JP2000350928A - Composite diaphragm, composite diaphragm module and its manufacture - Google Patents
Composite diaphragm, composite diaphragm module and its manufactureInfo
- Publication number
- JP2000350928A JP2000350928A JP11163863A JP16386399A JP2000350928A JP 2000350928 A JP2000350928 A JP 2000350928A JP 11163863 A JP11163863 A JP 11163863A JP 16386399 A JP16386399 A JP 16386399A JP 2000350928 A JP2000350928 A JP 2000350928A
- Authority
- JP
- Japan
- Prior art keywords
- semipermeable membrane
- composite semipermeable
- composite
- water
- membrane
- 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
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、流体を処理するた
めの複合半透膜、複合半透膜モジュール、およびその製
造方法に関するものである。本発明による複合半透膜及
び複合半透膜モジュールは海水の淡水化、かん水の脱
塩、上水の製造、食品プロセス、排水の処理や濃縮、有
価物の回収などに用いられる。特に、飲用に供する水の
製造に有効である。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a composite semipermeable membrane for treating a fluid, a composite semipermeable membrane module, and a method for manufacturing the same. The composite semipermeable membrane and the composite semipermeable membrane module according to the present invention are used for desalination of seawater, desalination of brackish water, production of tap water, food processing, treatment and concentration of wastewater, and recovery of valuable resources. In particular, it is effective in producing drinking water.
【０００２】[0002]
【従来の技術】選択分離性と水透過性に優れた複合半透
膜として、界面重合法を用い、多孔質支持体の表面に分
離活性能を有するポリアミド薄膜を形成させた複合半透
膜が考案されている。具体的には米国特許第３１９１８
１５号明細書、同第３７４４６４２号明細書、特開昭５
５−１４７１０６号公報、特表昭５６−５０００６２号
公報、PBレポ−ト８３−１９１７７５、特開平２−７８
４２８公報などが開示されている。これら複合半透膜の
製造においては、多孔質支持体に、多官能アミンを含む
水溶液を塗布し、ついで多官能酸ハライドを含む有機溶
液に接触させる、いわゆるin-situ 界面重合法がしばし
ば用いられる。このような界面重合法では多くの場合、
多孔質支持体の濡れ性の向上や、相間移動触媒としての
働きから、多官能アミンを含む水溶液中に陰イオン界面
活性剤を混在させることが行われている。2. Description of the Related Art As a composite semipermeable membrane excellent in selective separation properties and water permeability, a composite semipermeable membrane in which a polyamide thin film having separation activity is formed on the surface of a porous support using an interfacial polymerization method. It has been devised. Specifically, US Pat.
No. 15, Japanese Patent No. 3744642, Japanese Unexamined Patent Publication No.
JP-A-5-147106, JP-T-56-500062, PB report 83-191775, JP-A-2-78
428 and the like are disclosed. In the production of these composite semipermeable membranes, a so-called in-situ interfacial polymerization method is often used in which an aqueous solution containing a polyfunctional amine is applied to a porous support and then contacted with an organic solution containing a polyfunctional acid halide. . In such an interfacial polymerization method, in many cases,
In order to improve the wettability of a porous support and to act as a phase transfer catalyst, an anionic surfactant is mixed in an aqueous solution containing a polyfunctional amine.
【０００３】かかる複合半透膜はその優れた選択分離性
と水透過性から、逆浸透処理あるいはナノろ過、限外ろ
過等に用いられる。具体的には、海水の淡水化、かん水
の脱塩、河川水や地下水の浄水などの上水製造、純水製
造、家庭用もしくは業務用浄水器、食品プロセス、排水
の処理や濃縮、有価物の回収などに用いられる。[0003] Such a composite semipermeable membrane is used for reverse osmosis treatment, nanofiltration, ultrafiltration and the like because of its excellent selective separation property and water permeability. Concretely, desalination of seawater, desalination of brackish water, production of clean water such as purification of river water and groundwater, production of pure water, domestic or commercial water purifier, food process, treatment and concentration of wastewater, valuable resources It is used for collecting and the like.
【０００４】これら膜分離プロセスの目的は、不純物あ
るいは有価物を含む被処理液体をろ過し、浄化された透
過水と、濃縮された不純物あるいは有価物とに分離する
ことにある。しかるに、これら膜分離プロセスの運転初
期にはしばしば透過水中に不純物が混入することが起こ
る。複合半透膜の選択分離性は十分に高く、被処理液体
に含まれる不純物は除去するが、運転初期には複合半透
膜モジュール自身から不純物が溶出し、結果として浄化
された透過水が得られない場合があった。[0004] The purpose of these membrane separation processes is to filter the liquid to be treated containing impurities or valuables to separate the permeated water purified and the concentrated impurities or valuables. However, in the early stage of the operation of these membrane separation processes, impurities often enter the permeated water. The selective separation of the composite semipermeable membrane is sufficiently high to remove impurities contained in the liquid to be treated, but at the beginning of operation, impurities elute from the composite semipermeable membrane module itself, resulting in purified permeated water. Was not always possible.
【０００５】このような欠点を解決する方策として、複
合半透膜を酸水溶液で処理する方法（特開昭６０−１５
６５０７公報、特開平７−８０２５９号公報）、複合半
透膜をアルカリ水溶液で処理する方法（特開昭５５−１
５９８０７公報、PBレポ−ト８３−１９１７７５、特開
平７−８０２５９号公報）、複合半透膜を熱水で処理す
る方法（特開昭６３−２８７５０７公報、特開平１−１
６８３０６公報、特開平７−８０２６０号公報）、塩素
含有水溶液で処理する方法（特開平７−８０２６１号公
報）などが開示されている。かかる処理により、複合半
透膜から出る不純物が大幅に低減できることが記載され
ている。As a measure for solving such a drawback, a method of treating a composite semipermeable membrane with an aqueous acid solution (Japanese Patent Laid-Open No. 60-15 / 1985)
6507, JP-A-7-80259), a method of treating a composite semipermeable membrane with an aqueous alkaline solution (JP-A-55-1)
59807, PB report 83-191775, JP-A-7-80259), a method of treating a composite semipermeable membrane with hot water (JP-A-63-287507, JP-A-1-1-1)
68306, JP-A-7-80260), a method of treating with a chlorine-containing aqueous solution (JP-A-7-80261), and the like. It is described that by such a treatment, impurities emitted from the composite semipermeable membrane can be significantly reduced.
【０００６】[0006]
【発明が解決しようとする課題】しかしながら、上記逆
浸透膜の処理方法では、界面重合反応時の未反応物であ
る多官能アミンや多官能酸ハライドは十分に洗浄・除去
できるが、陰イオン界面活性剤は複合半透膜中に残留し
十分には除去できない。陰イオン界面活性剤は、膜分離
プロセスの運転中に極微量ではあるが、長期間にわたっ
て透過水中に徐放されるという問題点がある。However, in the above method for treating a reverse osmosis membrane, polyfunctional amines and polyfunctional acid halides which are not reacted during the interfacial polymerization reaction can be sufficiently washed and removed. The activator remains in the composite semipermeable membrane and cannot be sufficiently removed. The amount of anionic surfactant is very small during the operation of the membrane separation process, but has a problem that it is gradually released into permeated water for a long period of time.
【０００７】陰イオン界面活性剤は、水道水の水質基準
により０. ２m g/L 以下と定められ、発泡や異臭味を生
じさせない濃度レベルであり、人体には無害であると考
えられているが、一方で、ガンや奇形の原因になると主
張する学者もおり、膜モジュ- ルからの溶出は極力少な
いことが望ましい。[0007] The anionic surfactant is determined to be 0.2 mg / L or less according to the standard of tap water and has a concentration level that does not cause foaming or off-flavor, and is considered to be harmless to the human body. However, on the other hand, some scholars argue that they cause cancer and malformation, and it is desirable that elution from the membrane module be as small as possible.
【０００８】本発明は、前記問題を解決するため、陰イ
オン界面活性剤の残留量が少ない複合半透膜、複合半透
膜モジュールおよびその製造方法を提供することを目的
とする。[0008] In order to solve the above problems, an object of the present invention is to provide a composite semipermeable membrane, a composite semipermeable membrane module, and a method for producing the same, in which the residual amount of an anionic surfactant is small.
【０００９】[0009]
【課題を解決するための手段】前記目的を達成するため
の本発明における第１番目の発明は、多孔質支持体の表
面をポリアミド薄膜で被覆した複合半透膜において、該
複合半透膜から抽出される陰イオン界面活性剤の量が、
複合半透膜重量１kg当たり９g 以下であり、より好まし
くは複合半透膜重量１kg当たり５g 以下であり、さらに
好ましくは複合半透膜重量１kg当たり２. ５g 以下であ
ることを特徴とする複合半透膜である。Means for Solving the Problems The first invention of the present invention for achieving the above object is a composite semipermeable membrane in which the surface of a porous support is coated with a polyamide thin film. The amount of anionic surfactant extracted is
A composite semipermeable membrane having a weight of not more than 9 g per kg, more preferably not more than 5 g per kg of the composite semipermeable membrane, and still more preferably not more than 2.5 g per kg of the composite semipermeable membrane. It is a permeable membrane.
【００１０】第１番目の発明の複合半透膜の製造方法と
しては、多孔質支持体の表面にポリアミド薄膜を形成さ
せた後、アルコール水溶液で浸漬処理することを特徴と
する。さらに続けて、５０℃以上の熱水、酸水溶液、ア
ルカリ水溶液のうち少なくとも一つ以上の溶液で処理し
てもよい。The first method of producing a composite semipermeable membrane according to the present invention is characterized in that a polyamide thin film is formed on the surface of a porous support and then immersed in an aqueous alcohol solution. Further, the treatment may be performed with at least one of hot water at 50 ° C. or higher, an aqueous acid solution, and an aqueous alkali solution.
【００１１】第２番目の発明は、多孔質支持体の表面を
ポリアミド薄膜で被覆した複合半透膜を構成要素とする
複合半透膜モジュールにおいて、該複合半透膜から抽出
される陰イオン界面活性剤の量が、複合半透膜重量１kg
当たり９g 以下であり、より好ましくは複合半透膜重量
１kg当たり５g 以下であり、さらに好ましくは複合半透
膜重量１kg当たり２. ５g 以下であることを特徴とする
複合半透膜モジュ−ルである。A second aspect of the present invention is a composite semipermeable membrane module comprising a composite semipermeable membrane in which the surface of a porous support is coated with a polyamide thin film, wherein an anion interface extracted from the composite semipermeable membrane is provided. The amount of activator is 1 kg of composite semi-permeable membrane
Per unit weight of the composite semi-permeable membrane, more preferably not more than 5 g per kg of the composite semi-permeable membrane, more preferably not more than 2.5 g per kg of the composite semi-permeable membrane. is there.
【００１２】第２番目の発明の複合半透膜モジュールの
製造方法としては、多孔質支持体の表面にポリアミド薄
膜を形成させた複合膜形成物を構成要素とする複合半透
膜組立体の内部を、アルコール水溶液で満たす、もしく
は加圧通水することを特徴とする。さらに続けて、５０
℃以上の熱水、酸水溶液、アルカリ水溶液のうち少なく
とも一つ以上の溶液で該複合半透膜組立体内部を満た
し、もしくは加圧通水してもよい。[0012] A second method of manufacturing a composite semipermeable membrane module according to the present invention includes a method of manufacturing a composite semipermeable membrane assembly comprising, as a constituent, a composite membrane formed by forming a polyamide thin film on the surface of a porous support. Is filled with an aqueous alcohol solution or pressurized water is passed through. Continuing, 50
The inside of the composite semipermeable membrane assembly may be filled with at least one of hot water at a temperature of not less than ° C, an aqueous acid solution, and an aqueous alkali solution, or may be pressurized.
【００１３】[0013]
【発明の実施の形態】本発明を以下に詳細に説明する。
本発明における第１番目の発明は、多孔質支持体の表面
にin-situ 界面重合法により、陰イオン界面活性剤の存
在下に多官能アミンと多官能酸ハライドからなる架橋ポ
リアミド薄膜を形成させた複合半透膜において、該複合
半透膜から抽出される陰イオン界面活性剤の量が、複合
半透膜重量１kg当たり９g 以下であり、より好ましくは
複合半透膜重量１kg当たり５g 以下であり、さらに好ま
しくは複合半透膜重量１kg当たり２. ５g 以下であるこ
とを特徴とする複合半透膜である。DETAILED DESCRIPTION OF THE INVENTION The present invention will be described in detail below.
According to a first aspect of the present invention, a crosslinked polyamide thin film comprising a polyfunctional amine and a polyfunctional acid halide is formed on the surface of a porous support by in-situ interfacial polymerization in the presence of an anionic surfactant. In the composite semipermeable membrane, the amount of the anionic surfactant extracted from the composite semipermeable membrane is 9 g or less per 1 kg of the composite semipermeable membrane, more preferably 5 g or less per 1 kg of the composite semipermeable membrane. And more preferably 2.5 g or less per 1 kg of the weight of the composite semipermeable membrane.
【００１４】第１番目の発明の複合半透膜の製造方法と
しては、多孔質支持体の表面にin-situ 界面重合法によ
り、陰イオン界面活性剤の存在下に多官能アミンと多官
能酸ハライドからなる架橋ポリアミド薄膜を形成させた
後、アルコール水溶液で浸漬処理することを特徴とす
る。さらに続けて、５０℃以上の熱水、酸水溶液、アル
カリ水溶液のうち少なくとも一つ以上の溶液で処理して
もよい。The first method of producing the composite semipermeable membrane according to the present invention is as follows: a polyfunctional amine and a polyfunctional acid are added to the surface of a porous support by in-situ interfacial polymerization in the presence of an anionic surfactant. After forming a crosslinked polyamide thin film made of a halide, the film is immersed in an aqueous alcohol solution. Further, the treatment may be performed with at least one of hot water at 50 ° C. or higher, an aqueous acid solution, and an aqueous alkali solution.
【００１５】第２番目の発明は、多孔質支持体の表面に
in-situ 界面重合法により、陰イオン界面活性剤の存在
下に多官能アミンと多官能酸ハライドからなる架橋ポリ
アミド薄膜を形成させた複合半透膜を構成要素とする複
合半透膜モジュールにおいて、該複合半透膜から抽出さ
れる陰イオン界面活性剤の量が、複合半透膜重量１kg当
たり９g 以下であり、より好ましくは複合半透膜重量１
kg当たり５g 以下であり、さらに好ましくは複合半透膜
重量１kg当たり２. ５g 以下であることを特徴とする複
合半透膜モジュールである。[0015] The second invention is directed to a method for forming a surface of a porous support.
A composite semipermeable membrane module comprising a composite semipermeable membrane in which a crosslinked polyamide thin film composed of a polyfunctional amine and a polyfunctional acid halide is formed in the presence of an anionic surfactant by an in-situ interfacial polymerization method, The amount of the anionic surfactant extracted from the composite semipermeable membrane is 9 g or less per kg of the composite semipermeable membrane, and more preferably, the composite semipermeable membrane has a weight of 1 kg.
A composite semipermeable membrane module characterized by being 5 g or less per kg, more preferably 2.5 g or less per kg of the composite semipermeable membrane weight.
【００１６】第２番目の発明の複合半透膜モジュールの
製造方法としては、多孔質支持体の表面にin-situ 界面
重合法により、陰イオン界面活性剤の存在下に多官能ア
ミンと多官能酸ハライドからなる架橋ポリアミド薄膜を
形成させた複合半透膜を構成要素とする複合半透膜組立
体の内部を、アルコール水溶液で満たす、もしくは加圧
通水することを特徴とする。さらに続けて、５０℃以上
の熱水、酸水溶液、アルカリ水溶液のうち少なくとも一
つ以上の溶液で該複合半透膜組立体内部を満たし、もし
くは加圧通水してもよい。[0016] In a second method for producing a composite semipermeable membrane module according to the present invention, a polyfunctional amine and a polyfunctional amine are present on the surface of a porous support by an in-situ interfacial polymerization method in the presence of an anionic surfactant. The inside of a composite semipermeable membrane assembly comprising a composite semipermeable membrane on which a crosslinked polyamide thin film made of an acid halide is formed as a component is filled with an aqueous alcohol solution or water is passed under pressure. Subsequently, the inside of the composite semipermeable membrane assembly may be filled with at least one of hot water at 50 ° C. or higher, an aqueous acid solution, and an aqueous alkali solution, or may be pressurized and flow water.
【００１７】本発明において、多孔質支持体とは実質的
に分離活性能を持たない層であり、該多孔質支持体表面
に形成された実質的に分離活性能を有する超薄膜に機械
的強度を付与するものである。多孔質支持体の形態は特
に限定されないが、平膜もしくは中空糸状膜の形態がよ
く用いられる。中空糸状膜の場合、内圧型、外圧型のい
ずれであってもよい。In the present invention, the porous support is a layer having substantially no separation activity, and the ultrathin film having substantially separation activity which is formed on the surface of the porous support has a mechanical strength. Is given. Although the form of the porous support is not particularly limited, a form of a flat membrane or a hollow fiber membrane is often used. In the case of a hollow fiber membrane, any of an internal pressure type and an external pressure type may be used.
【００１８】多孔質支持体の素材は特に限定されない
が、ポリスルホン、スルホン化ポリスルホン、ポリエー
テルスルホン、スルホン化ポリエーテルスルホン、ポリ
アミド、酢酸セルロース、ポリアクリロニトリル、ポリ
イミド等を単独、もしくは複数ブレンドしたものを使用
することができる。これら素材の中では、機械的強度や
耐熱性、耐薬品性に優れたポリスルホン、あるいはポリ
エーテルスルホンなどが好適に用いられる。Although the material of the porous support is not particularly limited, polysulfone, sulfonated polysulfone, polyethersulfone, sulfonated polyethersulfone, polyamide, cellulose acetate, polyacrylonitrile, polyimide or the like may be used singly or as a blend. Can be used. Among these materials, polysulfone having excellent mechanical strength, heat resistance, and chemical resistance, or polyether sulfone is preferably used.
【００１９】多孔質支持体の製造方法は特に限定されな
いが、例えばポリマー、良溶媒、貧溶媒、界面活性剤を
混合溶解した製膜原液を、吐出ノズルを介して気体雰囲
気下に押し出し続いて凝固液中に導く乾湿式法、もしく
は吐出ノズルから直接凝固液中に導く湿式法が好適に用
いられる。一例を示すと、チューブインオリフィス型紡
糸ノズルを用いて外周部から製膜原液（ポリスルホン２
０重量部、トリエチレングリコール４重量部、N,N-ジメ
チルアセトアミド(DMAc)７５. ５重量部、ラウリルベン
ゼンスルホン酸ナトリウム０. ５重量部）、内周部から
芯液（DMAc３０重量部、水７０重量部）を同時に空気中
に吐出し、続いて凝固液中（DMAc５重量部、水９５重量
部）へ導くことによって、外表面に数十nmの微細孔を有
する多孔質支持体が得られる。得られた多孔質支持体
は、５０℃から1 ００℃の熱水処理を施してもよい。The method for producing the porous support is not particularly limited. For example, a stock solution obtained by mixing and dissolving a polymer, a good solvent, a poor solvent, and a surfactant is extruded through a discharge nozzle into a gaseous atmosphere, and then solidified. A dry-wet method for introducing into a liquid or a wet method for directly introducing into a coagulating liquid from a discharge nozzle is preferably used. As an example, using a tube-in-orifice type spinning nozzle, a film forming stock solution (polysulfone 2
0 parts by weight, 4 parts by weight of triethylene glycol, 75.5 parts by weight of N, N-dimethylacetamide (DMAc), 0.5 part by weight of sodium laurylbenzenesulfonate), and a core liquid (30 parts by weight of DMAc, water) 70 parts by weight) into the air at the same time and subsequently into the coagulating liquid (5 parts by weight of DMAc, 95 parts by weight of water) to obtain a porous support having fine pores of several tens nm on the outer surface. . The obtained porous support may be subjected to a hot water treatment at 50 ° C. to 100 ° C.
【００２０】本発明においては、上記多孔質支持体に、
一分子中に２個以上の反応性アミノ基を有する多官能ア
ミンおよび陰イオン界面活性剤を含有する、多官能アミ
ン水溶液を被覆・含浸する。In the present invention, the above-mentioned porous support comprises:
A polyfunctional amine aqueous solution containing a polyfunctional amine having two or more reactive amino groups in one molecule and an anionic surfactant is coated and impregnated.
【００２１】本発明における多官能アミンは特に限定さ
れるものではないが、例えば、脂環族多官能アミン、脂
肪族多官能アミン、芳香族多官能アミンを含み、具体的
には、ピペラジン、２, ５- ジメチルピペラジン、アミ
ノメチルピペリジン、エチレンジアミン、１, ２- ジア
ミノプロパン、１, ２ ジアミノ- ２- メチルプロパ
ン、２, ２ ジメチル- １, ３- プロパンジアミン、２
- エチル- ２- メチル-１, ３- プロパンジアミン、ジ
アミノベンゼン、トリアミノベンゼン、フェニレンジア
ミン、ジアミノジフェニルメタン、ジアミノジフェニル
エ−テル、ジアミノジフェニルスルホン、ジアミノ安息
香酸等が挙げられる。これらアミノ化合物を単独で、も
しくは複数ブレンドして用いてもよい。The polyfunctional amine in the present invention is not particularly limited, and includes, for example, alicyclic polyfunctional amines, aliphatic polyfunctional amines, and aromatic polyfunctional amines. , 5-dimethylpiperazine, aminomethylpiperidine, ethylenediamine, 1,2-diaminopropane, 1,2 diamino-2-methylpropane, 2,2 dimethyl-1,3-propanediamine,
-Ethyl-2-methyl-1,3-propanediamine, diaminobenzene, triaminobenzene, phenylenediamine, diaminodiphenylmethane, diaminodiphenylether, diaminodiphenylsulfone, diaminobenzoic acid and the like. These amino compounds may be used alone or as a mixture of two or more.
【００２２】また、陰イオン界面活性剤としては特に限
定されるものではないが、代表的にはLAS （直鎖アルキ
ルベンゼンスルホン酸ナトリウム）、ABS （アルキルベ
ンゼンスルホン酸ナトリウム）、AS（アルキル硫酸ナト
リウム）、アルキルジフェニルエ−テルジスルフィドな
どが含まれる。Although the anionic surfactant is not particularly limited, it is typically LAS (sodium linear alkylbenzene sulfonate), ABS (sodium alkylbenzene sulfonate), AS (sodium alkyl sulfate), Alkyl diphenyl ether disulfide and the like.
【００２３】LAS およびABS は一般式：CnH2n+1-Ar-SO3
Naで表され、式中ｎは任意であるが、優れた界面活性能
と相間移動触媒能からn=８〜１４が好ましい。特に好ま
しくは、工業的に利用可能なラウリルベンゼンスルホン
酸ナトリウムであるが、これはn=１２化合物を主成分と
するn=８〜１４混合物として安価に入手可能である。LAS and ABS have the general formula: C n H 2n + 1 -Ar-SO 3
In the formula, n is arbitrary, but n is preferably 8 to 14 from the viewpoint of excellent surface activity and phase transfer catalysis. Particularly preferred is sodium laurylbenzenesulfonate, which is industrially available, and can be obtained at a low cost as a mixture of n = 8 to 14 mainly composed of n = 12 compounds.
【００２４】LSは一般式：CnH2n+1-O-SO3Na で表され、
式中ｎは任意であるが、優れた界面活性能と相間移動触
媒能からn=８〜１８が好ましい。特に好ましくは、n=１
２化合物を主成分とするラウリル硫酸ナトリウムが、工
業的に安価に利用可能である。LS is represented by a general formula: C n H 2n + 1 -O-SO 3 Na,
In the formula, n is arbitrary, but n is preferably 8 to 18 from the viewpoint of excellent surface activity and phase transfer catalysis. Particularly preferably, n = 1
Sodium lauryl sulfate containing two compounds as main components is industrially available at low cost.
【００２５】また、前記多官能アミンと陰イオン界面活
性剤を含む水溶液には、酸捕捉剤として、水酸化ナトリ
ウム、炭酸水素ナトリウム、リン酸二水素ナトリウム、
リン酸水素二ナトリウム等の無機アルカリ、トリエチル
アミン、トリエチレンジアミン等の３級アミンを添加し
てもよい。The aqueous solution containing the polyfunctional amine and the anionic surfactant may contain, as an acid scavenger, sodium hydroxide, sodium hydrogen carbonate, sodium dihydrogen phosphate,
An inorganic alkali such as disodium hydrogen phosphate or a tertiary amine such as triethylamine or triethylenediamine may be added.
【００２６】前記多官能アミンと反応しうる多官能酸ハ
ライドは特に限定されるものではないが、例えば、脂環
族多官能酸ハライド、脂肪族多官能酸ハライド、芳香族
多官能酸ハライドを含み、具体的には、シクロヘキサン
トリカルボン酸ハライド、テレフタル酸ハライド、イソ
フタル酸ハライド、トリメシン酸ハライド、トリメリッ
ト酸ハライド、ピロメリット酸ハライド、ベンゾフェノ
ンテトラカルボン酸ハライド等が挙げられる。これら酸
ハロゲン化物を単独で、もしくは複数ブレンドして用い
てもよい。The polyfunctional acid halide capable of reacting with the polyfunctional amine is not particularly limited, and includes, for example, an alicyclic polyfunctional acid halide, an aliphatic polyfunctional acid halide and an aromatic polyfunctional acid halide. Specific examples thereof include cyclohexanetricarboxylic acid halide, terephthalic acid halide, isophthalic acid halide, trimesic acid halide, trimellitic acid halide, pyromellitic acid halide, and benzophenonetetracarboxylic acid halide. These acid halides may be used alone or as a mixture of two or more.
【００２７】上記多官能酸ハライドを溶解する溶媒は、
水と非混和性で、多官能酸ハライドを溶解し多孔質支持
体を溶解しないものであればよい。たとえば、n-ヘキサ
ン、ヘプタン、オクタン、ノナン、デカン、ウンデカ
ン、ドデカン等である。The solvent for dissolving the polyfunctional acid halide is as follows:
Any material may be used as long as it is immiscible with water and dissolves the polyfunctional acid halide but does not dissolve the porous support. For example, n-hexane, heptane, octane, nonane, decane, undecane, dodecane and the like.
【００２８】分離活性能を有する架橋ポリアミド薄膜の
形成方法を以下に例示する。前記多孔質支持体を、前記
多官能アミン水溶液中に浸漬し、余分な水溶液を液切り
・乾燥する。続いて前記多官能酸ハライドを含む有機溶
液に接触させ、in-situ 界面重合法により該多孔質支持
体の表面を架橋ポリアミド薄膜で被覆する。これを乾燥
させて余分な有機溶媒を除去した後、純水中で洗浄す
る。A method for forming a crosslinked polyamide thin film having separation activity is described below. The porous support is immersed in the polyfunctional amine aqueous solution, and the excess aqueous solution is drained and dried. Subsequently, the porous support is brought into contact with the organic solution containing the polyfunctional acid halide, and the surface of the porous support is coated with a crosslinked polyamide thin film by in-situ interfacial polymerization. This is dried to remove excess organic solvent, and then washed in pure water.
【００２９】上記で得られた複合膜形成物は、すでに十
分な分離活性能を有しており、該複合膜形成物をケーシ
ングに収納し、被処理水の流入口と、濃縮水の排出口
と、複合半透膜透過水の取水口とを有する分離膜モジュ
ールとして組立て、膜分離プロセスに組み込み、使用す
ることは可能である。The composite membrane-forming product obtained above has a sufficient separation activity, and the composite membrane-forming product is housed in a casing, and the inlet of the water to be treated and the outlet of the concentrated water It is possible to assemble as a separation membrane module having an intake port for the combined semipermeable membrane permeated water and incorporate it into the membrane separation process for use.
【００３０】しかしながら、このようにして得られた膜
分離モジュールでは、膜分離プロセスの運転初期におい
ては、水道水質基準である０. ２m g/L を上回る量の陰
イオン界面活性剤を含有する膜透過水が得られる。水道
水質基準に合致する膜透過水を得るためには、少なくと
も３時間以上、好ましくは１０時間以上の加圧通水下に
おける膜分離モジュールの洗浄が必要である。また、こ
のような洗浄を実施したとしても、依然として０. １mg
/Lを上回る量の陰イオン界面活性剤を含有する膜透過水
が長期間にわたって得られる。However, in the membrane separation module thus obtained, in the initial stage of the operation of the membrane separation process, a membrane containing an anionic surfactant in an amount exceeding 0.2 mg / L, which is a tap water quality standard. Permeate is obtained. In order to obtain membrane permeated water that meets tap water quality standards, it is necessary to wash the membrane separation module under pressurized water for at least 3 hours or more, preferably 10 hours or more. In addition, even if such washing is performed, it is still 0.1 mg.
Membrane permeated water containing an amount of anionic surfactant in excess of / L is obtained over a long period of time.
【００３１】本発明におけるアルコール水溶液は特に限
定されるものではないが、たとえば、メタノール、エタ
ノール、iso −プロパノ−ル、tert−ブタノール等が使
用できる。アルコール水溶液の濃度は、アルコールの種
類や処理時間、処理方法により異なるが１０〜８０重量
部、より好ましくは３０〜７０重量部水溶液を使用する
ことができる。The aqueous alcohol solution in the present invention is not particularly limited, but for example, methanol, ethanol, iso-propanol, tert-butanol and the like can be used. The concentration of the aqueous alcohol solution varies depending on the type of alcohol, the treatment time, and the treatment method, but an aqueous solution of 10 to 80 parts by weight, more preferably 30 to 70 parts by weight can be used.
【００３２】本発明における酸水溶液は特に限定される
ものではく、塩酸、硫酸、硝酸、リン酸等の無機酸、酢
酸、クエン酸等の有機酸のごとく、水に可溶で、水溶液
としたときに酸性を示すものであればよい。酸水溶液は
pH１〜４、より好ましくはpH２〜３の水溶液が好適に用
いられる。これは、酸水溶液がpH１未満では酸加水分解
により複合半透膜自信が劣化する恐れがあり、pH４以上
では十分な洗浄効果が得られないためである。The aqueous acid solution in the present invention is not particularly limited, and is soluble in water, such as an inorganic acid such as hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid, and an organic acid such as acetic acid and citric acid. What is sometimes acidic may be sufficient. Acid aqueous solution
An aqueous solution having a pH of 1 to 4, more preferably a pH of 2 to 3 is suitably used. This is because if the pH of the aqueous acid solution is lower than 1, acid hydrolysis may deteriorate the composite semipermeable membrane, and if the pH is 4 or higher, a sufficient washing effect cannot be obtained.
【００３３】本発明におけるアルカリ水溶液は特に限定
されるものではないが、水酸化ナトリウム、水酸化カリ
ウム、水酸化カルシウム、アンモニア等のごとく、水に
可溶で、水溶液としたときにアルカリ性を示すものであ
ればよい。アルカリ水溶液はpH９〜１２の水溶液が好適
に用いられる。分離活性能を有する架橋ポリアミド薄膜
は特にアルカリ加水分解を受けやすく、該ポリアミドを
構成するモノマー成分にもよるが、アルカリ水溶液がpH
１２以上ではアルカリ加水分解により複合半透膜自体が
劣化する恐れがある。また、pH９未満では十分な洗浄効
果が得られない。The alkaline aqueous solution in the present invention is not particularly limited, but is soluble in water and exhibits alkalinity when formed into an aqueous solution, such as sodium hydroxide, potassium hydroxide, calcium hydroxide, and ammonia. Should be fine. As the alkaline aqueous solution, an aqueous solution having a pH of 9 to 12 is suitably used. A crosslinked polyamide thin film having separation activity is particularly susceptible to alkali hydrolysis, and although depending on the monomer components constituting the polyamide, an alkaline aqueous solution has a pH
When it is 12 or more, the composite semipermeable membrane itself may be deteriorated by alkali hydrolysis. If the pH is lower than 9, a sufficient washing effect cannot be obtained.
【００３４】本発明における熱水は特に限定されるもの
ではないが、前記複合膜形成物や複合半透膜組立体と接
触したときに、それらと反応しうる基質を含まない水を
使用し、好適には逆浸透ろ過水やイオン交換水等が使用
できる。また、該熱水の温度は５０℃以上、より好まし
くは６０℃以上のものを好適に用いることができる。Although the hot water in the present invention is not particularly limited, water which does not contain a substrate capable of reacting with the composite membrane-forming product or the composite semipermeable membrane assembly when it comes into contact with the hot water is used. Preferably, reverse osmosis filtered water, ion-exchanged water, or the like can be used. The temperature of the hot water is preferably 50 ° C. or higher, more preferably 60 ° C. or higher.
【００３５】アルコール水溶液による複合膜形成物の処
理方法は、簡便な方法として浸漬法、充填法もしくは加
圧通水法が用いられる。As a simple method of treating the composite film-formed product with an aqueous alcohol solution, a dipping method, a filling method or a pressurized water flow method is used.
【００３６】浸漬法では、前記in-situ 界面重合法によ
り得られた複合膜形成物を前記アルコ−ル水溶液に１分
〜５時間、より好ましくは５分〜３時間浸漬し、次いで
純水で洗浄することにより本発明の複合半透膜が得られ
る。In the immersion method, the composite film-forming product obtained by the in-situ interfacial polymerization method is immersed in the alcohol aqueous solution for 1 minute to 5 hours, more preferably 5 minutes to 3 hours, and then with pure water. By washing, the composite semipermeable membrane of the present invention is obtained.
【００３７】また、前記複合膜形成物をケーシングに収
納し、被処理水の流入口と、濃縮水の排出口と、複合半
透膜透過水の取水口とを有する複合半透膜組立体として
組立て、該複合半透膜組立体の内部に前記アルコール水
溶液を充填する、充填法を用いることができる。処理時
間は１分〜５時間、より好ましくは５分〜３時間静置も
しくはゆっくりと振とうすることで、前記浸漬法と同様
の効果がある。次いで純水で洗浄することにより本発明
の複合半透膜モジュールが得られる。Further, the composite membrane-formed product is housed in a casing, and is provided as a composite semipermeable membrane assembly having an inlet for treated water, an outlet for concentrated water, and an intake for composite permeated water. Assembling, a filling method of filling the inside of the composite semipermeable membrane assembly with the alcohol aqueous solution can be used. The treatment time is 1 minute to 5 hours, more preferably 5 minutes to 3 hours, and the same effect as that of the immersion method can be obtained by shaking or gently shaking. Subsequently, the composite semipermeable membrane module of the present invention is obtained by washing with pure water.
【００３８】本発明の複合半透膜モジュールを得るもう
一つの方法として、アルコール水溶液を前記複合半透膜
組立体の被処理水流入口より導入し、膜間圧力差を生じ
せしめ、濃縮水と膜透過水とを得る加圧通水法を利用で
きる。加圧通水法による場合は、前記濃縮水と膜透過水
を放流するワンパス運転を行ってもよく、また浴比を適
切に設定した上で前記濃縮水と膜透過水を供給側へ戻す
循環運転を行ってもよい。膜間圧力差は、アルコール水
溶液が透過側へ流れ出ればよく、例えば、ポンプにより
０. ０５〜５M Pa程度の加圧給水を行う。処理時間は浸
漬法よりも短時間でよく、１分〜３時間加圧通水すれば
よい。加圧通水法では、アルコール水溶液が複合半透膜
内部にまで十分に侵入し、陰イオン界面活性剤を除去す
る効果が高まるが、ポンプを駆動するためのエネルギ-
コストを考慮すると、１ 時間以内がより好ましい。加
圧通水処理の後、純水に置換して再度加圧通水・洗浄す
ることで本発明の複合半透膜モジュールが得られる。As another method for obtaining the composite semipermeable membrane module of the present invention, an aqueous alcohol solution is introduced from the inlet of the water to be treated of the composite semipermeable membrane assembly to generate a transmembrane pressure difference. A pressurized water flow method for obtaining permeated water can be used. In the case of the pressurized water flow method, a one-pass operation of discharging the concentrated water and the membrane permeated water may be performed, or a circulation that returns the concentrated water and the membrane permeated water to the supply side after appropriately setting a bath ratio. You may drive. The pressure difference between the membranes may be such that the alcohol aqueous solution flows out to the permeation side. For example, a pressurized water supply of about 0.05 to 5 MPa is performed by a pump. The treatment time may be shorter than that of the immersion method, and the water may be passed under pressure for 1 minute to 3 hours. In the pressurized water flow method, the alcohol aqueous solution sufficiently penetrates into the inside of the composite semipermeable membrane, and the effect of removing the anionic surfactant is enhanced, but the energy required to drive the pump is increased.
Considering the cost, it is more preferable within one hour. After the pressurized water passage treatment, the composite semipermeable membrane module of the present invention can be obtained by substituting pure water for pressurized water passage and washing again.
【００３９】本発明においてはさらに、前記アルコール
水溶液で処理した複合半透膜形成物および、複合半透膜
組立体を酸水溶液、アルカリ水溶液、熱水のいずれか一
つ、もしくは複数の組合せで処理してもよい。処理方法
は前記アルコール水溶液による処理の場合のごとく、浸
漬法、充填法、加圧通水法のいずれも用いることができ
る。In the present invention, the composite semipermeable membrane-formed product and the composite semipermeable membrane assembly treated with the alcohol aqueous solution are further treated with one or more of an aqueous acid solution, an aqueous alkaline solution, and hot water. May be. As the treatment method, as in the case of the treatment with the alcohol aqueous solution, any of the dipping method, the filling method, and the pressurized water passing method can be used.
【００４０】また本発明の複合半透膜および複合半透膜
モジュールの用途は、限外ろ過、ナノろ過、逆浸透があ
る。特に、飲用に供する海水淡水化、かん水の脱塩、河
川水や地下水からの上水製造、純水製造、家庭用もしく
は業務用浄水器、食品プロセスに有効である。さらに
は、排水の処理や濃縮、有価物の回収に用いてもよい。
しかしながら、本発明はこれらの膜の用途に限定される
ものではない。The applications of the composite semipermeable membrane and the composite semipermeable membrane module of the present invention include ultrafiltration, nanofiltration, and reverse osmosis. In particular, it is effective for desalination of seawater for drinking, desalination of brackish water, production of clean water from river water or groundwater, production of pure water, domestic or commercial water purifiers, and food processes. Furthermore, it may be used for treatment and concentration of wastewater, and recovery of valuable resources.
However, the invention is not limited to these membrane applications.
【００４１】[0041]
【実施例】以下に実施例により本発明を具体的に説明す
るが、本発明はこれらに限定されるものではない。な
お、実施例において、複合半透膜に残留する陰イオン界
面活性剤の抽出はソクスレー抽出法により行い、該抽出
液中の陰イオン界面活性剤量は高速液体クロマトグラフ
による分離・定量により測定した。抽出に用いた複合半
透膜は絶乾ののち秤量し、残留陰イオン界面活性剤の量
を単位膜重量当たりに換算した。ソクスレー抽出は、複
合半透膜片を細断し、メタノールを抽出溶媒として、一
昼夜かけて実施した。上記高速液体クロマトグラフの測
定条件については、逆相系カラムPRP-１（ハミルトン社
製）を用い、移動相をアセトニトリル4 ０重量部、０.
２M 過塩素酸ナトリウム溶液6 ０重量部の混合水溶液、
移動相流量１. ０m L/min 、カラム温度５０℃とし、検
出器にはUV検出器（波長２２５nm）を用いた。EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. In Examples, the extraction of the anionic surfactant remaining in the composite semipermeable membrane was performed by the Soxhlet extraction method, and the amount of the anionic surfactant in the extract was measured by separation and quantification using a high-performance liquid chromatograph. . The composite semipermeable membrane used for the extraction was weighed after being completely dried, and the amount of the residual anionic surfactant was converted per unit membrane weight. The Soxhlet extraction was carried out over a day and night using the composite semipermeable membrane pieces cut into small pieces and using methanol as an extraction solvent. Regarding the measurement conditions of the high performance liquid chromatograph, a reverse phase column PRP-1 (manufactured by Hamilton) was used, and the mobile phase was 40 parts by weight of acetonitrile and 0.1 part by mass.
A mixed aqueous solution of 60 parts by weight of a 2M sodium perchlorate solution,
The mobile phase flow rate was 1.0 mL / min, the column temperature was 50 ° C., and a UV detector (wavelength: 225 nm) was used as the detector.
【００４２】（実施例１）ポリスルホン２０重量部、ト
リエチレングリコール４重量部、N,N-ジメチルアセトア
ミド(DMAc ) ７５. ５ 重量部、ラウリルベンゼンスル
ホン酸ナトリウム０. ５重量部からなる製膜原液を、チ
ュ−ブインオリフィス型紡糸ノズルを用いて外周部か
ら、DMAc３０重量部、水７０重量部からなる芯液を内周
部から、それぞれ同時に押し出し、６cmの空気中を走行
した後、DMAc５重量部、水９５重量部からなる凝固液中
に１５m/min の速度で引き取り、水洗工程を経て、中空
糸型多孔質支持体（外径３５０μm ／内径２００μm ）
を得た。該多孔質支持体を、ピペラジン２重量部、トリ
エチレンジアミン１重量部、ラウリルベンゼンスルホン
酸ナトリウム０. ０７重量部からなるアミン水溶液中に
１分間接触させ、該多孔質支持体を引き上げた後、余分
なアミン水溶液を液切りし、トリメシン酸クロリド１重
量部を含むヘキサン溶液、フッ素系溶媒（フロリナート
FC−７０、住友３M 社製）、１重量部酢酸水溶液に順
次接触させることで、該多孔質支持体の外表面にポリア
ミド薄膜を形成させた、複合膜形成物を得た。該複合膜
形成物を、５０重量部のエタノ−ル水溶液中に１５分間
浸漬し、純水で十分に水洗することで複合半透膜を得
た。該複合半透膜に残留するラウリルベンゼンスルホン
酸ナトリウムを、ソクスレ−抽出、高速液体クロマトグ
ラフにより定量し、単位膜重量当たりの残留量を決定し
た。結果を表１に示す。Example 1 A stock solution comprising 20 parts by weight of polysulfone, 4 parts by weight of triethylene glycol, 75.5 parts by weight of N, N-dimethylacetamide (DMAc), and 0.5 part by weight of sodium laurylbenzenesulfonate Using a tube-in-orifice type spinning nozzle, a core liquid consisting of 30 parts by weight of DMAc and 70 parts by weight of water was simultaneously extruded from the inner part from the outer part, and after running in 6 cm of air, 5 parts by weight of DMAc was obtained. And a hollow fiber-type porous support (outer diameter 350 μm / inner diameter 200 μm) through a coagulating liquid consisting of 95 parts by weight of water at a speed of 15 m / min and a washing step.
I got The porous support is brought into contact with an aqueous amine solution consisting of 2 parts by weight of piperazine, 1 part by weight of triethylenediamine, and 0.07 parts by weight of sodium laurylbenzenesulfonate for 1 minute, and after pulling up the porous support, Aqueous amine solution was drained, hexane solution containing 1 part by weight of trimesic acid chloride, fluorinated solvent (Fluorinert)
FC-70, manufactured by Sumitomo 3M Co., Ltd.) was successively contacted with an aqueous solution of 1 part by weight of acetic acid to obtain a composite film formed by forming a polyamide thin film on the outer surface of the porous support. The composite film-formed product was immersed in 50 parts by weight of an aqueous ethanol solution for 15 minutes, and sufficiently washed with pure water to obtain a composite semipermeable membrane. The sodium laurylbenzenesulfonate remaining in the composite semipermeable membrane was quantified by Soxhlet extraction and high performance liquid chromatography to determine the amount remaining per unit membrane weight. Table 1 shows the results.
【００４３】（実施例２〜３）実施例１において、該複
合膜形成物を、エタノール処理に続き、pH３またはpH２
の塩酸水溶液に１時間浸漬し、純水で十分に水洗した以
外は全く同一の操作を行った。結果を表１に示す。(Examples 2 to 3) In Example 1, the composite film-forming product was treated with ethanol, and then treated with pH 3 or pH 2
The same operation was performed except that the sample was immersed in an aqueous solution of hydrochloric acid for 1 hour and washed thoroughly with pure water. Table 1 shows the results.
【００４４】（実施例４〜５）実施例１ において、該
複合膜形成物を、エタノール処理に続き、pH９またはpH
１０の水酸化ナトリウム水溶液に１時間浸漬し、純水で
十分に水洗した以外は全く同一の操作を行った。結果を
表１に示す。(Examples 4 and 5) In Example 1, the composite membrane-formed product was treated with ethanol at pH 9 or pH 9.
The same operation was performed except that the sample was immersed in an aqueous sodium hydroxide solution of No. 10 for 1 hour and thoroughly washed with pure water. Table 1 shows the results.
【００４５】（実施例６）実施例１において、該複合膜
形成物を、エタノール処理に続き、７０℃の熱水に３時
間浸漬した以外は全く同一の操作を行った。結果を表１
に示す。Example 6 The same operation as in Example 1 was performed except that the composite film-formed product was immersed in hot water at 70 ° C. for 3 hours following the ethanol treatment. Table 1 shows the results
Shown in
【００４６】（比較例１）実施例１において、該複合膜
形成物を、エタノール処理を施さず、純水のみで洗浄し
た以外は全く同一の操作を行った。結果を表１に示す。Comparative Example 1 The same operation as in Example 1 was carried out except that the composite film-formed product was not treated with ethanol and was washed only with pure water. Table 1 shows the results.
【００４７】（実施例７）実施例１で得た中空糸状の該
複合膜形成物を多数本束ね、側面に液体流入口と排出口
を有する、人工透析器型の円筒状ケースに、該膜束を該
ケ−スの両端部からわずかにはみ出すように挿入し、ケ
ース外部と内部とを仕切るように、該ケース両端部を該
膜束と共にポッティング樹脂で封止した。封止した端部
の一方のみ、ケ−スからはみ出している膜束と接着樹脂
とをカッターで切断し、中空部を開口した。このように
して得られた複合半透膜組立体を膜分離装置に装着し、
5 ０重量部のメタノール水溶液を送液ポンプにより操作
圧力０. ３M Pa、液温２５℃で、濃縮水と膜透過水を供
給液タンクに戻す循環運転（加圧通水）を１５分間行っ
た。次いで、純水で十分にすすぎ、複合半透膜モジュー
ルを得た。該複合半透膜モジュールを解体し、内部の複
合半透膜を取り出し、該複合半透膜に残留するラウリル
ベンゼンスルホン酸ナトリウムを、ソクスレー抽出、高
速液体クロマトグラフにより定量し、単位膜重量当たり
の残留量を決定した。結果を表２に示す。(Example 7) A number of the hollow fiber composite membrane-forming products obtained in Example 1 were bundled, and the membrane was placed in an artificial dialysis machine type cylindrical case having a liquid inlet and an outlet on the side. The bundle was inserted so as to slightly protrude from both ends of the case, and both ends of the case were sealed together with the membrane bundle with a potting resin so as to separate the inside and outside of the case. At only one of the sealed ends, the film bundle and the adhesive resin protruding from the case were cut with a cutter to open a hollow portion. The composite semipermeable membrane assembly obtained in this way is mounted on a membrane separation device,
A circulation operation (pressurized water passing) of returning the concentrated water and the membrane permeated water to the supply liquid tank at an operating pressure of 0.3 MPa and a liquid temperature of 25 ° C. was performed for 15 parts by weight of a 50 parts by weight methanol aqueous solution by a liquid sending pump for 15 minutes. . Next, it was sufficiently rinsed with pure water to obtain a composite semipermeable membrane module. The composite semipermeable membrane module is disassembled, the internal composite semipermeable membrane is taken out, and sodium laurylbenzenesulfonate remaining in the composite semipermeable membrane is quantified by Soxhlet extraction and high performance liquid chromatography. The residual amount was determined. Table 2 shows the results.
【００４８】（実施例８〜９）実施例７において、該複
合半透膜組立体を、エタノール処理に続き、pH３または
pH２の塩酸水溶液で、同様の条件で１時間の加圧通水を
行い、純水で十分に水洗した以外は全く同一の操作を行
った。結果を表２に示す。(Examples 8 to 9) In Example 7, the composite semipermeable membrane assembly was treated with ethanol at pH 3 or
Exactly the same operation was carried out except that a pressurized water flow was performed for 1 hour with a hydrochloric acid aqueous solution of pH 2 under the same conditions for one hour, and the water was sufficiently washed with pure water. Table 2 shows the results.
【００４９】（実施例１０〜１１）実施例７において、
該複合半透膜組立体を、エタノール処理に続き、pH９ま
たはpH１０の水酸化ナトリウム水溶液で、同様の条件で
１時間の加圧通水を行い、純水で十分に水洗した以外は
全く同一の操作を行った。結果を表２に示す。(Embodiments 10 to 11)
The composite semipermeable membrane assembly was subjected to ethanol treatment, and then subjected to pressurized water passing for one hour under the same conditions with an aqueous solution of sodium hydroxide at pH 9 or pH 10 under the same conditions, and thoroughly washed with pure water. The operation was performed. Table 2 shows the results.
【００５０】（実施例１２）実施例７において、該複合
半透膜組立体を、エタノール処理に続き、６０℃の熱水
で、同様の条件で１０時間の加圧通水を行い、純水で十
分に水洗した以外は全く同一の操作を行った。結果を表
２に示す。Example 12 In Example 7, the composite semipermeable membrane assembly was subjected to pressurized water passing through hot water at 60 ° C. for 10 hours under the same conditions as the pure water after ethanol treatment. The same operation was performed except that the sample was thoroughly washed with water. Table 2 shows the results.
【００５１】（比較例２）実施例７において、該複合半
透膜組立体を、エタノール処理を施さず、純水のみで洗
浄した以外は全く同一の操作を行った。結果を表１に示
す。(Comparative Example 2) The same operation as in Example 7 was performed except that the composite semipermeable membrane assembly was not treated with ethanol and was washed only with pure water. Table 1 shows the results.
【００５２】[0052]
【発明の効果】以上説明したように、本発明の複合半透
膜および複合半透膜モジュールは、陰イオン界面活性剤
の残留量が少なく、膜分離装置の運転初期においても、
膜モジュールからの陰イオン界面活性剤の溶出量を極め
て低く押さえることができ、異臭味や発泡を生じず、安
全な飲用に供する水を製造することができる。As described above, in the composite semipermeable membrane and the composite semipermeable membrane module of the present invention, the residual amount of the anionic surfactant is small, and even in the initial operation of the membrane separation device,
The amount of the anionic surfactant eluted from the membrane module can be kept extremely low, and it is possible to produce safe drinking water that does not generate an unpleasant odor or foaming.
【００５３】[0053]
【表１】 [Table 1]
【００５４】[0054]
【表２】 [Table 2]
───────────────────────────────────────────────────── フロントページの続き Ｆターム(参考） 4D006 GA03 GA06 HA18 HA19 HA41 LA06 MA01 MA03 MA07 MA22 MA33 MB11 MB15 MB16 MB20 MC18 MC39 MC54 MC56X MC58 MC62X MC63 MC83 NA04 NA05 NA41 NA54 NA62 PA01 PA02 PA04 PB03 PB04 PB05 PB08 PC11 PC51 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4D006 GA03 GA06 HA18 HA19 HA41 LA06 MA01 MA03 MA07 MA22 MA33 MB11 MB15 MB16 MB20 MC18 MC39 MC54 MC56X MC58 MC62X MC63 MC83 NA04 NA05 NA41 NA54 NA62 PA01 PA02 PA04 PB03 PB04 PB05 PB08 PC11 PC51
Claims (12)
被覆した複合半透膜において、該複合半透膜から抽出さ
れる陰イオン界面活性剤の量が、複合半透膜重量１kg当
たり９g 以下であることを特徴とする複合半透膜。1. In a composite semipermeable membrane in which the surface of a porous support is coated with a polyamide thin film, the amount of anionic surfactant extracted from the composite semipermeable membrane is 9 g or less per 1 kg of the weight of the composite semipermeable membrane. A composite semipermeable membrane characterized by the following.
面活性剤の量が、複合半透膜重量１kg当たり５g 以下で
ある請求項１記載の複合半透膜。2. The composite semipermeable membrane according to claim 1, wherein the amount of the anionic surfactant extracted from the composite semipermeable membrane is 5 g or less per 1 kg of the composite semipermeable membrane weight.
面活性剤の量が、複合半透膜重量１kg当たり２. ５g 以
下である請求項１記載の複合半透膜。3. The composite semipermeable membrane according to claim 1, wherein the amount of the anionic surfactant extracted from the composite semipermeable membrane is 2.5 g or less per 1 kg of the composite semipermeable membrane weight.
求項１乃至３のいずれかに記載の複合半透膜。4. The composite semipermeable membrane according to claim 1, wherein the composite semipermeable membrane is a hollow fiber type membrane.
形成させた後、アルコ−ル水溶液で浸漬処理することを
特徴とする請求項１乃至４のいずれかに記載の複合半透
膜の製造方法。5. The production of a composite semipermeable membrane according to claim 1, wherein a polyamide thin film is formed on the surface of the porous support, and then immersed in an aqueous alcohol solution. Method.
形成させた後、アルコ−ル水溶液で浸漬処理し、続いて
５０℃以上の熱水、酸水溶液及びアルカリ水溶液のうち
少なくとも一つ以上の溶液で処理することを特徴とする
請求項１から４のいずれかに記載の複合半透膜の製造方
法。6. After forming a polyamide thin film on the surface of the porous support, the polyamide thin film is immersed in an aqueous alcohol solution, and subsequently at least one of hot water, an acidic aqueous solution and an alkaline aqueous solution at 50 ° C. or higher. The method for producing a composite semipermeable membrane according to any one of claims 1 to 4, wherein the treatment is performed with a solution.
被覆した複合半透膜を構成要素とする複合半透膜モジュ
ールにおいて、該複合半透膜から抽出される陰イオン界
面活性剤の量が、複合半透膜重量１kg当たり９g 以下で
あることを特徴とする複合半透膜モジュール。7. In a composite semipermeable membrane module comprising a composite semipermeable membrane in which the surface of a porous support is coated with a polyamide thin film, the amount of anionic surfactant extracted from the composite semipermeable membrane is reduced. A composite semipermeable membrane module having a weight of 9 g or less per kg of the composite semipermeable membrane.
面活性剤の量が、複合半透膜重量１kg当たり５g 以下で
ある請求項７記載の複合半透膜モジュール。8. The composite semipermeable membrane module according to claim 7, wherein the amount of the anionic surfactant extracted from the composite semipermeable membrane is 5 g or less per 1 kg of the composite semipermeable membrane weight.
面活性剤の量が、複合半透膜重量１kg当たり２. ５g 以
下である請求項７記載の複合半透膜モジュール。9. The composite semipermeable membrane module according to claim 7, wherein the amount of the anionic surfactant extracted from the composite semipermeable membrane is 2.5 g or less per kg of the composite semipermeable membrane weight.
請求項７乃至９のいずれかに記載の複合半透膜モジュー
ル。10. The composite semipermeable membrane module according to claim 7, wherein said composite semipermeable membrane is a hollow fiber type membrane.
薄膜を形成させた複合膜形成物を構成要素とする複合半
透膜組立体の内部を、アルコ−ル水溶液で満たすか、も
しくは加圧通水することを特徴とする請求項７乃至１０
のいずれかに記載の複合半透膜モジュールの製造方法。11. The interior of a composite semipermeable membrane assembly comprising a composite membrane forming product in which a crosslinked polyamide thin film is formed on the surface of a porous support, is filled with an aqueous alcohol solution, or is pressurized. 11. Water is applied by water.
The method for producing a composite semipermeable membrane module according to any one of the above.
を形成させた複合膜形成物を構成要素とする複合半透膜
組立体の内部を、アルコ−ル水溶液で満たし、もしくは
加圧通水したのち、５０℃以上の熱水、酸水溶液及びア
ルカリ水溶液のうち少なくとも一つ以上の溶液で該複合
半透膜組立体内部を満たすか、もしくは加圧通水するこ
とを特徴とする請求項７乃至１０のいずれかに記載の複
合半透膜モジュ−ルの製造方法。12. The interior of a composite semipermeable membrane assembly comprising a composite membrane forming product in which a polyamide thin film is formed on the surface of a porous support as a component is filled with an aqueous alcohol solution, or water is passed under pressure. After that, the inside of the composite semipermeable membrane assembly is filled with at least one of hot water at 50 ° C. or higher, an aqueous acid solution and an aqueous alkali solution, or pressurized water is passed. The method for producing a composite semipermeable membrane module according to any one of claims 10 to 13.
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| US8518310B2 (en) | 2006-10-10 | 2013-08-27 | Nitto Denko Corporation | Process for producing a dried composite semipermeable membrane |
| KR20140073275A (en) * | 2012-12-06 | 2014-06-16 | 도레이케미칼 주식회사 | Nano separator membrane for seawater desalination and preparation method thereof |
| US8851297B2 (en) | 2006-10-10 | 2014-10-07 | Nitto Denko Corporation | Composite semipermeable membrane and process for producing the same |
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| KR20140073275A (en) * | 2012-12-06 | 2014-06-16 | 도레이케미칼 주식회사 | Nano separator membrane for seawater desalination and preparation method thereof |
| KR101590218B1 (en) | 2012-12-06 | 2016-02-12 | 도레이케미칼 주식회사 | Polyamide type Nano separator membrane for seawater-pretreatment of seawater desalination and preparation method thereof |
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