JPH0566170B2 - - Google Patents
Info
- Publication number
- JPH0566170B2 JPH0566170B2 JP25734285A JP25734285A JPH0566170B2 JP H0566170 B2 JPH0566170 B2 JP H0566170B2 JP 25734285 A JP25734285 A JP 25734285A JP 25734285 A JP25734285 A JP 25734285A JP H0566170 B2 JPH0566170 B2 JP H0566170B2
- Authority
- JP
- Japan
- Prior art keywords
- membrane
- gel layer
- molecular weight
- polymer
- base material
- 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.)
- Expired - Lifetime
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- Separation Using Semi-Permeable Membranes (AREA)
Description
（産業上の利用分野）
本発明は限外濾過用ダイナミツク膜及びこれを
用いる限外濾過方法、特に、所謂自己排除型ダイ
ナミツク膜を用いる高分子量重合体の限外濾過方
法に関する。
（従来の技術）
既に知られているように、所謂自己排除型ダイ
ナミツク膜による限外濾過は、分離濃縮すべき糖
やタンパク質等の高分子量重合体溶質自体にて、
分離性をもたない多孔質基材の表面や細孔内にそ
れらが凝集したゲル層を形成し、このゲル層の分
離機能を利用して、上記溶質を含む溶液を処理し
て、この溶質を濃縮分離する方法である。従つ
て、多孔質基材はゲル層の支持体としての機能を
有し、従来、かかる多孔質基材としては、安定な
ゲル層を形成するために、孔径0.01〜10〓ｍの細
孔を有するセラミツク焼結体や親水性重合体から
なる多孔質膜が用いられているが、特に、親水性
を有するのみならず、耐酸性、耐アルカリ性、耐
熱性、強度等にすぐれるところから、セラミツク
焼結体が広く用いられている。
このように、セラミツク焼結体からなる基材は
多くの点ですぐれてはいるが、反面、親水性であ
るために、ゲル層が強固に付着しており、使用後
のゲル層の除去が容易ではないので、再生性に劣
る。例えば、ゲル層の洗浄除去によるダイナミツ
ク膜の基材の再性の方法として、従来、スポンジ
ボールによる掻き落としや、薬品による化学分解
等が利用されるが、特に、前者の方法によるとき
は、通常、ゲル層が基材の細孔内にも形成されて
いるので、完全には除去することができない。
他方、従来からフツ素樹脂系多孔質膜が耐薬品
性にすぐれることはよく知られているが、フツ素
樹脂系多孔質膜は、疎水性であるで、例えば、平
均孔径0.1〓ｍ程度の細孔を有する多孔質膜に純
水を透過させるには、少なくとも６Kg／cm2以上の
加圧を要し、従来、ダイナミツク膜の基材として
は不適当であるとされている。
（発明の目的）
しかし、本発明者らは、所定の範囲の平均孔径
を有するフツ素樹脂系多孔質膜を基材として用い
て自己排除型ダイナミツク膜を形成するとき、フ
ツ素樹脂系多孔質膜の疎水性にもかかわらず、低
圧力下に限外濾過し得るダイナミツク膜を形成す
ることができるうえに、多孔質膜が疎水性であ
り、耐薬品性にすぐれるめに、前述したスポンジ
ボールによる洗浄によつて、容易にゲル層を除去
することができ、また、次亜塩素酸塩のような化
学薬品による洗浄をも行なうことができ、このよ
うに、再生性にもすぐれることを見出して、本発
明に至つたものである。
従つて、本発明は、操作性及び再生性のいずれ
にもすぐれる自己排除型ダイナミツク膜及びかか
る膜を用いる限外濾過方法を提供することを目的
とする。
（発明の構成）
本発明によるダイナミツク膜は、平均孔径0.05
〜40〓ｍの細孔を有するフツ素樹脂系多孔質膜か
らなる基材に分子量500以上の高分子量重合体か
らなるゲル層が形成されていることを特徴とす
る。
また、本発明による限外濾過方法は、平均孔径
0.05〜40〓ｍの細孔を有するフツ素樹脂系多孔質
膜からなる基材に分子量500以上の高分子量重合
体を含む溶液を圧力差によつて透過させ、上記基
材に上記重合体のゲル層からなるダイナミツク膜
を形成し、この膜にて上記重合体を含む溶液を処
理して、この溶液から上記重合体を分離すること
を特徴とする。
本発明において、ダイナミツク膜の基材として
用いるフツ素樹脂系多孔質膜は、特に、ポリテト
ラフルオロエチレンからなる多孔質膜が好適であ
り、更に、比較的低圧力にて水透過性を有し、し
かも、重合体のゲル層を容易に形成し得るため
に、その細孔の平均孔径は0.05〜40〓ｍであるこ
とが必要である。特に、多孔質膜の有する細孔の
平均孔径が0.2〜10〓ｍの範囲であり、且つ、多
孔度が50％以上であることが好ましい。他方、か
かるフツ素樹脂系多孔質膜に分離機能のすぐれた
ゲル層を形成し得るためには、重合体の分子量は
500以上であることが必要であり、好ましくは
3000以上である。
本発明によるダイナミツク膜は、上記のような
フツ素樹脂系多孔質膜からなる基材に高分子量重
合体を含む水溶液を圧力差を利用して膜透過さ
せ、多孔質膜にこの重合体のゲル層を形成させる
ことによつて得ることができる。通常、上記水溶
液を加圧下に膜透過させればよい。
（発明の効果）
このようにしてけ得られる本発明によるダイナ
ミツク膜は、自己排除型膜として安定したすぐれ
た性能を有し、従来のセラミツク基材を用いる自
己排除型ダイナミツク膜と同等若しくはそれ以上
の性能を有する。しかも、基材であるフツ素樹脂
系多孔質膜が疎水性であるので、形成されている
ゲル層を前述したスポンジボール洗浄によつて容
易に除去することができ、また、耐薬品性にすぐ
れるので、例えば、次亜塩素酸水溶液によつて
も、洗浄再生することができる。
（実施例）
以下に実施例を挙げて本発明を説明するが、本
発明はこれら実施例により何ら限定されるもので
はない。
実施例 １
平均孔径2.5〓ｍの細孔を有するポリテトラフ
ルオロエチレン多孔質膜を直径1.6cm、長さ40cm、
有効膜面積180cm2の管状にし、所定の濃度の卵白
アルブミン水溶液を温度25℃、圧力２Kg／cm2にて
流量6l／秒の割合で上記多孔質膜の内側に供給し
て透過させた。第１図に透過流束及び除去率を示
すように、約20〜30分後に透過流束及び卵白アル
ブミンの除去率が安定し、ゲル層が形成されたこ
とが示される。
このようにして得たダイナミツク膜について、
温度25℃、圧力２Kg／cm2での純水の透過流束を測
定した。次に、これらのダイナミツク膜のそれぞ
れをスポンジボール洗浄、次亜塩素酸洗浄又は水
洗浄した後、上記と同じ条件下に再び卵白アルブ
ミン水溶液の透過流束を測定した。
比較のために、平均孔径2.0〓ｍの細孔を有す
るセラミツク基材を用いて、濃度1000ppmの卵白ア
ルブミン水溶液を透過させて、ダイナミツク膜を
形成し、上記と同様にして、洗浄後の透過流束を
測定した。
結果を表に示すように、本発明に従つて形成さ
れたダイナミツク膜によれば、単なる水洗浄によ
つても、透過流束は大幅に回復するが、特に、ス
ポンジボール洗浄又は次亜塩素酸洗浄によれば、
透過流束は、ゲル層形成前のそれと同じにまで回
復し、上記洗浄によつてゲル層が完全に除去され
たことが示される。しかし、セラミツク基材を用
いたダイナミツク膜によれば、単なる水洗浄によ
つては、透過流束の回復はなく、ゲル層が何ら除
去されていないことが示され、スポンジボール洗
浄又は次亜塩素酸洗浄によつても、透過流束の回
復が小さいことから、ゲル層の除去が極めて不完
全であることが示される。
実施例 ２
実施例１において、溶質としてデンプン、ゼラ
チン又はペクチンを用いた以外は、実施例１と同
様にしてダイナミツク膜を形成した。結果を第２
図に示すように、いずれの場合も安定した高い除
(Industrial Application Field) The present invention relates to a dynamic membrane for ultrafiltration and an ultrafiltration method using the same, and particularly to a method for ultrafiltration of high molecular weight polymers using a so-called self-exclusion type dynamic membrane. (Prior art) As is already known, ultrafiltration using a so-called self-exclusion type dynamic membrane separates and concentrates high molecular weight polymer solutes such as sugars and proteins themselves.
