the liquid in which the specific gas is dissolved, only the specific gas permeates the wall of the filter 11 and is discharged from the housing 12 through the specific gas recovery port 17 to the outside of the system. On the other hand, the liquid that has passed through the filter 11 is discharged from the processed material discharge port 16 to the outside of the system.
【００３２】ハウジング１２はステンレス等の金属、ガ
ラスまたはセラミックス等の剛性および気密性が高い材
料によって構成され、概略円筒形状であることが望まし
い。固定用部材１３は、例えばドーナツ形状の樹脂、金
属、多孔質または緻密質のセラミックス等により構成さ
れフィルタ１１をハウジング１２に支持固定するもので
ある。The housing 12 is made of a material having high rigidity and airtightness, such as metal such as stainless steel, glass or ceramics, and preferably has a substantially cylindrical shape. The fixing member 13 is made of, for example, a donut-shaped resin, metal, porous or dense ceramics, and supports and fixes the filter 11 to the housing 12.
【００３３】なお、らせん状のフィルタ１１の内部に直
線状の多孔質支持管表面に無機分離膜を被着形成したフ
ィルタを挿入し、これらを組み合わせて用いることもで
き、これによりハウジングの容積内のガス分離膜の面積
を増し、ガス分離特性を高めることができる。It is also possible to insert a filter in which an inorganic separation membrane is formed on the surface of a linear porous support tube inside the spiral filter 11, and use these filters in combination. The area of the gas separation membrane can be increased, and the gas separation characteristics can be improved.
【００３４】[0034]
【実施例】（実施例１）まず、純度９９．９％、平均粒
径０．１μｍのアルミナと、有機バインダと、潤滑剤
と、可塑剤と水とを混合し、押出しノズルの押出し方向
との角度θ＝３°にて押し出し成形することによってら
せん状の管状体に成形した後、大気中、１２００℃にて
焼成し、内径２．０ｍｍ、肉厚０．３ｍｍ、支持管の長
さが２５０ｃｍ、らせん内径Ｌ５０ｍｍのらせん状支持
管で、平均細孔径０．２μｍ、気孔率３９％を有するα
−アルミナ質多孔質支持管を作製した。(Example 1) First, alumina having a purity of 99.9% and an average particle diameter of 0.1 μm, an organic binder, a lubricant, a plasticizer, and water were mixed. Is formed into a helical tubular body by extrusion at an angle θ = 3 °, and then fired at 1200 ° C. in the air to have an inner diameter of 2.0 mm, a wall thickness of 0.3 mm, and a support tube having a length of A spiral support tube having a spiral inner diameter of 250 cm and a spiral inner diameter of L50 mm, having an average pore diameter of 0.2 μm and a porosity of 39%.
-An alumina porous support tube was prepared.
【００３５】次に、水１００ｍｏｌに対してアルミニウ
ムセカンダリーブトキシドを１ｍｏｌ添加して加水分解
し、更に硝酸を添加した後、１６時間還流してベーマイ
トゾルを作製した。そして、前記α―アルミナらせん状
多孔質支持管の端部にシリンジを取り付け、シリンジを
用いて得られたベーマイトゾルを吸い上げ、３分間保持
して、排出し、室温で１時間乾燥した後、５００℃で焼
成する一連の工程を１５回繰り返し、支持体の内周表面
に膜厚０．１μｍのγアルミナを形成したらせん状のフ
ィルタを作製した。Next, 1 mol of aluminum secondary butoxide was added to 100 mol of water for hydrolysis, nitric acid was further added, and the mixture was refluxed for 16 hours to prepare a boehmite sol. Then, a syringe was attached to the end of the α-alumina spiral porous support tube, and the obtained boehmite sol was sucked up using the syringe, held for 3 minutes, discharged, dried at room temperature for 1 hour, and dried at room temperature for 500 hours. A series of steps of baking at ℃ was repeated 15 times to produce a spiral filter having γ-alumina having a thickness of 0.1 μm formed on the inner peripheral surface of the support.
【００３６】一方、フィルタについてアルゴン吸着法に
よる細孔径分布測定を行ったところ、図４に示すように
平均細孔径０．８ｎｍ、かつ１ｎｍ以下の細孔径が全細
孔容積中８０％以上の細孔容積を占めていることが分か
った。On the other hand, when the pore size distribution of the filter was measured by the argon adsorption method, as shown in FIG. 4, the average pore size was 0.8 nm, and the pore size of 1 nm or less was 80% or more of the total pore volume. It was found to occupy the pore volume.
