JPH01258724A - Production of gas separation membrane - Google Patents
Production of gas separation membraneInfo
- Publication number
- JPH01258724A JPH01258724A JP8588588A JP8588588A JPH01258724A JP H01258724 A JPH01258724 A JP H01258724A JP 8588588 A JP8588588 A JP 8588588A JP 8588588 A JP8588588 A JP 8588588A JP H01258724 A JPH01258724 A JP H01258724A
- Authority
- JP
- Japan
- Prior art keywords
- water
- base body
- gas separation
- separation membrane
- 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
- 239000012528 membrane Substances 0.000 title claims abstract description 34
- 238000000926 separation method Methods 0.000 title claims abstract description 26
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000011148 porous material Substances 0.000 claims abstract description 8
- 229910010272 inorganic material Inorganic materials 0.000 claims abstract description 7
- 239000011147 inorganic material Substances 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 6
- 238000001704 evaporation Methods 0.000 claims abstract description 5
- 229920000642 polymer Polymers 0.000 claims description 9
- 239000003960 organic solvent Substances 0.000 claims description 7
- 239000002904 solvent Substances 0.000 abstract description 10
- 238000000034 method Methods 0.000 abstract description 9
- 239000000463 material Substances 0.000 abstract description 4
- 239000010409 thin film Substances 0.000 abstract description 3
- 239000011248 coating agent Substances 0.000 abstract description 2
- 238000000576 coating method Methods 0.000 abstract description 2
- 239000010408 film Substances 0.000 abstract description 2
- 239000002352 surface water Substances 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 29
- 239000000919 ceramic Substances 0.000 description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 239000003507 refrigerant Substances 0.000 description 4
- VFWCMGCRMGJXDK-UHFFFAOYSA-N 1-chlorobutane Chemical compound CCCCCl VFWCMGCRMGJXDK-UHFFFAOYSA-N 0.000 description 2
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- 238000005057 refrigeration Methods 0.000 description 2
- VOPWNXZWBYDODV-UHFFFAOYSA-N Chlorodifluoromethane Chemical compound FC(F)Cl VOPWNXZWBYDODV-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- RJCQBQGAPKAMLL-UHFFFAOYSA-N bromotrifluoromethane Chemical compound FC(F)(F)Br RJCQBQGAPKAMLL-UHFFFAOYSA-N 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- MSVGHYYKWDQHFV-BQYQJAHWSA-N ditert-butyl (e)-but-2-enedioate Chemical compound CC(C)(C)OC(=O)\C=C\C(=O)OC(C)(C)C MSVGHYYKWDQHFV-BQYQJAHWSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- -1 polydimethylsiloxane Polymers 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
本発明は気体の分離濃縮をするための気体分離膜の製造
方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a method for manufacturing a gas separation membrane for separating and concentrating gases.
従来の技術
近年、有機高分子膜を用いた気体分離膜が空気中より酸
素を効率よく安価に濃縮できることから、燃焼機器や汚
泥処理設備、健康機器、医療機器などの分野での応用が
期待されている。また、混合冷媒を使用した冷凍サイク
ルにおいて、混合冷媒濃度を任意に変えることができる
ならば、効率のよい冷凍サイクルを構成することができ
るようになる。Conventional technology In recent years, gas separation membranes using organic polymer membranes have been able to efficiently and inexpensively concentrate oxygen from the air, and are expected to be used in fields such as combustion equipment, sludge treatment equipment, health equipment, and medical equipment. ing. Furthermore, in a refrigeration cycle using a mixed refrigerant, if the mixed refrigerant concentration can be changed arbitrarily, an efficient refrigeration cycle can be constructed.
一般に、均質な膜における気体の透過量は、次の関係式
で表される。Generally, the amount of gas permeation through a homogeneous membrane is expressed by the following relational expression.
ただし ｑ、：気体ｉの透過量（ｃｃ）ＰＩ：気体透過
係数（ｃｃ−ｃｍ ／ ｃｎｆ ・秒・ｃｍＨｇ）ΔＰ
ｌ：気体ｉの膜両面での分圧差（ｃｍ Ｈｇ ）ｔ ：
透過時間（秒）
Ａ ：膜面積（ｃｎｆ）
ｅ ：膜厚（ｃ＋ｕ）
この関係式から明らかなように、膜厚ｅを薄（すればす
るほど、気体の透過量を多（することができる。このよ
うな膜厚の薄い気体分離膜を得る方法のひとつとして、
水面上に溶媒に溶解した有機高分子を展開して高分子薄
膜を形成し、これを多孔質支持体に担持させるという方
法が提案されている（特開昭５６−９２９２６号公報、
特開昭５８−３５７２２号公報など）。However, q,: permeation amount of gas i (cc) PI: gas permeability coefficient (cc-cm/cnf・sec・cmHg)ΔP
l: Partial pressure difference (cm Hg) of gas i on both sides of the membrane t:
Permeation time (seconds) A: Membrane area (cnf) e: Membrane thickness (c+u) As is clear from this relational expression, the thinner the membrane thickness e, the greater the amount of gas permeation. .One of the methods to obtain such a thin gas separation membrane is as follows.
A method has been proposed in which organic polymers dissolved in a solvent are spread on the water surface to form a thin polymer film, and this is supported on a porous support (Japanese Patent Laid-Open No. 56-92926,
(Japanese Unexamined Patent Publication No. 58-35722, etc.).
このように膜Ｓ２を薄くするために、気体分離膜単体で
は機械的強度がないため、前述のように多孔質支持体上
に展開して、担持させるという方法が実際的である。ま
た、さらに膜厚ｅを薄（するために、限外濾過などに用
いられている多孔質支持体などを使用することも検討さ
れている（特公昭６１−４８９６５号公報）。In order to make the membrane S2 thin as described above, since the gas separation membrane alone does not have mechanical strength, it is practical to spread it on a porous support and support it as described above. Furthermore, in order to further reduce the membrane thickness e, the use of porous supports used in ultrafiltration and the like is being considered (Japanese Patent Publication No. 48965/1983).
発明が解決しようとする課題
しかしながら、上述のように溶媒に溶解させた高分子溶
液を水面上に展開させて薄膜化した気体分離膜を、高分
子の多孔質支持体に担持させた気体分離複合膜は、気体
供給側と気体透過側との圧力差が大きい分離器に用いる
場合、太き圧力差によって支持体が伸びたり破損したり
する。支持体が伸びると、それに担持されている気体分
離膜も伸びたり、破損したりして、気体分離の機能を失
ってしまう。そこで、支持体を補強することも考えられ
るが、高分子多孔質支持体を伸びないようにするのは実
際上不可能といっても過言でない。また、強度の点を考
慮すれば、無機材料からなる多孔質支持体を使用するこ
とが考えられる。ところが、気体分離膜の材料たとえば
ポリ４−メチルペンテン−１やポリフマル酸エステルな
どによっては、水面展開して薄膜化した気体分離膜を直
接無機多孔質支持体に担持させることは非常に困難なこ
とである。一方、有機溶媒に溶解させた高分子溶液を無
機多孔質支持体に直接塗布すると、３膜の気体分離膜を
得ることができないという課題もあった。Problems to be Solved by the Invention However, as described above, a gas separation composite in which a gas separation membrane formed by spreading a polymer solution dissolved in a solvent onto a water surface to form a thin film is supported on a porous polymer support. When a membrane is used in a separator with a large pressure difference between the gas supply side and the gas permeation side, the support may stretch or be damaged due to the large pressure difference. When the support stretches, the gas separation membrane supported on it also stretches or breaks, and loses its gas separation function. Therefore, reinforcing the support may be considered, but it is no exaggeration to say that it is practically impossible to prevent the porous polymer support from stretching. Furthermore, in consideration of strength, it is conceivable to use a porous support made of an inorganic material. However, depending on the material of the gas separation membrane, such as poly-4-methylpentene-1 or polyfumaric acid ester, it is extremely difficult to directly support the gas separation membrane, which has been developed into a thin film on the water surface, on an inorganic porous support. It is. On the other hand, when a polymer solution dissolved in an organic solvent is directly applied to an inorganic porous support, there is also the problem that a three-layer gas separation membrane cannot be obtained.
本発明は、上記課題にかんがみ、薄い均質膜を形成する
ことができ、しかも圧力差の大きな分離器にも適用でき
る気体分離膜の製造方法を提供しようとするものである
。In view of the above problems, the present invention aims to provide a method for producing a gas separation membrane that can form a thin homogeneous membrane and can also be applied to separators with large pressure differences.
課題を解決するための手段
本発明の気体分離膜の製造方法は、無機材料からなる多
孔質支持体に水を含浸する工程と、多孔質支持体の表面
の水を除去する工程と、多孔質支持体の表面に水に不溶
の有機溶媒で溶解した高分子溶液を塗布する工程と、有
機溶媒を蒸発させ、気体分離膜を形成する工程と、多孔
質支持体の孔に残存している水を乾燥除去する工程とを
有し、この順序で実施することを特徴とする。Means for Solving the Problems The method for producing a gas separation membrane of the present invention includes a step of impregnating a porous support made of an inorganic material with water, a step of removing water on the surface of the porous support, and a step of impregnating a porous support made of an inorganic material with water. A process of applying a polymer solution dissolved in a water-insoluble organic solvent to the surface of the support, a process of evaporating the organic solvent to form a gas separation membrane, and a process of coating the surface of the support with water remaining in the pores of the porous support. and a step of removing by drying, and is characterized by being carried out in this order.
作 用
無機材料からなる多孔質支持体に水を含浸させ、気体分
離膜を担持する面の水を除去し、水に不溶の有機溶媒で
溶解した高分子溶液を塗布すると、水を除去した面上に
は高分子溶液が載るが、水に不溶であるため、水が残存
している支持体の孔内には浸透して行かず、支持体の表
面に薄い均質な膜が形成される。しかも、支持体が無機
材料で構成されているため、大きな圧力差にも耐えるこ
とができる。Function: A porous support made of an inorganic material is impregnated with water, the water is removed from the surface supporting the gas separation membrane, and a polymer solution dissolved in a water-insoluble organic solvent is applied. The polymer solution is placed on top, but since it is insoluble in water, water does not penetrate into the remaining pores of the support, forming a thin homogeneous film on the surface of the support. Furthermore, since the support is made of an inorganic material, it can withstand large pressure differences.
実施例
以下、本発明にかかる気体分離膜の製造方法について、
その実施例にもとづいて説明する。Examples Below, the method for manufacturing a gas separation membrane according to the present invention,
An explanation will be given based on an example thereof.
〔実施例１〕
高純度のアルミナからなる、内径６ＩＩｎ、外径１０川
、表面孔径０．１μｍの多孔質セラミック管の両端部分
それぞれに端から約１０ｍ＋ａ程度までエボリシ樹脂を
塗布硬化させて、その両端部分の孔を埋めた。このセラ
ミック管を純水中に約５分間浸漬し、その孔内に水を十
分に浸透させた。そして、それから取り出し、表面の水
を濾紙でふき取ってから、セラミック管の両端に弗素樹
脂枠を詰めた。[Example 1] Evolisi resin was applied to both ends of a porous ceramic tube made of high-purity alumina and had an inner diameter of 6IIn, an outer diameter of 10mm, and a surface pore diameter of 0.1μm, and was cured to about 10m+a from the end. Filled the holes at both ends. This ceramic tube was immersed in pure water for about 5 minutes to allow water to sufficiently penetrate into the pores. Then, it was taken out, the water on the surface was wiped off with filter paper, and fluororesin frames were packed at both ends of the ceramic tube.
そして、ジｔ−ブチルフマレート酢酸ビニルとの共重合
体の４％塩化ｎブチル溶液に浸漬し、ゆっくり引上げて
、常温で塩化ｎブチル溶媒を蒸発させた。さらに、約３
０分間常温に放置してから、温度６０℃で１０時間乾燥
させて、多孔質セラミック管一体型の気体分離膜を作製
した。Then, it was immersed in a 4% n-butyl chloride solution of a copolymer of di-t-butyl fumarate and vinyl acetate, and slowly pulled up to evaporate the n-butyl chloride solvent at room temperature. Furthermore, about 3
After being left at room temperature for 0 minutes, it was dried at a temperature of 60° C. for 10 hours to produce a gas separation membrane integrated with a porous ceramic tube.
〔実施例２〕
実施例１における多孔質セラミック管と同じセラミック
管を使用し、実施例１と同じ手順で処理してから、ポリ
ジメチルシロキサンとポリスルホンとポリヒドロキシス
チレンとの共重合体の５％ベンゼン溶液に浸漬し、ゆっ
くり引上げた。そして、常温でベンゼン溶媒を蒸発させ
た。約３０分間常温に放置してから、温度６０℃で１０
時間乾燥させて、多孔質セラミック管一体型の気体分離
膜を作製した。[Example 2] The same porous ceramic tube as in Example 1 was used, treated with the same procedure as in Example 1, and then treated with 5% of a copolymer of polydimethylsiloxane, polysulfone, and polyhydroxystyrene. It was immersed in a benzene solution and slowly pulled out. Then, the benzene solvent was evaporated at room temperature. Leave it at room temperature for about 30 minutes, then heat it at 60℃ for 10 minutes.
After drying for a period of time, a gas separation membrane integrated with a porous ceramic tube was produced.
〔実施例３〕
実施例１における多孔質セラミック管と同じセラミック
管を使用し、実施例１と同じ手順で処理してから、ポリ
４−メチルペンテン−１の４％シクロヘキサン溶液に浸
漬し、ゆっ（り引上げた。[Example 3] The same porous ceramic tube as in Example 1 was used, treated in the same manner as in Example 1, and then immersed in a 4% cyclohexane solution of poly-4-methylpentene-1 and slowly soaked. (I raised it.
そして、常温でシクロヘキサン溶媒を蒸発させた。Then, the cyclohexane solvent was evaporated at room temperature.
約３０分間常温に放置してから、温度６０℃で１０時間
乾燥させ、多孔質セラミック管一体型の気体分離膜を作
製した。After being left at room temperature for about 30 minutes, it was dried at a temperature of 60° C. for 10 hours to produce a gas separation membrane integrated with a porous ceramic tube.
実施例１〜３による気体分離膜を用いて冷媒の透過性能
を測定した。冷媒としては、モノクロロジフルオロメタ
ンとトリフルオロブロモメタンを使用し、供給側の圧力
を５ ｋｇ ／ ｃｉとし、透過側は大気開放とした。The refrigerant permeation performance was measured using the gas separation membranes according to Examples 1 to 3. Monochlorodifluoromethane and trifluorobromomethane were used as refrigerants, the pressure on the supply side was 5 kg/ci, and the permeate side was opened to the atmosphere.
測定結果を下表に示す。The measurement results are shown in the table below.
（以下余白）
発明の効果
以上のように、本発明は無機多孔質支持体に水を、含浸
させ、表面の水を除去した後、水に不溶の有機溶媒で溶
解した高分子溶液を塗布し、この溶媒窓を蒸発させて、
この多孔質支持体の孔に残存する水を乾燥させることに
より、圧力差の大きい分離器に利用できる薄い均質な気
体分離膜を得ることができる(The following is a blank space) Effects of the Invention As described above, the present invention impregnates an inorganic porous support with water, removes the water on the surface, and then applies a polymer solution dissolved in a water-insoluble organic solvent. , by evaporating this solvent window,
By drying the water remaining in the pores of this porous support, a thin, homogeneous gas separation membrane that can be used in separators with large pressure differences can be obtained.
Claims (1)
前記多孔質支持体の表面の水を除去する工程と、前記多
孔質支持体の表面に水に不溶の有機溶媒で溶解した高分
子溶液を塗布する工程と、前記有機溶媒を蒸発させ、気
体分離膜を形成する工程と、前記多孔質支持体の孔に残
存している水を乾燥除去する工程とを有し、前記順序で
実施することをを特徴とする気体分離膜の製造方法。a step of impregnating a porous support made of an inorganic material with water;
a step of removing water on the surface of the porous support; a step of applying a polymer solution dissolved in a water-insoluble organic solvent to the surface of the porous support; and a step of evaporating the organic solvent to separate the gas. A method for producing a gas separation membrane, comprising a step of forming a membrane and a step of drying and removing water remaining in the pores of the porous support, which are carried out in the above order.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8588588A JPH01258724A (en) | 1988-04-07 | 1988-04-07 | Production of gas separation membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8588588A JPH01258724A (en) | 1988-04-07 | 1988-04-07 | Production of gas separation membrane |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01258724A true JPH01258724A (en) | 1989-10-16 |
Family
ID=13871363
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8588588A Pending JPH01258724A (en) | 1988-04-07 | 1988-04-07 | Production of gas separation membrane |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01258724A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003012821A (en) * | 2001-07-03 | 2003-01-15 | Japan U-Pica Co Ltd | Method for producing fiber-reinforced porous cured molding having cavity |
| US20090280262A1 (en) * | 2008-05-08 | 2009-11-12 | Chung Yuan Christian University | Method for forming composite membrane with porous coating layer and apparatus thereof |
| JP2011101837A (en) * | 2009-11-10 | 2011-05-26 | Fujifilm Corp | Separation membrane, and method of producing the same |
| JP2011518661A (en) * | 2008-04-08 | 2011-06-30 | フジフィルム・マニュファクチュアリング・ヨーロッパ・ベスローテン・フエンノートシャップ | Membrane preparation method |
-
1988
- 1988-04-07 JP JP8588588A patent/JPH01258724A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003012821A (en) * | 2001-07-03 | 2003-01-15 | Japan U-Pica Co Ltd | Method for producing fiber-reinforced porous cured molding having cavity |
| JP2011518661A (en) * | 2008-04-08 | 2011-06-30 | フジフィルム・マニュファクチュアリング・ヨーロッパ・ベスローテン・フエンノートシャップ | Membrane preparation method |
| US20090280262A1 (en) * | 2008-05-08 | 2009-11-12 | Chung Yuan Christian University | Method for forming composite membrane with porous coating layer and apparatus thereof |
| JP2011101837A (en) * | 2009-11-10 | 2011-05-26 | Fujifilm Corp | Separation membrane, and method of producing the same |
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