JP2002346560A - Method for treating water and membrane for water treatment - Google Patents
Method for treating water and membrane for water treatmentInfo
- Publication number
- JP2002346560A JP2002346560A JP2001159733A JP2001159733A JP2002346560A JP 2002346560 A JP2002346560 A JP 2002346560A JP 2001159733 A JP2001159733 A JP 2001159733A JP 2001159733 A JP2001159733 A JP 2001159733A JP 2002346560 A JP2002346560 A JP 2002346560A
- Authority
- JP
- Japan
- Prior art keywords
- water
- water treatment
- temperature
- environment
- responsive polymer
- 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
Landscapes
- Water Treatment By Sorption (AREA)
- Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、水の処理方法、該
方法に用いる水処理用膜、及び該水処理用膜の洗浄方法
に関する。The present invention relates to a method for treating water, a membrane for treating water used in the method, and a method for cleaning the membrane for treating water.
【０００２】[0002]
【従来の技術】水に含まれる物質を除去して水を処理す
る方法として、従来より種々の方法が提案され様々な文
献に開示されている。そのような方法の一つとして、サ
イズにより分離する精密濾過法が挙げられる。しかし、
この精密濾過法では、界面活性剤、イオン、内分泌撹乱
物質（いわゆる環境ホルモン）など低・中分子量の物質
の排除ができない、という問題を有する。2. Description of the Related Art As a method for treating water by removing a substance contained in water, various methods have been conventionally proposed and disclosed in various documents. One of such methods is a microfiltration method in which separation is performed according to size. But,
This microfiltration method has a problem that it is not possible to exclude low and medium molecular weight substances such as surfactants, ions and endocrine disrupting substances (so-called environmental hormones).
【０００３】また、M.Kim, K.Saito, S.Furusaki, T.Su
go, I.Ishida, J. Chromatography,585, 45(1991)は、
吸着法と膜法を組み合わせた例を開示している。しかし
ながら、透過経路の短い膜では吸着カラムと比較して吸
着容量には限りがあり、頻繁に破過することが考えられ
る。また、頻繁に脱着を行うためには、溶離液を頻繁に
使用することとなる。該溶離液として有機溶剤、酸、高
濃度イオン水溶液などが挙げられるが、これらを頻繁に
使用すると上水道への混入が懸念される、という問題が
生じる。Also, M. Kim, K. Saito, S. Furusaki, T. Su
go, I. Ishida, J. Chromatography, 585, 45 (1991)
An example in which the adsorption method and the membrane method are combined is disclosed. However, a membrane having a short permeation path has a limited adsorption capacity as compared with an adsorption column, and may frequently break through. Further, in order to carry out the desorption frequently, the eluent is frequently used. Examples of the eluent include an organic solvent, an acid, and a high-concentration ion aqueous solution. However, if these are frequently used, there is a problem that contamination with water supply may occur.
【０００４】[0004]
【発明が解決しようとする課題】即ち、従来の方法は、
1) 界面活性剤、イオン、内分泌撹乱物質（いわゆる環
境ホルモン）など低・中分子量の物質の排除、及び2)有
機溶剤などの上水道に不所望な溶媒の混入、などの課題
を有していた。そこで、本発明の目的は、低・中分子量
の物質を除去できる吸着法を用い、且つ有機溶剤などの
不所望な溶媒を上水道に混入させずに該低・中分子量の
物質を脱着させる洗浄工程を有する、簡便な方法を提供
することにある。That is, the conventional method is as follows.
1) Elimination of low and medium molecular weight substances such as surfactants, ions, and endocrine disrupting substances (so-called environmental hormones), and 2) Incorporation of undesired solvents in waterworks such as organic solvents. . Accordingly, an object of the present invention is to provide a cleaning step of using an adsorption method capable of removing low and medium molecular weight substances, and desorbing the low and medium molecular weight substances without mixing an undesired solvent such as an organic solvent into the water supply. And to provide a simple method.
【０００５】[0005]
【課題を解決するための手段】本発明者らは、濾過を行
うことができる膜を用いると共に、該膜の材質そのもの
が環境変化に応答して変化して吸脱着を行うシステムを
用いることにより、上記課題を解決できることを見出し
た。即ち、本発明者らは、次の発明により、上記課題を
解決できることを見出した。Means for Solving the Problems The present inventors use a membrane capable of performing filtration and use a system in which the material itself of the membrane changes in response to an environmental change to perform adsorption and desorption. It has been found that the above problem can be solved. That is, the present inventors have found that the following problems can be solved by the following invention.
【０００６】＜１＞ 多孔性基材表面に環境応答性ポリ
マーを付着してなる水処理用膜に環境変化を施し且つ水
を処理する方向とは逆方向に水を流して該水処理用膜を
洗浄する工程を有する水処理用膜の洗浄方法。<1> A water treatment film obtained by attaching an environmentally responsive polymer to the surface of a porous base material and subjecting the water treatment film to environmental change and flowing water in a direction opposite to the water treatment direction. A method for cleaning a membrane for water treatment, comprising the step of cleaning water.
【０００７】＜２＞ 多孔性基材表面に環境応答性ポリ
マーを付着してなる水処理用膜に処理すべき水を流して
水処理用膜を透過させて水を処理する水処理工程、及び
前記水処理用膜に環境変化を施し且つ前記水処理用膜の
前記透過方向とは逆方向に水を流して前記水処理用膜を
洗浄する膜洗浄工程を有する水の処理方法。<2> a water treatment step of flowing water to be treated through a water treatment membrane having an environment-responsive polymer adhered to the surface of a porous base material and permeating the water treatment membrane to treat the water; A water treatment method comprising a membrane washing step of subjecting the water treatment membrane to an environmental change and flowing water in a direction opposite to the transmission direction of the water treatment membrane to wash the water treatment membrane.
【０００８】＜３＞ 上記＜２＞において、環境応答性
ポリマーは、前記多孔性基材表面と化学結合を介して付
着されるのがよい。 ＜４＞ 上記＜２＞又は＜３＞において、環境応答性ポ
リマーは、環境変化により親疎水性が可逆的に変化する
のがよい。 ＜５＞ 上記＜４＞において、環境変化が物理的環境変
化又は化学的環境変化であるのがよい。<3> In the above item <2>, the environment-responsive polymer may be attached to the surface of the porous substrate through a chemical bond. <4> In the above item <2> or <3>, the environment-responsive polymer may have its hydrophilicity / hydrophobicity reversibly changed by an environmental change. <5> In the above item <4>, the environmental change may be a physical environmental change or a chemical environmental change.
【０００９】＜６＞ 上記＜４＞において、環境応答性
ポリマーは、物理的環境により、親疎水性が可逆的に変
化するのがよい。 ＜７＞ 上記＜２＞〜＜６＞において、環境応答性ポリ
マーは、温度により親疎水性が可逆的に変化するアクリ
ルアミド系ポリマーであるのがよい。 ＜８＞ 上記＜７＞において、アクリルアミド系ポリマ
ーがポリ（N-イソプロピルアクリルアミド）であるのが
よい。<6> In the above item <4>, the environmentally responsive polymer preferably changes reversibly in hydrophilicity / hydrophobicity depending on a physical environment. <7> In the above items <2> to <6>, the environment-responsive polymer is preferably an acrylamide-based polymer whose hydrophilicity / hydrophobicity reversibly changes depending on temperature. <8> In the above item <7>, the acrylamide-based polymer may be poly (N-isopropylacrylamide).
【００１０】＜９＞ 上記＜２＞〜＜８＞において、水
処理工程における処理すべき水の第１の温度が２０〜１
００℃であり、該第１の温度において前記環境応答性ポ
リマーは疎水性を示し且つ疎水性物質を吸着し、これに
より処理すべき水から前記疎水性物質が除去され、洗浄
工程における逆方向に流す水の第２の温度は第１の温度
よりも低く且つ０〜７５℃であり、該第２の温度におい
て前記環境応答性ポリマーは親水性を示し且つ疎水性物
質を脱着し、逆方向に流す水により水処理用膜を洗浄す
るのがよい。<9> In the above items <2> to <8>, the first temperature of the water to be treated in the water treatment step is 20 to 1
00 ° C., at which temperature the environment-responsive polymer exhibits hydrophobicity and adsorbs hydrophobic substances, thereby removing the hydrophobic substances from the water to be treated, and in the opposite direction in the washing step. The second temperature of the flowing water is lower than the first temperature and between 0 and 75 ° C., at which the environmentally responsive polymer exhibits hydrophilicity and desorbs hydrophobic substances, The water treatment membrane is preferably washed with flowing water.
【００１１】＜１０＞ 上記＜２＞〜＜８＞において、
水処理工程における処理すべき水の第１の温度が２０〜
１００℃であり、該第１の温度において前記環境応答性
ポリマーは収縮し、疎水性を示し且つ疎水性物質を吸着
し、これにより処理すべき水から前記疎水性物質が除去
され、洗浄工程における逆方向に流す水の第２の温度は
第１の温度よりも低く且つ０〜７５℃であり、該第２の
温度において前記環境応答性ポリマーは膨潤し、親水性
を示し且つ疎水性物質を脱着し、逆方向に流す水により
水処理用膜を洗浄するのがよい。<10> In the above items <2> to <8>,
The first temperature of the water to be treated in the water treatment step is 20 to
100 ° C., at which temperature the environmentally responsive polymer shrinks, shows hydrophobicity and adsorbs hydrophobic substances, thereby removing the hydrophobic substances from the water to be treated, The second temperature of the water flowing in the opposite direction is lower than the first temperature and between 0 and 75 ° C., at which the environment-responsive polymer swells, shows hydrophilicity and removes hydrophobic substances. The water treatment membrane is preferably washed with water that is desorbed and flows in the opposite direction.
【００１２】＜１１＞ 多孔性基材表面に環境応答性ポ
リマーを付着してなる水処理用膜であって、処理すべき
水を流す際に該水処理用膜を透過して水を処理し、該水
処理用膜の洗浄する際、水処理用膜は環境変化が施され
且つ前記水処理用膜の前記透過方向とは逆方向に水を流
して前記水処理用膜を洗浄することを特徴とする水処理
用膜。<11> A water treatment membrane obtained by attaching an environment-responsive polymer to the surface of a porous substrate, wherein the water to be treated is passed through the water treatment membrane to treat the water. When washing the water treatment membrane, the water treatment membrane is subjected to environmental changes and flowing water in a direction opposite to the permeation direction of the water treatment membrane to wash the water treatment membrane. Characteristic membrane for water treatment.
【００１３】＜１２＞ 上記＜１１＞において、環境応
答性ポリマーは、多孔性基材表面と化学結合を介して付
着されるのがよい。 ＜１３＞ 上記＜１１＞又は＜１２＞において、環境応
答性ポリマーは、環境変化により親疎水性が可逆的に変
化するのがよい。 ＜１４＞ 上記＜１３＞において、環境変化が物理的環
境変化又は化学的環境変化であるのがよい。<12> In the above item <11>, the environment-responsive polymer may be attached to the surface of the porous substrate through a chemical bond. <13> In the above item <11> or <12>, the environment-responsive polymer may have its hydrophilicity / hydrophobicity reversibly change due to an environmental change. <14> In the above item <13>, the environmental change may be a physical environmental change or a chemical environmental change.
【００１４】＜１５＞ 上記＜１３＞において、環境応
答性ポリマーは、物理的環境により、親疎水性が可逆的
に変化するのがよい。 ＜１６＞ 上記＜１１＞〜＜１５＞のいずれかにおい
て、環境応答性ポリマーは、温度により親疎水性が可逆
的に変化するアクリルアミド系ポリマーであるのがよ
い。 ＜１７＞ 上記＜１６＞において、アクリルアミド系ポ
リマーがポリ（N-イソプロピルアクリルアミド）である
のがよい。<15> In the above item <13>, the environmentally responsive polymer may have its hydrophilicity / hydrophobicity reversibly change depending on the physical environment. <16> In any one of the above items <11> to <15>, the environment-responsive polymer may be an acrylamide polymer whose hydrophilicity / hydrophobicity reversibly changes depending on temperature. <17> In the above item <16>, the acrylamide-based polymer may be poly (N-isopropylacrylamide).
【００１５】＜１８＞ 上記＜１１＞〜＜１７＞のいず
れかにおいて、処理すべき水の第１の温度が２０〜１０
０℃であり、該第１の温度において前記環境応答性ポリ
マーは疎水性を示し且つ疎水性物質を吸着し、これによ
り処理すべき水から前記疎水性物質が除去され、逆方向
に流す水の第２の温度は第１の温度よりも低く且つ０〜
７５℃であり、該第２の温度において前記環境応答性ポ
リマーは親水性を示し且つ疎水性物質を脱着し、逆方向
に流す水により水処理用膜を洗浄するのがよい。<18> In any one of the above items <11> to <17>, the first temperature of the water to be treated may be from 20 to 10.
0 ° C., at which the environmentally responsive polymer is hydrophobic and adsorbs hydrophobic substances at the first temperature, whereby the hydrophobic substances are removed from the water to be treated and the water flowing in the opposite direction The second temperature is lower than the first temperature and
The second temperature is 75 ° C., and the environment-responsive polymer exhibits hydrophilicity and desorbs a hydrophobic substance, and the water treatment membrane may be washed with water flowing in the opposite direction.
【００１６】＜１９＞ 上記＜１１＞〜＜１７＞のいず
れかにおいて、処理すべき水の第１の温度が２０〜１０
０℃であり、該第１の温度において前記環境応答性ポリ
マーは収縮し、疎水性を示し且つ疎水性物質を吸着し、
これにより処理すべき水から前記疎水性物質が除去さ
れ、逆方向に流す水の第２の温度は第１の温度よりも低
く且つ０〜７５℃であり、該第２の温度において前記環
境応答性ポリマーは膨潤し、親水性を示し且つ疎水性物
質を脱着し、逆方向に流す水により水処理用膜を洗浄す
るのがよい。<19> In any one of the above items <11> to <17>, the first temperature of the water to be treated may be from 20 to 10.
0 ° C., wherein at the first temperature the environment-responsive polymer shrinks, exhibits hydrophobicity and adsorbs hydrophobic substances,
This removes the hydrophobic material from the water to be treated, the second temperature of the water flowing in the opposite direction is lower than the first temperature and between 0 and 75 ° C., at which the environmental response It is preferred that the water-soluble membrane be swollen, exhibit hydrophilicity and desorb hydrophobic substances, and the water treatment membrane be washed with water flowing in the opposite direction.
【００１７】[0017]
【発明の実施の形態】以下、本発明をより詳細に説明す
る。本発明の水処理用膜は、多孔性基材表面に環境応答
性ポリマーを付着してなる。本発明の水処理用膜に用い
られる多孔性基材は、水に耐久性を有する材料であれ
ば、いかなる材料も用いることができ、特に制限されな
い。BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail. The water treatment membrane of the present invention is obtained by attaching an environment-responsive polymer to the surface of a porous substrate. As the porous substrate used for the water treatment membrane of the present invention, any material can be used as long as it has durability to water, and is not particularly limited.
【００１８】多孔性基材の多孔性は、目的とする水処理
速度に依存するが、環境応答性ポリマーを付着させた状
態で、細孔径が１０〜１０００μｍ、好ましくは５０〜
５００μｍとなるように、その多孔性が設計されてなる
のがよい。具体的には、多孔性基材は、孔径が１０００
μｍ以下、好ましくは０．０１〜１００μｍ、より好ま
しくは０．１〜１０μｍである連通孔を有するのがよ
い。The porosity of the porous substrate depends on the target water treatment rate, but the pore size is 10 to 1000 μm, preferably 50 to 1000 μm with the environment-responsive polymer attached.
The porosity is preferably designed to be 500 μm. Specifically, the porous substrate has a pore size of 1000
It is preferable to have a communication hole of not more than μm, preferably 0.01 to 100 μm, more preferably 0.1 to 10 μm.
【００１９】本発明の水処理用膜は、多孔性基材表面に
環境応答性ポリマーを付着してなる。該環境応答性ポリ
マーは、多孔性基材の表面に、種々の形態で付着されて
いればよく、好ましくは該ポリマーは、多孔性基材表面
と化学結合を介して付着されているのがよい。化学結合
を介して付着される形態として、ポリマーが基材表面に
グラフト結合するのがよい。なお、多孔性基材の孔は連
通孔であるのがよい。また、多孔性基材の表面とは、基
材のすべての表面を意味し、連通孔の表面をも含む意で
ある。The water treatment membrane of the present invention is obtained by attaching an environmentally responsive polymer to the surface of a porous substrate. The environmentally responsive polymer may be attached to the surface of the porous substrate in various forms, and preferably, the polymer is attached to the surface of the porous substrate via a chemical bond. . As a form to be attached via a chemical bond, the polymer is preferably graft-bonded to the surface of the base material. The pores of the porous substrate are preferably communication holes. Further, the surface of the porous substrate means all surfaces of the substrate, and includes the surface of the communication hole.
【００２０】本発明の水処理用膜に用いられる環境応答
性ポリマーは、物理的環境又は化学的環境により、親疎
水性が可逆的に変化するのがよい。物理的環境とは、温
度、光量、磁場、電場等を意味し、化学的環境とは、処
理すべき水又は水処理用膜の洗浄液のｐＨ、塩濃度、及
び組成等を意味する。特に、環境応答性ポリマーは、物
理的環境、特に温度又は光量により、親疎水性が可逆的
に変化するのがよい。The environmentally responsive polymer used in the water treatment membrane of the present invention preferably has its hydrophilicity / hydrophobicity reversibly changed depending on a physical environment or a chemical environment. The physical environment means a temperature, a light amount, a magnetic field, an electric field and the like, and the chemical environment means a pH, a salt concentration, a composition and the like of water to be treated or a cleaning solution of a water treatment membrane. In particular, the environmentally responsive polymer may have its hydrophilicity / hydrophobicity reversibly change depending on the physical environment, particularly temperature or light quantity.
【００２１】環境応答性ポリマーとして、物理的環境変
化、特に温度変化により応答するポリマーを挙げること
ができる。特に、温度により変化が生じるポリマーとし
て、アクリルアミド系ポリマーを挙げることができる。
このポリマーは、相対的に高温で疎水性を示し且つ収縮
する一方、相対的に低温で親水性を示し膨潤する特性を
有する。アクリルアミド系ポリマーとして、３２℃付近
を境に可逆的な親疎水性変化を示すポリ（Ｎ−イソプロ
ピルアクリルアミド）、７２℃付近を境に可逆的な親疎
水性変化を示すポリ（Ｎ−エチルアクリルアミド）、２
７℃付近を境に可逆的な親疎水性変化を示すポリ（Ｎ−
ｎ−プロピルメタアクリルアミド）、４３℃付近を境に
可逆的な親疎水性変化を示すポリ（Ｎ−イソプロピルメ
タアクリルアミド、５６℃付近を境に可逆的な親疎水性
変化を示すポリ（Ｎ−アクリルピロリジン）等を挙げる
ことができる。Examples of the environmentally responsive polymer include polymers that respond to changes in the physical environment, particularly to changes in temperature. In particular, examples of the polymer that changes depending on the temperature include an acrylamide-based polymer.
The polymer has the property of being hydrophobic and shrink at relatively high temperatures, while being hydrophilic and swelling at relatively low temperatures. As an acrylamide polymer, poly (N-isopropylacrylamide) showing a reversible hydrophilic / hydrophobic change around 32 ° C., poly (N-ethylacrylamide) showing a reversible hydrophilic / hydrophilic change around 72 ° C., 2
Poly (N-) showing a reversible hydrophilic / hydrophobic change around 7 ° C
n-propylmethacrylamide), poly (N-isopropylmethacrylamide) exhibiting reversible hydrophilic / hydrophobic change around 43 ° C., poly (N-acrylpyrrolidine) exhibiting reversible hydrophilic / hydrophobic change around 56 ° C. And the like.
【００２２】上記の温度により変化が生じる環境応答性
ポリマーのうち、ポリ（Ｎ−イソプロピルアクリルアミ
ド）は、親疎水性、及びそれによる疎水性物質の吸脱着
のコントロールが工業規模で行いやすいという点で、好
適である。Poly (N-isopropylacrylamide) is one of the environmentally responsive polymers whose temperature is changed by the above-mentioned temperature. It is suitable.
【００２３】光照射により変化が生じる環境応答性ポリ
マーとして、アゾ基を側鎖に持つ高分子を挙げることが
できる。例えば、アゾ基を側鎖に持つ高分子は、紫外線
照射により、シス−トランスの異性変化を可逆的に起こ
し、物質との親和性が変化する。このため、上記物質を
除去すべき対象物質として、紫外線照射の有無によっ
て、除去すべき物質の吸脱着を行うことができ、これを
水処理に応用することができる。Examples of the environmentally responsive polymer which is changed by light irradiation include a polymer having an azo group in a side chain. For example, a polymer having an azo group in a side chain causes reversible cis-trans isomerization upon irradiation with ultraviolet light, thereby changing the affinity with a substance. For this reason, as a target substance to be removed, the substance to be removed can be absorbed and desorbed depending on the presence or absence of ultraviolet irradiation, and this can be applied to water treatment.
【００２４】本発明の水処理用膜は、いかなる形状であ
ってもよい。例えば、平膜上、中空糸状、管状、膜状な
どの形状を挙げることができるが、これらに限定されな
い。また、本発明の水処理用膜の厚さは、特に限定され
ず、例えば一般に厚さが１μｍ〜１０００μｍである
膜、一般に厚さが１００μｍ〜１００ｃｍである不織布
などを用いることができる。The water treatment membrane of the present invention may have any shape. For example, shapes such as a flat membrane, a hollow fiber shape, a tubular shape, and a membrane shape can be exemplified, but the shape is not limited thereto. The thickness of the water treatment film of the present invention is not particularly limited, and for example, a film having a thickness of generally 1 μm to 1000 μm, a nonwoven fabric having a thickness of generally 100 μm to 100 cm, or the like can be used.
【００２５】本発明は、上記水処理用膜を用いて、水を
処理する方法も提供する。本発明の方法における「水処
理」の「水」とは、上水及び下水に拘わらず、いかなる
水をも包含する。また、「水処理」の「処理」とは、具
体的には、大きな分子を濾去し、膜を透過する可能性の
ある分子、即ち小さな分子を吸着して除去することを意
味する。なお、大きな分子の濾去は、上記水処理用膜の
連通孔を透過できないことによって達成することができ
る。The present invention also provides a method for treating water using the above-mentioned water treatment membrane. The “water” of the “water treatment” in the method of the present invention includes any water regardless of tap water and sewage. The term “treatment” in “water treatment” specifically means that large molecules are removed by filtration, and molecules that may pass through the membrane, that is, small molecules are adsorbed and removed. The filtration of large molecules can be achieved by impermeability through the communication holes of the water treatment membrane.
【００２６】本発明の水の処理方法は、具体的には、水
処理工程、及び水処理用膜の洗浄工程を有する。水処理
工程は、上記水処理用膜に、処理すべき水を流して水処
理用膜を透過させて水を処理する。これにより、上述の
ように、大きな分子が濾去される。また、この際、水処
理用膜に設けられる環境応答性ポリマーの特性により、
小さな分子を吸着し、該小さな分子と水とが分離され
る。このように、大きな分子と小さな分子とが除去され
た状態の水が上記水処理用膜を透過する。The water treatment method of the present invention specifically includes a water treatment step and a water treatment membrane cleaning step. In the water treatment step, water to be treated flows through the water treatment membrane, and the water is permeated through the water treatment membrane to treat the water. This filters out large molecules as described above. At this time, due to the characteristics of the environment-responsive polymer provided in the water treatment membrane,
The small molecules are adsorbed and the small molecules are separated from water. Thus, the water from which the large molecules and the small molecules have been removed passes through the water treatment membrane.
【００２７】この水処理工程を長期に亘って行うと、大
きな分子及び／又は小さな分子により、膜透過（フラッ
クス）の程度が衰えてくる。ここで、水処理用膜の洗浄
工程を行う。洗浄工程を行う時期は、処理すべき水の流
量、処理すべき水に含まれる大きな分子及び／又は小さ
な分子の量などに依存するが、一般的に、定期的に行う
のが好ましい。If this water treatment step is performed for a long time, large molecules and / or small molecules reduce the degree of membrane permeation (flux). Here, a step of cleaning the water treatment membrane is performed. When to perform the washing step depends on the flow rate of the water to be treated, the amount of large molecules and / or small molecules contained in the water to be treated, and the like, but it is generally preferable to perform the washing step periodically.
【００２８】洗浄工程は、上記環境応答性ポリマーの特
性を反転させる外部環境を与えるのがよい。具体的に
は、温度により変化が生じる環境応答性ポリマーの場
合、温度を変化させるのがよい。より具体的には、３２
℃付近を境に可逆的な親疎水性変化を示すポリ（Ｎ−イ
ソプロピルアクリルアミド）の場合、次のように行うの
がよい。The washing step preferably provides an external environment that inverts the characteristics of the environment-responsive polymer. Specifically, in the case of an environment-responsive polymer that changes with temperature, it is preferable to change the temperature. More specifically, 32
In the case of poly (N-isopropylacrylamide) showing a reversible change in hydrophilicity / hydrophobicity around a temperature of around ° C., it is preferable to carry out as follows.
【００２９】即ち、水処理工程での水の温度（「第１の
温度」と記載する場合がある）を２０℃〜１００℃、好
ましくは２５〜５０℃、より好ましくは２５〜４０℃と
するのがよい。好ましくは、第１の温度は、用いる温度
により親水性から疎水性へと可逆的に変化する環境応答
性ポリマーの該変化温度以上であるのがよい。例えば、
環境応答性ポリマーとしてポリ（Ｎ−イソプロピルアク
リルアミド）を用いる場合、第１の温度は、３２℃以
上、好ましくは３５〜４０℃であるのがよい。この温度
で、環境応答性ポリマーとしてのポリ（Ｎ−イソプロピ
ルアクリルアミド）は疎水性を示し、そのため疎水性物
質、例えば界面活性剤、イオン又は内分泌攪乱物質（い
わゆる環境ホルモン）などを吸着することができる。That is, the temperature of water in the water treatment step (sometimes referred to as “first temperature”) is 20 ° C. to 100 ° C., preferably 25 ° C. to 50 ° C., and more preferably 25 ° C. to 40 ° C. Is good. Preferably, the first temperature is equal to or higher than the temperature at which the environment-responsive polymer reversibly changes from hydrophilic to hydrophobic depending on the temperature used. For example,
When poly (N-isopropylacrylamide) is used as the environmentally responsive polymer, the first temperature is 32 ° C. or higher, and preferably 35 to 40 ° C. At this temperature, poly (N-isopropylacrylamide) as an environmentally responsive polymer exhibits hydrophobicity, so that it can adsorb hydrophobic substances such as surfactants, ions or endocrine disruptors (so-called environmental hormones). .
【００３０】次いで、定期的に、洗浄工程を行う。洗浄
工程での、水の温度（「第２の温度」と記載する場合が
ある）は、第１の温度よりも低く且つ０〜７５℃、好ま
しくは１０〜３０℃、より好ましくは１５〜２５℃とす
るのがよい。好ましくは、用いる温度により疎水性から
親水性へと可逆的に変化する環境応答性ポリマーの該変
化温度以下であるのがよい。例えば、環境応答性ポリマ
ーとしてポリ（Ｎ−イソプロピルアクリルアミド）を用
いる場合、第２の温度は、３２℃以下、好ましくは１５
〜３０℃であるのがよい。この温度で、環境応答性ポリ
マーとしてのポリ（Ｎ−イソプロピルアクリルアミド）
は親水性を示し、そのため疎水性物質、例えば界面活性
剤、イオン又は内分泌攪乱物質（いわゆる環境ホルモ
ン）などを脱着することができる。また、この洗浄工程
において、単に、環境を変化させるだけでなく、水処理
工程での水の透過方向とは逆の方向から、上記温度の水
を流すのがよい。Next, a cleaning step is periodically performed. In the washing step, the temperature of water (sometimes described as “second temperature”) is lower than the first temperature and is 0 to 75 ° C., preferably 10 to 30 ° C., more preferably 15 to 25 ° C. ℃ is good. Preferably, the temperature is lower than the temperature at which the environment-responsive polymer reversibly changes from hydrophobic to hydrophilic depending on the temperature used. For example, when poly (N-isopropylacrylamide) is used as the environment-responsive polymer, the second temperature is 32 ° C. or less, preferably 15 ° C. or less.
The temperature is preferably up to 30 ° C. At this temperature, poly (N-isopropylacrylamide) as an environmentally responsive polymer
Is hydrophilic, so that it can desorb hydrophobic substances such as surfactants, ions or endocrine disruptors (so-called environmental hormones). In this washing step, it is preferable to not only change the environment but also to flow the water at the above-mentioned temperature from a direction opposite to the direction of water permeation in the water treatment step.
【００３１】温度を第２の温度へと変化させることによ
り、環境応答性ポリマー（例えばポリ（Ｎ−イソプロピ
ルアクリルアミド））は、親水性を示す。このため、吸
着されていた疎水性物質は脱着される。また、環境応答
性ポリマー（例えばポリ（Ｎ−イソプロピルアクリルア
ミド））は親疎水性変化と共に、膨潤・収縮変化をも呈
する。即ち、環境応答性ポリマー（例えばポリ（Ｎ−イ
ソプロピルアクリルアミド））は、疎水性の際に収縮
し、親水性の際に膨潤する。この膨潤は、膜の連通孔を
閉じる作用をもたらす。このため、逆方向に流した水
を、透過方向に流れにくくする傾向が生じる。したがっ
て、膜の洗浄工程によって脱着した、低・中分子量の物
質が、該洗浄工程において膜を透過する可能性を低く抑
えることができる。By changing the temperature to the second temperature, the environment-responsive polymer (for example, poly (N-isopropylacrylamide)) becomes hydrophilic. Thus, the adsorbed hydrophobic substance is desorbed. In addition, an environmentally responsive polymer (for example, poly (N-isopropylacrylamide)) exhibits a swelling / shrinking change together with a hydrophilic / hydrophobic change. That is, an environment-responsive polymer (for example, poly (N-isopropylacrylamide)) shrinks when hydrophobic and swells when hydrophilic. This swelling has the effect of closing the communication holes of the membrane. For this reason, there is a tendency that water flowing in the opposite direction is less likely to flow in the permeation direction. Therefore, it is possible to reduce the possibility that the low- and medium-molecular-weight substances desorbed in the membrane washing step permeate the membrane in the washing step.
【００３２】図１は、上記水処理工程及び洗浄工程を模
式的に示した図である。高温（図１中、(A)）で水処理
工程を行い、この際に大きな分子４を濾去し、かつ小さ
な分子３、特にこの場合は疎水性物質を濾去する。処理
された水は図１(A)中、Ａの方向に流れる。次いで、低
温図１中、(B)）で洗浄工程を行う。その洗浄液の供給
方向（Ｂ方向）は、上記水処理工程の濾過方向（Ａ方
向）とは逆方向とする。このように工程を設けることに
より、水処理用膜のフラックスを低下させることなく、
所望の分子を水から除去することができる。FIG. 1 is a diagram schematically showing the water treatment step and the washing step. A water treatment step is carried out at an elevated temperature ((A) in FIG. 1), whereby the large molecules 4 are filtered off and the small molecules 3, in this case in particular hydrophobic substances, are filtered off. The treated water flows in the direction of A in FIG. Next, a cleaning step is performed at (B) in FIG. The supply direction (B direction) of the cleaning liquid is opposite to the filtration direction (A direction) in the water treatment step. By providing such a process, without lowering the flux of the water treatment membrane,
The desired molecules can be removed from the water.
【００３３】なお、上記において、温度により変化が生
じる環境応答性ポリマーについて詳述したが、他の環境
応答性ポリマーについても、同様な作用を示すように、
水の処理方法を設計することができる。In the above, the environmentally responsive polymer which changes depending on the temperature has been described in detail. However, other environmentally responsive polymers have the same effect as described above.
Water treatment method can be designed.
【００３４】[0034]
【実施例】以下、実施例を用いて本発明を具体的に説明
するが、実施例は単に例示であって、本発明を限定する
ものと解釈してはならない。EXAMPLES Hereinafter, the present invention will be described specifically with reference to Examples, but the Examples are merely illustrative and should not be construed as limiting the present invention.
【００３５】（実施例１） ＜水処理用膜の調製＞多孔性基材Ａとして、細孔径０．
３μｍ、膜厚１１０μｍ、空孔率６６％である、多孔性
の高密度ポリエチレンフィルムを用いた。また、重合モ
ノマーＢとして、興人（株）社製N-イソプロピルアクリ
ルアミド（以下「NIPAM」と略記する場合がある））を
用いた。なお、このモノマーＢを重合して得られるポリ
マーＣは、３２℃付近で可逆的な膨潤収縮および親疎水
性変化を示すポリマー、ポリ（N-イソプロピルアクリル
アミド）である。(Example 1) <Preparation of membrane for water treatment>
A porous high-density polyethylene film having a thickness of 3 μm, a thickness of 110 μm, and a porosity of 66% was used. Further, N-isopropylacrylamide (hereinafter sometimes abbreviated as “NIPAM”) manufactured by Kojin Co., Ltd. was used as the polymerization monomer B. The polymer C obtained by polymerizing the monomer B is a polymer that exhibits reversible swelling / shrinking and a change in hydrophilicity / hydrophobicity at around 32 ° C., which is poly (N-isopropylacrylamide).
【００３６】基材にラジカルを生成させるプラズマ照射
反応と、そのラジカルからグラフト的にモノマーＢを重
合するグラフト重合反応の二段階に分けて、製膜を行っ
た。第一段階、即ちプラズマ照射反応は、Ａｒ雰囲気下
（１０Ｐａ）で上記基材Ａ（膜面積７×７ｃｍ）にプラ
ズマを所定時間６０秒、所定電力３０Ｗで照射し、ラジ
カルを生成させた。Film formation was performed in two stages, a plasma irradiation reaction for generating radicals on the substrate and a graft polymerization reaction for polymerizing monomer B from the radicals. In the first stage, that is, the plasma irradiation reaction, the substrate A (film area 7 × 7 cm) was irradiated with plasma at a predetermined power of 30 W for a predetermined time of 60 seconds in an Ar atmosphere (10 Pa) to generate radicals.
【００３７】第二段階であるグラフト重合反応は、この
ラジカルとモノマーＢとを接触させ、グラフト的に反応
を行った。基材Ａが空気と接触しないように、Ａｒ雰囲
気下（１０Ｐａ）のままで、所定濃度のモノマーＢの溶
液と基材Ａとを液相で接触させ、所定温度（３０℃）で
所定時間グラフト重合反応を行った。この結果、水処理
用膜Ｘを得た。第一段階及び第二段階での諸条件を表１
（表１−１及び１−２）にまとめる。In the second stage, the graft polymerization reaction, the radical was brought into contact with the monomer B, and the reaction was carried out like a graft. In order to prevent the substrate A from coming into contact with air, a solution of the monomer B having a predetermined concentration is brought into contact with the substrate A in a liquid phase under an Ar atmosphere (10 Pa), and grafting is performed at a predetermined temperature (30 ° C.) for a predetermined time. A polymerization reaction was performed. As a result, a water treatment membrane X was obtained. Table 1 shows the conditions in the first and second stages.
(Tables 1-1 and 1-2) are summarized.
【００３８】[0038]
【表１】 [Table 1]
【００３９】得られた水処理用膜Ｘの透過型ＦＴ−ＩＲ
を調べた結果、基材ＡにモノマーＢがグラフト重合した
ことが確認された。Transmission FT-IR of the obtained water treatment membrane X
As a result, it was confirmed that the monomer B was graft-polymerized on the substrate A.
【００４０】＜膜透過実験１＞水処理用膜Ｘについて、
粒子径が０．８μｍであるポリメチルメタクリレート
（ＰＭＭＡ）を５重量％含有する懸濁液Ｄ（溶媒：水）
を用いて、膜透過実験を行った。懸濁液Ｄを４０℃で供
給し、濾過を行った。一定時間、即ち１０分間隔で２５
℃の純水を供給側、即ち上記懸濁液と同方向に流すサー
モショック法と、２５℃の純水を透過側から供給側に流
す、即ち透過方向とは逆方向に流すサーモショック逆洗
法をそれぞれ検討した。<Membrane Permeation Experiment 1> Regarding the membrane X for water treatment,
Suspension D containing 5% by weight of polymethyl methacrylate (PMMA) having a particle diameter of 0.8 μm (solvent: water)
Was used to conduct a membrane permeation experiment. Suspension D was supplied at 40 ° C., and filtration was performed. 25 for a fixed time, that is, every 10 minutes
The thermoshock method in which pure water at 25 ° C is supplied in the same direction as the suspension, and the thermoshock backwash in which pure water at 25 ° C flows from the permeate side to the supply side, ie, flows in the opposite direction to the permeate direction. Each method was examined.
【００４１】図２は、上記サーモショック法とサーモシ
ョック逆洗法との結果を示すグラフである。黒丸はサー
モショック法をプロットし、白丸はサーモショック逆洗
法をプロットする。図２において、サーモショック法
は、０分から１０分までの間、フラックスが減衰し、１
０分経過時にサーモショックを施すと、さらにフラック
スが減少することがわかる。これは、懸濁液中のＰＭＭ
Ａが細孔に阻止され膜面に堆積し、その結果、透過を阻
害しフラックスを低下させていることによるものと考え
られる。また、サーモショックを与えると、膜のポリ
（ＮＩＰＡＭ）が膨潤し、透過を阻害することがわか
る。FIG. 2 is a graph showing the results of the thermoshock method and the thermoshock backwash method. The closed circles plot the thermoshock method, and the open circles plot the thermoshock backwash method. In FIG. 2, in the thermoshock method, the flux is attenuated from 0 to 10 minutes, and
It can be seen that applying a thermoshock after 0 minutes further reduces the flux. This is the PMM in suspension
It is considered that A was blocked by the pores and deposited on the film surface, and as a result, permeation was inhibited and the flux was reduced. Further, it can be seen that when a thermoshock is applied, poly (NIPAM) in the membrane swells and inhibits permeation.
【００４２】一方、サーモショック逆洗法は、０分から
１０分までの間、サーモショック法と同様に、そのフラ
ックスが徐々に減衰していることがわかる。但し、サー
モショック逆洗法は、１０分経過時に２５℃の水を透過
方向とは逆方向に流すことにより、フラックスが回復す
ることがわかる。これは、透過を阻害していたＰＭＭＡ
の堆積層が、逆洗により剥がれ、水処理用膜が洗浄され
たことによる。その後の各１０分間は、０〜１０分と同
様の挙動を示すが、１０分毎に洗浄（カーモショック逆
洗）工程を行うことにより、そのフラックスが回復し、
水処理用膜が洗浄されていることがわかる。On the other hand, in the thermoshock backwash method, the flux is gradually attenuated from 0 minutes to 10 minutes, as in the thermoshock method. However, in the thermoshock backwashing method, it was found that the flux was recovered by flowing water at 25 ° C. in the direction opposite to the permeation direction after 10 minutes. This is because PMMA was blocking permeation
This is due to the fact that the deposited layer was peeled off by back washing and the water treatment film was washed. The subsequent 10 minutes show the same behavior as 0 to 10 minutes, but by performing the washing (carmoshock backwashing) step every 10 minutes, the flux is recovered,
It can be seen that the water treatment membrane has been washed.
【００４３】＜膜透過実験２＞水処理用膜Ｘについて、
低・中分子量物質の吸脱着に関する膜透過実験２を行っ
た。用いた膜Ｘは、重合量０．１２ｍｇ／ｃｍ２である
膜を２枚重ねたものであった。低・中分子量物質のモデ
ルとして、非イオン性界面活性剤ポリ（オキシエチレン
ノニルフェニルエーテル）（分子量６６０．１、NP-10
（ニッコー化学社製））を用いた。<Membrane Permeation Experiment 2> Regarding the membrane X for water treatment,
A membrane permeation experiment 2 on adsorption and desorption of low and medium molecular weight substances was performed. The film X used was obtained by stacking two films having a polymerization amount of 0.12 mg / cm 2 . Non-ionic surfactant poly (oxyethylene nonylphenyl ether) (molecular weight 660.1, NP-10
(Manufactured by Nikko Chemicals)).
【００４４】供給液として、上記NP-10の３００ｐｐｍ
水溶液を用いた。供給液の温度を、所定時間、膜Ｘに含
まれるポリ（ＮＩＰＡＭ）の相転移点（約３２℃）より
も高温（３８℃）とし、その後、所定時間、低温（２０
℃）として、膜Ｘに該供給液を透過させ、膜表面におけ
るNP-10の吸脱着現象を確認した。なお、操作圧力は、
高温時０．２５ｋｇ／ｃｍ２であり、低温時０．５ｋｇ
／ｃｍ２であった。図３は、膜透過実験２の結果である
吸脱着現象を示すグラフである。図３は、横軸に時間、
左縦軸に白丸が示す透過フラックス（ｋｇ・ｍ−２・ｈ
−１）、及び右縦軸に黒丸が示す透過液のNP-10濃度
（ｐｐｍ）を示し、上部に記載する「３８℃」及び「２
０℃」はその時間における供給液の温度を示す。As the supply liquid, 300 ppm of the above NP-10
An aqueous solution was used. The temperature of the supply liquid is set to a temperature (38 ° C.) higher than the phase transition point (about 32 ° C.) of the poly (NIPAM) contained in the film X for a predetermined time, and then the temperature is set to a low temperature (20 ° C.) for a predetermined time.
° C), the supply liquid was permeated through the membrane X, and the adsorption and desorption of NP-10 on the membrane surface was confirmed. The operating pressure is
0.25 kg / cm 2 at high temperature and 0.5 kg at low temperature
/ Cm 2 . FIG. 3 is a graph showing the adsorption / desorption phenomenon as a result of the membrane permeation experiment 2. FIG. 3 shows time on the horizontal axis,
The permeation flux ( kgm -2h
-1 ), and the NP-10 concentration (ppm) of the permeate indicated by black circles on the right vertical axis, and "38 ° C."
“0 ° C.” indicates the temperature of the supply liquid at that time.
【００４５】図３の透過フラックス（白丸）を見ると、
低温（２０℃）時に透過性が低く、高温（３８℃）時に
透過性が高いことがわかる。これは、ポリ（ＮＩＰＡ
Ｍ）の挙動、即ち低温時に膨潤し（透過性を減少さ
せ）、高温時に収縮する（透過性を増大させる）挙動と
一致する。また、図３の透過液のNP-10濃度（黒丸）を
見ると、高温（３８℃）時、特に高温へと切り替えた当
初、NP-10濃度が低くなることがわかる。これは、高温
時、ポリ（ＮＩＰＡＭ）が疎水性を示し、NP-10を吸着
するためと考えられる。高温を持続すると、透過液のNP
-10の濃度が徐々に高まり、供給液の濃度と同程度にな
ることがわかる。これは、ポリ（ＮＩＰＡＭ）の吸着能
以上に、NP-10が供給されたことによるものと考えられ
る。Looking at the transmission flux (open circle) in FIG.
It can be seen that the permeability is low at low temperatures (20 ° C.) and high at high temperatures (38 ° C.). This is a poly (NIPA
This is consistent with the behavior of M), that is, the behavior of swelling (reducing permeability) at low temperatures and contracting (increase permeability) at high temperatures. Also, the NP-10 concentration (solid circle) of the permeate shown in FIG. 3 indicates that the NP-10 concentration becomes low at a high temperature (38 ° C.), especially at the beginning of switching to a high temperature. This is considered to be because poly (NIPAM) exhibits hydrophobicity at high temperature and adsorbs NP-10. If the high temperature is maintained, the NP
It can be seen that the concentration of -10 gradually increases and becomes almost equal to the concentration of the supply liquid. This is considered to be due to the fact that NP-10 was supplied beyond the ability to adsorb poly (NIPAM).
【００４６】また、低温（２０℃）時、特に低温へと切
り替えた当初、透過液のNP-10濃度が著しく増大するこ
とがわかる。これは、低温時、ポリ（ＮＩＰＡＭ）が親
水性を示し、NP-10を急激に脱着するためと考えられ
る。以上の現象は、温度サイクルを重ねても確認される
ことが図３からわかる。It can also be seen that at low temperatures (20 ° C.), especially at the beginning of switching to low temperatures, the NP-10 concentration of the permeate increases significantly. This is considered to be because poly (NIPAM) exhibits hydrophilicity at a low temperature and rapidly desorbs NP-10. It can be seen from FIG. 3 that the above phenomenon is confirmed even after repeated temperature cycles.
【００４７】透過実験１及び２から、処理すべき水の温
度、膜の洗浄する際の温度、及び水流方向を制御するこ
とにより、低・中分子量物質を吸脱着させ且つ大分子量
物質を除去する膜の洗浄工程を有する水処理方法を提供
できることがわかる。From the permeation experiments 1 and 2, low and medium molecular weight substances are adsorbed and desorbed and large molecular weight substances are removed by controlling the temperature of the water to be treated, the temperature at which the membrane is washed, and the direction of the water flow. It can be seen that a water treatment method having a membrane washing step can be provided.
【００４８】[0048]
【発明の効果】本発明により、低・中分子量の物質を除
去できる吸着法を用い、且つ有機溶剤などの不所望な溶
媒を上水道に混入させずに該低・中分子量の物質を脱着
させる洗浄工程を有する、簡便な方法を提供することが
できる。According to the present invention, washing is performed by using an adsorption method capable of removing low and medium molecular weight substances, and desorbing the low and medium molecular weight substances without mixing an undesired solvent such as an organic solvent into the water supply. A simple method having steps can be provided.
【図１】 本発明の水処理方法を模式的に示す図であ
る。FIG. 1 is a view schematically showing a water treatment method of the present invention.
【図２】 膜透過実験１における、サーモショック法と
サーモショック逆洗法との結果を示すグラフである。FIG. 2 is a graph showing the results of a thermoshock method and a thermoshock backwash method in a membrane permeation experiment 1.
【図３】 膜透過実験２の結果である吸脱着現象を示す
グラフである。FIG. 3 is a graph showing an adsorption / desorption phenomenon as a result of a membrane permeation experiment 2.
１ 基材、 ２ 環境応答性ポリマー、 ２’ 膨潤し
た環境応答性ポリマー、 ３ 小さな分子、 ４ 大き
な分子。1 base material, 2 environment-responsive polymer, 2 'swollen environment-responsive polymer, 3 small molecule, 4 large molecule.
フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｂ０１Ｊ 20/26 Ｂ０１Ｊ 20/26 Ｂ 20/28 20/28 Ｚ 20/34 20/34 Ｇ Ｈ Ｃ０２Ｆ 1/28 Ｃ０２Ｆ 1/28 Ａ Ｃ０８Ｊ 7/04 ＣＥＳ Ｃ０８Ｊ 7/04 ＣＥＳＺ // Ｃ０８Ｌ 23:02 Ｃ０８Ｌ 23:02 Ｆターム(参考） 4D006 GA07 KA87 KB30 KC15 KC27 MA01 MA02 MA03 MA06 MA31 MB09 MB10 MB14 MB19 MC23X MC54X NA43 NA45 PB06 PB59 4D024 AA02 AB04 BA17 BB08 DA03 DA07 DB05 4F006 AA12 AA51 AB12 BA00 CA09 DA00 4G066 AC13C AC33B AD11B AE20 BA03 CA01 CA04 FA07 GA11 GA27 Continued on the front page (51) Int.Cl. 7 Identification symbol FI Theme coat II (reference) B01J 20/26 B01J 20/26 B 20/28 20/28 Z 20/34 20/34 GH C02F 1/28 C02F 1 / 28 A C08J 7/04 CES C08J 7/04 CESZ // C08L 23:02 C08L 23:02 F-term (reference) 4D006 GA07 KA87 KB30 KC15 KC27 MA01 MA02 MA03 MA06 MA31 MB09 MB10 MB14 MB19 MC23X MC54X NA43 NA45 PB024 PB59 AA02 AB04 BA17 BB08 DA03 DA07 DB05 4F006 AA12 AA51 AB12 BA00 CA09 DA00 4G066 AC13C AC33B AD11B AE20 BA03 CA01 CA04 FA07 GA11 GA27
Claims (19)
付着してなる水処理用膜に環境変化を施し且つ水を処理
する方向とは逆方向に水を流して該水処理用膜を洗浄す
る工程を有する水処理用膜の洗浄方法。1. A method for subjecting a water treatment film obtained by attaching an environment-responsive polymer to the surface of a porous base material to environmental change and flowing water in a direction opposite to a direction in which the water is treated to form the water treatment film. A method for cleaning a water treatment membrane, comprising a step of cleaning.
付着してなる水処理用膜に処理すべき水を流して水処理
用膜を透過させて水を処理する水処理工程、及び前記水
処理用膜に環境変化を施し且つ前記水処理用膜の前記透
過方向とは逆方向に水を流して前記水処理用膜を洗浄す
る膜洗浄工程を有する水の処理方法。2. A water treatment step of flowing water to be treated through a water treatment membrane formed by adhering an environment-responsive polymer to the surface of a porous base material and permeating the water treatment membrane to treat the water; A water treatment method, comprising: subjecting a water treatment membrane to an environmental change and flowing a water in a direction opposite to the permeation direction of the water treatment membrane to wash the water treatment membrane.
基材表面と化学結合を介して付着される請求項２記載の
方法。3. The method according to claim 2, wherein the environment-responsive polymer is attached to the surface of the porous substrate through a chemical bond.
化により親疎水性が可逆的に変化する請求項２又は３記
載の方法。4. The method according to claim 2, wherein the environmentally responsive polymer reversibly changes in hydrophilicity / hydrophobicity due to the environmental change.
的環境変化である請求項４記載の方法。5. The method according to claim 4, wherein the environmental change is a physical environmental change or a chemical environmental change.
により、親疎水性が可逆的に変化する請求項４記載の方
法。6. The method according to claim 4, wherein said environment-responsive polymer reversibly changes in hydrophilicity / hydrophobicity depending on a physical environment.
親疎水性が可逆的に変化するアクリルアミド系ポリマー
である請求項２〜６のいずれか１項記載の方法。7. The method according to claim 2, wherein the environment-responsive polymer is an acrylamide-based polymer whose hydrophilicity / hydrophobicity reversibly changes with temperature.
（N-イソプロピルアクリルアミド）である請求項７記載
の方法。8. The method according to claim 7, wherein the acrylamide-based polymer is poly (N-isopropylacrylamide).
１の温度が２０〜１００℃であり、該第１の温度におい
て前記環境応答性ポリマーは疎水性を示し且つ疎水性物
質を吸着し、これにより処理すべき水から前記疎水性物
質が除去され、洗浄工程において、逆方向に流す水の第
２の温度は第１の温度よりも低く且つ０〜７５℃であ
り、該第２の温度において前記環境応答性ポリマーは親
水性を示し且つ疎水性物質を脱着し、逆方向に流す水に
より水処理用膜を洗浄する請求項２〜８のいずれか１項
記載の方法。9. In the water treatment step, the first temperature of the water to be treated is 20 to 100 ° C., at which the environment-responsive polymer exhibits hydrophobicity and adsorbs a hydrophobic substance. Wherein the hydrophobic substance is removed from the water to be treated, and in the washing step, the second temperature of the water flowing in the reverse direction is lower than the first temperature and 0 to 75 ° C .; The method according to any one of claims 2 to 8, wherein at temperature the environment-responsive polymer is hydrophilic and desorbs hydrophobic substances, and the water treatment membrane is washed with water flowing in the opposite direction.
第１の温度が２０〜１００℃であり、該第１の温度にお
いて前記環境応答性ポリマーは収縮し、疎水性を示し且
つ疎水性物質を吸着し、これにより処理すべき水から前
記疎水性物質が除去され、洗浄工程において、逆方向に
流す水の第２の温度は第１の温度よりも低く且つ０〜７
５℃であり、該第２の温度において前記環境応答性ポリ
マーは膨潤し、親水性を示し且つ疎水性物質を脱着し、
逆方向に流す水により水処理用膜を洗浄する請求項２〜
８のいずれか１項記載の方法。10. In the water treatment step, the first temperature of the water to be treated is 20 to 100 ° C., at which the environment-responsive polymer shrinks, exhibits hydrophobicity and is hydrophobic. , Whereby the hydrophobic substance is removed from the water to be treated. In the washing step, the second temperature of the water flowing in the opposite direction is lower than the first temperature and 0 to 7
5 ° C., at which temperature the environmentally responsive polymer swells, exhibits hydrophilicity and desorbs hydrophobic substances,
The water treatment membrane is washed with water flowing in the reverse direction.
9. The method according to any one of 8 above.
を付着してなる水処理用膜であって、処理すべき水を流
す際に該水処理用膜を透過して水を処理し、該水処理用
膜の洗浄する際、水処理用膜は環境変化が施され且つ前
記水処理用膜の前記透過方向とは逆方向に水を流して前
記水処理用膜を洗浄することを特徴とする水処理用膜。11. A water treatment membrane comprising an environment-responsive polymer adhered to a surface of a porous substrate, wherein the water to be treated is passed through the water treatment membrane to treat water, When washing the water treatment membrane, the water treatment membrane is subjected to an environmental change, and the water is washed by flowing water in a direction opposite to the transmission direction of the water treatment membrane. For water treatment.
性基材表面と化学結合を介して付着される請求項１１記
載の水処理用膜。12. The water treatment membrane according to claim 11, wherein the environment-responsive polymer is attached to the surface of the porous substrate through a chemical bond.
変化により親疎水性が可逆的に変化する請求項１１又は
１２記載の水処理用膜。13. The water treatment membrane according to claim 11, wherein the environmentally responsive polymer reversibly changes in hydrophilicity / hydrophobicity due to the environmental change.
学的環境変化である請求項１３記載の水処理用膜。14. The water treatment membrane according to claim 13, wherein the environmental change is a physical environmental change or a chemical environmental change.
境により、親疎水性が可逆的に変化する請求項１３記載
の水処理用膜。15. The water treatment membrane according to claim 13, wherein the hydrophilicity of the environment-responsive polymer is reversibly changed depending on a physical environment.
り親疎水性が可逆的に変化するアクリルアミド系ポリマ
ーである請求項１１〜１５のいずれか１項記載の水処理
用膜。16. The water treatment membrane according to claim 11, wherein the environment-responsive polymer is an acrylamide-based polymer whose hydrophilicity / hydrophobicity reversibly changes with temperature.
（N-イソプロピルアクリルアミド）である請求項１６記
載の水処理用膜。17. The water treatment membrane according to claim 16, wherein the acrylamide-based polymer is poly (N-isopropylacrylamide).
００℃であり、該第１の温度において前記環境応答性ポ
リマーは疎水性を示し且つ疎水性物質を吸着し、これに
より処理すべき水から前記疎水性物質が除去され、逆方
向に流す水の第２の温度は第１の温度よりも低く且つ０
〜７５℃であり、該第２の温度において前記環境応答性
ポリマーは親水性を示し且つ疎水性物質を脱着し、逆方
向に流す水により水処理用膜を洗浄する請求項１１〜１
７のいずれか１項記載の水処理用膜。18. The first temperature of the water to be treated is 20 to 1
00 ° C., at the first temperature the environment-responsive polymer is hydrophobic and adsorbs hydrophobic substances, whereby the hydrophobic substances are removed from the water to be treated and the water flowing in the opposite direction The second temperature is lower than the first temperature and 0
-75 ° C., wherein at the second temperature the environment-responsive polymer exhibits hydrophilicity and desorbs hydrophobic substances, and the water treatment membrane is washed with water flowing in the reverse direction.
The membrane for water treatment according to any one of Claims 7 to 7.
００℃であり、該第１の温度において前記環境応答性ポ
リマーは収縮し、疎水性を示し且つ疎水性物質を吸着
し、これにより処理すべき水から前記疎水性物質が除去
され、逆方向に流す水の第２の温度は第１の温度よりも
低く且つ０〜７５℃であり、該第２の温度において前記
環境応答性ポリマーは膨潤し、親水性を示し且つ疎水性
物質を脱着し、逆方向に流す水により水処理用膜を洗浄
する請求項１１〜１７のいずれか１項記載の水処理用
膜。19. The first temperature of the water to be treated is 20 to 1
00 ° C., at which temperature the environmentally responsive polymer shrinks, exhibits hydrophobicity and adsorbs hydrophobic substances, thereby removing the hydrophobic substances from the water to be treated and in the opposite direction The second temperature of the flowing water is lower than the first temperature and between 0 and 75 ° C., at which the environment-responsive polymer swells, shows hydrophilicity and desorbs hydrophobic substances, The water treatment membrane according to any one of claims 11 to 17, wherein the water treatment membrane is washed with water flowing in a reverse direction.
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|---|---|---|---|
| JP2001159733A JP2002346560A (en) | 2001-05-28 | 2001-05-28 | Method for treating water and membrane for water treatment |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001159733A JP2002346560A (en) | 2001-05-28 | 2001-05-28 | Method for treating water and membrane for water treatment |
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| Publication Number | Publication Date |
|---|---|
| JP2002346560A true JP2002346560A (en) | 2002-12-03 |
Family
ID=19003265
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2001159733A Pending JP2002346560A (en) | 2001-05-28 | 2001-05-28 | Method for treating water and membrane for water treatment |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007061677A (en) * | 2005-08-29 | 2007-03-15 | Toshiba Corp | Temperature-responsive hollow fiber membrane, temperature-responsive hollow fiber membrane module, and filtering device using the same |
| JP2007130532A (en) * | 2005-11-08 | 2007-05-31 | Toshiba Corp | Temperature responsive membrane, temperature responsive membrane module, and membrane filtration system using the same |
| JP2008229503A (en) * | 2007-03-20 | 2008-10-02 | Toshiba Corp | Membrane, membrane module and membrane filter system |
| US7662289B2 (en) | 2007-01-16 | 2010-02-16 | Nalco Company | Method of cleaning fouled or scaled membranes |
| JP2011152544A (en) * | 2011-05-02 | 2011-08-11 | Toshiba Corp | Membrane filtration system using temperature-responsive membrane |
| CN104190266A (en) * | 2014-09-12 | 2014-12-10 | 天津工业大学 | Method for regulating structure and properties of PVDF-g-PNIPAAm copolymer membrane |
| EP2760569A4 (en) * | 2011-09-28 | 2015-06-03 | Univ King Abdullah Sci & Tech | Grafted membranes and substrates having surfaces with switchable superoleophilicity and superoleophobicity and applications thereof |
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2001
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007061677A (en) * | 2005-08-29 | 2007-03-15 | Toshiba Corp | Temperature-responsive hollow fiber membrane, temperature-responsive hollow fiber membrane module, and filtering device using the same |
| JP2007130532A (en) * | 2005-11-08 | 2007-05-31 | Toshiba Corp | Temperature responsive membrane, temperature responsive membrane module, and membrane filtration system using the same |
| US7662289B2 (en) | 2007-01-16 | 2010-02-16 | Nalco Company | Method of cleaning fouled or scaled membranes |
| JP2008229503A (en) * | 2007-03-20 | 2008-10-02 | Toshiba Corp | Membrane, membrane module and membrane filter system |
| JP2011152544A (en) * | 2011-05-02 | 2011-08-11 | Toshiba Corp | Membrane filtration system using temperature-responsive membrane |
| EP2760569A4 (en) * | 2011-09-28 | 2015-06-03 | Univ King Abdullah Sci & Tech | Grafted membranes and substrates having surfaces with switchable superoleophilicity and superoleophobicity and applications thereof |
| US9708199B2 (en) | 2011-09-28 | 2017-07-18 | King Abdullah University Of Science And Technology | Grafted membranes and substrates having surfaces with switchable superoleophilicity and superoleophobicity and applications thereof |
| US10307716B2 (en) | 2011-09-28 | 2019-06-04 | King Abdullah University Of Science And Technology | Grafted membranes and substrates having surfaces with switchable superoleophilicity and superoleophobicity and applications thereof |
| JP2015186794A (en) * | 2014-03-10 | 2015-10-29 | 国立研究開発法人産業技術総合研究所 | Optical control technique for liquid film penetration |
| CN104190266A (en) * | 2014-09-12 | 2014-12-10 | 天津工业大学 | Method for regulating structure and properties of PVDF-g-PNIPAAm copolymer membrane |
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