JP2000334280A - Production of multiple reverse osmosis membrane - Google Patents
Production of multiple reverse osmosis membraneInfo
- Publication number
- JP2000334280A JP2000334280A JP11147686A JP14768699A JP2000334280A JP 2000334280 A JP2000334280 A JP 2000334280A JP 11147686 A JP11147686 A JP 11147686A JP 14768699 A JP14768699 A JP 14768699A JP 2000334280 A JP2000334280 A JP 2000334280A
- Authority
- JP
- Japan
- Prior art keywords
- reverse osmosis
- osmosis membrane
- membrane
- composite reverse
- sodium hypochlorite
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
- Y02A20/131—Reverse-osmosis
Abstract
Description
【０００１】[0001]
【発明の分野】本発明は、液状混合物から選択的にその
成分を分離する複合逆浸透膜の製造方法に関する。さら
に詳しくは、本発明は多孔性支持体上にポリアミドを主
成分とする薄膜(分離活性層)を備え、高塩阻止率でかつ
高透過性の複合逆浸透膜を製造する方法に関する。かか
る逆浸透膜は、超純水の製造、かん水または海水の脱塩
などに好適であり、また染色排水や電着塗料排水などの
公害発生原因である廃棄物から、その中に含まれる汚染
源あるいは有用成分を除去回収し、排水のクローズ化に
寄与する。また、食品工業などにおいて有効成分の濃縮
などにも用いることができる。FIELD OF THE INVENTION The present invention relates to a method for producing a composite reverse osmosis membrane for selectively separating components from a liquid mixture. More specifically, the present invention relates to a method for producing a composite reverse osmosis membrane having a high salt rejection rate and a high permeability, comprising a thin film (separation active layer) containing polyamide as a main component on a porous support. Such a reverse osmosis membrane is suitable for production of ultrapure water, desalination of brackish water or seawater, and the like. It removes and collects useful components and contributes to closing wastewater. It can also be used for concentration of active ingredients in the food industry and the like.
【０００２】[0002]
【従来の技術】従来、非対称逆浸透膜とは構造の異なっ
た逆浸透膜として、多孔性支持体上に異質的に選択分離
性を有する薄膜を形成してなる複合逆浸透膜が知られて
いる。現在、かかる逆浸透膜としては、多官能芳香族ア
ミンと多官能芳香族酸ハロゲン化物との界面重合によっ
て得られるポリアミドからなる薄膜を、支持体上に形成
したものが種々提案されている(例えば、特開昭５５−
１４７１０６号、特開昭６２−１２１６０３号、特開昭
６３−２１８２０８号、特開平２−１８７１３５号な
ど)。また、多官能芳香族アミンと多官能脂環式酸ハロ
ゲン化物との界面重合により得られるポリアミドからな
る薄膜を支持体上に形成した複合逆浸透膜も提案されて
いる(例えば、特開昭６１−４２３０８号など)。2. Description of the Related Art Conventionally, as a reverse osmosis membrane having a structure different from that of an asymmetric reverse osmosis membrane, there has been known a composite reverse osmosis membrane formed by forming a thin film having a selective separation property on a porous support. I have. At present, as such a reverse osmosis membrane, various ones in which a thin film made of polyamide obtained by interfacial polymerization of a polyfunctional aromatic amine and a polyfunctional aromatic acid halide formed on a support have been proposed (for example, JP-A-55-
147106, JP-A-62-121603, JP-A-63-218208, JP-A-2-187135, etc.). Further, a composite reverse osmosis membrane in which a thin film made of a polyamide obtained by interfacial polymerization of a polyfunctional aromatic amine and a polyfunctional alicyclic acid halide is formed on a support has been proposed (for example, Japanese Patent Application Laid-Open No. No. -42308).
【０００３】また、これら複合逆浸透膜の水透過性をさ
らに向上させるため、添加剤として水酸化ナトリウムや
リン酸三ナトリウムなど、界面反応にて生成するハロゲ
ン化水素を除去しうる成分や、アシル化触媒、また界面
反応時の反応場の界面張力を減少させる化合物なども提
案されている(例えば特開昭６３−１２３１０号、特開
平６−４７２６０号、特開平８−２２４４５２号な
ど)。Further, in order to further improve the water permeability of these composite reverse osmosis membranes, a component such as sodium hydroxide or trisodium phosphate which can remove hydrogen halide generated by an interfacial reaction, Catalysts and compounds that reduce the interfacial tension in the reaction field during the interfacial reaction have also been proposed (for example, JP-A-63-12310, JP-A-6-47260, JP-A-8-224452).
【０００４】[0004]
【発明が解決しようとする課題】しかしながら、例え
ば、逆浸透膜を用いる造水プラントではランニングコス
トの一層の低減をはかるため、より高度の脱塩性能と透
水性が求められている。このような要求に対し、従来、
分離活性層として架橋ポリアミド重合体を設けた複合逆
浸透膜に対し、塩素を含む水溶液を接触処理させる方法
が知られている(特公昭６３―３６８０３号、特公平０
５−１０５１号、特開平０５−３２９３４４号など)。
しかしながら、このような方法でも、高度の透水性を有
する膜に対しては充分満足すべき脱塩性能は得られず、
また処理方法によっては本来の透水性が低下するなどの
問題が生じている。However, for example, in a desalination plant using a reverse osmosis membrane, higher desalination performance and higher water permeability are required in order to further reduce running costs. In response to such demands,
A method of contacting an aqueous solution containing chlorine with a composite reverse osmosis membrane provided with a crosslinked polyamide polymer as a separation active layer is known (JP-B-63-36803, JP-B-0-36803).
5-1051, JP-A-05-329344).
However, even with such a method, a sufficiently satisfactory desalination performance cannot be obtained for a membrane having high water permeability,
Further, depending on the treatment method, there is a problem that the original water permeability is lowered.
【０００５】[0005]
【発明の目的及び概要】本発明の目的は、このような従
来技術の問題を解決し高脱塩性と高透水性を共に備えた
複合逆浸透膜を得ることにある。本発明は、多孔性支持
体上に架橋ポリアミド重合体を主成分とする分離活性層
を設けた複合逆浸透膜を調製し、その両膜面間に圧力差
を設けてｐＨ9.0〜13.0の水素イオン濃度下において次
亜塩素酸ナトリウム水溶液を接触させることを特徴とす
る複合逆浸透膜の製造方法を提供するものである。SUMMARY OF THE INVENTION An object of the present invention is to solve the problems of the prior art and to obtain a composite reverse osmosis membrane having both high desalination and high water permeability. The present invention prepares a composite reverse osmosis membrane provided with a separation active layer containing a crosslinked polyamide polymer as a main component on a porous support, and provides a pressure difference between both membrane surfaces to adjust the pH to 9.0 to 13.0. An object of the present invention is to provide a method for producing a composite reverse osmosis membrane, which comprises contacting an aqueous solution of sodium hypochlorite under a hydrogen ion concentration.
【０００６】本発明の製造法において、逆浸透膜の両膜
面に負荷される圧力差は、０.１〜１０ＭＰａ(１kg/cm2
〜１００kg/cm2)であるのが好ましい。得られた複合逆
浸透膜は、供給液0.05%食塩水、操作圧力0.5MPa、温度2
5℃、ｐＨ7の条件で評価したときに食塩阻止率が98%以
上、透過水量が0.5m3/(m2・日)以上であるのが好まし
い。In the production method of the present invention, the pressure difference applied to both surfaces of the reverse osmosis membrane is 0.1 to 10 MPa (1 kg / cm 2).
１００100 kg / cm 2 ). The obtained composite reverse osmosis membrane was supplied with a 0.05% saline solution, an operating pressure of 0.5 MPa, and a temperature of 2.
When evaluated under the conditions of 5 ° C. and pH 7, the salt rejection is preferably 98% or more, and the amount of permeated water is preferably 0.5 m 3 / (m 2 · day) or more.
【０００７】[0007]
【発明の詳細な開示】(次亜塩素酸ナトリウム)本発明の
製造方法において、複合逆浸透膜の両膜面の接触処理に
用いる次亜塩素酸ナトリウム水溶液のｐＨは9.0〜13.0
である。次亜塩素酸ナトリウム水溶液のｐＨが9.0未満
であると、充分な透水性、脱塩性能を有する複合逆浸透
膜が得られず、場合によっては透水性の低下をひきおこ
すことがあるため好ましくない。一方、ｐＨが13.0を越
えると、膜に劣化が生じ脱塩性能が急激に低下すること
があり好ましくない。DETAILED DESCRIPTION OF THE INVENTION (Sodium hypochlorite) In the production method of the present invention, the pH of the aqueous solution of sodium hypochlorite used for the contact treatment of both membrane surfaces of the composite reverse osmosis membrane is 9.0 to 13.0.
It is. If the pH of the aqueous sodium hypochlorite solution is less than 9.0, a composite reverse osmosis membrane having sufficient water permeability and desalting performance cannot be obtained, and in some cases, the water permeability may be reduced, which is not preferable. On the other hand, if the pH exceeds 13.0, the membrane is deteriorated, and the desalination performance may suddenly decrease, which is not preferable.
【０００８】かかるｐＨ調製はＮaＯＨなど種々のアル
カリを用いることができる。接触処理に用いられる次亜
塩素酸ナトリウム水溶液中の遊離塩素の濃度は、特に限
定はされないが、好ましくは5〜500ppmである。これよ
り濃度範囲が低いと一定の性能に達成するまでに時間が
かかり効率が悪く、一方必要以上に濃度を高くしてもそ
れ以上の性能向上の効果は望めないため経済的ではな
い。また、膜の劣化が生じ好ましくない。かかる接触処
理に供される複合膜の形状は、特に限定されるものでは
なく、平膜状、あるいはスパイラルエレメント状など種
々の膜形状のものにいずれも適用することができる。For such pH adjustment, various alkalis such as NaOH can be used. The concentration of free chlorine in the aqueous sodium hypochlorite solution used for the contact treatment is not particularly limited, but is preferably 5 to 500 ppm. If the concentration range is lower than this, it takes a long time to achieve a certain performance, and the efficiency is poor. On the other hand, if the concentration is increased more than necessary, no further effect of performance improvement can be expected, so it is not economical. In addition, the film is undesirably deteriorated. The shape of the composite film subjected to the contact treatment is not particularly limited, and any of various film shapes such as a flat film shape and a spiral element shape can be applied.
【０００９】また、複合膜に対して次亜塩素酸ナトリウ
ム水溶液を接触処理する際の膜両側間に供する圧力は複
合膜、エレメント構成部材、処理装置等の耐性に問題の
ない範囲内においては制限を受けるものではないが、両
面の圧力差は好ましくは０.1〜１０ＭＰａ、さらに好ま
しくは0.5〜5Mpaである。接触処理をこれより逆浸透膜
の両面間に圧力差のない状態で行うと、充分な透水性、
脱塩性能が得られず好ましくない。Further, the pressure applied between both sides of the membrane when the aqueous sodium hypochlorite solution is subjected to the contact treatment with the composite membrane is limited as long as there is no problem in the resistance of the composite membrane, the element constituting members, the processing apparatus and the like. However, the pressure difference between the two surfaces is preferably 0.1 to 10 MPa, more preferably 0.5 to 5 MPa. When the contact treatment is performed in a state where there is no pressure difference between both surfaces of the reverse osmosis membrane, sufficient water permeability,
It is not preferable because desalination performance cannot be obtained.
【００１０】本発明において、次亜塩素酸ナトリウム水
溶液による接触処理に付される複合逆浸透膜は、従来公
知の方法により多孔性支持体上に架橋ポリアミド重合体
を主成分とする分離活性層を設けた複合逆浸透膜を調製
したものであってよい。下記にさらに詳細に説明する。In the present invention, the composite reverse osmosis membrane subjected to the contact treatment with an aqueous solution of sodium hypochlorite is obtained by forming a separation active layer containing a crosslinked polyamide polymer as a main component on a porous support by a conventionally known method. The prepared composite reverse osmosis membrane may be prepared. This will be described in more detail below.
【００１１】(架橋ポリアミド重合体)本発明で分離活性
層となる架橋ポリアミド重合体は一般的には１分子中に
２つ以上の反応性のアミノ基を有する多官能アミンと、
多官能性酸ハロゲン化物との界面縮重合によって得るこ
とができる。(Crosslinked Polyamide Polymer) In the present invention, a crosslinked polyamide polymer serving as a separation active layer is generally a polyfunctional amine having two or more reactive amino groups in one molecule,
It can be obtained by interfacial polycondensation with a polyfunctional acid halide.
【００１２】(多官能アミン)かかるアミン成分は１分子
中に２つ以上の反応性のアミノ基を有する多官能性アミ
ンであれば特に限定されず、例えばｍ−フェニレンジア
ミン、ｐ―フェニレンジアミン、1,3,5-トリアミノベン
ゼン、1,2,4-トリアミノベンゼン、3,5-ジアミノ安息香
酸、2,4-ジアミノトルエン、2,6-ジアミノトルエン、2,
4-ジアミノアニソール、アミドール、キシリレンジアミ
ンなどの芳香族多官能アミン、エチレンジアミン、プロ
ピレンジアミン、トリス(2-アミノエチル)アミンなどの
脂肪族多官能アミン、1,3-ジアミノシクロヘキサン、1,
2-ジアミノシクロヘキサン、1,4-ジアミノシクロヘキサ
ン、ピペラジン、2,5-ジメチルピペラジン、4-アミノメ
チルピペラジンなどの脂環式多官能アミンなどがあげら
れる。これらのアミンは単独で用いられてもよく、また
混合物として用いることも可能である。(Polyfunctional amine) The amine component is not particularly limited as long as it is a polyfunctional amine having two or more reactive amino groups in one molecule. For example, m-phenylenediamine, p-phenylenediamine, 1,3,5-triaminobenzene, 1,2,4-triaminobenzene, 3,5-diaminobenzoic acid, 2,4-diaminotoluene, 2,6-diaminotoluene, 2,
Aromatic polyfunctional amines such as 4-diaminoanisole, amidole and xylylenediamine; aliphatic polyfunctional amines such as ethylenediamine, propylenediamine and tris (2-aminoethyl) amine; 1,3-diaminocyclohexane;
Alicyclic polyfunctional amines such as 2-diaminocyclohexane, 1,4-diaminocyclohexane, piperazine, 2,5-dimethylpiperazine, and 4-aminomethylpiperazine; These amines may be used alone or as a mixture.
【００１３】(酸ハロゲン化物)また、本発明で用いる多
官能性酸ハロゲン化物は特に限定されず、例えばトリメ
シン酸クロライド、テレフタル酸クロライド、イソフタ
ル酸クロライド、ビフェニルジカルボン酸クロライド、
ナフタレンジカルボン酸ジクロライド、ベンゼントリス
ルホン酸クロライド、ベンゼンジスルホン酸クロライ
ド、クロロスルホニルベンゼンジカルボン酸クロライド
などの芳香族多官能性酸ハロゲン化物、プロパントリカ
ルボン酸クロライド、ブタントリカルボン酸クロライ
ド、ペンタントリカルボン酸クロライドグルタリルハラ
イド、アジポイルハライドなどの脂肪族多官能性酸ハロ
ゲン化物、シクロプロパントリカルボン酸クロライド、
シクロブタンテトラカルボン酸クロライド、シクロペン
タントリカルボン酸クロライド、シクロペンタンテトラ
カルボン酸クロライド、シクロヘキサントリカルボン酸
クロライド、テトラハイドロフランテトラカルボン酸ク
ロライド、シクロペンタンジカルボン酸クロライド、シ
クロブタンジカルボン酸クロライド、シクロヘキサンジ
カルボン酸クロライド、テトラハイドロフランジカルボ
ン酸クロライドなどの脂環式多官能性酸ハロゲン化物な
どがあげられる。これらの多官能性酸ハロゲン化物は単
独で用いられてもよく、また混合物として用いることも
可能である。(Acid halide) The polyfunctional acid halide used in the present invention is not particularly limited. For example, trimesic acid chloride, terephthalic acid chloride, isophthalic acid chloride, biphenyldicarboxylic acid chloride,
Aromatic polyfunctional acid halides such as naphthalenedicarboxylic acid dichloride, benzenetrisulfonic acid chloride, benzenedisulfonic acid chloride, chlorosulfonylbenzenedicarboxylic acid chloride, propanetricarboxylic acid chloride, butanetricarboxylic acid chloride, pentanetricarboxylic acid chloride glutaryl halide , Aliphatic polyfunctional acid halides such as adipoyl halide, cyclopropanetricarboxylic acid chloride,
Cyclobutanetetracarboxylic acid chloride, cyclopentanetricarboxylic acid chloride, cyclopentanetetracarboxylic acid chloride, cyclohexanetricarboxylic acid chloride, tetrahydrofurantetracarboxylic acid chloride, cyclopentanedicarboxylic acid chloride, cyclobutanedicarboxylic acid chloride, cyclohexanedicarboxylic acid chloride, tetrahydro Alicyclic polyfunctional acid halides such as furandicarboxylic acid chloride; These polyfunctional acid halides may be used alone or as a mixture.
【００１４】(多孔性支持体)本発明において上記薄膜を
支持する多孔性支持体は、薄膜を支持しうるものであれ
ば特に限定されず、例えば、ポリスルホン、ポリエーテ
ルスルホンのようなポリアリールエーテルスルホン、ポ
リイミド、ポリフッ化ビニリデンなど種々のものをあげ
ることができるが、特に化学的、機械的、熱的に安定で
ある点からポリスルホン、ポリアリールエーテルスルホ
ンからなる多孔性支持体が好ましく用いられる。かかる
多孔性支持体は、通常約25〜125μm、好ましくは約40〜
75μmの厚みを有するが、必ずしもこれらに限定される
ものではない。(Porous Support) In the present invention, the porous support for supporting the thin film is not particularly limited as long as it can support the thin film. Examples of the porous support include polyarylethers such as polysulfone and polyethersulfone. Various materials such as sulfone, polyimide, polyvinylidene fluoride and the like can be mentioned, but a porous support made of polysulfone or polyaryl ether sulfone is particularly preferably used because it is chemically, mechanically and thermally stable. Such a porous support is generally about 25 to 125 μm, preferably about 40 to 125 μm.
It has a thickness of 75 μm, but is not necessarily limited to these.
【００１５】(添加剤)本発明における架橋ポリアミド重
合体を界面縮重合によって得る際に、その反応場に、製
膜を容易にし、あるいは得られる複合逆浸透膜の性能を
向上させるための目的で各種の試薬を存在させることが
可能である。これらの試薬として、例えばポリビニルア
ルコール、ポリビニルピロリドン、ポリアクリル酸など
の重合体、ソルビトール、グリセリンなどのような多価
アルコール、特開平−１８７１３５号に記載のテトラア
ルキルアンモニウムハライドやトリアルキルアンモニウ
ムと有機酸の塩などのアミン塩、ドデシルベンゼンスル
ホン酸ナトリウム、ドデシル硫酸ナトリウム、ラウリル
硫酸ナトリウムなどの界面活性剤、界面縮重合反応にて
生成するハロゲン化水素を除去しうる水酸化ナトリウ
ム、リン酸三ナトリウム、あるいは公知のアシル化触
媒、また、特開平８−２２４４５２号記載の溶解度パラ
メーターが8〜14(cal/cm3)1/2の化合物などがあげられ
る。(Additives) When the crosslinked polyamide polymer of the present invention is obtained by interfacial polycondensation, it is used in the reaction field for the purpose of facilitating membrane formation or improving the performance of the obtained composite reverse osmosis membrane. Various reagents can be present. Examples of these reagents include polymers such as polyvinyl alcohol, polyvinyl pyrrolidone and polyacrylic acid, polyhydric alcohols such as sorbitol and glycerin, and tetraalkylammonium halides and trialkylammoniums described in JP-A-187135 and organic acids. Amine salts such as salts, sodium dodecylbenzenesulfonate, sodium dodecyl sulfate, surfactants such as sodium lauryl sulfate, sodium hydroxide, trisodium phosphate capable of removing hydrogen halide generated by interfacial polycondensation reaction, Alternatively, there may be mentioned known acylation catalysts, and compounds having a solubility parameter of 8 to 14 (cal / cm 3 ) 1/2 described in JP-A-8-224452.
【００１６】(評価)前記構成において、得られた複合膜
は、供給液0.05%食塩水、操作圧力0.5MPa、温度25℃、
ｐＨ7の条件で評価したときに食塩阻止率が98%以上、透
過水量が0.5m3/(m2・日)以上であることが好ましい。さ
らに好ましくは食塩阻止率が99%、透過水量が0.7m3/(m2
・日)である。このレベルの食塩阻止率、透過水量が得ら
れれば、実際の運転圧力を0.5MPa以下、例えば0.3MPaと
し、かつ十分なレベルでイオンを除去することができる
ため、本複合逆浸透膜を用いた設備の配管を塩ビで組む
ことが可能であるため経済的に安価ですむ。また水道水
レベルの圧力でも十分に使用が可能である。(Evaluation) In the above-mentioned configuration, the obtained composite membrane was prepared by supplying a 0.05% saline solution, an operating pressure of 0.5 MPa, a temperature of 25 ° C.
When evaluated under the condition of pH 7, the salt rejection is preferably 98% or more, and the amount of permeated water is preferably 0.5 m 3 / (m 2 · day) or more. More preferably, the salt rejection is 99%, and the amount of permeated water is 0.7 m 3 / (m 2
・ Day). If this level of salt rejection and permeate volume can be obtained, the actual operating pressure is 0.5 MPa or less, for example, 0.3 MPa, and ions can be removed at a sufficient level, so the present composite reverse osmosis membrane was used. Since the equipment piping can be assembled with PVC, it is economically inexpensive. Further, it can be sufficiently used even at a tap water level pressure.
【００１７】[0017]
【実施例】つぎに本発明を実施例及び比較例によりさら
に具体的に説明する。 [実施例１]ｍ−フェニレンジアミン２．５重量％、ラウ
リル硫酸ナトリウム０．１５重量％、トリエチルアミン
２．５重量％、カンファースルホン酸５．０重量％、イ
ソプロピルアルコール３０重量％を含有する水溶液を、
多孔性ポリスルホン支持膜に接触させた後、余分の水溶
液を除去した。ついでかかる支持膜の表面にトリメシン
酸クロライド０．１８重量％を含有するイソオクタン溶
液を接触させ、界面縮重合反応を行った。その後１２０
℃の熱風乾燥機中で３分間保持し、多孔性支持膜上に重
合体薄膜を形成して複合逆浸透膜を得た。Next, the present invention will be described more specifically with reference to examples and comparative examples. Example 1 An aqueous solution containing 2.5% by weight of m-phenylenediamine, 0.15% by weight of sodium lauryl sulfate, 2.5% by weight of triethylamine, 5.0% by weight of camphorsulfonic acid, and 30% by weight of isopropyl alcohol was prepared. ,
After contact with the porous polysulfone support membrane, excess aqueous solution was removed. Then, an isooctane solution containing 0.18% by weight of trimesic acid chloride was brought into contact with the surface of the support film to perform an interfacial polycondensation reaction. Then 120
The mixture was kept in a hot air drier at 3 ° C. for 3 minutes to form a polymer thin film on the porous support membrane to obtain a composite reverse osmosis membrane.
【００１８】別に次亜塩素酸ナトリウム水溶液(２０ｐ
ｐｍ)をＮａＯＨにてｐＨ９．０に調整した処理液を準
備し、この溶液を前記複合逆浸透膜に対して、１．５Ｍ
Ｐａ(両面の圧力差)で３０分間加圧通水処理をおこなっ
た。このようにして得られた複合逆浸透膜を、０．０５
％食塩水を原水として、２５℃、ｐＨ７、０．５ＭＰａ
の圧力で試験を行ったところ、食塩の阻止率は９９．４
％、透過流束は０．６６ｍ３／（ｍ２・日）であった。Separately, an aqueous solution of sodium hypochlorite (20 p
pm) was adjusted to pH 9.0 with NaOH, and this solution was applied to the composite reverse osmosis membrane at 1.5 M
A pressurized water flow treatment was performed at Pa (pressure difference between both surfaces) for 30 minutes. The composite reverse osmosis membrane thus obtained was
% Saline solution as raw water, 25 ° C, pH 7, 0.5MPa
The test was carried out at a pressure of
%, And the permeation flux was 0.66 m 3 / (m 2 · day).
【００１９】[実施例２]次亜塩素酸ナトリウム水溶液の
ｐＨを１１．０に調整した以外は実施例１と同様にして
複合逆浸透膜を得た。評価結果を表１に示す。Example 2 A composite reverse osmosis membrane was obtained in the same manner as in Example 1 except that the pH of the aqueous solution of sodium hypochlorite was adjusted to 11.0. Table 1 shows the evaluation results.
【００２０】[実施例３]次亜塩素酸ナトリウム水溶液の
ｐＨを１２．０に調整した以外は実施例１と同様にして
複合逆浸透膜を得た。評価結果を表１に示す。Example 3 A composite reverse osmosis membrane was obtained in the same manner as in Example 1 except that the pH of the aqueous solution of sodium hypochlorite was adjusted to 12.0. Table 1 shows the evaluation results.
【００２１】[比較例１]次亜塩素酸ナトリウム水溶液に
よる加圧通水処理を行わなかった以外は実施例１と同様
にして複合逆浸透膜を得た。評価結果を表１に示す。[Comparative Example 1] A composite reverse osmosis membrane was obtained in the same manner as in Example 1 except that the pressurized water passage treatment with an aqueous solution of sodium hypochlorite was not performed. Table 1 shows the evaluation results.
【００２２】[比較例２]次亜塩素酸ナトリウム水溶液の
ｐＨ調整を行わず(ｐＨ７．７)に加圧通水処理をおこな
った以外は実施例１と同様にして複合逆浸透膜を得た。
評価結果を表１に示す。[Comparative Example 2] A composite reverse osmosis membrane was obtained in the same manner as in Example 1 except that the aqueous solution of sodium hypochlorite was not subjected to pH adjustment (pH 7.7) but subjected to a pressurized water passage treatment. .
Table 1 shows the evaluation results.
【００２３】[比較例３]次亜塩素酸ナトリウム水溶液に
よる接触処理を、ｐＨ調整をおこなわない２０ｐｐｍ次
亜塩素酸ナトリウム水溶液に常圧で３０分間浸漬する方
法とした以外は実施例１と同様にして複合逆浸透膜を得
た。評価結果を表１に示す。Comparative Example 3 A contact treatment with an aqueous solution of sodium hypochlorite was carried out in the same manner as in Example 1 except that the contact treatment was carried out at normal pressure for 30 minutes in a 20 ppm aqueous solution of sodium hypochlorite without pH adjustment. Thus, a composite reverse osmosis membrane was obtained. Table 1 shows the evaluation results.
【００２４】[0024]
【表１】 [Table 1]
【００２５】[0025]
【発明の効果】本発明によれば、多孔性支持体上に架橋
ポリアミド重合体を主成分とする分離活性層を設けた複
合逆浸透膜において高脱塩性と高透水性が共に得られ
る。According to the present invention, both high desalting property and high water permeability can be obtained in a composite reverse osmosis membrane in which a separation active layer mainly composed of a crosslinked polyamide polymer is provided on a porous support.
───────────────────────────────────────────────────── フロントページの続き Ｆターム(参考） 4D006 GA03 HA41 HA61 KA01 KA03 KD24 KE03R KE04R KE06R KE15Q KE15R MA07 MA31 MC29 MC54X MC58 MC62 MC63 NA41 NA48 NA54 NA61 NA64 PB03 PB08 PB34 PB35 PC02 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4D006 GA03 HA41 HA61 KA01 KA03 KD24 KE03R KE04R KE06R KE15Q KE15R MA07 MA31 MC29 MC54X MC58 MC62 MC63 NA41 NA48 NA54 NA61 NA64 PB03 PB08 PB34 PB35 PC02
Claims (3)
を主成分とする分離活性層を設けた複合逆浸透膜を調製
し、その両膜面間に圧力差を設けてｐＨ9.0〜13.0の水
素イオン濃度下において次亜塩素酸ナトリウム水溶液を
接触させることを特徴とする複合逆浸透膜の製造方法。1. A composite reverse osmosis membrane comprising a porous support and a separation active layer comprising a crosslinked polyamide polymer as a main component is prepared, and a pressure difference is provided between both membrane surfaces to adjust the pH to 9.0 to 13.0. A method for producing a composite reverse osmosis membrane, comprising contacting an aqueous solution of sodium hypochlorite at a hydrogen ion concentration of at least.
が、０.１〜１０ＭＰａである請求項１の複合逆浸透膜
の製造法 。2. The method for producing a composite reverse osmosis membrane according to claim 1, wherein a pressure difference applied to both membrane surfaces of the reverse osmosis membrane is 0.1 to 10 MPa.
温度25℃、ｐＨ7の条件で評価したときに食塩阻止率が9
8%以上、透過水量が0.5m3/(m2・日)以上である請求項１
の複合逆浸透膜の製造方法。3. A supply liquid of 0.05% saline, an operating pressure of 0.5 MPa,
The salt rejection was 9 when evaluated under conditions of temperature 25 ° C and pH 7.
2. The method according to claim 1, wherein the amount of permeated water is 0.5 m 3 / (m 2 · day) or more.
A method for producing a composite reverse osmosis membrane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11147686A JP2000334280A (en) | 1999-05-27 | 1999-05-27 | Production of multiple reverse osmosis membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11147686A JP2000334280A (en) | 1999-05-27 | 1999-05-27 | Production of multiple reverse osmosis membrane |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2000334280A true JP2000334280A (en) | 2000-12-05 |
Family
ID=15436001
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11147686A Pending JP2000334280A (en) | 1999-05-27 | 1999-05-27 | Production of multiple reverse osmosis membrane |
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| Country | Link |
|---|---|
| JP (1) | JP2000334280A (en) |
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| WO2002076594A1 (en) * | 2001-03-19 | 2002-10-03 | Nitto Denko Corporation | Composite semipermeable membrane, method for preparing the same and method for water treatment using the same |
| JP2003080042A (en) * | 2001-09-10 | 2003-03-18 | Nitto Denko Corp | Composite semipermeable membrane and method for manufacturing the same |
| JP2005186059A (en) * | 2003-12-03 | 2005-07-14 | Toray Ind Inc | Processing method for semi-permeable membrane, modified semi-permeable membrane and production method for the same |
| EP1645326A1 (en) * | 2004-10-05 | 2006-04-12 | Nitto Denko Corporation | Reverse osmosis membrane and method for producing the same |
| US7081202B2 (en) | 2001-03-19 | 2006-07-25 | Nitto Denko Corporation | Composite semipermeable membrane, production method thereof, and water treatment method using the same |
| JP2008218679A (en) * | 2007-03-05 | 2008-09-18 | Kandenko Co Ltd | Cooling water supply method and apparatus for high-capacity transformer |
| JP2008302324A (en) * | 2007-06-08 | 2008-12-18 | Kurita Water Ind Ltd | Blocking rate improvement method of permeation membrane, permeation membrane with improved blocking rate, and permeation membrane treatment method and apparatus |
| JP2009006315A (en) * | 2007-05-30 | 2009-01-15 | Toray Ind Inc | Method for producing composite semipermeable membrane |
| JP2009006314A (en) * | 2007-05-31 | 2009-01-15 | Toray Ind Inc | Method for producing composite semipermeable membrane |
| CN102423646A (en) * | 2011-08-17 | 2012-04-25 | 浙江大学 | Nano-filtration membrane for separating organic compounds and salts, and preparation method thereof |
| CN103285752A (en) * | 2013-06-26 | 2013-09-11 | 浙江大学 | Polyamide nanofiltration membrane containing sulfoacid betaine type colloid nanometer particle and preparation method thereof |
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| US7081202B2 (en) | 2001-03-19 | 2006-07-25 | Nitto Denko Corporation | Composite semipermeable membrane, production method thereof, and water treatment method using the same |
| WO2002076594A1 (en) * | 2001-03-19 | 2002-10-03 | Nitto Denko Corporation | Composite semipermeable membrane, method for preparing the same and method for water treatment using the same |
| CN1292826C (en) * | 2001-03-19 | 2007-01-03 | 日东电工株式会社 | Composite semipermeable membrane, method for preparing same and method for water treatment using same |
| JP2003080042A (en) * | 2001-09-10 | 2003-03-18 | Nitto Denko Corp | Composite semipermeable membrane and method for manufacturing the same |
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| JP2008218679A (en) * | 2007-03-05 | 2008-09-18 | Kandenko Co Ltd | Cooling water supply method and apparatus for high-capacity transformer |
| JP2009006315A (en) * | 2007-05-30 | 2009-01-15 | Toray Ind Inc | Method for producing composite semipermeable membrane |
| JP2009006314A (en) * | 2007-05-31 | 2009-01-15 | Toray Ind Inc | Method for producing composite semipermeable membrane |
| JP2008302324A (en) * | 2007-06-08 | 2008-12-18 | Kurita Water Ind Ltd | Blocking rate improvement method of permeation membrane, permeation membrane with improved blocking rate, and permeation membrane treatment method and apparatus |
| CN102423646A (en) * | 2011-08-17 | 2012-04-25 | 浙江大学 | Nano-filtration membrane for separating organic compounds and salts, and preparation method thereof |
| CN103285752A (en) * | 2013-06-26 | 2013-09-11 | 浙江大学 | Polyamide nanofiltration membrane containing sulfoacid betaine type colloid nanometer particle and preparation method thereof |
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