JPS6344904A - Separating membrane for liquid mixture - Google Patents
Separating membrane for liquid mixtureInfo
- Publication number
- JPS6344904A JPS6344904A JP61187712A JP18771286A JPS6344904A JP S6344904 A JPS6344904 A JP S6344904A JP 61187712 A JP61187712 A JP 61187712A JP 18771286 A JP18771286 A JP 18771286A JP S6344904 A JPS6344904 A JP S6344904A
- Authority
- JP
- Japan
- Prior art keywords
- membrane
- ethanol
- coupling agent
- silane coupling
- liquid
- 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.)
- Granted
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0081—After-treatment of organic or inorganic membranes
- B01D67/0093—Chemical modification
- B01D67/00931—Chemical modification by introduction of specific groups after membrane formation, e.g. by grafting
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/36—Pervaporation; Membrane distillation; Liquid permeation
- B01D61/365—Osmotic distillation or osmotic evaporation
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Water Supply & Treatment (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Transplantation (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、液体混合物の分離膜、詳しくは有機液体と水
との混合物（以後有機液体／水の混合物と略記）から有
機液体を優先的に透過させる分離膜に関するものである
。Detailed Description of the Invention (Industrial Application Field) The present invention provides a separation membrane for liquid mixtures, specifically, a separation membrane for separating organic liquids from a mixture of organic liquids and water (hereinafter abbreviated as an organic liquid/water mixture). The invention relates to a separation membrane that allows water to pass through the membrane.
（従来技術）
；］
これは分離膜を介して片側に分離される対象である揮発
性有機液体／水の混合物を流し、もう一方何をポンプに
より真空に引くもしくは不活性がスをキャリアとして流
すことにより膜透過物を蒸気として得、透過物を冷却す
ることにより捕集する方法である。(Prior art) ;] This is a process in which a volatile organic liquid/water mixture to be separated is passed through a separation membrane on one side, and the other is evacuated by a pump or an inert gas is passed as a carrier. In this method, the membrane permeate is obtained as vapor, and the permeate is collected by cooling.
（発明が解決しようとする問題点）
しかしながら難分離性揮発性有機液体／水の混合物の代
表例であるエタノール／水 系についてはエタノール（
ＥｔＯＨ）を優先的に透過させる膜は数少なく、既知の
ものではシリコーンゴム膜（特開昭５２−６８０７８号
、膜７３５３（１９８２）参照）が有名であり、その他
では最近ポリｌ−ＩＪメチルシリルプロピン膜（特開昭
６０−７５３０６号参照）やポリフルオロアルキルアク
リレートグラフトポリスチレンをコートシたシリコーン
ゴム膜（Ｐｏｌｙ−ｍｅｒ Ｐｒｅｐｒｉｎｔｓ Ｊａ
ｐａｎ ３４ （７） １８４１ （１９８５）参照）
が報告されているが、いずれも透過性能が充分でないか
、もしくは膜の作成に高度の技術を要するかで高い透過
性能の膜は一般的には得られにくいのが現状である。(Problem to be solved by the invention) However, regarding the ethanol/water system, which is a typical example of a difficult-to-separate volatile organic liquid/water mixture, ethanol (
There are only a few membranes that preferentially permeate EtOH, and the most well-known known ones are silicone rubber membranes (see JP-A No. 52-68078, Membrane 7353 (1982)); Pin film (see JP-A-60-75306) and silicone rubber film coated with polyfluoroalkyl acrylate grafted polystyrene (Polymer Preprints Ja
(see Pan 34 (7) 1841 (1985))
However, at present, it is generally difficult to obtain a membrane with high permeability, either because the permeation performance is not sufficient or because the membrane creation requires advanced technology.
上記に鑑み本発明はこのような問題点を解消するため開
発されたものである。In view of the above, the present invention has been developed to solve these problems.
（１問題点を解決するための手段）
即ち、本発明の液体混合物の分離膜は、揮発性有機液体
／水の混合物を浸透気化分離する膜において、シリコー
ンゴムの薄膜、または有機シリコーン化合物をモノマー
としてプラズマ重合させた薄膜を長鎖アルキル基を有す
るシランカップリング剤により表面処理したことを特徴
とするものである。(Means for Solving Problem 1) That is, the liquid mixture separation membrane of the present invention is a membrane for separating a volatile organic liquid/water mixture by pervaporation, and a thin film of silicone rubber or a monomer of an organic silicone compound. This method is characterized in that a plasma-polymerized thin film is surface-treated with a silane coupling agent having a long-chain alkyl group.