【００３７】次に、得られフィルタの両端をポリウレタ
ン製の固定用部材にて固定した後、さらに、内径６０ｍ
ｍ、長さ５０ｍｍの概略円筒形状のステンレス製ハウジ
ング内に固定して図３に示すガス分離フィルタ装置を作
製した。Next, after fixing both ends of the obtained filter with a fixing member made of polyurethane, the inner diameter was further increased to 60 m.
A gas separation filter device shown in FIG. 3 was prepared by fixing the inside of a stainless steel housing having a length of 50 mm and a length of approximately 50 mm.
【００３８】得られたガス分離フィルタについて、被処
理物導入口より溶存酸素濃度が８ｐｐｍの純水を１０ｍ
ｌ／分の流速で流すとともに、特定ガス回収口を真空ポ
ンプで１５０ｔｏｒｒに減圧して脱気した。With respect to the obtained gas separation filter, 10 m of pure water having a dissolved oxygen concentration of 8 ppm was introduced from the inlet of the material to be treated.
While flowing at a flow rate of 1 / min, the specific gas recovery port was degassed by reducing the pressure to 150 torr with a vacuum pump.
【００３９】（実施例２）多孔質支持管の内径を１．０
ｍｍ、らせんの内径Ｌ５０ｍｍとする以外は実施例と全
く同様にガス分離フィルタを作製し、評価した。この結
果、処理済物排出口より排出された純水の溶存酸素濃度
を測定したところ１．０ｐｐｍであった。(Example 2) The inner diameter of the porous support tube was set to 1.0
A gas separation filter was prepared and evaluated in exactly the same manner as in the example except that the inner diameter of the gas and the inner diameter of the spiral were L50 mm. As a result, the concentration of dissolved oxygen in pure water discharged from the treated product outlet was measured and found to be 1.0 ppm.
【００４０】（比較例１）実施例２のらせん状の多孔質
支持管に代えて同じ長さの直線状の支持管とする以外は
実施例２と全く同様にしてガス分離フィルタを作製し
た。この時、ハウジングの形状は内径７０ｍｍ、長さ７
０ｍｍの細長い概略円筒形状となった。(Comparative Example 1) A gas separation filter was produced in exactly the same manner as in Example 2 except that the helical porous support tube of Example 2 was replaced with a linear support tube of the same length. At this time, the housing has an inner diameter of 70 mm and a length of 7 mm.
It became an elongated, roughly cylindrical shape of 0 mm.
【００４１】実施例と同様に評価した結果、処理済物排
出口１６より排出された純水の溶存酸素濃度を測定した
ところ２．５ｐｐｍであり、本発明のガス分離フィルタ
と比較して分離性能の低いものであった。As a result of evaluation in the same manner as in the example, the dissolved oxygen concentration of pure water discharged from the treated material discharge port 16 was measured to be 2.5 ppm, which was higher than that of the gas separation filter of the present invention. Was low.
【００４２】（比較例２）実施例２のフィルタに代えて
同じ形状のポリ−４−メチルペンテン−１を主成分とす
る中空糸膜からなるフィルタとする以外は実施例２と全
く同様にしてガス分離フィルタを作製した。実施例と同
様に評価した結果、処理済物排出口４より排出された純
水の溶存酸素濃度を測定したところ５ｐｐｍであり、本
発明のガス分離フィルタと比較して分離性能の低いもの
であった。(Comparative Example 2) A filter made of a hollow fiber membrane containing poly-4-methylpentene-1 as a main component and having the same shape in place of the filter of Example 2 was used in exactly the same manner as in Example 2. A gas separation filter was manufactured. As a result of evaluation in the same manner as in the example, the dissolved oxygen concentration of the pure water discharged from the treated material discharge port 4 was measured and found to be 5 ppm, which was lower in separation performance than the gas separation filter of the present invention. Was.
【００４３】[0043]
【発明の効果】以上詳述したとおり、本発明のガス分離
フィルタは、無機分離膜を具備するためにガス分離効率
が高く、耐熱性および耐薬品性が高めることができる。
また、フィルタがらせん形状であるために被処理物であ
る気体または液体が乱流状態となりガス分離効率を高め
ることができるとともに、ハウジングを所望の形状とす
ることができる。As described in detail above, the gas separation filter of the present invention is provided with an inorganic separation membrane, so that the gas separation efficiency is high and the heat resistance and chemical resistance can be improved.
Further, since the filter has a helical shape, the gas or liquid to be processed is in a turbulent state, so that the gas separation efficiency can be increased and the housing can have a desired shape.
【図面の簡単な説明】[Brief description of the drawings]
【図１】本発明のガス分離フィルタの一部切り欠き斜視
図である。FIG. 1 is a partially cutaway perspective view of a gas separation filter of the present invention.
【図２】本発明のガス分離フィルタの製造方法における
成形方法を説明するための図である。FIG. 2 is a view for explaining a forming method in a method for manufacturing a gas separation filter of the present invention.
【図３】本発明のガス分離フィルタを用いたガス分離フ
ィルタ装置の概略断面図である。FIG. 3 is a schematic sectional view of a gas separation filter device using the gas separation filter of the present invention.
【図４】実施例１のガス分離フィルタの無機分離膜の細
孔分布を示す図である。FIG. 4 is a view showing a pore distribution of an inorganic separation membrane of the gas separation filter of Example 1.
１ ガス分離フィルタ ２ らせん状支持管 ３ 無機分離膜 1 Gas separation filter 2 Helical support tube 3 Inorganic separation membrane
Claims (4)
管の内面または外面に無機分離膜を被着形成し、前記ら
せん状支持管の内面に特定ガスが混合または溶解した被
処理物を供給して前記無機分離膜に接触させ、該被処理
物中の特定ガスのみを前記無機分離膜を介して前記らせ
ん状支持管の外表面に透過させて前記特定ガスを分離、
回収することを特徴とするガス分離フィルタ。An inorganic separation membrane is formed on the inner surface or outer surface of a spiral support tube made of porous ceramics, and an object to which a specific gas is mixed or dissolved is supplied to the inner surface of the spiral support tube. Contacting the inorganic separation membrane, only the specific gas in the object to be processed is transmitted through the inorganic separation membrane to the outer surface of the helical support tube to separate the specific gas,
A gas separation filter characterized by being collected.
下であることを特徴とする請求項１記載のガス分離フィ
ルタ。2. The gas separation filter according to claim 1, wherein the inner diameter of the spiral support tube is 1.5 mm or less.
〜１００ｍｍであることを特徴とする請求項１または２
記載のガス分離フィルタ。3. The spiral support tube according to claim 2, wherein the inner diameter of the spiral is 30.
3 to 100 mm.
A gas separation filter as described.
加しスラリーを作製する工程と、該スラリーをノズルを
有する押出し成型用容器内に充填し、前記ノズル内にお
けるスラリーの押出し量に偏りをつけることによってら
せん状の管成形体を作製する工程と、該管成形体を焼成
して多孔質支持管を作製する工程と、該多孔質支持管の
表面に無機分離膜を形成するためのゾル溶液を成膜し、
ゲル化した後、酸化性雰囲気中で焼成して無機分離膜を
被着形成する工程と、を具備することを特徴とするガス
分離フィルタの製造方法。4. A step of adding an organic binder and a solvent to ceramic powder to prepare a slurry, filling the slurry into an extrusion container having a nozzle, and biasing the amount of slurry extruded in the nozzle. A step of producing a helical tubular molded article, a step of firing the tubular molded article to produce a porous support tube, and a sol solution for forming an inorganic separation membrane on the surface of the porous support pipe. Film,
And baking in an oxidizing atmosphere after gelling to deposit and form an inorganic separation membrane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11150976A JP2000334250A (en) | 1999-05-31 | 1999-05-31 | Gas separating filter and its production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11150976A JP2000334250A (en) | 1999-05-31 | 1999-05-31 | Gas separating filter and its production |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2000334250A true JP2000334250A (en) | 2000-12-05 |
Family
ID=15508574
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11150976A Pending JP2000334250A (en) | 1999-05-31 | 1999-05-31 | Gas separating filter and its production |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2000334250A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002074421A1 (en) * | 2001-03-16 | 2002-09-26 | The Robert Gordon University | Apparatus and method for separating gases |
| JP2015009239A (en) * | 2013-06-26 | 2015-01-19 | アイデックス ヘルス アンド サイエンス エルエルシー | Fluid degassing module with helical membrane |
-
1999
- 1999-05-31 JP JP11150976A patent/JP2000334250A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002074421A1 (en) * | 2001-03-16 | 2002-09-26 | The Robert Gordon University | Apparatus and method for separating gases |
| US7048778B2 (en) | 2001-03-16 | 2006-05-23 | The Robert Gordon University | Apparatus and method for separating gases |
| US7297184B2 (en) | 2001-03-16 | 2007-11-20 | Robert Gordon University | Apparatus and method for separating gases |
| EP1920818A3 (en) * | 2001-03-16 | 2008-08-13 | The Robert Gordon University | Apparatus and method for separating gases |
| JP2015009239A (en) * | 2013-06-26 | 2015-01-19 | アイデックス ヘルス アンド サイエンス エルエルシー | Fluid degassing module with helical membrane |
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