JPH05329344A - Production of composite semipermeable membrane - Google Patents
Production of composite semipermeable membraneInfo
- Publication number
- JPH05329344A JPH05329344A JP14036892A JP14036892A JPH05329344A JP H05329344 A JPH05329344 A JP H05329344A JP 14036892 A JP14036892 A JP 14036892A JP 14036892 A JP14036892 A JP 14036892A JP H05329344 A JPH05329344 A JP H05329344A
- Authority
- JP
- Japan
- Prior art keywords
- composite semipermeable
- semipermeable membrane
- sodium hypochlorite
- aqueous solution
- composite
- 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
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は各種液体混合物を選択分
離するための複合半透膜の製造方法に関する。さらに詳
しくは、後処理によってその性能を向上させる方法に関
する。FIELD OF THE INVENTION The present invention relates to a method for producing a composite semipermeable membrane for selective separation of various liquid mixtures. More specifically, it relates to a method of improving its performance by post-treatment.
【０００２】[0002]
【従来の技術】近年、活性層とこれを支持する異種素材
から製造してなる複合半透膜が種々提案されており、従
来の非対称膜に比べて選択分離性や透過性の面で優れた
性能を有している。従来提案されている複合膜として
は、たとえばポリスルホン膜支持体の上に芳香族系ポリ
アミド膜をインサイチューで製膜する方法などがある
（特開昭６３−５４９０５号公報、特開平１−１８０２
０８号公報）。2. Description of the Related Art In recent years, various composite semipermeable membranes made of an active layer and different kinds of materials supporting the active layer have been proposed, which are superior in selective separation and permeability to conventional asymmetric membranes. Has performance. Conventionally proposed composite membranes include, for example, a method of forming an aromatic polyamide membrane on a polysulfone membrane support in situ (JP-A-63-54905, JP-A-1-1802).
08 publication).
【０００３】[0003]
【発明が解決しようとする課題】しかしながら、従来の
複合半透膜は、とくに塩阻止性能が今だ満足な値に到達
していないのが現状である。例えば半導体の洗浄に用い
られる超純水は近年の集積度の一層の高度化に伴ってよ
り優れたレベルの水質が要求されてきており、このため
超純水の製造に用いられる複合半透膜に対する要求はさ
らに高まっている。However, under the present circumstances, the conventional composite semipermeable membranes have not reached a satisfactory value particularly in the salt blocking performance. For example, ultrapure water used for cleaning semiconductors has been required to have a higher level of water quality as the degree of integration has become more sophisticated in recent years. Therefore, the composite semipermeable membrane used for the production of ultrapure water is required. The demand for is increasing.
【０００４】本発明は、前記従来技術の問題を解決する
ため、塩阻止性能を高めた複合半透膜を提供することを
目的とする。In order to solve the above-mentioned problems of the prior art, it is an object of the present invention to provide a composite semipermeable membrane having improved salt blocking performance.
【０００５】[0005]
【課題を解決するための手段】前記目的を達成するた
め、本発明の複合半透膜の製造方法は、活性層として架
橋ポリアミド系重合体からなる複合半透膜を水素イオン
濃度（ｐＨ）６未満の次亜塩素酸ナトリウム水溶液で接
触処理することを特徴とする。In order to achieve the above object, in the method for producing a composite semipermeable membrane of the present invention, a composite semipermeable membrane made of a crosslinked polyamide polymer as an active layer is used for hydrogen ion concentration (pH) 6 It is characterized in that the contact treatment is performed with an aqueous solution of sodium hypochlorite of less than
【０００６】[0006]
【作用】前記した本発明の構成によれば、活性層として
架橋ポリアミド系重合体からなる複合半透膜を水素イオ
ン濃度（ｐＨ）６未満の次亜塩素酸ナトリウム水溶液で
接触処理することにより、塩阻止性能を高めた複合半透
膜を簡便な方法で得ることができる。According to the above-mentioned constitution of the present invention, the composite semipermeable membrane comprising the crosslinked polyamide polymer as the active layer is subjected to contact treatment with an aqueous sodium hypochlorite solution having a hydrogen ion concentration (pH) of less than 6, A composite semipermeable membrane with improved salt blocking performance can be obtained by a simple method.
【０００７】[0007]
【実施例】以下に実施例を挙げて本発明を具体的に説明
する。本発明はこれら実施例に何ら限定されるものでは
ない。EXAMPLES The present invention will be specifically described below with reference to examples. The present invention is not limited to these examples.
【０００８】本発明における複合半透膜とは実質的に選
択分離機能を有する活性層と、これと異なる素材から作
られる支持層からなる物であり、近年種々の複合半透膜
が提案されているが、活性層としては脱塩性能、透水性
能の点から界面重縮合によって得られた架橋ポリアミド
系重合体が好ましい。具体的には、該活性層は一分子中
に２個以上のアミノ基を有する酸ハロゲン化物との界面
重縮合によって得られる架橋ポリアミドを主成分とする
ものである。多官能アミンとしては、例えばｍ−フェニ
レンジアミン、ｐ−フェニレンジアミン、１，２，４−
トリアミノベンゼン、エチレンジアミン、ピペラジン
等、酸ハロゲン化物としては、例えば１，３，５−ベン
ゼントリカルボン酸、１，３−ベンゼンジカルボン酸、
１，４−ベンゼンジカルボン酸、１，２，３，４−シク
ロペンタンテトラカルボン酸、１，３，５−シクロヘキ
サントリカルボン酸、１，３−シクロヘキサンジカルボ
ン酸などを用いることができる。The composite semipermeable membrane in the present invention is a material comprising an active layer substantially having a selective separation function and a support layer made of a material different from the active layer, and various composite semipermeable membranes have been proposed in recent years. However, the active layer is preferably a crosslinked polyamide polymer obtained by interfacial polycondensation from the viewpoint of desalination performance and water permeability. Specifically, the active layer is mainly composed of a crosslinked polyamide obtained by interfacial polycondensation with an acid halide having two or more amino groups in one molecule. Examples of polyfunctional amines include m-phenylenediamine, p-phenylenediamine, 1,2,4-
Examples of acid halides such as triaminobenzene, ethylenediamine and piperazine include 1,3,5-benzenetricarboxylic acid, 1,3-benzenedicarboxylic acid,
1,4-benzenedicarboxylic acid, 1,2,3,4-cyclopentanetetracarboxylic acid, 1,3,5-cyclohexanetricarboxylic acid, 1,3-cyclohexanedicarboxylic acid and the like can be used.
【０００９】本発明における処理とは上記のようにでき
上がった複合半透膜をさらに処理するものである。具体
的には、複合半透膜を次亜塩素酸ナトリウム水溶液で処
理するものであり、この場合次亜塩素酸ナトリウムの水
素イオン濃度（ｐＨ）を６未満に調整する必要がある。
これは次亜塩素酸ナトリウムがｐＨによって変化するた
めである。すなわち、次亜塩素酸ナトリウム（ＮａＯＣ
ｌ）は水中で次亜塩素酸（ＨＣｌＯ）を生じる［下記式
（化１（１））］。The treatment in the present invention is to further treat the composite semipermeable membrane produced as described above. Specifically, the composite semipermeable membrane is treated with an aqueous solution of sodium hypochlorite. In this case, it is necessary to adjust the hydrogen ion concentration (pH) of sodium hypochlorite to be less than 6.
This is because sodium hypochlorite changes with pH. That is, sodium hypochlorite (NaOC
l) produces hypochlorous acid (HClO) in water [the following formula (Formula 1 (1))].
【００１０】[0010]
【化１】 [Chemical 1]
【００１１】次亜塩素酸ナトリウムはｐＨ９以上ではほ
とんど次亜塩素酸イオン（ＣｌＯ-）として存在し［前
記式（化１）（２）］、酸性側にｐＨを移動していくと
解離が抑制され、次亜塩素酸（ＨＣｌＯ）として存在す
る。Sodium hypochlorite almost exists as hypochlorite ion (ClO − ) at a pH of 9 or more [the above formulas (Formula 1) and (2)], and dissociation is suppressed when the pH is moved to the acidic side. And is present as hypochlorous acid (HClO).
【００１２】さらにｐＨを酸性側にすると、ｐＨ６でほ
ぼ１００％次亜塩素酸として存在し、それより酸性側で
は次亜塩素酸は減少していき、遊離塩素を生じる［前記
式（化１）（３）］。Further, when the pH is made acidic, almost 100% of hypochlorous acid is present at pH 6, and hypochlorous acid is gradually decreased on the acidic side to generate free chlorine [the above formula (Formula 1)]. (3)].
【００１３】本発明において、性能を向上させる活性種
は次亜塩素酸であり、逆に次亜塩素酸イオンは性能を低
下させると考えられる。それゆえ次亜塩素酸が存在する
ｐＨ９以下で処理する事が必要であるが、次亜塩素酸イ
オンが共存する場合、同時に劣化反応が進行し結果的に
高い性能の向上は望めず、効率が悪い。そのため本処理
は次亜塩素酸イオンがほとんど存在しないｐＨ６未満が
有効である。しかしながら極端な酸性条件（ｐＨ＜２）
での処理は、次亜塩素酸の含量が少なくなるだけでな
く、複合半透膜の種類によっては劣化のため性能が低下
する場合があり、また用いる装置が腐食によって劣化す
るなど好ましくない場合が多い。In the present invention, the active species for improving the performance is hypochlorous acid, and conversely, hypochlorite ion is considered to reduce the performance. Therefore, it is necessary to treat at a pH of 9 or less where hypochlorous acid exists, but when hypochlorite ions coexist, deterioration reaction progresses at the same time, and as a result, high performance improvement cannot be expected and efficiency is high. bad. Therefore, this treatment is effective at a pH of less than 6 at which hypochlorite ion hardly exists. However, extreme acidic conditions (pH <2)
In addition to reducing the content of hypochlorous acid, the treatment may deteriorate the performance due to deterioration depending on the type of the composite semipermeable membrane, and it may be unfavorable because the equipment used deteriorates due to corrosion. Many.
【００１４】また、次亜塩素酸ナトリウム水溶液の濃度
は特に限定されないが、好ましくは５〜５００ｐｐｍで
ある。濃度が低い場合一定の性能に達するまでに時間が
かかり効率が悪く、一方必要以上濃度を高くしても性能
の向上は望めず、経済的でない。The concentration of the aqueous solution of sodium hypochlorite is not particularly limited, but it is preferably 5 to 500 ppm. When the concentration is low, it takes time to reach a certain performance, resulting in poor efficiency. On the other hand, even if the concentration is increased more than necessary, the performance cannot be expected to be improved, which is not economical.
【００１５】本発明において複合半透膜の処理方法は特
に限定されず、複合半透膜の活性層が上記の次亜塩素酸
ナトリウム水溶液と接触すれば良い。例えば、次亜塩素
酸ナトリウム水溶液中に複合半透膜を浸漬する程度でも
十分効果は発揮される。また、複合半透膜を膜モジュー
ルとして巻き付けた後、次亜塩素酸ソーダ水溶液を所定
の時間封入する、膜モジュール中を次亜塩素酸ソーダ水
溶液を循環させる、あるいは一定圧力をかけ水を透過さ
せながら循環させるなどの方法が可能である。In the present invention, the method for treating the composite semipermeable membrane is not particularly limited, as long as the active layer of the composite semipermeable membrane is brought into contact with the above aqueous solution of sodium hypochlorite. For example, the effect is sufficiently exhibited even by immersing the composite semipermeable membrane in the aqueous solution of sodium hypochlorite. After winding the composite semipermeable membrane as a membrane module, the sodium hypochlorite aqueous solution is sealed for a predetermined time, the sodium hypochlorite aqueous solution is circulated in the membrane module, or a constant pressure is applied to allow water to permeate. While circulating, it is possible.
【００１６】実施例１ 最終濃度として２．０重量％のｍ−フェニレンジアミン
と、２．０重量％のテトラメチルアンモニウムヒドロキ
シド、及び０．１重量％のドデシルベンジルスルホン酸
ナトリウムを水中に含有する水溶液を作製した。酢酸を
使用してこの溶液のｐＨ値が最終的に５．７となるよう
に調整した。この水溶液を厚さ６０〜７０μｍの微孔性
ポリスルホン基材上に注ぎかけることにより、基材をそ
の溶液で被覆して液体層を形成した。２分間そのまま放
置して、次にその基材の余分な水溶液を除去した。次い
で、０．０５重量％の１，３，５−ベンゼントリカルボ
ン酸及び０．０７５重量％の１，３−ベンゼンジカルボ
ン酸塩化物を"Isopar"（エクソン社商品名）中に含有す
る有機溶剤を前記の液体層の上に注ぎ、１分間放置して
反応させた。次に有機溶媒を基材から除去し、９５℃で
６分間オーブン乾燥した。Example 1 A final concentration of 2.0% by weight of m-phenylenediamine, 2.0% by weight of tetramethylammonium hydroxide and 0.1% by weight of sodium dodecylbenzyl sulfonate are contained in water. An aqueous solution was prepared. The pH value of this solution was adjusted to a final value of 5.7 using acetic acid. The aqueous solution was poured onto a microporous polysulfone substrate having a thickness of 60 to 70 μm to coat the substrate with the solution to form a liquid layer. Let stand for 2 minutes and then remove excess aqueous solution of the substrate. Then, an organic solvent containing 0.05% by weight of 1,3,5-benzenetricarboxylic acid and 0.075% by weight of 1,3-benzenedicarboxylic acid chloride in "Isopar" (trade name of Exxon Corporation) was added. It was poured on the above liquid layer and left to react for 1 minute. The organic solvent was then removed from the substrate and oven dried at 95 ° C for 6 minutes.
【００１７】この複合半透膜を２０ｐｐｍ次亜塩素酸ナ
トリウム水溶液（ｐＨ＝５．０になるようにＨＣｌで調
整）で圧力１５ｋｇｆ／ｃｍ2 、温度２０℃の条件下で
３０分加圧処理を行った。This composite semipermeable membrane was subjected to a pressure treatment with a 20 ppm sodium hypochlorite aqueous solution (adjusted with HCl so that pH = 5.0) under a pressure of 15 kgf / cm 2 and a temperature of 20 ° C. for 30 minutes. went.
【００１８】このようにして得られた複合半透膜を、１
５００ｐｐｍ ＮａＣｌ（ｐＨ＝６．５に調整）を原水
に用いて、圧力１５ｋｇｆ／ｃｍ2 、温度２０℃の条件
下で逆浸透試験を行った。結果を表１に示した。なお表
中の阻止率とは、 阻止率（％）＝［１−（透過水中の溶質濃度）／（原水
中の溶質濃度）］×１００にて定義される。The composite semipermeable membrane thus obtained is
A reverse osmosis test was conducted using 500 ppm NaCl (adjusted to pH = 6.5) as raw water under the conditions of a pressure of 15 kgf / cm 2 and a temperature of 20 ° C. The results are shown in Table 1. The rejection rate in the table is defined by the rejection rate (%) = [1- (solute concentration in permeated water) / (solute concentration in raw water)] × 100.
【００１９】またＳＰ比とは、次亜塩素酸ナトリウム水
溶液処理前後のＳＰ（溶質透過率、１００−阻止率
（％））の比率を表す。 比較例１ 実施例１において、次亜塩素酸ナトリウム水溶液での加
圧処理を行わずそのまま逆浸透試験を行った。結果を表
１に示した。The SP ratio means the ratio of SP (solute permeability, 100-rejection rate (%)) before and after treatment with an aqueous solution of sodium hypochlorite. Comparative Example 1 In Example 1, the reverse osmosis test was performed as it was without applying pressure treatment with the aqueous solution of sodium hypochlorite. The results are shown in Table 1.
【００２０】実施例２ 実施例１において、次亜塩素酸ナトリウム水溶液のｐＨ
を５．５に調整して加圧処理を行った。得られた複合半
透膜を実施例１と同様に逆浸透試験をおこなった。結果
を表１に示した。Example 2 In Example 1, the pH of the aqueous sodium hypochlorite solution
Was adjusted to 5.5 and pressure treatment was performed. A reverse osmosis test was conducted on the obtained composite semipermeable membrane in the same manner as in Example 1. The results are shown in Table 1.
【００２１】実施例３ 実施例１において、次亜塩素酸ナトリウム水溶液のｐＨ
を７．０に調整して加圧処理をおこなった。得られた複
合半透膜を実施例１と同様に逆浸透試験をおこなった。
結果を表１に示した。Example 3 In Example 1, the pH of the aqueous solution of sodium hypochlorite
Was adjusted to 7.0 and pressure treatment was performed. A reverse osmosis test was conducted on the obtained composite semipermeable membrane in the same manner as in Example 1.
The results are shown in Table 1.
【００２２】実施例４ 実施例１において、次亜塩素酸ナトリウム水溶液のｐＨ
を水酸化ナトリウムを用いて１０に調整して加圧処理を
行った。得られた複合半透膜を実施例１と同様に逆浸透
試験をおこなった。結果を表１に示した。Example 4 In Example 1, the pH of the aqueous solution of sodium hypochlorite
Was adjusted to 10 with sodium hydroxide and pressure-treated. A reverse osmosis test was conducted on the obtained composite semipermeable membrane in the same manner as in Example 1. The results are shown in Table 1.
【００２３】[0023]
【表１】 [Table 1]
【００２４】表１に示す結果から明らかなように、本発
明の次亜塩素酸ナトリウムによる後処理を行うことで、
比較例の未処理の場合に比べて塩阻止率を大幅に向上さ
せることができる。As is clear from the results shown in Table 1, by performing the post-treatment with sodium hypochlorite of the present invention,
The salt rejection can be significantly improved as compared with the untreated case of the comparative example.
【００２５】[0025]
【発明の効果】本発明は、既存の技術によって製造され
る複合半透膜の性能を簡便な方法によって向上させるこ
とができるという顕著な効果が得られる。とくに塩阻止
性能を高めた複合半透膜を簡便な方法で得ることができ
る。INDUSTRIAL APPLICABILITY The present invention has the remarkable effect that the performance of the composite semipermeable membrane manufactured by the existing technique can be improved by a simple method. In particular, a composite semipermeable membrane having improved salt blocking performance can be obtained by a simple method.
Claims (1)
性層として架橋ポリアミド系重合体からなる複合半透膜
を水素イオン濃度（ｐＨ）６未満の次亜塩素酸ナトリウ
ム水溶液で接触処理することを特徴とする複合半透膜の
製造方法。1. A method for producing a composite semipermeable membrane, which comprises subjecting a composite semipermeable membrane made of a crosslinked polyamide polymer as an active layer to a contact treatment with an aqueous sodium hypochlorite solution having a hydrogen ion concentration (pH) of less than 6. A method for producing a composite semipermeable membrane, comprising:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14036892A JPH05329344A (en) | 1992-06-01 | 1992-06-01 | Production of composite semipermeable membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14036892A JPH05329344A (en) | 1992-06-01 | 1992-06-01 | Production of composite semipermeable membrane |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH05329344A true JPH05329344A (en) | 1993-12-14 |
Family
ID=15267203
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP14036892A Pending JPH05329344A (en) | 1992-06-01 | 1992-06-01 | Production of composite semipermeable membrane |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH05329344A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999022836A2 (en) * | 1997-11-04 | 1999-05-14 | The Dow Chemical Company | Treatment of composite polyamide membranes with hypochlorite to improve performance |
| JP2000334280A (en) * | 1999-05-27 | 2000-12-05 | Nitto Denko Corp | Production of multiple reverse osmosis membrane |
| JP2002095938A (en) * | 2000-09-21 | 2002-04-02 | Toyobo Co Ltd | Composite semipermeable membrane, its manufacturing method, and composite semipermeable membrane separation element having it built-in |
| JP2003010656A (en) * | 2001-07-02 | 2003-01-14 | Japan Organo Co Ltd | Separation membrane, method for modifying the same, and apparatus and method for membrane separation |
| WO2003022411A1 (en) * | 2001-09-10 | 2003-03-20 | Nitto Denko Corporation | Semipermeable composite membrane and process for producing the same |
| CN106582329A (en) * | 2016-12-09 | 2017-04-26 | 苏州科胜仓储物流设备有限公司 | Reverse osmosis flame-retardant waterproof layer and preparing method thereof |
| US11517861B2 (en) | 2018-07-09 | 2022-12-06 | Lg Chem, Ltd. | Water treatment separation membrane, water treatment module comprising same, and manufacturing method therefor |
-
1992
- 1992-06-01 JP JP14036892A patent/JPH05329344A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999022836A2 (en) * | 1997-11-04 | 1999-05-14 | The Dow Chemical Company | Treatment of composite polyamide membranes with hypochlorite to improve performance |
| WO1999022836A3 (en) * | 1997-11-04 | 1999-10-28 | Dow Chemical Co | Treatment of composite polyamide membranes with hypochlorite to improve performance |
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