以下、本発明を発明の経緯と共に詳細に説明する。Hereinafter, the present invention will be explained in detail along with the history of the invention.
前記のとおり揮発性有機液体／水の混合物の代表例であ
るエタノール／水 系からエタノールを優先的に透過さ
せる膜は数少なく、その性能を再現性良く、一般的に発
揮し得る膜は現在のところシリコーンゴム膜のみである
。シリコーンゴム膜はポリジメチルシロキサン骨格から
なり、素材としてきわめて疎水性が高く、エタノールと
の親和性が大きいためエタノール優先透過膜となってい
ると考えられる。As mentioned above, there are only a few membranes that preferentially permeate ethanol from the ethanol/water system, which is a typical example of a volatile organic liquid/water mixture, and currently there are no membranes that can generally demonstrate this performance with good reproducibility. Only silicone rubber membrane. The silicone rubber membrane consists of a polydimethylsiloxane skeleton, and is considered to be an ethanol preferentially permeable membrane because it is extremely hydrophobic as a material and has a high affinity for ethanol.
一方浸透気化法における透過は一般的に溶解−拡散機構
が認められており、浸透気化分離膜においてエタノール
優先透過性を向上させるためには分離膜へのエタノール
の溶解性を高めること、分離脱中でのエタノールの拡散
性を増大することが重要と考えられる。On the other hand, permeation in the pervaporation method is generally recognized to be based on a dissolution-diffusion mechanism, and in order to improve the preferential permeability of ethanol in the pervaporation separation membrane, it is necessary to increase the solubility of ethanol in the separation membrane, and to separate and desorb the ethanol. It is considered important to increase the diffusivity of ethanol at
拡散性を増大することは分離膜の厚みを薄くすることで
解決できると考えられる。溶解性を高めることは、ポリ
ジメチルシロキサンよりもさらに疎水性の高い薄層を分
離膜表面に形成することによりなし得ると推定し検討を
続けた結果、シリコーンゴム膜の表面層を長鎖アルキル
基を持つシランカップリング剤で処理することにより、
より疎水性の高い表面層を形成させ得る可能性があるこ
とに想到し、本発明を完成するに至った。It is thought that increasing the diffusivity can be solved by reducing the thickness of the separation membrane. We presumed that increasing solubility could be achieved by forming a thin layer on the surface of the separation membrane that was even more hydrophobic than polydimethylsiloxane, and as a result of continued investigation, we found that the surface layer of the silicone rubber membrane could be formed with long-chain alkyl groups. By treating with a silane coupling agent that has
The present invention was completed based on the idea that there is a possibility of forming a surface layer with higher hydrophobicity.
即ち本発明はエタノール／水の混合物を主な分離対象と
する浸透気化膜に関するもので、長鎖アルキル基を有す
るシランカップリング剤によりシリコーンゴム膜表面を
処理することにより得られる膜である。That is, the present invention relates to a pervaporation membrane that primarily separates ethanol/water mixtures, and is a membrane obtained by treating the surface of a silicone rubber membrane with a silane coupling agent having a long-chain alkyl group.
（作用）
使用するシランカップリング剤は疎水性の強い官能基を
持つほど性能が高くなると予想され、アルキル基では０
８以上のものが望ましい。もちろんＣ鎖の長さは長いほ
どよいが、分離膜を処理するうえでシランカップリング
剤が液状であることが好壕しくそれにより自ずから限界
は生じてくる。(Effect) It is expected that the performance of the silane coupling agent used will be higher as it has a more hydrophobic functional group;
8 or more is desirable. Of course, the longer the length of the C chain, the better, but it is preferable for the silane coupling agent to be in liquid form when treating separation membranes, and this naturally imposes a limit.
一般的に入手できるものではオクタデシル基（Ｃ１８Ｈ
，−）を持つものが最も適当である。疎水性の官能基は
アルキル基である必要はなく、不飽和結合を含むものや
、フルオロカーボン鎖などであってコーンゴム膜はポリ
ジメチルシロキサン骨格、ポリハイドロメチルシロキサ
ン骨格を有するものなら何でも良いが、本用途に供し得
るほどの薄膜とし得るためには溶剤可溶で、加熱架橋型
のものが望ましい、しかしこれに限定されるものではな
い。Generally available ones include octadecyl group (C18H
, -) is the most appropriate. The hydrophobic functional group does not have to be an alkyl group, but can be anything that contains an unsaturated bond or a fluorocarbon chain, and the cone rubber membrane has a polydimethylsiloxane skeleton or a polyhydromethylsiloxane skeleton. In order to obtain a thin film that can be used for various purposes, it is preferable to use a solvent-soluble and heat-crosslinking type, but the present invention is not limited thereto.
またシリコーンゴム膜は薄膜化した際には分離膜に用い
得るほどの強度はないため、適当な支持膜上に作成する
。これにより２０μｍ以下の薄膜であっても分離膜とし
て使用できる強度を得ることができる。しかし数μｍ以
下の薄膜を得るためには上記の方法は用いられず、この
際にはプラズマ重合法が利用できる。有機シリコーン化
合物をモノマーとして適当な支持膜−Ｌにプラズマ重合
物を堆積させることにより、１μｍ以下のシリコーンゴ
ム類似の薄膜を得ることができ、本用途に好適な膜が得
られる。Furthermore, since silicone rubber membranes do not have enough strength to be used as separation membranes when made thin, they are prepared on a suitable support membrane. As a result, even a thin film of 20 μm or less can have enough strength to be used as a separation membrane. However, in order to obtain a thin film of several μm or less, the above method cannot be used, and in this case, a plasma polymerization method can be used. By depositing a plasma polymer on a suitable support film-L using an organic silicone compound as a monomer, a thin film similar to silicone rubber of 1 μm or less can be obtained, and a film suitable for this purpose can be obtained.
シランカップリング剤による処理は一般的にはシランカ
ップリング剤をシリコーンゴム膜表面に適当な時間接触
させ、そののち、シリコーンゴム膜を熱処理することに
よってなされる。しかしこ（実施例）
以下に本発明の理解を助けるため実施例を述べる。Treatment with a silane coupling agent is generally carried out by bringing the silane coupling agent into contact with the surface of the silicone rubber film for an appropriate period of time, and then heat-treating the silicone rubber film. However, Examples will be described below to help understand the present invention.
・実施例１゜
住友電工製フロロボア（商品名）ＦＰＯ２２上にトーレ
シリコーン製５Ｅ６７２０をフレオン１１３に約１０ｗ
ｔ係に溶解したものを塗布し、１００℃で１ｈｒ熱処理
することにより約２０μｍ厚のシリコーンゴム膜を得た
。この膜をホルダーに固定し、膜の表面にオクタデシル
ジェトキシメチルシランｆ １ ｈｒ接触させた後１２
Ｄ℃１ｈｒの熱処理を行ない、目的の膜を得た。この膜
の分離性能をエタノール／水の混合液の浸透気化実験で
試したところ透過速度１．６ Ｘ １０−２に９／ボｈ
ｒ、ｔＯＨ−
分離係数α −１６，３が得られた。（第１表扁１参
照）
第 １ 表
オクタテシルジエトキシメチルシ
実施例２゜
ポリプラスチックス社製ジュラガード（商品名）２４０
０上にヘキサメチルトリシロキザンをプラズマ重合する
ことにより、厚さ約１μｍの膜を得た。この膜を実施例
１．と同様の方法で処理を行ない、分離性能を測定した
ところ、透過速度１．５ Ｘ １０−２Ｋｑ／ ｍ７ｈ
ｒ 、分離係数αＥｔＯＨ＝ Ｉ Ｂ、０が得られた。・Example 1゜Approximately 10W of Toray Silicone 5E6720 and Freon 113 on Sumitomo Electric Fluorobor (trade name) FPO22
A silicone rubber film having a thickness of approximately 20 μm was obtained by applying the dissolved material to a coating material and heat-treating it at 100° C. for 1 hour. After fixing this membrane to a holder and contacting the surface of the membrane with octadecyljethoxymethylsilane f 1 hr,
Heat treatment was performed at D° C. for 1 hr to obtain the desired film. The separation performance of this membrane was tested in a pervaporation experiment of an ethanol/water mixture, and the permeation rate was 1.6 x 10-2 to 9/h.
r,tOH- A separation factor α of −16,3 was obtained. (See Table 1, Table 1) Table 1: Octatecyldiethoxymethyl Example 2゜Duraguard (trade name) 240 manufactured by Polyplastics Co., Ltd.
By plasma polymerizing hexamethyltrisiloxane on 0, a film with a thickness of about 1 μm was obtained. This film was prepared in Example 1. When the separation performance was measured using the same method as above, the permeation rate was 1.5 x 10-2Kq/m7h.
r, a separation factor αEtOH = IB,0 was obtained.
（第１表１θ２参照）
（発明の効果）
以上の様に本発明の液体混合物の分離膜によれは次の様
な効果がある。(See Table 1 1θ2) (Effects of the Invention) As described above, the separation membrane of the liquid mixture of the present invention has the following effects.
シリコーンゴム膜及びその類似の膜の性能をはるかに越
える分離性能の膜が得られる。A membrane with separation performance that far exceeds that of silicone rubber membranes and similar membranes is obtained.
Claims (4)
る膜において、シリコーンゴムの薄膜、または有機シリ
コーンモノマーをプラズマ重合させて作成した薄膜を長
鎖アルキル基を有するシランカップリング剤で該薄膜を
表面処理したことを特徴とする液体混合物の分離膜。(1) In a membrane that pervaporates and separates a mixture of a volatile organic liquid and water, a thin film of silicone rubber or a thin film made by plasma polymerizing an organic silicone monomer is coated with a silane coupling agent having a long-chain alkyl group. A separation membrane for liquid mixtures characterized by a surface-treated thin film.
−Ｓｉ−（ＯＱ）＿ｊ、ここでＳｉはシリコン原子、Ｏ
は酸素原子を示し、ＲはＣ＿８Ｈ＿１＿７−以上の長鎖
アルキル基、Ｐ、ＱはＣＨ＿３−、Ｃ＿２Ｈ＿５−、Ｃ
Ｈ＿３ＣＯ−のいずれかであり、ｎ＋ｍ＋ｊ＝４、３≧
ｎ≧１、３≧ｊ≧１、２≧ｍ≧０を満たす構造を有する
化合物を用いる特許請求の範囲第（１）項記載の液体混
合物の分離膜。(2) Structural formula R_nP_m as a silane coupling agent
-Si-(OQ)_j, where Si is a silicon atom, O
represents an oxygen atom, R is a long-chain alkyl group of C_8H_1_7- or more, P, Q are CH_3-, C_2H_5-, C
H_3CO-, n+m+j=4, 3≧
A separation membrane for a liquid mixture according to claim (1), which uses a compound having a structure satisfying n≧1, 3≧j≧1, 2≧m≧0.
キシメチルシランを用いる特許請求の範囲第（２）項記
載の液体混合物の分離膜。(3) A separation membrane for a liquid mixture according to claim (2), which uses octadecyldiethoxymethylsilane as a silane coupling agent.
請求の範囲第（１）項記載の液体混合物の分離膜。(4) A separation membrane for a liquid mixture according to claim (1), wherein the volatile organic liquid is ethanol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61187712A JPS6344904A (en) | 1986-08-12 | 1986-08-12 | Separating membrane for liquid mixture |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61187712A JPS6344904A (en) | 1986-08-12 | 1986-08-12 | Separating membrane for liquid mixture |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6344904A true JPS6344904A (en) | 1988-02-25 |
| JPH0368734B2 JPH0368734B2 (en) | 1991-10-29 |
Family
ID=16210850
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61187712A Granted JPS6344904A (en) | 1986-08-12 | 1986-08-12 | Separating membrane for liquid mixture |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6344904A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5215667A (en) * | 1991-08-20 | 1993-06-01 | Exxon Chemical Patents Inc. | Method for separating water soluble noble metal catalyst from a noble metal catalyzed hydroformylation reaction |
| US5288818A (en) * | 1991-08-20 | 1994-02-22 | Exxon Chemical Patents Inc. | Method for separating a water soluble noble metal catalyst from a noble metal catalyzed hydroformylation reaction |
| JPH07275677A (en) * | 1994-04-11 | 1995-10-24 | Nec Corp | Organic acid separation membrane and method for producing the same |
-
1986
- 1986-08-12 JP JP61187712A patent/JPS6344904A/en active Granted
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5215667A (en) * | 1991-08-20 | 1993-06-01 | Exxon Chemical Patents Inc. | Method for separating water soluble noble metal catalyst from a noble metal catalyzed hydroformylation reaction |
| US5288818A (en) * | 1991-08-20 | 1994-02-22 | Exxon Chemical Patents Inc. | Method for separating a water soluble noble metal catalyst from a noble metal catalyzed hydroformylation reaction |
| JPH07275677A (en) * | 1994-04-11 | 1995-10-24 | Nec Corp | Organic acid separation membrane and method for producing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0368734B2 (en) | 1991-10-29 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |