JPS60807A - Surface treatment of selective gas permeable membrane - Google Patents
Surface treatment of selective gas permeable membraneInfo
- Publication number
- JPS60807A JPS60807A JP58109530A JP10953083A JPS60807A JP S60807 A JPS60807 A JP S60807A JP 58109530 A JP58109530 A JP 58109530A JP 10953083 A JP10953083 A JP 10953083A JP S60807 A JPS60807 A JP S60807A
- Authority
- JP
- Japan
- Prior art keywords
- membrane
- permeable membrane
- gas permeable
- selective gas
- solvent
- 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
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
- B01D67/0088—Physical treatment with compounds, e.g. swelling, coating or impregnation
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (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
本発明は塵埃、オイルミスト等の付着あるいは吸着によ
り気体透過流量の減少した選択性気体透過膜を溶剤によ
シ表面洗浄することにより気体透過流量を増加させるた
めの処理法に関するものである。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention improves the gas permeation rate by cleaning the surface of a selective gas permeation membrane whose gas permeation rate has decreased due to adhesion or adsorption of dust, oil mist, etc. with a solvent. This relates to a processing method for increasing the amount.
従来例の構成とその問題点 近年、脱法によるガス分離としてはＨｅ精製。Conventional configuration and its problems In recent years, He purification has been used as a gas separation method.
希ガス分離、酸素富化、エタノール、酢酸合成等のリサ
イクルガスの分離、精製等広い範囲で応用されるように
なってきている。It has come to be applied in a wide range of applications such as rare gas separation, oxygen enrichment, separation and purification of recycled gases such as ethanol and acetic acid synthesis.
従来の蒸留、深冷分離等の分離技術は相変化を伴うため
消費エネルギーが大きいが、これに対し膜分離は相変化
がなく、コンパクトな装置で操作が容易である等の利点
から省資源、省エネルギー技術として重要な開発課題と
なっている。産業において、また人間の社会生活上にお
いて有用な資源の一つとして酸素（混合ガスとして空気
）がある。Conventional separation technologies such as distillation and cryogenic separation require a large amount of energy because they involve a phase change.Membrane separation, on the other hand, does not cause a phase change and has the advantages of being compact and easy to operate, saving resources and saving energy. This is an important development issue as an energy-saving technology. Oxygen (air as a mixed gas) is one of the useful resources in industry and in human social life.
言うまでもなく大気の２１係を占める酸素は内燃機関、
燃焼機器、製鉄９食品工業、汚泥処理１発酵、医療機器
等、産業上最も重要な無尽蔵の資源である。従って空気
より酸素を効率よく安価に分離濃縮する方法は、省資源
、省エネルギーの点からも強く望まれている。こういっ
た点から近年注目されているのが高分子膜を用いた分離
方法である。Needless to say, the oxygen that makes up 21 parts of the atmosphere is the internal combustion engine.
It is the most important inexhaustible resource for industries such as combustion equipment, steel manufacturing, food industry, sludge treatment, fermentation, and medical equipment. Therefore, a method for efficiently and inexpensively separating and concentrating oxygen from air is strongly desired from the standpoint of resource and energy conservation. From this point of view, separation methods using polymer membranes have been attracting attention in recent years.
高分子膜としては選択分離性の高り、シかも透過性の良
い膜が望まれる。現在まで高分子膜を用いての混合ガス
の分離に関して既にいくつかの文献特許等で報告なされ
ている。As a polymer membrane, a membrane with high selective separation and good permeability is desired. Up to now, there have already been reports on the separation of mixed gases using polymer membranes in several documents and patents.
これらの高分子膜はいずれも選択分離性を高くした場合
、透過性が悪くなる傾向にある。When the selective separation properties of any of these polymer membranes are increased, the permeability tends to deteriorate.
′！、た、選択分離性を持たせるため脱法による気体分
離方法は、高分子膜としていわゆる穴のない（２５Å以
下）均質膜を用いる必要がある。′! In addition, in order to provide selective separation, the gas separation method by escape method requires the use of a so-called homogeneous membrane without holes (25 Å or less) as the polymer membrane.
高分子膜拐料として均質膜と多孔質膜の境界に位置する
のがシリコーンゴムだと言われている。また、一般的に
均質膜における気体透過に関して次のような関係が成立
する。Silicone rubber is said to be a polymer membrane filler located at the boundary between homogeneous membranes and porous membranes. Additionally, the following relationship generally holds regarding gas permeation in a homogeneous membrane.
ｑｉ：気体ｉの透過量０Ｑ
ｉｌ：気体透過係数（ＣＧ −ｃｍ／ｃａ ｍ ｓｅｃ
＊ ＣｍＨｇ ）Δｐｉ：気体ｉの膜両面での分圧差
（ＣｍＨｇ ）ｔ ：透過時間（Ｓｅｃ）
Ａ ：膜面積（ｃ〃ｆ）
１ ：膜厚 （ｃｍ）
気体透過量を増加９分離性を良くするには各気体の膜両
面での分圧差を増加させなければならない。qi: permeation amount of gas i 0Q il: gas permeability coefficient (CG - cm/cam sec
*CmHg) Δpi: Partial pressure difference of gas i on both sides of the membrane (CmHg) t: Permeation time (Sec) A: Membrane area (c〃f) 1: Membrane thickness (cm) Increase gas permeation rate 9 Improve separation To achieve this, it is necessary to increase the partial pressure difference of each gas on both sides of the membrane.
この方法として加圧、減圧法を用いている。For this purpose, pressurization and depressurization methods are used.
このように空気よシス体を分離濃縮するには多量の空気
と穴のない、いわゆる均質膜を用いなければならない。In order to separate and concentrate air and cis-forms in this way, it is necessary to use a large amount of air and a so-called homogeneous membrane without holes.
このことは空気から気体を分離濃縮する一種の空気のフ
ィルターであり、空気中の塵埃、オイルミスト等はこの
高分子膜のフィルターによシ透過を明止さｎる。This is a type of air filter that separates and concentrates gases from the air, and dust, oil mist, etc. in the air are prevented from permeating through this polymer membrane filter.
そして、高分子膜の透過面に塵埃、オイルミスト等が付
着あるいは強制的に吸着されると、気体の透過を阻止し
、気体透過流量が低減してしまう。When dust, oil mist, etc. adhere to or are forcibly adsorbed on the permeation surface of the polymer membrane, gas permeation is blocked and the gas permeation flow rate is reduced.
すなわち、高分子膜は非常に透過性が悪く、透過性を高
める事が一つの重要な課題になっているにもかかわらず
、更に透過効率が悪くなってしまう。That is, polymer membranes have very poor permeability, and although increasing permeability is an important issue, the permeation efficiency becomes even worse.
！、たこの空気中の塵埃、オイルミスト等による流量減
少は使用される環境に著しく影響され・る０空気中の塵
埃、オイルミストの気体透過に与える影響は脱法による
気体分離を行なう技術上解決しなければならない重要な
課題である。! The reduction in flow rate due to dust, oil mist, etc. in the air is significantly affected by the environment in which the product is used.The effect of dust and oil mist in the air on gas permeation can be solved by technology that performs gas separation by eliminating methods. This is an important issue that must be addressed.
発明の目的
本発明はこのような問題点を解決するもので簡単な方法
で選択性気体透過膜の透過性が劣化するのを防ぐことを
目的とするものである。OBJECTS OF THE INVENTION The present invention solves these problems and aims to prevent the permeability of a selective gas permeable membrane from deteriorating by a simple method.
発明の構成
この目的全達成するために本発明は、選択性気体透過膜
の表面を、この選択性気体透過膜を溶解し難くかつオイ
ルミストを良く溶解する鎖状炭化素水系、フッ素化塩素
化炭化水素系またはその混合物からなる溶剤を用いて洗
浄する方法である。Structure of the Invention In order to achieve all of these objects, the present invention provides a method for coating the surface of a selective gas permeable membrane with a linear hydrocarbon aqueous system, fluorinated chlorinated, etc. This is a cleaning method using a hydrocarbon solvent or a mixture thereof.
用いる溶剤は選択性気体透過膜を溶解せず、オイルミス
トを溶解、除去あるいは塵埃の除去を行なうものである
。例えば洗浄用溶剤として、鎖状炭化水素系溶剤、好ま
しくはｎ＝６．７のｎ−ヘキサン、ヘプタ／またはフッ
素化塩素化炭化水素系溶剤好ましくはトリクロロ−トリ
クロロエタン。The solvent used does not dissolve the selective gas permeable membrane, but dissolves and removes oil mist or removes dust. For example, as a cleaning solvent, a linear hydrocarbon solvent, preferably n-hexane with n=6.7, hepta/or a fluorinated chlorinated hydrocarbon solvent, preferably trichloro-trichloroethane.
またはそれらの混合系溶媒が良い。従って、選択性気体
透過膜の特性をそのまま保持でき、しかも除去法として
は溶剤中に浸漬、溶剤の噴霧、超音波洗浄等簡単な方法
でできる。また透過流量をオイルミスト、塵埃の付着、
吸着する前の流量まで回復することができる。Or a mixed solvent is good. Therefore, the characteristics of the selective gas permeable membrane can be maintained as they are, and the membrane can be removed by simple methods such as immersion in a solvent, spraying with a solvent, and ultrasonic cleaning. In addition, the permeation flow rate can be adjusted to reduce the amount of oil mist, dust, etc.
The flow rate can be restored to the level before adsorption.
選択性気体透過膜を溶解しないため種々の厚さの場合に
も適用でき、また膜の形状は平膜、複合膜。Since the selective gas permeable membrane does not dissolve, it can be applied to various thicknesses, and the membrane shape can be flat or composite.
中空系、スパイラル状でもいずれの場合にも適用でき特
に限定するものではない。It can be applied to either a hollow system or a spiral shape, and is not particularly limited.
実施例の説明 次に、本発明の具体的な実施例について説明する。Description of examples Next, specific examples of the present invention will be described.
（実施例１）
シリコーン系共重合体を透過膜として用い、多孔質支持
体（ポリプロピレン）上に形成した複合膜を使用して実
験を行なった。(Example 1) An experiment was conducted using a composite membrane formed on a porous support (polypropylene) using a silicone copolymer as a permeable membrane.
透過膜は約０．２μでラングミュア法により水面上に膜
を形成し使用した。The permeable membrane had a thickness of approximately 0.2μ and was formed on the water surface by the Langmuir method.
寿命試験環境は特に塵埃、オイルミストの多く発生する
所で行ない、この試料を用いた。The life test environment was conducted in a place where a lot of dust and oil mist were generated, and this sample was used.
そして、洗浄は、ｎ−へキサン中に１分間浸漬すること
に１９行なった。第１図にこの洗浄時の様子を示してお
り、図において１は多孔質支持体、２は選択性気体透過
膜、３は溶剤槽、４は洗浄用溶剤である。Then, washing was carried out by dipping in n-hexane for 1 minute 19 times. FIG. 1 shows the state during this cleaning, in which 1 is a porous support, 2 is a selective gas permeable membrane, 3 is a solvent tank, and 4 is a cleaning solvent.
この結果、表１かられかるように、ｎ−ヘキサンに浸漬
することによシ透過流量はほぼ寿命試験前の初期値まで
回復し、しかも分離特性はそのままの特性を保持させる
ことができる。As a result, as shown in Table 1, by immersion in n-hexane, the permeation flow rate can be recovered to almost the initial value before the life test, and the separation characteristics can be maintained as they are.
第２図ａ、ｂに洗浄前と洗浄後の様子を示しており、５
は膜表面に何層した塵埃、６は膜表面に付着したオイル
ミストで、あり、この第２図ａ、ｂかられかるように洗
浄によジオイルミストは除去され、また塵埃も大部分除
去されることとなる。Figures 2a and b show the state before and after cleaning.
6 is the number of layers of dust on the membrane surface, and 6 is the oil mist attached to the membrane surface.As can be seen from Figure 2 a and b, the di-oil mist was removed by cleaning, and most of the dust was also removed. It will be done.
（実姉例２）
実施例１の試ｆ４’ｆｉ＝用い、浴剤としてｎ−ヘキサ
ンを用い超音波洗浄（２Ａ、１分間）を行なったっこの
結果表１に示すように、ｎ−へキサ／中で超音波洗浄す
ることによシ寿命試験前の初期値まで流量は回復し、し
かも分離特性はそのま捷の特性全保持している。(Sister Example 2) Using the test f4'fi of Example 1, ultrasonic cleaning (2A, 1 minute) was performed using n-hexane as a bath agent. As shown in Table 1, the results showed that n-hexane/ By performing ultrasonic cleaning inside the tube, the flow rate was restored to the initial value before the life test, and the separation characteristics remained intact.
（実姉例３）
実姉例１の試料を用い、溶剤としてイソへブタンを用い
約１分間の浸漬を行なった。(Sister Example 3) Using the sample of Actual Sister Example 1, immersion was performed for about 1 minute using isohebutane as a solvent.
この結果、表１でわかるようにイソへブタンに浸漬する
ことにより実施例１．２と同様な効果がある。As a result, as shown in Table 1, the same effect as in Example 1.2 can be obtained by immersing in isohebutane.
表１
酸素透過速度は酸素１気ａＥを印加し、１０ｃｒＡの膜
面積を透過する速度である。σは分離係数である。Table 1 The oxygen permeation rate is the rate at which oxygen permeates through a membrane area of 10 crA when 1 atmosphere aE of oxygen is applied. σ is the separation factor.
（実姉例４）
透過膜厚約０．３μのシリコーン系共重合体を多孔質支
持体（ポリプロピレン）上に形成し複合膜として実験を
行なった。(Sister Example 4) A silicone-based copolymer having a permeable membrane thickness of approximately 0.3 μm was formed on a porous support (polypropylene), and an experiment was conducted as a composite membrane.
洗浄はトリクロロ−トリクロロエタン（ダイフロンＳ−
３、ダイキン工業■製）に浸漬１分間行なった。Cleaning is done with trichloro-trichloroethane (Dyflon S-
3, manufactured by Daikin Industries, Ltd.) for 1 minute.
その結果、表２に示すように、透過流量はほぼ寿命試験
前の初期値まで回復し、しかも分離特性はそのままの特
性を保持している。As a result, as shown in Table 2, the permeation flow rate almost recovered to the initial value before the life test, and the separation characteristics remained unchanged.
（実施例５）
透過膜厚約０．１μのシリコーン系共重合体を用い、ｎ
−ヘキサン中に浸漬、洗浄を行なった。その結果表２に
示すように実施例１〜４と同様な効果があった〇
（実施例６）
透過膜厚約０．３μのシリコーン系共重合体を用い、ｎ
−ヘキサン中に浸漬、洗浄を行なった。その結果表２に
示すように実施例１〜５と同様な効果があった。(Example 5) Using a silicone copolymer with a permeable membrane thickness of about 0.1μ,
- Immersed and washed in hexane. As shown in Table 2, the same effects as Examples 1 to 4 were obtained (Example 6) Using a silicone copolymer with a permeable membrane thickness of about 0.3 μm, n
- Immersed and washed in hexane. As shown in Table 2, the same effects as in Examples 1 to 5 were obtained.
表 ２
厚溶剤 初期特性寿命試験後洗浄（
Ｑ２：０．５９Ｃ咋ｏ２：ｏ、１鴇ム２ ： ０．５
’殉例４０・３μ）０ン”３ａ ＝２．１５ ＝２．。Table 2 Thick Solvent Initial Characteristics Cleaning after Life Test (Q2: 0.59C 兇 2: 0, 1 氇Mu 2: 0.5
'Martyrdom 40.3μ)0n'3a =2.15 =2.
２−２．１３０２＝１，０へ々０２ ： ０．お寿似、
＝１０′５０・１μｎ−柑゛ ″ ａ ＝ ２．０６
＝ ２．。２−２．。２０２： ０，５９Ｃ％ｅＣ２：
０，２５Ｃ（、／Ｓｅｃ ２： ０．５−発明の効果
以上のように本発明の選択性気体透過膜の表面処理法は
、溶剤２で簡単に洗浄するだけで、透過性を回復させる
ことができるとともに、分離特性を初期の状態に保持す
ることができるという効果が得られる。2-2.1302=1,0Hehe02:0. Otobuki,
=10'50・1μn-Ki''a=2.06
= 2. . 2-2. . 202: 0,59C%eC2:
0.25C(,/Sec 2: 0.5-Effects of the Invention As described above, the surface treatment method of the selective gas permeable membrane of the present invention allows the permeability to be restored by simply cleaning with Solvent 2. In addition, the separation characteristics can be maintained in the initial state.
第１図は本発明による表面処理法を実姉じている状態の
一例を示す概略図、第２図ａ、ｂは本発表 切による表
面処理法の効果を示すために・洗浄前と洗浄後の膜表面
の状態を示す拡大図である。
２・・・・・・選択性気体透過膜、４・・・・・・洗浄
用溶剤、６・・・・・・膜表面に付着した塵埃、６・・
・・・・膜表面に付着したオイルミスト。Figure 1 is a schematic diagram showing an example of a state similar to the surface treatment method according to the present invention, and Figures 2 a and b are presented in this study. FIG. 3 is an enlarged view showing the state of the membrane surface. 2... Selective gas permeable membrane, 4... Cleaning solvent, 6... Dust attached to the membrane surface, 6...
...Oil mist attached to the membrane surface.
Claims (1)
し雛くかつオイルミストを良く溶解する鎖状炭化水素系
、フッ素化塩素化炭化水素系またはその混合物からなる
溶剤を用いて洗浄することを特徴とする選択性気体透過
膜の表面処理法。The surface of the selective gas permeable membrane is cleaned using a solvent consisting of a chain hydrocarbon type, a fluorinated chlorinated hydrocarbon type, or a mixture thereof, which dissolves the selective gas permeable membrane and dissolves oil mist well. A surface treatment method for a selective gas permeable membrane, characterized by:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58109530A JPS60807A (en) | 1983-06-17 | 1983-06-17 | Surface treatment of selective gas permeable membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58109530A JPS60807A (en) | 1983-06-17 | 1983-06-17 | Surface treatment of selective gas permeable membrane |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS60807A true JPS60807A (en) | 1985-01-05 |
Family
ID=14512587
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58109530A Pending JPS60807A (en) | 1983-06-17 | 1983-06-17 | Surface treatment of selective gas permeable membrane |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60807A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0337499A3 (en) * | 1983-11-26 | 1989-11-29 | Matsushita Electric Industrial Co., Ltd. | Method for regenerating used gas-permeable films |
| US4906256A (en) * | 1989-03-23 | 1990-03-06 | Membrane Technology & Research, Inc. | Membrane process for treatment of fluorinated hydrocarbon-laden gas streams |
-
1983
- 1983-06-17 JP JP58109530A patent/JPS60807A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0337499A3 (en) * | 1983-11-26 | 1989-11-29 | Matsushita Electric Industrial Co., Ltd. | Method for regenerating used gas-permeable films |
| US4906256A (en) * | 1989-03-23 | 1990-03-06 | Membrane Technology & Research, Inc. | Membrane process for treatment of fluorinated hydrocarbon-laden gas streams |
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