They form a gel layer in which they aggregate on the surface or within the pores of a porous substrate that does not have separability, and the separation function of this gel layer is used to process the solution containing the solute. This is a method of concentrating and separating. Therefore, the porous base material has a function as a support for the gel layer, and conventionally, such porous base materials have pores with a pore diameter of 0.01 to 10〓m in order to form a stable gel layer. Ceramic sintered bodies and porous membranes made of hydrophilic polymers are used, but ceramics are particularly popular because they not only have hydrophilic properties but also have excellent acid resistance, alkali resistance, heat resistance, strength, etc. Sintered bodies are widely used. As described above, the base material made of ceramic sintered body is excellent in many respects, but on the other hand, because it is hydrophilic, the gel layer adheres firmly and it is difficult to remove the gel layer after use. Since it is not easy, reproducibility is poor. For example, methods such as scraping with a sponge ball or chemical decomposition using chemicals are conventionally used to regenerate the base material of a dynamic membrane by washing and removing the gel layer. Since the gel layer is also formed within the pores of the base material, it cannot be completely removed. On the other hand, it has been well known that fluororesin-based porous membranes have excellent chemical resistance, but fluororesin-based porous membranes are hydrophobic and have, for example, an average pore diameter of about 0.1〓m. In order to allow pure water to pass through a porous membrane having pores of 1,000 lbs., a pressure of at least 6 kg/cm 2 or more is required, and it has been conventionally considered that this material is unsuitable as a base material for dynamic membranes. (Object of the Invention) However, when forming a self-excluding dynamic membrane using a fluororesin porous membrane having an average pore diameter within a predetermined range as a base material, Despite the hydrophobicity of the membrane, it is possible to form a dynamic membrane that can perform ultrafiltration under low pressure, and the porous membrane is hydrophobic and has excellent chemical resistance, so the above-mentioned sponge The gel layer can be easily removed by cleaning with a ball, and cleaning with chemicals such as hypochlorite can also be performed, and thus it has excellent recyclability. This discovery led to the present invention. Therefore, an object of the present invention is to provide a self-exclusion type dynamic membrane that is excellent in both operability and reproducibility, and an ultrafiltration method using such a membrane. (Structure of the Invention) The dynamic membrane according to the present invention has an average pore diameter of 0.05.
It is characterized in that a gel layer made of a high molecular weight polymer having a molecular weight of 500 or more is formed on a base material made of a fluororesin porous membrane having pores of ~40〓m. In addition, the ultrafiltration method according to the present invention has an average pore diameter of
A solution containing a high molecular weight polymer having a molecular weight of 500 or more is permeated through a base material made of a fluororesin porous membrane having pores of 0.05 to 40〓m by a pressure difference. The present invention is characterized in that a dynamic membrane consisting of a gel layer is formed, a solution containing the above polymer is treated with this membrane, and the above polymer is separated from the solution. In the present invention, the fluororesin porous membrane used as the base material of the dynamic membrane is particularly preferably a porous membrane made of polytetrafluoroethylene, and furthermore, has water permeability at relatively low pressure. Moreover, in order to easily form a polymer gel layer, the average pore diameter of the pores must be 0.05-40〓m. In particular, it is preferable that the average pore diameter of the pores of the porous membrane is in the range of 0.2 to 10 m, and the porosity is 50% or more. On the other hand, in order to form a gel layer with excellent separation function on such a fluororesin porous membrane, the molecular weight of the polymer must be
Must be at least 500, preferably
More than 3000. The dynamic membrane according to the present invention is produced by passing an aqueous solution containing a high molecular weight polymer through the base material made of the above-mentioned fluororesin porous membrane using a pressure difference. It can be obtained by forming a layer. Usually, the above aqueous solution may be passed through a membrane under pressure. (Effects of the Invention) The dynamic membrane of the present invention thus obtained has stable and excellent performance as a self-exclusion type membrane, and is equivalent to or better than the self-exclusion type dynamic membrane using a conventional ceramic base material. Has performance. Moreover, since the fluororesin porous membrane that is the base material is hydrophobic, the formed gel layer can be easily removed by the sponge ball cleaning described above, and it has excellent chemical resistance. Therefore, cleaning and regeneration can also be performed using, for example, an aqueous hypochlorous acid solution. (Examples) The present invention will be described below with reference to Examples, but the present invention is not limited to these Examples in any way. Example 1 A polytetrafluoroethylene porous membrane having pores with an average pore diameter of 2.5 m was prepared with a diameter of 1.6 cm and a length of 40 cm.
The porous membrane was shaped into a tube with an effective membrane area of 180 cm 2 , and an aqueous ovalbumin solution of a predetermined concentration was supplied to the inside of the porous membrane at a flow rate of 6 l/sec at a temperature of 25° C. and a pressure of 2 Kg/cm 2 to permeate it. As shown in FIG. 1, the permeation flux and removal rate of ovalbumin stabilized after about 20 to 30 minutes, indicating that a gel layer was formed. Regarding the dynamic film obtained in this way,
The permeation flux of pure water was measured at a temperature of 25° C. and a pressure of 2 Kg/cm 2 . Next, after each of these dynamic membranes was washed with a sponge ball, hypochlorous acid, or water, the permeation flux of the aqueous ovalbumin solution was measured again under the same conditions as above. For comparison, a ceramic substrate with pores with an average pore diameter of 2.0 m was used to form a dynamic membrane by permeating an ovalbumin aqueous solution with a concentration of 1000 ppm. The bundle was measured. As the results are shown in the table, the permeation flux of the dynamic membrane formed according to the present invention can be significantly recovered even by simple water washing, but especially after sponge ball washing or hypochlorous acid. According to the wash,
The permeation flux recovered to the same value as before the formation of the gel layer, indicating that the gel layer was completely removed by the washing. However, according to the dynamic membrane using a ceramic base material, the permeation flux did not recover by simple water washing, indicating that the gel layer was not removed at all, and sponge ball washing or hypochlorite Even with acid washing, the recovery of permeate flux is small, indicating that removal of the gel layer is extremely incomplete. Example 2 A dynamic membrane was formed in the same manner as in Example 1 except that starch, gelatin, or pectin was used as the solute. Second result
As shown in the figure, in both cases a stable and high
【表】
去率を有する自己排除型ダイナミツク膜が形成さ
れている。[Table] A self-excluding dynamic film with a high rate of removal is formed.
第１図は卵白アルブミンを用いてフツ素系樹脂
多孔質膜基材にダイナミツク膜を形成する際の透
過流束及び除去率と時間との関係を示すグラフ、
第２図はデンプン、ゼラチン又はペクチンを用い
た場合の実施例１と同じグラフである。
FIG. 1 is a graph showing the relationship between permeation flux, removal rate, and time when forming a dynamic membrane on a fluororesin porous membrane substrate using ovalbumin;
FIG. 2 is the same graph as in Example 1 using starch, gelatin or pectin.
Claims (1)
樹脂系多孔質膜からなる基材に分子量500以上の
高分子量重合体からなるゲル層が形成されている
ことを特徴とする限外濾過用ダイナミツク膜。 ２ 平均孔径0.05〜40〓ｍの細孔を有するフツ素
樹脂系多孔質膜からなる基材に分子量500以上の
高分子量重合体を含む溶液を圧力差によつて透過
させ、上記基材に上記重合体のゲル層からなるダ
イナミツク膜を形成し、この膜にて上記重合体を
含む溶液を処理して、この溶液から上記重合体を
分離することを特徴とする限外濾過方法。[Scope of Claims] 1. A gel layer made of a high molecular weight polymer having a molecular weight of 500 or more is formed on a base material made of a fluororesin porous membrane having pores with an average pore diameter of 0.05 to 40〓m. Dynamic membrane for ultrafiltration with special features. 2 A solution containing a high molecular weight polymer having a molecular weight of 500 or more is permeated through a base material made of a fluororesin porous membrane having pores with an average pore diameter of 0.05 to 40〓m by a pressure difference, and the above-mentioned An ultrafiltration method comprising forming a dynamic membrane consisting of a gel layer of a polymer, treating a solution containing the polymer with the membrane, and separating the polymer from the solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25734285A JPS62117603A (en) | 1985-11-15 | 1985-11-15 | Dynamic membrane and ultrafiltration method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25734285A JPS62117603A (en) | 1985-11-15 | 1985-11-15 | Dynamic membrane and ultrafiltration method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62117603A JPS62117603A (en) | 1987-05-29 |
| JPH0566170B2 true JPH0566170B2 (en) | 1993-09-21 |
Family
ID=17305033
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP25734285A Granted JPS62117603A (en) | 1985-11-15 | 1985-11-15 | Dynamic membrane and ultrafiltration method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62117603A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3920611B2 (en) | 2001-09-28 | 2007-05-30 | ヤマウチ株式会社 | Cushion material for heat press and method for producing the same |
| JP5346784B2 (en) * | 2009-11-25 | 2013-11-20 | オルガノ株式会社 | Separation membrane manufacturing method, separation membrane, and separation membrane module having ion exclusion performance |
| JP6022602B2 (en) * | 2013-10-29 | 2016-11-09 | 学校法人北里研究所 | Jig for cryopreserving vitrified cells or tissues |
-
1985
- 1985-11-15 JP JP25734285A patent/JPS62117603A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62117603A (en) | 1987-05-29 |
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