JPH057053B2 - - Google Patents
Info
- Publication number
- JPH057053B2 JPH057053B2 JP18400885A JP18400885A JPH057053B2 JP H057053 B2 JPH057053 B2 JP H057053B2 JP 18400885 A JP18400885 A JP 18400885A JP 18400885 A JP18400885 A JP 18400885A JP H057053 B2 JPH057053 B2 JP H057053B2
- Authority
- JP
- Japan
- Prior art keywords
- membrane
- polysulfone
- ultrafiltration
- sulfonated
- water
- 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 - Fee Related
Links
- 239000012528 membrane Substances 0.000 claims description 53
- 238000000108 ultra-filtration Methods 0.000 claims description 18
- 229920002492 poly(sulfone) Polymers 0.000 claims description 16
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid group Chemical group S(O)(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 239000012510 hollow fiber Substances 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 238000000034 method Methods 0.000 description 8
- 239000000126 substance Substances 0.000 description 7
- 238000006277 sulfonation reaction Methods 0.000 description 7
- 125000001174 sulfone group Chemical group 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 230000035699 permeability Effects 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 238000011001 backwashing Methods 0.000 description 2
- 239000010730 cutting oil Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000005211 surface analysis Methods 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、限外ロ過膜の製造方法に関する。更
に詳しくは、膜表面部分をスルホン化ポリサルホ
ンで形成せしめる限外ロ過膜の製造方法に関す
る。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for manufacturing an ultrafiltration membrane. More specifically, the present invention relates to a method for producing an ultrafiltration membrane in which the surface portion of the membrane is made of sulfonated polysulfone.
限外ロ過は、液中に分散した微量油分、細菌、
その他の微粒子をとり除くための唯一の省エネル
ギー分離プロセスであり、その使用分野は様々で
ある。
Ultrafiltration removes trace amounts of oil, bacteria, and
It is the only energy-saving separation process for removing other particulates, and its applications are diverse.
ところで、限外ロ過においては、限外ロ過膜の
膜面に堆積あるいは吸着される物質は、しばしば
膜の目詰りをひき起して膜の抵抗を高め、ロ過効
率を低下させる。そのため、限外ロ過膜の運転に
際してはクロスフロー方式をとり、なるべく膜面
への堆積を抑えるようにしている。 By the way, in ultrafiltration, substances deposited or adsorbed on the membrane surface of the ultrafiltration membrane often cause clogging of the membrane, increasing the resistance of the membrane and reducing the filtration efficiency. Therefore, when operating the ultrafiltration membrane, a cross-flow method is used to suppress deposition on the membrane surface as much as possible.
しかしながら、このような方式を採用しても、
膜表面はやはり汚染を受け、透過抵抗が徐々に上
昇してくる現象がみられる。これは、ロ過対象液
中の分散物質が膜表面に吸着され、膜の孔を塞ぐ
ために起るものと考えられる。そして、このよう
な物質が一旦膜表面に吸着されると、逆洗、洗浄
などをくり返しても膜から離れず、いわゆるプラ
ギング現象を起して、最後には限外ロ過膜の透過
率を殆んどゼロにしてしまうようになる。 However, even if such a method is adopted,
The membrane surface is still contaminated, and a phenomenon in which the permeation resistance gradually increases is observed. This is thought to occur because the dispersed substances in the liquid to be filtered are adsorbed on the membrane surface and close the pores of the membrane. Once such substances are adsorbed on the membrane surface, they do not leave the membrane even after repeated backwashing, washing, etc., causing a so-called plugging phenomenon, which ultimately reduces the transmittance of the ultrafiltration membrane. It becomes almost zero.
ここで、このような物質について考えてみる
に、水中に安定分散し、膜だけでしか除去できな
い物質は、粒子相互のもつ電気的反発作用で安定
化しているものと考えられ、自然界ではそれぞれ
の粒子が負電荷をもつているものが多い。そこ
で、膜表面にこのような粒子が吸着され難いよう
にするためには、膜表面の負電荷を豊富にした
り、膜表面の水和層の厚さを増やして親水性にす
るなどの方法が考えられている。 Now, if we think about such substances, it is thought that substances that are stably dispersed in water and that can only be removed by membranes are stabilized by the electrical repulsion between the particles, and in nature, each substance Many particles have a negative charge. Therefore, in order to make it difficult for such particles to be adsorbed on the membrane surface, methods such as enriching the membrane surface with negative charges or increasing the thickness of the hydration layer on the membrane surface to make it hydrophilic are available. It is considered.
このような観点から、限外ロ過膜材料として有
望なポリサルホンに、極性基であるスルホン基を
導入することが試みられている。しかしながら、
膜材料に直接極性基を導入することには、次のよ
うな欠点がみられる。
From this point of view, attempts have been made to introduce sulfone groups, which are polar groups, into polysulfone, which is a promising material for ultrafiltration membranes. however,
Directly introducing polar groups into membrane materials has the following disadvantages.
(1) 膜の親水性が高まるにつれ、水中での膜強度
が低下するようになる。(1) As the hydrophilicity of the membrane increases, the strength of the membrane in water decreases.
(2) 製膜時に水をゲル化浴として用いることが多
いため、ゲル化の際水を抱き込んで重合体が凝
集してしまい、極性基の導入率を高くすると膜
を形成せず、製膜が不可能となる。(2) Since water is often used as a gelling bath during film formation, water is trapped during gelation and the polymer aggregates. membrane becomes impossible.
このような欠点を解消するために、ポリサルホ
ンおよびスルホン化ポリサルホンの混合物膜状体
よりなる限外ロ過膜が先に本出願人によつて提案
されており（特願昭60−93318号）、一応所期の目
的は達成されたものの、膜状体が均一な混合物か
ら形成されているという構造上、スルホン化ポリ
サルホンによるスルホン基の導入が膜汚染に関与
する表面において不十分とならざるを得ない。ま
た、スルホン化ポリサルホンを限外ロ過膜材料に
コーテイングする方法なども考えられるが、この
場合には塗布膜の耐剥離性に問題がみられる。 In order to overcome these drawbacks, the applicant previously proposed an ultrafiltration membrane made of a membrane-like mixture of polysulfone and sulfonated polysulfone (Japanese Patent Application No. 93318/1982). Although the intended purpose was achieved, due to the structure of the membrane, which is formed from a homogeneous mixture, the introduction of sulfone groups by sulfonated polysulfone was inevitably insufficient on the surface involved in membrane contamination. do not have. Another possible method is to coat the ultrafiltration membrane material with sulfonated polysulfone, but in this case there is a problem with the peeling resistance of the coating.
そこで、かかる課題の根本的な解決方法を求め
て更に検討を重ねた結果、本発明者は直接ポリサ
ルホンの膜状体をスルホン化することにより、膜
表面のスルホン基などを集中的に導入しかつ剥離
性の点でも問題のない限外ロ過膜が得られること
を見出した。 Therefore, as a result of further investigation in search of a fundamental solution to this problem, the present inventors were able to intensively introduce sulfone groups on the membrane surface by directly sulfonating the polysulfone membrane. It has been found that an ultrafiltration membrane with no problem in removability can be obtained.
〔問題点を解決するための手段〕および〔作用〕
従つて、本発明は限外ロ過膜の製造方法に係
り、限外ロ過膜の製造は、ポリサルホンの膜状体
をスルホン化剤中に浸漬し、膜表面部分をスルホ
ン化することにより行われる。[Means for Solving the Problems] and [Operations] Therefore, the present invention relates to a method for producing an ultrafiltration membrane, and the production of the ultrafiltration membrane involves adding a film-like body of polysulfone to a sulfonating agent. This is done by immersing the membrane in water to sulfonate the membrane surface.
スルホン化されるポリサルホンの膜状体として
は、一般に乾湿式法で製造された平膜状、中空糸
状のものなどが用いられる。これらの膜状体は、
例えば２〜18Nの硫酸をスルホン化剤に用い、約
80〜90℃の液中に約３〜15日間程度浸漬すること
により、スルホン化される。浸漬２日目位から膜
状体は赤味をおびるようになり、所望されるスル
ホン化度に応じて所定日数浸漬する。その後、純
粋でよく洗浄し、洗浄水が中性になる迄水洗を続
け、硫酸を除去する。 As the polysulfone membrane to be sulfonated, flat membranes or hollow fibers produced by a dry-wet method are generally used. These membranous bodies are
For example, using 2-18N sulfuric acid as a sulfonating agent, approximately
It is sulfonated by immersing it in a solution at 80 to 90°C for about 3 to 15 days. The film-like material becomes reddish from about the second day of immersion, and is immersed for a predetermined number of days depending on the desired degree of sulfonation. Afterwards, wash thoroughly with pure water and continue washing with water until the washing water becomes neutral to remove sulfuric acid.
前述の如く、ポリサルホン樹脂自体をスルホン
化してから製膜すると製膜性に劣り、例えばスル
ホン化度（重合体のくり返し単位当りのスルホン
基の数）が0.7を越えるともはや乾湿式法では平
膜状あるいは中空糸状に製膜できなくなり、製膜
し得るスルホン化度にすると、膜表面部分のスル
ホン基の数が少なくなつて所期の目的を達成し得
ないが、本発明方法にあつては、膜状体の形状が
保持されたまま、その表面部分のみがスルホン化
されるため、スルホン化度0.1〜0.7のスルホン化
ポリサルホンを形成させても、そこに十分な耐汚
染性の性質を付与することができる。
As mentioned above, if the polysulfone resin itself is sulfonated before being formed into a film, the film forming properties will be poor.For example, if the degree of sulfonation (the number of sulfone groups per repeating unit of the polymer) exceeds 0.7, it will no longer be possible to form a flat film using the dry-wet method. If the degree of sulfonation is such that it becomes impossible to form a film in the form of a hollow fiber or a hollow fiber, the number of sulfone groups on the surface of the film decreases, making it impossible to achieve the desired purpose.However, in the method of the present invention, Since only the surface portion of the film is sulfonated while the shape of the membrane is maintained, even if a sulfonated polysulfone with a degree of sulfonation of 0.1 to 0.7 is formed, sufficient stain resistance is imparted to it. can do.
次に、実施例について本発明を説明する。 Next, the present invention will be explained with reference to examples.
実施例
乾湿式法で製膜されたポリサルホン平膜（厚さ
0.1〜0.3mm）を、80〜90℃の18N硫酸中に10日間
浸漬させた後、水洗、乾燥させた。このスルホン
化処理膜について、ESCAによる表面分析からス
ルホン化度0.4の値が、またＳの元素分析からそ
れの増加率25％の値がそれぞれ得られたことか
ら、表面部分がスルホン化度0.4のスルホン化ポ
リサルホンが得られたことが分る。Example Polysulfone flat membrane (thickness:
0.1 to 0.3 mm) was immersed in 18N sulfuric acid at 80 to 90°C for 10 days, then washed with water and dried. Regarding this sulfonated membrane, a value of 0.4 degree of sulfonation was obtained from surface analysis by ESCA, and a value of 25% increase rate was obtained from elemental analysis of S. Therefore, the surface portion has a degree of sulfonation of 0.4. It can be seen that sulfonated polysulfone was obtained.
また、このような膜表面のスルホン化処理によ
り、限外ロ過膜としての性能が変化したかどうか
を調べたが、硫酸浸漬の前後で、いずれも透過係
数は10〜20cm3／cm2・hr・Kg／cm2で、また分画分子
量は20000で、膜性能に変化はみられなかつた。 We also investigated whether the performance as an ultrafiltration membrane changed due to the sulfonation treatment of the membrane surface, but the permeability coefficient was 10 to 20 cm 3 /cm 2 before and after immersion in sulfuric acid. hr・Kg/cm 2 and molecular weight cutoff was 20,000, and no change was observed in membrane performance.
更に、切削油（ユシロ化学製品ユシローケン
EC−５）の150倍液の透過試験を、液温25℃、流
量３／分、操作圧１気圧、中空糸有効膜面積
0.2m2の条件下で、30分間毎に逆洗をくり返しな
がら行なうと、150時間後には、スルホン化して
いない中空糸の透水量は50％迄低下したが、同じ
中空糸をスルホン化したものの透水量は80％以上
の値を維持していた。なお、切削油の排除率は、
いずれも98％以上である。 In addition, cutting oil (Yushiro Chemical Products Yushiroken)
A permeation test of a liquid 150 times that of EC-5) was conducted at a liquid temperature of 25°C, a flow rate of 3/min, an operating pressure of 1 atm, and a hollow fiber effective membrane area.
When backwashing was repeated every 30 minutes under conditions of 0.2 m 2 , the water permeability of the non-sulfonated hollow fibers decreased to 50% after 150 hours; Water permeability remained above 80%. In addition, the rejection rate of cutting oil is
Both are over 98%.
Claims (1)
漬し、膜表面部分をスルホン化することを特徴と
する限外ロ過膜の製造方法。 ２ ポリサルホンの膜状体が平膜状である特許請
求の範囲第１項記載の限外ロ過膜の製造方法。 ３ ポリサルホンの膜状体が中空糸状である特許
請求の範囲第１項記載の限外ロ過膜の製造方法。 ４ スルホン化剤が硫酸である特許請求の範囲第
１項記載の限外ロ過膜の製造方法。[Claims] 1. A method for producing an ultrafiltration membrane, which comprises immersing a polysulfone membrane in a sulfonating agent to sulfonate the surface of the membrane. 2. The method for producing an ultrafiltration membrane according to claim 1, wherein the polysulfone membrane is in the form of a flat membrane. 3. The method for producing an ultrafiltration membrane according to claim 1, wherein the polysulfone membrane has a hollow fiber shape. 4. The method for producing an ultrafiltration membrane according to claim 1, wherein the sulfonating agent is sulfuric acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18400885A JPS6245303A (en) | 1985-08-23 | 1985-08-23 | Preparation of ultrafiltration membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18400885A JPS6245303A (en) | 1985-08-23 | 1985-08-23 | Preparation of ultrafiltration membrane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6245303A JPS6245303A (en) | 1987-02-27 |
| JPH057053B2 true JPH057053B2 (en) | 1993-01-28 |
Family
ID=16145710
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP18400885A Granted JPS6245303A (en) | 1985-08-23 | 1985-08-23 | Preparation of ultrafiltration membrane |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6245303A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02157026A (en) * | 1988-12-08 | 1990-06-15 | Sumitomo Bakelite Co Ltd | Charge type ultrafiltration film and its manufacture |
-
1985
- 1985-08-23 JP JP18400885A patent/JPS6245303A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6245303A (en) | 1987-02-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109847586B (en) | High-flux reverse osmosis membrane and preparation method and application thereof | |
| Strathmann | Synthetic membranes and their preparation | |
| EP1654053B1 (en) | Hollow fibre membrane comprising pvme and method of production | |
| WO2002102500A1 (en) | Membrane polymer compositions | |
| JP2005516764A (en) | Halar film | |
| WO2014192883A1 (en) | Composite semipermeable membrane | |
| CN115318110B (en) | Method for preparing high-selectivity nanofiltration membrane based on regulation and control of weak-polarity organic solvent | |
| JPS6219205A (en) | Preparation of ultrafilter membrane | |
| CN110141980A (en) | A kind of inner pressed hollow fiber nanofiltration membrane and preparation method thereof | |
| US4319008A (en) | Polyether admixture and semi-permeable membranes comprised thereof | |
| JPS5891732A (en) | Porous polyvinylidene fluoride resin membrane and preparation thereof | |
| JPH04349927A (en) | Preparation of precise filter membrane | |
| JPH057053B2 (en) | ||
| JPS61249504A (en) | Ultrafilter membrane | |
| KR20120077011A (en) | Water treatment membrane of poly(ethylenechlorotrifluoroethylene) and manufacturing method thereof | |
| DE3730024A1 (en) | MOLDING FOR PRINTING SLICK CASTING FOR PRODUCING MOLDED PARTS FROM CERAMIC MEASURES | |
| JPH0468010B2 (en) | ||
| JP3169404B2 (en) | Method for producing semipermeable membrane with high water permeability | |
| CN114669194A (en) | Preparation method of single-multivalent ion high-resolution nanofiltration membrane | |
| JP4164730B2 (en) | Selective separation membrane | |
| JPS62160109A (en) | Manufacture of microporous filter membrane | |
| JP4164774B2 (en) | Method for producing selective separation membrane | |
| JPS63137703A (en) | Manufacture of forming material for sulfonated polysulfone membrane | |
| JP2512909B2 (en) | Method for producing hollow fiber porous membrane | |
| JPS63166404A (en) | Hollow yarn filter membrane and manufacture thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |