JP2000024470A - Cleaning of liquid separation membrane - Google Patents
Cleaning of liquid separation membraneInfo
- Publication number
- JP2000024470A JP2000024470A JP10211735A JP21173598A JP2000024470A JP 2000024470 A JP2000024470 A JP 2000024470A JP 10211735 A JP10211735 A JP 10211735A JP 21173598 A JP21173598 A JP 21173598A JP 2000024470 A JP2000024470 A JP 2000024470A
- Authority
- JP
- Japan
- Prior art keywords
- separation membrane
- membrane
- surfactant
- liquid separation
- film
- 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.)
- Granted
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
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、液状混合物中の成分を
選択的に分離する液体分離膜の洗浄方法に関する。さら
に詳しくは、多孔性支持体上にポリアミドを主成分とす
る薄膜を備えた複合液体分離膜から未反応残存物を除去
する方法に関する。かかる液体分離膜は、超純水の製
造、海水またはかん水の脱塩等に好適であり、また公害
原因となる染色廃水や電着塗料廃水などから、汚染源あ
るいは有効物質を除去回収しプロセスのクローズド化を
可能とする。また、食品工業などにおける有効成分の濃
縮などにも用いられる。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for cleaning a liquid separation membrane for selectively separating components in a liquid mixture. More particularly, the present invention relates to a method for removing unreacted residues from a composite liquid separation membrane having a thin film mainly composed of polyamide on a porous support. Such a liquid separation membrane is suitable for production of ultrapure water, desalination of seawater or brackish water, etc., and removes and collects a pollution source or an effective substance from dyeing wastewater or electrodeposition paint wastewater, which is a cause of pollution, and closes the process. Is possible. It is also used for concentration of active ingredients in the food industry and the like.
【０００２】[0002]
【従来の技術】非対称液体分離膜とは構造の異なった液
体分離膜として、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液体分離膜が知られて
いる。現在、かかる液体分離膜として、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
たものが多数提案されている(例えば、特開昭55−14710
6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も提
案されている(例えば、特開昭61−42308号など)。また
前記複合液体分離膜の水透過性をさらに向上させるため
添加剤(水酸化ナトリウムやリン酸三ナトリウムなど)を
用い、界面反応にて生成するハロゲン化水素を除去する
方法や、公知のアシル化触媒、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、特願平
6−319716号など)。2. Description of the Related Art As a liquid separation membrane having a structure different from that of an asymmetric liquid separation membrane, a composite liquid separation membrane formed by forming a heterogeneous thin film having selective separation properties on a porous support is known. At present, as such a liquid separation membrane, a large number of thin films made of a 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-55-14710
6, JP-A-62-121603, JP-A-63-218208, JP-A-2-187135, etc.). Further, there has also been proposed one 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 (for example, JP-A-61-42308). Such). Further, in order to further improve the water permeability of the composite liquid separation membrane, using an additive (such as sodium hydroxide or trisodium phosphate), a method of removing hydrogen halide generated by an interfacial reaction, or a known acylation Catalysts and compounds that reduce the interfacial tension in the reaction field during interfacial reactions have also been proposed.
(For example, JP-A-63-12310, JP-A-6-47260, Japanese Patent Application No.
No. 6-319716).
【０００３】[0003]
【発明が解決しようとする課題】しかしながら、これら
従来の分離膜を使用し、実際に透過液あるいは非透過液
として濃縮あるいは精製された目的物質を得ようとする
と、膜あるいは膜モジュールを構成する部材から溶出、
流出する不純物により目的とする液の純度の低下を招
く。このため、これら分離膜および膜モジュールは使用
に先立ち充分な洗浄をおこなう必要がある。しかしなが
ら、このような洗浄操作は一般に長時間あるいは高エネ
ルギーを要したり、膜の透過流束の低下を生ずるなど好
ましくない膜性能変化をひきおこすことがある。However, when these conventional separation membranes are used to obtain a target substance which is actually concentrated or purified as a permeate or a non-permeate, the members constituting the membrane or the membrane module are required. Eluting from
The outflowing impurities cause a decrease in the purity of the target liquid. For this reason, these separation membranes and membrane modules need to be sufficiently washed before use. However, such a washing operation generally requires a long time or high energy, and may cause undesired changes in membrane performance such as a decrease in the permeation flux of the membrane.
【０００４】本発明の目的は分離膜の性能に与える影響
が少なく、かつ分離膜から効率的に未反応残存物を除去
することのできる洗浄方法を提供することにある。[0004] An object of the present invention is to provide a cleaning method which has little effect on the performance of a separation membrane and can efficiently remove unreacted residues from the separation membrane.
【０００５】[0005]
【課題を解決するための手段】本願発明は架橋ポリアミ
ド系スキン層を有する液体分離膜に対して、有機物を含
む水溶液を接触させ未反応残存物を除去することを特徴
とする液体分離膜の洗浄方法を提供するものである。According to the present invention, a liquid separation membrane having a crosslinked polyamide skin layer is brought into contact with an aqueous solution containing an organic substance to remove unreacted residues. It provides a method.
【０００６】本発明の洗浄方法に用いられる有機物は水
溶性で、膜性能に悪影響を与えないことが要求され、界
面活性剤；グリセリンやグリコール類などの一価又は多
価のアルコール類；有機酸とトリアルキルアミンの塩な
どが挙げられる。これらのうち、特に界面活性剤及び一
価アルコール類が好ましい。The organic substance used in the cleaning method of the present invention is required to be water-soluble and not adversely affect the membrane performance, and a surfactant; a monohydric or polyhydric alcohol such as glycerin or glycols; And trialkylamine salts. Of these, surfactants and monohydric alcohols are particularly preferred.
【０００７】前記界面活性剤としては、アニオン界面活
性剤、両性界面活性剤、カチオン界面活性剤、非イオン
界面活性剤をいずれも用いることができ、被洗浄膜の膜
性能に対する影響、および未反応残存物の除去効率を考
慮して好適な界面活性剤を選択することができる。As the surfactant, any of an anionic surfactant, an amphoteric surfactant, a cationic surfactant and a nonionic surfactant can be used. A suitable surfactant can be selected in consideration of the removal efficiency of the residue.
【０００８】これらのうちアニオン界面活性剤として
は、例えば高級脂肪酸アルカリ塩、アルキルスルホン酸
塩、アルキル硫酸塩、アルキルアリールスルホン酸塩、
スルホコハク酸エステル塩などが挙げられるがこれらに
限定されるものではない。Among these, examples of the anionic surfactant include alkali salts of higher fatty acids, alkyl sulfonates, alkyl sulfates, alkyl aryl sulfonates,
Examples include, but are not limited to, sulfosuccinate salts.
【０００９】両性界面活性剤としては、例えば下記一般
式(Ｉ)〜(III)：As the amphoteric surfactant, for example, the following general formulas (I) to (III):
【化１】 （式中、Ｒ、Ｒ′及びＲ″はアルキル基を意味する）で
示される化合物などが挙げられるがこれらに限定される
ものではない。Embedded image (Wherein, R, R ′ and R ″ mean an alkyl group) and the like, but are not limited thereto.
【００１０】カチオン界面活性剤としては、例えば高級
アミンハロゲン酸塩、ハロゲン化アルキルピリジニウ
ム、第四アンモニウム塩などが挙げられるがこれらに限
定されるものではない。Examples of the cationic surfactant include, but are not limited to, higher amine halides, alkylpyridinium halides, and quaternary ammonium salts.
【００１１】非イオン界面活性剤としては、例えばポリ
エチレングリコールアルキルエーテル、ポリエチレング
リコール脂肪酸エステル、ソルビタン脂肪酸エステル、
脂肪酸モノグリセリドなどが挙げられるがこれらに限定
されるものではない。Examples of the nonionic surfactant include polyethylene glycol alkyl ether, polyethylene glycol fatty acid ester, sorbitan fatty acid ester,
Fatty acid monoglycerides and the like are included, but not limited thereto.
【００１２】これらの界面活性剤は単独で、あるいは二
種類以上を混合して水溶液として用いることができる。
さらには水溶液中に適宜添加剤を加えてもよい。These surfactants can be used alone or as a mixture of two or more.
Further, an additive may be appropriately added to the aqueous solution.
【００１３】またアルコール類としては一価又は二価以
上の多価アルコールが用いられる。一価アルコールとし
ては、エチルアルコール、イソプロピルアルコール、１
−プロパノール、ｔ−ブタノールなどが挙げられる。多
価アルコールとしてはエチレングリコール、プロピレン
グリコール、ジエチレングリコール、トリエチレングリ
コールなどのグリコール類、グリセリンなどが挙げられ
る。有機酸とトリアルキルアミンの組み合わせとして
は、カンファースルホン酸／トリエチルアミン、ベンゼ
ンスルホン酸／トリエチルアミンなどが挙げられる。As the alcohols, monohydric or polyhydric alcohols having two or more valences are used. Monohydric alcohols include ethyl alcohol, isopropyl alcohol,
-Propanol, t-butanol and the like. Examples of the polyhydric alcohol include glycols such as ethylene glycol, propylene glycol, diethylene glycol, and triethylene glycol, and glycerin. Examples of the combination of an organic acid and a trialkylamine include camphorsulfonic acid / triethylamine, benzenesulfonic acid / triethylamine, and the like.
【００１４】かかる水溶液中の有機物の濃度について
は、物質の種類によって未反応残存物の除去効果や膜性
能低下の抑制効果が異なり特に限定されるものではない
が、１０ｐｐｍ〜１０％、好ましくは５０ｐｐｍ〜５％
とすることができる。濃度が１０ｐｐｍ未満の場合には
未反応残存物の除去によって生じる膜透過流束の低下が
大きい。一方、濃度が１０％以上の場合には洗浄液のコ
スト及び、洗浄後の廃液の処理コストが高くなり、液中
の有機物の吸着により膜透過流束が低下する、あるいは
蒸気濃度が高く環境に悪影響を及ぼすなどの不都合を生
じる。なお、アルコール水溶液の場合の濃度は１〜９０
％、好ましくは１０〜８０％である。The concentration of the organic substance in the aqueous solution is not particularly limited because the effect of removing the unreacted residue and the effect of suppressing the deterioration of the film performance vary depending on the kind of the substance, but are not particularly limited, but 10 ppm to 10%, preferably 50 ppm. ~ 5%
It can be. When the concentration is less than 10 ppm, the reduction of the membrane permeation flux caused by the removal of unreacted residues is large. On the other hand, when the concentration is 10% or more, the cost of the cleaning liquid and the cost of treating the waste liquid after the cleaning are increased, and the membrane permeation flux is reduced due to the adsorption of organic substances in the liquid, or the vapor concentration is high and the environment is adversely affected. Causes inconveniences such as The concentration in the case of the aqueous alcohol solution is 1 to 90.
%, Preferably 10 to 80%.
【００１５】洗浄温度は水溶液が液体として存在しうる
範囲であれば特に限定されないが、未反応残存物の除去
効果および取り扱いの容易さから１０〜９０℃が好まし
い。また、洗浄時分離膜と該水溶液との接触時間は数秒
〜２時間、好ましくは１０秒〜１時間である。接触時間
がこれより短いと未反応残存物の除去効果が不充分であ
り、また２時間を越えても除去効果が平衡に達し効率的
ではない。The washing temperature is not particularly limited as long as the aqueous solution can exist as a liquid, but is preferably from 10 to 90 ° C. in view of the effect of removing unreacted residues and easy handling. The contact time between the separation membrane during washing and the aqueous solution is several seconds to 2 hours, preferably 10 seconds to 1 hour. If the contact time is shorter than this, the effect of removing unreacted residues is insufficient, and even if it exceeds 2 hours, the effect of removal reaches equilibrium and is not efficient.
【００１６】かかる洗浄処理をおこなう際に、複合液体
分離膜はその形状になんら制限を受けるものではない。
すなわち平膜状あるいはスパイラルエレメントに加工さ
れた形状など考えられるあらゆる膜形状において処理を
施すことが可能である。In performing such a washing treatment, the shape of the composite liquid separation membrane is not limited at all.
That is, it is possible to perform the treatment in any conceivable film shape such as a flat film shape or a shape processed into a spiral element.
【００１７】また、複合液体膜の洗浄処理において、分
離膜と水溶液とを接触させる方法としては、浸漬法およ
び通水法のいずれであってもかまわない。通水法による
場合の圧力については複合膜あるいは部材の耐性の範囲
内であればなんら制限を受けるものではない。In the washing treatment of the composite liquid membrane, a method of bringing the separation membrane into contact with the aqueous solution may be any of a dipping method and a water passing method. The pressure in the case of the water passing method is not limited at all if it is within the range of the resistance of the composite membrane or the member.
【００１８】本発明にて洗浄処理される液体分離膜とし
ては、架橋ポリアミド系スキン層を有するものであれば
よいが、典型的には多孔性支持体上に２以上の反応性ア
ミノ基を有する化合物を含む溶液を被覆する工程、及び
該溶液層に多官能性酸ハロゲン化物を含む溶液を接触さ
せる工程などによりアミン成分と酸ハロゲン成分とを反
応させて架橋反応を行い製造した分離膜が挙げられる。
このような分離膜は例えば下記の方法により製膜され
る。The liquid separation membrane to be washed in the present invention may be any one having a crosslinked polyamide skin layer, but typically has two or more reactive amino groups on a porous support. A separation membrane produced by performing a crosslinking reaction by reacting an amine component and an acid halide component by, for example, a step of coating a solution containing a compound, and a step of contacting a solution containing a polyfunctional acid halide with the solution layer. Can be
Such a separation membrane is formed, for example, by the following method.
【００１９】（アミン成分）前記アミン成分は、２つ以
上の反応性のアミノ基を有する多官能アミンであれば特
に限定されず、芳香族、脂肪族、または脂環式の多官能
アミンがあげられる。芳香族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、１,３,５−トリアミノベンゼン、１,２,４−トリア
ミンベンゼン、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
が挙げられる。(Amine Component) The amine component is not particularly limited as long as it is a polyfunctional amine having two or more reactive amino groups, and examples thereof include aromatic, aliphatic and alicyclic polyfunctional amines. Can be Examples of the aromatic polyfunctional amine include m-phenylenediamine, p-phenylenediamine, 1,3,5-triaminobenzene, 1,2,4-triaminebenzene, 3,5-diaminobenzoic acid, 2,4 -Diaminotoluene, 2,6-diaminotoluene, 2,4-diaminoanisole, amidole, xylylenediamine and the like.
【００２０】また脂脂族多官能アミンとしては、例え
ば、エチレンジアミシ、プロピレンジアミシ、トリス
(２−アミノエチル)アミンなどが挙げられる。The aliphatic polyfunctional amines include, for example, ethylene diamine, propylene diamine, tris
(2-aminoethyl) amine and the like.
【００２１】また脂環式多官能アミンとしては、例え
ば、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
チルピペラジシなどが挙げられる。これらのアミンは単
独、又は混合して用いることができる。Examples of the alicyclic polyfunctional amine include 1,3-diaminocyclohexane, 1,2-diaminocyclohexane, 1,4-diaminocyclohexane, piperazine, 2,5-dimethylpiperazine, and 4-aminomethylpipe. Radio and the like. These amines can be used alone or as a mixture.
【００２２】（酸ハロゲン化物）また、多官能性酸ハロ
ゲン化物も、特に限定されず、芳香族、脂肪族、脂環式
などの多官能性酸ハロゲン化物が挙げられる。(Acid halide) The polyfunctional acid halide is also not particularly limited, and examples thereof include aromatic, aliphatic and alicyclic polyfunctional acid halides.
【００２３】芳香族多官能性酸ハロゲン化物としては、
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
酸クロライドなどが挙げられる。Examples of the aromatic polyfunctional acid halide include:
For example, trimesic acid chloride, terephthalic acid chloride, isophthalic acid chloride, biphenyl dicarboxylic acid chloride, naphthalenedicarboxylic acid dichloride,
Examples thereof include benzenetrisulfonic acid chloride, benzenedisulfonic acid chloride, and chlorosulfonylbenzenedicarboxylic acid chloride.
【００２４】脂肪族多官能性酸ハロゲン化物としては、
例えば、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
が挙げられる。Examples of the aliphatic polyfunctional acid halide include:
For example, propane tricarboxylic acid chloride, butane tricarboxylic acid chloride, pentane tricarboxylic acid chloride, glutaryl halide, adipoyl halide and the like can be mentioned.
【００２５】また脂環式多官能性酸ハロゲン化物として
は、例えば、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が挙げられる。Examples of the alicyclic polyfunctional acid halides include, for example, cyclopropanetricarboxylic acid chloride, cyclobutanetetracarboxylic acid chloride, cyclopentanetricarboxylic acid chloride, cyclopentanetetracarboxylic acid chloride, cyclohexanetricarboxylic acid chloride, tetrahydrochloride Furantetracarboxylic acid chloride, cyclopentanedicarboxylic acid chloride, cyclobutanedicarboxylic acid chloride, cyclohexanedicarboxylic acid chloride, tetrahydrofurandicarboxylic acid chloride and the like can be mentioned.
【００２６】（支持体）本発明の洗浄方法に供される上
記薄膜を支持する多孔性支持体は、薄膜を支持し得るも
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、ポリフツ化ビニリデンなど種々のも
のを挙げることができるが、特に化学的、機械的、熱的
安定性から、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膜が好ましい。かかる多孔性支
持体は、通常約２５〜ｌ２５μｍ、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。(Support) The porous support for supporting the thin film provided in the washing method of the present invention is not particularly limited as long as it can support the thin film, and examples thereof include polysulfone and polyethersulfone. Although various materials such as polyarylethersulfone, polyimide, and polyvinylidene fluoride can be used, a porous support film made of polysulfone or polyarylethersulfone is particularly preferable from the viewpoint of chemical, mechanical and thermal stability. 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.
【００２７】（製膜溶液の調製）多官能アミンを含有す
る溶液は製膜を容易にし、または得られる複合逆浸透膜
の性能を向上させるために、さらに、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
などの重合体や、ソルビトール、グリセリンなどのよう
な多価アルコールを少量含有させてもよい。(Preparation of a membrane-forming solution) A solution containing a polyfunctional amine is further used to facilitate the film-forming or to improve the performance of the obtained composite reverse osmosis membrane. A small amount of a polymer such as acrylic acid or a polyhydric alcohol such as sorbitol or glycerin may be contained.
【００２８】また、特開平2-187135号公報に記載のアミ
ン塩、例えばテトラアルキルアンモニウムハライドやト
リアルキルアミンと有機酸との塩などを用いると製膜が
容易になったり、アミン溶液の支持体への吸収性がよく
なり好ましい。When an amine salt described in JP-A-2-187135, for example, a salt of a tetraalkylammonium halide or a trialkylamine with an organic acid, is used, film formation is facilitated or a support of an amine solution is used. It is preferable because it has good absorbability.
【００２９】また、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を添加してもよい。これらの界面活
性剤は、多官能アミンを含有する溶液の多孔性支持体へ
の濡れ性の改善に効果がある。さらに上記界面での重縮
合反応を促進するために界面反応にて生成するハロゲン
化水素を除去し得る水酸化ナトリウムやリン酸三ナトリ
ウムを用い、あるいは公知のアシル化触媒などを用いる
ことも有益である。また、透過流束を高めるために特願
平6−319716号に記載されているように溶解度バラメー
タが８〜1４(cal/cm3)1/2の化合物を添加してもよい。Further, a surfactant such as sodium dodecylbenzenesulfonate, sodium dodecyl sulfate and sodium lauryl sulfate may be added. These surfactants are effective in improving the wettability of the solution containing the polyfunctional amine on the porous support. It is also advantageous to use sodium hydroxide or trisodium phosphate capable of removing hydrogen halide generated by the interfacial reaction to promote the polycondensation reaction at the interface, or to use a known acylation catalyst or the like. is there. Further, as described in Japanese Patent Application No. 6-319716, a compound having a solubility parameter of 8 to 14 (cal / cm 3 ) 1/2 may be added to increase the permeation flux.
【００３０】酸ハロゲン化物の溶液に用いられる溶媒は
水非混和性有機溶剤が挙げられ、特にヘキサン、ヘプタ
ン、オクタン、ノナン、シクロヘキサンなどの炭化水
素、四塩化炭素、トリクロロトリフルオロエタン、ジフ
ロロテトラクロルエタン、ヘキサクロルエタンなどのハ
ロゲン化炭化水素などが好ましい。The solvent used for the solution of the acid halide includes a water-immiscible organic solvent, and in particular, hydrocarbons such as hexane, heptane, octane, nonane, and cyclohexane, carbon tetrachloride, trichlorotrifluoroethane, and difluorotetrafluorocarbon Halogenated hydrocarbons such as chloroethane and hexachloroethane are preferred.
【００３１】上記酸ハロゲン化物および多官能アミシの
濃度は特に限定されるものではないが、酸ハロゲン化物
は、通常０.０１〜５重量％、好ましくは０.０５〜１重
量％であり、多官能アミンは、通常０.１〜１０重量
％、好ましくは０.５〜１重量％である。The concentration of the acid halide and the polyfunctional amici acid is not particularly limited, but the acid halide is usually 0.01 to 5% by weight, preferably 0.05 to 1% by weight. The amount of the functional amine is usually 0.1 to 10% by weight, preferably 0.5 to 1% by weight.
【００３２】（製膜方法）このようにして、多孔性支持
体上に多官能アミンの溶液を被覆し、次いでその上に多
官能酸ハロゲン化物の溶液を被覆した後、それぞれ余分
の溶液を除去し、次いで、通常約２０〜１５０℃、好ま
しくは約７０〜１３０℃で、約１〜ｌ０分間、好ましく
は約２〜８分間架橋ポリアミドからなる水透過性の薄膜
を形成させる。この薄膜は、その厚さが、通常約０.０
５〜２μｍ、好ましくは約０.１〜１μｍの範囲にあ
る。また、本発明の複合液体分離膜の製造方法におい
て、特公昭63−36803号公報に記載されているように、
次亜塩素酸などによる塩素処理を行なって塩阻止性能を
さらに向上させることもできる。(Film-forming method) In this way, the solution of the polyfunctional amine is coated on the porous support, and then the solution of the polyfunctional acid halide is coated thereon. Then, a water-permeable thin film made of the crosslinked polyamide is formed usually at about 20 to 150 ° C, preferably about 70 to 130 ° C, for about 1 to 10 minutes, preferably for about 2 to 8 minutes. This thin film usually has a thickness of about 0.0
It is in the range of 5 to 2 μm, preferably about 0.1 to 1 μm. Further, in the method for producing a composite liquid separation membrane of the present invention, as described in JP-B-63-36803,
Chlorine treatment with hypochlorous acid or the like can be performed to further improve salt rejection performance.
【００３３】[0033]
【実施例】以下に実施例及び比較例を挙げて本発明を説
明するが、本発明はこれらにより何ら限定されるもので
はない。The present invention will be described below with reference to examples and comparative examples, but the present invention is not limited to these examples.
【００３４】［製造例］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％を含有するアミン水溶液を、多孔性ポリスルホン
支持膜に接触させて、余分の溶液を除去して支持膜上に
液層を形成した。次いで、かかる支持膜の表面に、トリ
メシン酸クロライド０.２重量％を含むイソオクタン溶
液を接触させた後、余分な溶液を乾燥除去し、複合液体
分離膜を得た。この分離膜を実施例１〜５にて洗浄に供
した。なお、得られた複合液体分離膜を平膜評価用セル
にセットし、約1500ppmのＮaＣlを含むｐＨ７.０の水溶
液について、１５kg/cm2の圧力で評価したところ、Ｎa
Ｃl阻止率は９９.７％、透過流束は１.２ｍ3／(ｍ2日)
であった。[Production Example] m-phenylenediamine 2.5
%, Sodium lauryl sulfate 0.15% by weight, triethylamine 2.5% by weight, camphorsulfonic acid 5.0%
An aqueous solution of amine containing weight% was brought into contact with the porous polysulfone support membrane to remove excess solution and form a liquid layer on the support membrane. Next, an isooctane solution containing 0.2% by weight of trimesic acid chloride was brought into contact with the surface of the support membrane, and the excess solution was dried and removed to obtain a composite liquid separation membrane. This separation membrane was subjected to washing in Examples 1 to 5. The resulting composite liquid separation membrane was set in a flat membrane evaluation cell, and an aqueous solution containing about 1500 ppm of NaCl and having a pH of 7.0 was evaluated at a pressure of 15 kg / cm 2.
The Cl rejection is 99.7% and the permeation flux is 1.2 m 3 / (m 2 days)
Met.
【００３５】［実施例１］製造例１で得られた複合液体
分離膜をアモーゲンＫ(第一工業製薬(株)製、両性界面
活性剤)５００ｐｐｍ水溶液に２０℃にて１分間浸漬
し、膜中の未反応物を洗浄した。得られた複合液体分離
膜を平膜評価用セルにセットし、約l5OOｐｐｍのＮaＣl
を含むｐＨ７.０の水溶液について、１５kｇ/ｃｍ2の圧
力で評価したところ、ＮaＣl阻止率は９９.７％、通過
流束は０.８９ｍ3/(ｍ2日)であった。また、膜中の未反
応残存物を５０％エタノール水溶液で抽出し、抽出液の
２１０ｎｍでの吸収強度を測定したところ、吸収強度は
比較例１で得られた膜の抽出液の吸収強度の０.５３倍
であった。Example 1 The composite liquid separation membrane obtained in Production Example 1 was immersed in a 500 ppm aqueous solution of Amogen K (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., amphoteric surfactant) at 20 ° C. for 1 minute. The unreacted material in the inside was washed. The obtained composite liquid separation membrane was set in a flat membrane evaluation cell, and about 150 ppm of NaCl was added.
Was evaluated at a pressure of 15 kg / cm 2. The NaCl rejection was 99.7%, and the passing flux was 0.89 m 3 / (m 2 days). The unreacted residue in the membrane was extracted with a 50% aqueous ethanol solution, and the absorption intensity of the extract at 210 nm was measured. The absorption intensity was 0% of the absorption intensity of the extract of the membrane obtained in Comparative Example 1. It was .53 times.
【００３６】［実施例２］５００ｐｐｍのｎ−ドデシル
ベンゼンスルホン酸ナトリウム水溶液に２０℃で１分間
浸漬し、膜中の来反応物を洗浄した以外は実施例１と同
様にして膜中の未反応物を洗浄した。得られた膜を実施
例１と同様に性能評価および抽出液のＵＶ吸収強度測定
を行った。その結果を表１に示す。Example 2 The same procedure as in Example 1 was carried out except that the reaction product in the film was washed by immersing it in a 500 ppm aqueous solution of sodium n-dodecylbenzenesulfonate for 1 minute at 20 ° C. The thing was washed. The obtained membrane was subjected to performance evaluation and UV absorption intensity measurement of the extract in the same manner as in Example 1. Table 1 shows the results.
【００３７】［実施例３］カチオーゲンＰＡＮ(第一工
業製薬(株)製、カチオン界面活性剤)５００ｐｐｍ水溶
液に２０℃で１分間浸漬し、膜中の未反応物を洗浄した
以外は実施例１と同様にして膜中の未反応物を洗浄し
た。得られた膜を実施例１と同様に性能評価および抽出
液のＵＶ吸収強度測定を行った。その結果を表１に示
す。Example 3 Example 1 was immersed in a 500 ppm aqueous solution of cationogen PAN (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., cationic surfactant) at 20 ° C. for 1 minute to wash unreacted substances in the membrane. The unreacted material in the film was washed in the same manner as described above. The obtained membrane was subjected to performance evaluation and UV absorption intensity measurement of the extract in the same manner as in Example 1. Table 1 shows the results.
【００３８】［実施例４］５００ｐｐｍのポリエチレン
グリコールアルキルエーテル(n-C4H9(OC2H4)6OH)水溶液
に２０℃で１分間浸漬し、膜中の未反応物を洗浄した以
外は実施例１と同様にして膜中の未反応物を洗浄した。
得られた膜を実施例１と同様に性能評価および抽出液の
ＵＶ吸収強度測定を行った。その結果を表１に示す。Example 4 The procedure was performed except that the film was immersed in a 500 ppm aqueous solution of polyethylene glycol alkyl ether (nC 4 H 9 (OC 2 H 4 ) 6 OH) at 20 ° C. for 1 minute to wash unreacted substances in the film. Unreacted materials in the film were washed in the same manner as in Example 1.
The obtained membrane was subjected to performance evaluation and UV absorption intensity measurement of the extract in the same manner as in Example 1. Table 1 shows the results.
【００３９】［実施例５］５００ｐｐｍのアモーゲンＫ
(第一工業製薬(株)製、両性界面活性剤)で２０℃、５k
ｇ／ｃｍ2にて１分間加圧通水し、膜中の未反応物を洗
浄した以外は実施例１と同様にして膜中の未反応物を洗
浄した。得られた膜を実施例１と同様に性能評価および
抽出液のＵＶ吸収強度測定を行った。その結果を表１に
示す。Example 5 500 ppm of Amogen K
(Daiichi Kogyo Seiyaku Co., Ltd., amphoteric surfactant) at 20 ° C, 5k
The unreacted material in the film was washed in the same manner as in Example 1 except that water was passed under pressure at g / cm 2 for 1 minute to wash the unreacted material in the film. The obtained membrane was subjected to performance evaluation and UV absorption intensity measurement of the extract in the same manner as in Example 1. Table 1 shows the results.
【００４０】［比較例１］実施例１において、純水(２
０℃)に１分間浸漬し、膜中の未反応物を洗浄した以外
は実施例１と同様にして膜中の未反応物を洗浄した。得
られた膜を実施例１と同様に性能評価および抽出液のＵ
Ｖ吸収強度測定を行った。結果を表１に示す。Comparative Example 1 In Example 1, pure water (2
(0 ° C.) for 1 minute, and the unreacted material in the film was washed in the same manner as in Example 1 except that the unreacted material in the film was washed. The obtained membrane was subjected to performance evaluation and extraction of U as in Example 1.
V absorption intensity measurement was performed. Table 1 shows the results.
【００４１】[0041]
【表１】 [Table 1]
【００４２】［製造例２］製造例１と同一条件にて再度
分離膜を製造し、実施例６〜１０の洗浄に供した。な
お、製造例１と同様にして測定したＮaＣl阻止率は９
９.６％、透過流束は１.２ｍ3/(ｍ2日)であった。[Production Example 2] A separation membrane was produced again under the same conditions as in Production Example 1, and was subjected to washing in Examples 6 to 10. The NaCl rejection measured in the same manner as in Production Example 1 was 9
At 9.6%, the permeation flux was 1.2 m 3 / (m 2 days).
【００４３】［実施例６］製造例２で得られた複合液体
分離膜を５０％イソプロピルアルコール水溶液に２５℃
で１分間浸漬し、膜中の未反応物を洗浄した。得られた
複合液体分離膜を平膜評価用セルにセットし、約l5OOpp
mのＮaＣlを含むｐＨ７.０の水溶液について、１５kg/c
ｍ2の圧力で評価したところ、ＮaＣl阻止率は99.6％、
透過流束は１.２ｍ3／(ｍ2日)であった。また、膜中の
未反応残存物を５０％エタノール水溶液で抽出し、抽出
液の２１０ｎｍでの吸収強度を測定したところ、吸収強
度は製造例２で得られた膜の抽出液の吸収強度の０.６
１倍であった。Example 6 The composite liquid separation membrane obtained in Production Example 2 was placed in a 50% aqueous isopropyl alcohol solution at 25 ° C.
For 1 minute to wash unreacted substances in the film. The obtained composite liquid separation membrane was set in a flat membrane evaluation cell, and
15 kg / c for an aqueous solution of pH 7.0 containing
When evaluated at a pressure of m 2 , the NaCl rejection was 99.6%,
The permeation flux was 1.2 m 3 / (m 2 days). The unreacted residue in the membrane was extracted with a 50% aqueous ethanol solution, and the absorption intensity of the extract at 210 nm was measured. The absorption intensity was 0% of the absorption intensity of the extract of the membrane obtained in Production Example 2. .6
It was one time.
【００４４】［実施例７］５０％イソプロピルアルコー
ル水溶液に５０℃で１分間浸漬し、膜中の未反応物を洗
浄した以外は実施例６と同様にして膜中の未反応物を洗
浄した。得られた膜を実施例６と同様に性能評価および
抽出液のＵＶ吸収強度測定をおこなった。その結果を表
２に示す。Example 7 The unreacted material in the film was washed in the same manner as in Example 6 except that the film was immersed in a 50% isopropyl alcohol aqueous solution at 50 ° C. for 1 minute to wash the unreacted material in the film. The obtained membrane was subjected to performance evaluation and UV absorption intensity measurement of the extract in the same manner as in Example 6. Table 2 shows the results.
【００４５】［実施例８］５０％イソプロピルアルコー
ル水溶液を用い２５℃、５kｇ／cm2にて１分間加圧通水
し、膜中の未反応物を洗浄した以外は実施例６と同様に
して膜中の未反応物を洗浄した。得られた膜を実施例６
と同様に性能評価および抽出液のＵＶ吸収強度測定を行
った。その結果を表２に示す。Example 8 The same procedure as in Example 6 was carried out except that a 50% aqueous isopropyl alcohol solution was used to pressurize water at 25 ° C. and 5 kg / cm 2 for 1 minute to wash unreacted substances in the membrane. Unreacted substances in the membrane were washed. The obtained film was prepared in Example 6.
The performance evaluation and the measurement of the UV absorption intensity of the extract were performed in the same manner as described above. Table 2 shows the results.
【００４６】［実施例９］２０％エチルアルコール水溶
液に２５℃で１分間浸漬し、膜中の未反応物を洗浄した
以外は実施例６と同様にして膜中の未反応物を洗浄し
た。得られた膜を実施例６と同様に性能評価および抽出
液のＵＶ吸収強度測定を行った。その結果を表２に示
す。Example 9 An unreacted material in a film was washed in the same manner as in Example 6 except that the film was immersed in a 20% ethyl alcohol aqueous solution at 25 ° C. for 1 minute to wash the unreacted material in the film. The obtained membrane was subjected to performance evaluation and UV absorption intensity measurement of the extract in the same manner as in Example 6. Table 2 shows the results.
【００４７】［実施例１０］５０％エチルアルコール水
溶液に２５℃で１分間浸漬し、膜中の未反応物を洗浄し
た以外は実施例６と同様にして膜中の未反応物を洗浄し
た。得られた膜を実施例６と同様に性能評価および抽出
液のＵＶ吸収強度測定を行った。その結果を表２に示
す。Example 10 An unreacted material in a film was washed in the same manner as in Example 6 except that the film was immersed in a 50% aqueous ethyl alcohol solution at 25 ° C. for 1 minute to wash the unreacted material in the film. The obtained membrane was subjected to performance evaluation and UV absorption intensity measurement of the extract in the same manner as in Example 6. Table 2 shows the results.
【００４８】［比較例２］実施例６において、純水に２
５℃で１分間浸漬し、膜中の未反応物を洗浄した以外は
実施例６と同様にして膜中の未反応物を洗浄した。得ら
れた膜を実施例６と同様に性能評価および抽出液のＵＶ
吸収強度測定を行った。その結果を表２に示す。Comparative Example 2 In Example 6, 2 parts of pure water
Unreacted materials in the film were washed in the same manner as in Example 6 except that the film was immersed at 5 ° C. for 1 minute to wash unreacted materials in the film. The obtained membrane was subjected to performance evaluation and UV extraction of the extract in the same manner as in Example 6.
Absorption intensity measurement was performed. Table 2 shows the results.
【００４９】[0049]
【表２】 [Table 2]
【００５０】[0050]
【発明の効果】本発明の洗浄方法によれば複合液体分離
膜の透水性、塩阻止性などの膜性能に与える影響を抑制
しながら、未反応残存物が効率よく除去される。かかる
方法により洗浄された液体分離膜を用いて分離処理を行
うと処理液中ヘの不純物の混入が小さいため、例えばか
ん水、海水の脱塩による淡水化や、半導体の製造に必要
とされる超純水の製造、食品産業における有用成分の分
離濃縮など、多くの分野で好適に用いることができる。According to the washing method of the present invention, unreacted residues are efficiently removed while suppressing the influence on the membrane performance such as water permeability and salt rejection of the composite liquid separation membrane. When the separation treatment is performed using the liquid separation membrane washed by such a method, contamination of the treatment liquid with impurities is small. For example, desalination by desalination of brackish water or seawater, or ultra-small water required for semiconductor production It can be suitably used in many fields such as production of pure water and separation and concentration of useful components in the food industry.
フロントページの続き Ｆターム(参考） 4D006 GA02 HA41 HA61 KA01 KB30 KC15 KC16 KD04 KD14 KD24 KD28 KD29 MA03 MA07 MA31 MB02 MC29 MC54X MC56X MC58 MC62 MC63 NA46 NA63 NA64 PB03 PB08 PC02 Continued on the front page F term (reference) 4D006 GA02 HA41 HA61 KA01 KB30 KC15 KC16 KD04 KD14 KD24 KD28 KD29 MA03 MA07 MA31 MB02 MC29 MC54X MC56X MC58 MC62 MC63 NA46 NA63 NA64 PB03 PB08 PC02
Claims (5)
分離膜に対して、有機物水溶液を接触させ未反応残存物
を除去することを特徴とする液体分離膜の洗浄方法。1. A method for cleaning a liquid separation membrane, comprising contacting an aqueous solution of an organic substance with a liquid separation membrane having a crosslinked polyamide skin layer to remove unreacted residues.
コール類、並びに有機酸とトリアルキルアミンとの塩か
らなる群から選ばれた少なくとも１種の化合物である請
求項１の洗浄方法。2. The cleaning method according to claim 1, wherein the organic substance is at least one compound selected from the group consisting of a surfactant, a monohydric or polyhydric alcohol, and a salt of an organic acid and a trialkylamine.
界面活性剤、カチオン界面活性剤及び非イオン界面活性
剤から選ばれた少なくとも１種の界面活性剤である請求
項１の洗浄方法。3. The cleaning method according to claim 1, wherein the surfactant is at least one surfactant selected from an anionic surfactant, an amphoteric surfactant, a cationic surfactant, and a nonionic surfactant.
モジュールの浸漬処理である請求項１の洗浄方法。4. The cleaning method according to claim 1, wherein the cleaning method is immersion treatment of the flat membrane and a membrane module obtained by processing the flat membrane.
モジュールの通水処理である請求項１の洗浄方法。5. The cleaning method according to claim 1, wherein the cleaning method is a process of passing water through the flat membrane and the membrane module obtained by processing the flat membrane.
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| JP21173598A JP4213789B2 (en) | 1998-07-10 | 1998-07-10 | Method for producing liquid separation membrane |
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|---|---|---|---|
| JP21173598A JP4213789B2 (en) | 1998-07-10 | 1998-07-10 | Method for producing liquid separation membrane |
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| JP2000024470A true JP2000024470A (en) | 2000-01-25 |
| JP4213789B2 JP4213789B2 (en) | 2009-01-21 |
Family
ID=16610729
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| JP (1) | JP4213789B2 (en) |
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