JPS6344903A - Separating membrane of liquid mixture and manufacture of the same - Google Patents
Separating membrane of liquid mixture and manufacture of the sameInfo
- Publication number
- JPS6344903A JPS6344903A JP18771186A JP18771186A JPS6344903A JP S6344903 A JPS6344903 A JP S6344903A JP 18771186 A JP18771186 A JP 18771186A JP 18771186 A JP18771186 A JP 18771186A JP S6344903 A JPS6344903 A JP S6344903A
- Authority
- JP
- Japan
- Prior art keywords
- liquid
- membrane
- monomer
- separation
- ethanol
- 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
- 239000012528 membrane Substances 0.000 title claims abstract description 47
- 239000007788 liquid Substances 0.000 title claims abstract description 31
- 239000000203 mixture Substances 0.000 title claims abstract description 19
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 239000000178 monomer Substances 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 10
- 150000001875 compounds Chemical class 0.000 claims abstract description 8
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 5
- 238000000926 separation method Methods 0.000 claims description 20
- 238000006116 polymerization reaction Methods 0.000 claims description 14
- 239000012263 liquid product Substances 0.000 claims description 8
- 238000005373 pervaporation Methods 0.000 claims description 7
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 229910001882 dioxygen Inorganic materials 0.000 claims description 3
- SWGZAKPJNWCPRY-UHFFFAOYSA-N methyl-bis(trimethylsilyloxy)silicon Chemical compound C[Si](C)(C)O[Si](C)O[Si](C)(C)C SWGZAKPJNWCPRY-UHFFFAOYSA-N 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 22
- 229920002379 silicone rubber Polymers 0.000 abstract description 10
- 239000004945 silicone rubber Substances 0.000 abstract description 10
- -1 polypropylene Polymers 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 239000004743 Polypropylene Substances 0.000 abstract description 2
- 230000035699 permeability Effects 0.000 abstract description 2
- 229920001155 polypropylene Polymers 0.000 abstract description 2
- 230000008016 vaporization Effects 0.000 abstract 2
- 238000009834 vaporization Methods 0.000 abstract 2
- 230000000149 penetrating effect Effects 0.000 abstract 1
- 230000000379 polymerizing effect Effects 0.000 abstract 1
- 238000000034 method Methods 0.000 description 14
- 239000000047 product Substances 0.000 description 10
- 239000012466 permeate Substances 0.000 description 4
- 239000012159 carrier gas Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000011344 liquid material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- JZUFKLXOESDKRF-UHFFFAOYSA-N Chlorothiazide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC2=C1NCNS2(=O)=O JZUFKLXOESDKRF-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の第１」用分野）
本発明は、液体混合物の分離膜、詳しくは有機従来揮発
性有機液体／水の混合物から揮発性有機液体を膜により
分離、濃縮する方法として浸透気化法（ｐｅｒ’Ｖａｐ
ｏｒａｔｉｏｎ ）が提案されている。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
、もしくは不活性ガスをキャリアガスとして流す（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。DETAILED DESCRIPTION OF THE INVENTION (First industrial field) The present invention relates to a membrane for separating liquid mixtures, specifically a method for separating and concentrating a volatile organic liquid from a mixture of conventional volatile organic liquid/water using a membrane. The pervaporation method (per'Vap) is a method for
) has been proposed. This is done by passing the volatile organic liquid/water mixture to be separated on one side through the separation membrane, and on the other side by pumping a vacuum or by flowing an inert gas as a carrier gas (depending on the membrane). This method obtains the permeate as a vapor and collects the permeate by cooling it.
難分離性揮発性有機液体／水の混合物の例としてエタノ
ール／水の混合物があるが、当混合物からエタノール（
ＥｔＯＨと略記）を優先的に透過する膜は既知のもので
はシリコーンゴム膜が代表的である。この膜ではエタノ
ール／水 系の分離性能として分離係数αＥｔＯＨ＝８
〜１０が得られている。An example of a difficult-to-separate volatile organic liquid/water mixture is an ethanol/water mixture.
Silicone rubber membranes are typical of known membranes that preferentially permeate EtOH (abbreviated as EtOH). This membrane has a separation coefficient αEtOH=8 for the separation performance of ethanol/water system.
~10 is obtained.
（発明が解決しようとする問題点）
しかしそれ以上の高い分離性能を持つ膜は、文献、特許
等に少数の報告があるものの、いずれも膜の作成に高度
の技術を要することが予想され、一般的に得られるエタ
ノール優先透過性の膜は相変わらずシリコーンゴム膜が
最良という現状であり、シリコーンゴム膜以上の高い分
離性能の膜が切望されている次第である。(Problem to be solved by the invention) However, although there are a few reports of membranes with even higher separation performance in the literature and patents, it is expected that advanced technology will be required to create the membrane. Silicone rubber membranes are still the best generally available membranes that preferentially permeate ethanol, and there is a strong desire for membranes with higher separation performance than silicone rubber membranes.
機液体／水の混合物を浸透気化分離する膜において、有
機シリコーン化合物をモノマーとしてプラズマ重合して
得られる液体状生成物を疎水性多孔膜に含浸させたこと
を特徴とするものである。A membrane for pervaporating and separating a liquid/water mixture is characterized in that a hydrophobic porous membrane is impregnated with a liquid product obtained by plasma polymerization of an organic silicone compound as a monomer.
又本発明の液体混合物の分離膜の製造方法は、揮発性有
機液体／水の混合物を浸透気化分離する膜の製造におい
て、有機シリコーン化合物をモノマーとして、反応容器
中に酸素ガスを共存させながらプラズマ重合を行ない、
液体状生成物を得、該液体状生成物を疎水性多孔膜に含
浸することを特徴とするものである。Furthermore, the method for producing a separation membrane for a liquid mixture of the present invention includes a method for producing a membrane for pervaporative separation of a volatile organic liquid/water mixture, using an organic silicone compound as a monomer and plasma while coexisting oxygen gas in a reaction vessel. Perform polymerization,
The method is characterized in that a liquid product is obtained and a hydrophobic porous membrane is impregnated with the liquid product.
以下本発明を、発明の経緯と共に詳細に説明する。The present invention will be explained in detail below along with the history of the invention.
前記の通りシリコーンゴム膜においてはエタノール／水
系の分離性能として分離係数αＥｔＯＨ＝８−１０が
得られるが、この性能は製膜方法などをいかに変更して
も向上せず、材料それ自体の特性となっている様子であ
る。As mentioned above, silicone rubber membranes have a separation coefficient of αEtOH=8-10 for ethanol/water systems, but this performance cannot be improved no matter how the membrane forming method is changed, and the characteristics of the material itself cannot be improved. It appears that this is the case.
一方浸透気化法における透過は一般的に溶解−が重要と
なる。On the other hand, dissolution is generally important for permeation in the pervaporation method.
溶解性についてはシリコーンゴム膜のようなポリシロキ
サン系素材を扱うかぎりでは極端に変化はしないと思わ
れるので、本発明者らは拡散性を改善することに検討の
中心をおいた。拡散性をシリコーンゴム以上に改良する
ためには膜材料を液体とするのが最も効果が期待できる
。そこでシリコーンゴムと類似の化学構造を持ち、液体
状でかつ浸透気化操作に耐える液体状物を作成するため
に有機シリコーン化合物をモノマーとしたプラズマ重合
法を利用した。Since it seems that the solubility will not change drastically as long as polysiloxane materials such as silicone rubber membranes are handled, the inventors focused their studies on improving the diffusibility. In order to improve the diffusivity more than silicone rubber, it is most effective to use a liquid membrane material. Therefore, we used a plasma polymerization method using an organic silicone compound as a monomer to create a liquid material that has a chemical structure similar to silicone rubber, is liquid, and can withstand pervaporation operations.
プラズマ重合法においてはモノマーの種類と重合条件の
制御によって生成物の性質を幅広く変更できるので、好
ましい条件を選択することにより望ましい性質を持った
生成物を作成できることが特徴である。In the plasma polymerization method, the properties of the product can be varied widely by controlling the type of monomer and the polymerization conditions, so a feature of the plasma polymerization method is that it is possible to create products with desired properties by selecting favorable conditions.
そこで本発明者らはこのプラズマ重合法を利用してシリ
コーンゴムと類似の構造を持つ液体状物・を作成し、液
体膜として評価すれば、良好なエタノール透過性を有す
る分離膜が得られる可能性に想到し、本発明を完成する
に至った。Therefore, the present inventors utilized this plasma polymerization method to create a liquid material with a structure similar to silicone rubber, and if evaluated as a liquid membrane, it is possible to obtain a separation membrane with good ethanol permeability. This led to the completion of the present invention.
膜がポリオルガノシロキサンと類似の構造をしているこ
とが推定されている。本発明においてはプラズマ重合に
より得られる生成物が液体状である１、ことが必要であ
るが、これらの液体状生成物においてもポリオルガノシ
ロキサンと類似の構造を保有することは容易に類推でき
る。It is estimated that the membrane has a structure similar to that of polyorganosiloxane. In the present invention, it is necessary that the product obtained by plasma polymerization be in a liquid state, and it can be easily inferred that these liquid products also have a structure similar to that of polyorganosiloxane.
本発明で用いる有機シリコーンモノマーとしては分子中
にシロキサン結合を持つものが望捷しい。The organic silicone monomer used in the present invention is preferably one having a siloxane bond in the molecule.
それらのモノマーを用いた時には七ツマー中のシロキサ
ン結合が生成物中にも反映し、ポリオルガノシロキザン
類似の構造を形成することになると推定できる。It can be assumed that when these monomers are used, the siloxane bonds in the heptamer will be reflected in the product, forming a structure similar to polyorganosiloxane.
寸だ、重合中に酸素ガスを共存させることにより、生成
物中のポリシロキザン構造の生成をより−ｍ向上させる
ことが可能である。これは共存する酸素が、活性種とな
り、シロキサン鎖の発達を助けた結果と考えることがで
きる。 ゛さらに、分子中に５ｉ−Ｈ基を含む
モノマーを用いたときに膜分離性能が良好であった。こ
れらのモノマーからの重合生成物中には５ｉ−Ｈ基が残
存性は、モノマー構造をできるだけこわさず、生成物中
に反映できるように全般的に非常に弱い条件で行なう必
要がある。すなわちモノマー導入量を極端に多くシ、パ
ワーはできるだけ小さくしなければならない。Indeed, by allowing oxygen gas to coexist during polymerization, it is possible to further improve the formation of a polysiloxane structure in the product. This can be considered to be the result of coexisting oxygen becoming an active species and aiding the development of siloxane chains. Furthermore, membrane separation performance was good when a monomer containing a 5i-H group in the molecule was used. In order to ensure that the 5i-H group remains in the polymerization product from these monomers, it is necessary to carry out the reaction under extremely weak conditions so that the monomer structure is not destroyed as much as possible and can be reflected in the product. In other words, the amount of monomer introduced must be extremely large and the power must be as small as possible.
このような方法を用いることにより良好な分離性能を持
つ分離膜が作成可能である。By using such a method, a separation membrane with good separation performance can be created.
（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。(Example) Examples will be described below to help understand the present invention.
実施例１゜
七ツマ−１，１，１，３，５，５，５−ヘプタメチルト
リシロキサンを１５℃に保ち、Ａｒキャリアーガス２
ＳＣＣｍ ＋０２１ Ｏ５ＣＣｍ＋ ５Ｗ ３０分のプ
ラズマ重合を行ない、液体状生成物を得た。この生成物
をポリプロピレン多孔膜ジュラガード（商品名）２４０
０（ポリプラスチックス社製）に含浸させ液体膜とした
。Example 1 7-1,1,1,3,5,5,5-heptamethyltrisiloxane was kept at 15°C and Ar carrier gas 2
SCCm +021 O5CCm+ 5W Plasma polymerization was performed for 30 minutes to obtain a liquid product. This product is used as polypropylene porous membrane Duragard (trade name) 240.
0 (manufactured by Polyplastics) to form a liquid film.
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６，１×を第１図に示す。The separation performance of this membrane was tested in a pervaporation experiment of an ethanol/water mixture, and the permeation rate was 6.1x, as shown in Figure 1.
実施例２゜
同様の方法で液体膜とし、評価したところ透過速度５．
３ Ｘ １０ ’Ｋｇ／ｄｈｒ 、分離係数αＥｔＯＨ
−１１，１が得られた（第１表５２）。Example 2 A liquid film was prepared in the same manner as in Example 2, and the permeation rate was 5.
3 x 10'Kg/dhr, separation coefficient αEtOH
-11.1 was obtained (Table 1, 52).
またその他のシリコーン化合物をモノマーとした重合生
成物の液体膜の結果を第１表に示す。In addition, Table 1 shows the results of liquid films of polymerized products using other silicone compounds as monomers.
第 １ 表
※キャリアガス法 Ｎ、、０．５ １／ｍｉｎ ２５℃
で測定（発明の効果）
以上のように本発明の液体混合物の分離膜によれば下記
の様な利点がある。Table 1 *Carrier gas method N, 0.5 1/min 25℃
Measurement (Effects of the Invention) As described above, the liquid mixture separation membrane of the present invention has the following advantages.
■既存のシリコーンゴム膜以上の分離性能が得られる。■Separation performance superior to existing silicone rubber membranes can be obtained.
ロキザン類似構造の液体状物を作成できる。A liquid substance with a structure similar to Roxane can be created.
■プラズマ重合法を利用することにより生成物の性質の
範囲を幅広く選択できる。■By using the plasma polymerization method, a wide range of product properties can be selected.
第１図は本発明の実施例に於けるヘプタメチルトリシロ
キサンプラズマ重合物のＩＲ（ＫＲ３−５板上に塗布し
て測定）を例示している。FIG. 1 illustrates the IR (measured by coating on a KR3-5 plate) of a heptamethyltrisiloxane plasma polymer in an example of the present invention.
Claims (1)
る膜において、有機シリコーン化合物をモノマーとして
プラズマ重合を行ない、液体状生成物を得、該液体状生
成物を疎水性多孔膜に含浸させたことを特徴とする液体
混合物の分離膜。 （３）分子中にＳｉ−Ｈ結合を含む有機シリコーン化合
物をモノマーとして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。 （４）１，１，１，３，５，５，５−ヘプタメチルトリ
シロキサンをモノマーとして用いた特許請求の範囲第（
２）項または第（３）項記載の液体混合物の分離膜。 （５）揮発性有機液体と水との混合物を浸透気化分離す
る膜の製造において、有機シリコーン化合物をモノマー
として反応容器中に酸素ガスを共存させながらプラズマ
重合を行ない、液体状生成物を得、該液体状生成物を疎
水性多孔膜に含浸することを特徴とする液体混合物の分
離膜の製造方法。 （６）１，１，１，３，５，５，５−ヘプタメチルトリ
シロキサンをモノマーとして用いる特許請求の範囲第（
５）項記載の液体混合物の分離膜の製造方法。[Claims] (1) In a membrane for pervaporative separation of a mixture of a volatile organic liquid and water, plasma polymerization is performed using an organic silicone compound as a monomer to obtain a liquid product; A separation membrane for a liquid mixture characterized by impregnating a hydrophobic porous membrane. (3) A separation membrane for a liquid mixture according to claim (1), in which an organic silicone compound containing a Si-H bond in the molecule is used as a monomer. (4) Claim No. 1 in which 1,1,1,3,5,5,5-heptamethyltrisiloxane is used as a monomer (
A separation membrane for a liquid mixture according to item 2) or item (3). (5) In the production of a membrane for pervaporative separation of a mixture of a volatile organic liquid and water, a liquid product is obtained by performing plasma polymerization using an organic silicone compound as a monomer while coexisting oxygen gas in a reaction vessel; A method for producing a separation membrane for liquid mixtures, which comprises impregnating a hydrophobic porous membrane with the liquid product. (6) Claim No. 1 in which 1,1,1,3,5,5,5-heptamethyltrisiloxane is used as a monomer (
5) A method for producing a separation membrane for a liquid mixture as described in item 5).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18771186A JPS6344903A (en) | 1986-08-12 | 1986-08-12 | Separating membrane of liquid mixture and manufacture of the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18771186A JPS6344903A (en) | 1986-08-12 | 1986-08-12 | Separating membrane of liquid mixture and manufacture of the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6344903A true JPS6344903A (en) | 1988-02-25 |
| JPH0368733B2 JPH0368733B2 (en) | 1991-10-29 |
Family
ID=16210831
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP18771186A Granted JPS6344903A (en) | 1986-08-12 | 1986-08-12 | Separating membrane of liquid mixture and manufacture of the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6344903A (en) |
-
1986
- 1986-08-12 JP JP18771186A patent/JPS6344903A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0368733B2 (en) | 1991-10-29 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |