JPH05245351A - Hollow fiber microfilter membrane and its production - Google Patents
Hollow fiber microfilter membrane and its productionInfo
- Publication number
- JPH05245351A JPH05245351A JP8468392A JP8468392A JPH05245351A JP H05245351 A JPH05245351 A JP H05245351A JP 8468392 A JP8468392 A JP 8468392A JP 8468392 A JP8468392 A JP 8468392A JP H05245351 A JPH05245351 A JP H05245351A
- Authority
- JP
- Japan
- Prior art keywords
- hollow fiber
- polyethylene
- ion exchange
- membrane
- fine particles
- 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
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
Description
【0001】[0001]
【産業上の利用分野】本発明は、液体中の懸濁物質とイ
オン性物質を共に除去できる中空繊維状精密濾過膜、例
えば原子力発電所などの用水に含まれるクラッド又は金
属イオンの除去などに有効な中空繊維状精密濾過膜及び
その製造方法に関するものである。BACKGROUND OF THE INVENTION The present invention relates to a hollow fiber microfiltration membrane capable of removing both suspended substances and ionic substances in a liquid, for example, removal of clad or metal ions contained in water used for nuclear power plants. The present invention relates to an effective hollow fiber microfiltration membrane and a method for producing the same.
【0002】[0002]
【従来の技術】従来のポリエチレン中空繊維状濾過膜
は、主に、除去したい物質の大きさと膜に存在する細孔
の大小とのふるいわけにより利用されている。そのた
め、粒径の小さい物質を除去するためには、膜の孔径を
小さくする必要がある。ところが、膜の孔径を小さくす
ると液の流量が小さくなる欠点がある。さらに、可溶性
のイオンを除去するには適していない。2. Description of the Related Art Conventional polyethylene hollow fiber filtration membranes are used mainly by sieving the size of the substance to be removed and the size of the pores present in the membrane. Therefore, in order to remove the substance having a small particle diameter, it is necessary to reduce the pore diameter of the membrane. However, there is a drawback that the flow rate of the liquid is reduced when the pore diameter of the membrane is reduced. Moreover, it is not suitable for removing soluble ions.
【0003】液体中の懸濁物質と可溶性の金属イオン等
を除去したい場合には、一般的に、精密濾過膜と、逆浸
透膜あるいはイオン交換樹脂塔とを併用する必要があ
る。しかし、特に原子力発電所においては、使用済み廃
棄物の問題や、安全性等からシステムの簡略化も望まれ
ており、懸濁物質と金属イオンを同時に除去できかつ液
の流量も大きいイオン交換性精密濾過膜の出現が期待さ
れている。In order to remove suspended substances and soluble metal ions in a liquid, it is generally necessary to use a microfiltration membrane and a reverse osmosis membrane or an ion exchange resin tower together. However, especially in nuclear power plants, it is desired to simplify the system due to the problems of used waste and safety, and it is possible to remove suspended substances and metal ions at the same time, and the flow rate of the liquid is large. The appearance of microfiltration membranes is expected.
【0004】イオン交換性膜については、従来、脱塩な
どに細孔のないイオン交換膜が利用されているが、精密
濾過膜に相当する孔径を有する膜については報告例は極
めて少ない。僅かに、ポリオレフィン精密濾過膜を電子
線照射した後、化学処理する(特開昭64−70108
号)等、後処理的にイオン交換能を付与する提案がなさ
れている。As ion exchange membranes, ion exchange membranes having no pores for desalting and the like have hitherto been used, but there have been very few reports of membranes having pore diameters corresponding to microfiltration membranes. The polyolefin microfiltration membrane is slightly irradiated with an electron beam and then chemically treated (Japanese Patent Laid-Open No. 64-70108).
No.) and the like have been proposed to give ion exchange capacity after treatment.
【0005】[0005]
【発明が解決しようとする課題】しかしながら、前記の
ような従来の方法は、基本となるポリオレフィンの水膨
潤性を招き、物性低下、流量低下が不可避である。さら
に、導入できる官能基の種類及び密度において著しい制
約があり、とても満足できるものは得難い。またこのよ
うな方法は工業的に実施する場合、設備、操作などの点
でも不利である。本発明者らは、このような従来の問題
点を解決すべく鋭意研究の結果、ポリエチレンの多孔性
中空繊維からなる多孔膜の多孔構造内に、吸着能やイオ
ン交換能を有する微粒子を分散させることにより、優れ
た選択透過性能とイオン交換能を併せ有する中空繊維状
精密濾過膜が得られるとの知見を得、本発明を完成し
た。本発明の目的は従来の欠点を除き、選択透過性能と
イオン交換能を併有する精密濾過膜及びその製造方法を
提供するにある。However, the above-mentioned conventional method causes water swelling property of the basic polyolefin, and it is unavoidable that physical properties and flow rate are lowered. Furthermore, there are significant restrictions on the type and density of functional groups that can be introduced, and it is difficult to obtain a very satisfactory one. Further, when such a method is industrially carried out, it is disadvantageous in terms of equipment and operation. As a result of earnest research to solve such conventional problems, the present inventors disperse fine particles having adsorption ability and ion exchange ability in the porous structure of a porous membrane made of porous hollow fibers of polyethylene. As a result, it was found that a hollow fibrous microfiltration membrane having both excellent selective permeation performance and ion exchange capacity can be obtained, and the present invention was completed. An object of the present invention is to provide a microfiltration membrane having both selective permeation performance and ion exchange ability and a method for producing the same, excluding the conventional drawbacks.
【0006】[0006]
【課題を解決するための手段】すなわち本発明の精密濾
過膜は、ポリエチレンよりなる多孔体とその多孔構造内
に保持された機能性微粒子より構成され、10ミクロン
以下のポアサイズを有する中空繊維状精密濾過膜であ
る。機能微粒子としては、イオン交換樹脂あるいはキレ
ート樹脂の微粉体が挙げられ、これが多孔構造間に分散
状態で保持されているものである。Means for Solving the Problems That is, the microfiltration membrane of the present invention is composed of a porous body made of polyethylene and functional fine particles retained in the porous structure, and is a hollow fibrous precision having a pore size of 10 microns or less. It is a filtration membrane. Examples of the functional fine particles include fine powders of ion exchange resins or chelate resins, which are held in a dispersed state between porous structures.
【0007】本発明の中空繊維状精密濾過膜の製造方法
としては、まず粒径5ミクロン〜20ミクロンのポリエ
チレン(以下、PEと記す)微粉体と粒径20ミクロン
以下のイオン交換樹脂微粒子あるいはキレート樹脂微粒
子が均一に分散されたポリビニルアルコール(以下、P
VAと記す)水溶液を紡糸原液とし、この紡糸原液を、
室温あるいは90℃以下の温度で保温しながら、二重管
ノズルから芯部の凝固液とともに押し出し、0.1〜5
0cmの空間層を経て、凝固浴で凝固させてまずPVA
中にPE微粉体とイオン交換樹脂微粒子キレート樹脂微
粒子が分散された前駆体中空繊維膜を得る。これを、熱
処理あるいは延伸熱処理することにより、PE粉体を融
着させた後、温水で洗浄し、PVAを溶出させるか溶出
後延伸することにより得られる。As the method for producing the hollow fiber microfiltration membrane of the present invention, first, a polyethylene (hereinafter referred to as PE) fine powder having a particle size of 5 to 20 microns and ion exchange resin fine particles or a chelate having a particle size of 20 microns or less. Polyvinyl alcohol (hereinafter referred to as P
An aqueous solution is used as the spinning dope, and this spinning dope is
While keeping the temperature at room temperature or 90 ° C. or lower, extrude from the double tube nozzle together with the coagulating liquid in the core portion for 0.1 to 5
After passing through a space layer of 0 cm, coagulate in a coagulation bath and then PVA.
A precursor hollow fiber membrane in which PE fine powder and ion exchange resin fine particles chelate resin fine particles are dispersed is obtained. This is heat-treated or stretch-heat-treated to fuse the PE powder, followed by washing with warm water to elute PVA or stretching after elution.
【0008】本発明に使用されるPVAは、好ましく
は、重合度500〜5000、ケン化度75%〜100
%が使用され、さらに好ましくは、重合度800〜50
00、ケン化度97%〜100%が使用される。The PVA used in the present invention preferably has a polymerization degree of 500 to 5000 and a saponification degree of 75% to 100.
% Is used, and more preferably the degree of polymerization is from 800 to 50.
00, a saponification degree of 97% to 100% is used.
【0009】機能性樹脂としては、特に限定されず、目
的に応じカチオン交換性樹脂、アニオン交換性樹脂ある
いはキレート樹脂などの微粉体が使用される。PVA/
PE比については、1/1〜1/9の範囲で使用され
る。好ましくは1/2〜1/5が適当である。PVA/
PEが1/1より大きいと、熱処理によりPEが融着さ
れないし、1/9より小さいと、紡糸が困難になる。イ
オン交換樹脂微粒子あるいはキレート樹脂微粒子の組成
比はPEに対して1%〜50%の範囲が好ましい。1%
以下では、イオン交換性能や吸着性能が発現しにくく、
50%以上では、中空繊維膜の実用的強度が得られな
い。The functional resin is not particularly limited, and fine powder such as cation exchange resin, anion exchange resin or chelate resin is used depending on the purpose. PVA /
The PE ratio is used in the range of 1/1 to 1/9. It is preferably 1/2 to 1/5. PVA /
When PE is larger than 1/1, PE is not fused by heat treatment, and when it is smaller than 1/9, spinning becomes difficult. The composition ratio of the ion exchange resin fine particles or the chelate resin fine particles is preferably in the range of 1% to 50% with respect to PE. 1%
In the following, the ion exchange performance and adsorption performance are difficult to develop,
If it is 50% or more, the practical strength of the hollow fiber membrane cannot be obtained.
【0010】紡糸原液中のPVA濃度は、特に限定しな
いが通常3%〜20%の範囲で使用される。また、造孔
剤、増粘剤などの目的で、紡糸原液中に、水溶性成分を
添加することも可能である。該水溶性成分としては、例
えばエチレングリコール、ジエチレングリコール、ポリ
エチレングリコール、ポリエチレンオキサイド、ポリビ
ニルピロリドン等やホウ酸、ホウ砂、尿素、塩化カルシ
ウムなどが挙げられる。The concentration of PVA in the spinning dope is not particularly limited, but is usually within the range of 3% to 20%. It is also possible to add a water-soluble component to the spinning dope for the purpose of forming a pore-forming agent, a thickener, and the like. Examples of the water-soluble component include ethylene glycol, diethylene glycol, polyethylene glycol, polyethylene oxide, polyvinylpyrrolidone, boric acid, borax, urea, calcium chloride and the like.
【0011】凝固浴及び芯部の凝固液は、PVAの非溶
媒で水と相溶性があればなんでもよいが、通常無機塩類
水溶液やメタノール、エタノール、アセトン等が使用さ
れ、特に硫酸ナトリウム水溶液又は硫酸アンモニウム水
溶液が適している。また、凝固液中にアンモニア等のア
ルカリ性添加物を入れることも可能である。The coagulating bath and the coagulating liquid of the core may be any as long as they are non-solvents of PVA and compatible with water, but aqueous solutions of inorganic salts, methanol, ethanol, acetone, etc. are usually used, especially sodium sulfate aqueous solution or ammonium sulfate. Aqueous solutions are suitable. It is also possible to put an alkaline additive such as ammonia in the coagulating liquid.
【0012】PVAの溶出条件に関しては、温水あるい
は沸騰水で洗浄処理することによりPVAの洗浄が完全
にでき更に膜構造を維持することができる。それより高
い温度での洗浄は、加圧系で行われることになるが、加
圧系のため実用的ではなく、また処理温度がPEの融点
に近い温度で処理するため膜構造が変化する。また、温
水より低温度で処理する場合、PVAの洗浄が不十分に
なりそれによる通液量の低下が著しい。本発明の方法に
より得られるイオン交換性を有する中空繊維状精密濾過
膜は、一般的には、外側と内側の比較的緻密な層とその
間のフィンガーライク状のボイド層の三層からなる断面
構造を有しているが、紡糸原液にほう酸、凝固液にアン
モニア等を添加した場合には、均質的な多孔構造を有す
る。そして、外側表面と内側表面には、10ミクロン以
下の細孔が存在し、さらにこの三層中、又は均質多孔中
にイオン交換樹脂微粒子あるいはキレート樹脂微粒子が
分散している構造となっている。Regarding the elution conditions of PVA, washing treatment with warm water or boiling water enables complete washing of PVA and further maintenance of the membrane structure. Cleaning at a temperature higher than that is performed by a pressure system, but it is not practical because it is a pressure system, and since the treatment temperature is close to the melting point of PE, the membrane structure changes. Further, when the treatment is carried out at a temperature lower than that of hot water, the cleaning of PVA becomes insufficient, resulting in a significant decrease in the liquid flow rate. The hollow fibrous microfiltration membrane having ion exchangeability obtained by the method of the present invention generally has a cross-sectional structure composed of three layers of outer and inner relatively dense layers and a finger-like void layer therebetween. However, when boric acid is added to the spinning dope and ammonia or the like is added to the coagulating liquid, it has a homogeneous porous structure. The outer surface and the inner surface have pores of 10 μm or less, and further, the ion exchange resin particles or the chelate resin particles are dispersed in the three layers or in the homogeneous pores.
【0013】[0013]
【実施例1】重合度2400、ケン化度98%のPVA
とPE微粉体(フローセンUF、製鉄化学工業社製商品
名)及びボールミルで粉砕した強カチオン交換樹脂(三
菱化成株式会社製ダイヤイオンPK228、以下IER
−SCと略記する)を使用し、PVA/PE/IER−
SC/水が1/3/0.6/9.7の組成で重量濃度が
7%/21%/4.2%/68%の紡糸原液をニーダー
で調製し、室温状態でその紡糸原液を二重管ノズルから
5cmのエアギャップを隔てた40%硫安水溶液からな
る凝固浴へ、40%硫安水溶液からなる芯液とともに押
し出し、乾湿式紡糸した。得られたPVA/PE/IE
R−SC中空繊維膜を硫安水溶液中で湿熱処理した後、
水洗、乾燥し、190℃で30秒間熱処理後、沸騰水で
PVAを洗浄溶出した。得られたPE/IER−SC中
空繊維膜は、外径1200ミクロン内径600ミクロン
で、空気透過速度2.1リットル/(min・cm2 ・
(kg/cm2 ))、バブルポイント(メタノール)は
0.42kg/cm2 を示し、中性塩分解容量は0.7
meq/gであった。純水透過速度は3650リットル
/(m2 ・h・(kgf/cm2 ))を示した。当然の
ことながら、得られる中空糸膜は、水に対するなじみが
良く水で濡らすだけで良好な通水性が得られるものであ
った。Example 1 PVA having a polymerization degree of 2400 and a saponification degree of 98%
And PE fine powder (FLOWSEN UF, trade name of Steel Chemical Industry Co., Ltd.) and a strong cation exchange resin crushed with a ball mill (DIAION PK228 manufactured by Mitsubishi Kasei Co., Ltd., hereinafter IER).
-Abbreviated as SC), PVA / PE / IER-
A spinning stock solution having a composition of SC / water of 1/3 / 0.6 / 9.7 and a weight concentration of 7% / 21% / 4.2% / 68% was prepared with a kneader, and the spinning stock solution was prepared at room temperature. The mixture was extruded into a coagulation bath consisting of a 40% ammonium sulfate aqueous solution with a core liquid consisting of a 40% ammonium sulfate aqueous solution, and a dry-wet spinning process was performed. Obtained PVA / PE / IE
After wet heat treating the R-SC hollow fiber membrane in an aqueous solution of ammonium sulfate,
It was washed with water, dried, and heat-treated at 190 ° C. for 30 seconds, and then PVA was washed and eluted with boiling water. The resulting PE / IER-SC hollow fiber membrane had an outer diameter of 1200 microns and an inner diameter of 600 microns, and an air permeation rate of 2.1 liters / (min · cm 2 ·.
(Kg / cm 2)), bubble point (methanol) showed a 0.42 kg / cm 2, neutral salt decomposition capacity 0.7
It was meq / g. The pure water permeation rate was 3650 liters / (m 2 · h · (kgf / cm 2 )). As a matter of course, the obtained hollow fiber membrane had good compatibility with water and could obtain good water permeability simply by wetting with water.
【0014】[0014]
【実施例2】重合度1200、ケン化度99%のPVA
を使用した他は実施例1と同じ原料と、さらに平均分子
量1000のポリエチレングリコール(以下、PEGと
略記す)とほう酸を使用し、PVA/PE/PEG/I
ER−SC/水/ほう酸が1/4/1/0.8/11/
0.05の組成で重量濃度が5.6%/22.4%/
5.6%/4.5%/62%/0.28%の紡糸原液を
ニーダーで調製し、50℃に保温した紡糸原液を二重管
ノズルから5cmのエアギャップを隔てた40%硫安水
溶液からなる凝固浴へ、1%アンモニア添加の40%硫
安水溶液からなる芯液とともに押し出し、乾湿式紡糸し
た。得られたPVA/PE/IER−SC/PEG/ほ
う酸中空繊維膜を硫安水溶液中で湿熱処理した後、水
洗、乾燥し、190℃で1分間熱処理後、沸騰水でPV
Aを洗浄溶出した。得られたPE/IER−SC中空繊
維膜は、外径1000ミクロン内径500ミクロンで、
空気透過速度3.0リットル/(min・cm2 ・(k
g/cm2 ))、バブルポイント(メタノール)は0.
12kg/cm2 を示し、中性塩分解容量は0.7me
q/gであった。Example 2 PVA having a polymerization degree of 1200 and a saponification degree of 99%
PVA / PE / PEG / I using the same raw material as in Example 1 except that polyethylene glycol (hereinafter abbreviated as PEG) having an average molecular weight of 1000 and boric acid were used.
ER-SC / water / boric acid 1/4/1 / 0.8 / 11 /
The composition is 0.05 and the weight concentration is 5.6% / 22.4% /
A spinning stock solution of 5.6% / 4.5% / 62% / 0.28% was prepared with a kneader, and the spinning stock solution kept at 50 ° C. was 40% ammonium sulfate aqueous solution with a 5 cm air gap from the double tube nozzle. Was co-extruded into a coagulation bath consisting of 1) together with a core liquid consisting of a 40% ammonium sulfate aqueous solution containing 1% ammonia, and dry-wet spinning was performed. The obtained PVA / PE / IER-SC / PEG / boric acid hollow fiber membrane was wet heat treated in an aqueous solution of ammonium sulfate, washed with water, dried, and heat treated at 190 ° C. for 1 minute, and then PV in boiling water.
A was washed and eluted. The PE / IER-SC hollow fiber membrane obtained had an outer diameter of 1000 microns and an inner diameter of 500 microns,
Air permeation rate 3.0 liters / (min · cm 2 · (k
g / cm 2 )), the bubble point (methanol) is 0.
12 kg / cm 2 and a neutral salt decomposition capacity of 0.7 me
It was q / g.
【0015】[0015]
【実施例3】実施例1と同じPVAとPE及びボールミ
ルで粉砕した強アニオン交換樹脂(三菱化成株式会社製
ダイヤイオンSA10A、以下IER−SAと記す)を
使用し、PVA/PE/IER−SA/水が1/4/
0.8/11の組成で重量濃度が6%/24%/4.8
%/65%の紡糸原液をニーダーで調製し、実施例1と
同様に紡糸した。得られたPVA/PE/IER−SA
中空繊維膜を硫安水溶液中で湿熱処理した後、水洗、乾
燥し、190℃で30秒間熱処理後、沸騰水でPVAを
洗浄溶出した。得られたPE/IER−SA中空繊維膜
は、外径1000ミクロン内径600ミクロンで、空気
透過速度1.2リットル/(min・cm2 ・(kgf
/cm2 ))、バブルポイント(メタノール)は0.8
7kg/cm2 を示し、中性塩分解容量は0.7meq
/gであった。Example 3 The same PVA and PE as in Example 1 and a strong anion exchange resin (Diaion SA10A manufactured by Mitsubishi Kasei Co., Ltd., hereinafter referred to as IER-SA) crushed by a ball mill were used, and PVA / PE / IER-SA was used. / 1/4 of water
0.8 / 11 composition and weight concentration 6% / 24% / 4.8
% / 65% stock solution for spinning was prepared in a kneader and spun as in Example 1. Obtained PVA / PE / IER-SA
The hollow fiber membrane was subjected to wet heat treatment in an aqueous solution of ammonium sulfate, washed with water, dried, heat treated at 190 ° C. for 30 seconds, and then washed and eluted with PVA by boiling water. The obtained PE / IER-SA hollow fiber membrane had an outer diameter of 1000 microns and an inner diameter of 600 microns, and an air permeation rate of 1.2 liters / (min · cm 2 · (kgf
/ Cm 2 )), bubble point (methanol) is 0.8
7 kg / cm 2 and a neutral salt decomposition capacity of 0.7 meq
/ G.
【0016】[0016]
【発明の効果】以上述べたとおり、本発明の濾過膜は、
液体中の懸濁成分を除去する精密濾過の作用は勿論のこ
と、イオン交換やキレート結合性を有するので液体中の
イオン等の可溶成分も同時に効率よく除去することがで
きその効果は極めて大きい。また、本発明方法によれ
ば、このようなイオン交換性あるいはキレート結合性を
有するポリエチレン製中空繊維状精密濾過膜を、ポリビ
ニルアルコールを利用してポリエチレン微粉体とイオン
交換樹脂微粒子あるいはキレート樹脂微粒子からなる紡
糸原液を中空繊維状に紡糸した後、熱処理、温水洗によ
り容易に製造することができる。As described above, the filtration membrane of the present invention is
In addition to the function of microfiltration to remove suspended components in liquid, it has ion exchange and chelate binding properties, so soluble components such as ions in liquid can be efficiently removed at the same time, and the effect is extremely large. .. Further, according to the method of the present invention, a polyethylene hollow fiber microfiltration membrane having such an ion-exchange or chelate-binding property is prepared from polyethylene fine powder and ion-exchange resin fine particles or chelate resin fine particles using polyvinyl alcohol. It can be easily manufactured by spinning a spinning dope of the following into a hollow fiber, followed by heat treatment and washing with warm water.
Claims (3)
構造内に保持された機能性微粒子より構成され、10ミ
クロン以下のポアサイズを有する中空繊維状精密濾過
膜。1. A hollow fiber microfiltration membrane having a pore size of 10 μm or less, which is composed of a porous body made of polyethylene and functional fine particles retained in the porous structure.
キレート樹脂である請求項1記載の中空繊維状精密濾過
膜。2. The hollow fibrous microfiltration membrane according to claim 1, wherein the functional fine particles are an ion exchange resin or a chelate resin.
20ミクロン以下の機能性微粒子をポリビニルアルコー
ル水溶液中に分散し凝固浴中へ中空繊維状に紡糸し、ポ
リエチレンを熱融着させた後ポリビニルアルコールを温
水洗し溶出させることを特徴とする中空繊維状精密濾過
膜の製造方法。3. Polyethylene powder of 5 to 20 microns and functional fine particles of 20 microns or less are dispersed in a polyvinyl alcohol aqueous solution and spun into hollow fibers in a coagulation bath, and polyethylene is heat-sealed and then polyvinyl alcohol is added. A method for producing a hollow fiber microfiltration membrane, which comprises washing with warm water to elute.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP8468392A JPH05245351A (en) | 1992-03-07 | 1992-03-07 | Hollow fiber microfilter membrane and its production |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP8468392A JPH05245351A (en) | 1992-03-07 | 1992-03-07 | Hollow fiber microfilter membrane and its production |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH05245351A true JPH05245351A (en) | 1993-09-24 |
Family
ID=13837491
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP8468392A Pending JPH05245351A (en) | 1992-03-07 | 1992-03-07 | Hollow fiber microfilter membrane and its production |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH05245351A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1996039246A1 (en) * | 1995-06-06 | 1996-12-12 | Millipore Investment Holdings Limited | Ion exchange polyethylene membrane and process |
-
1992
- 1992-03-07 JP JP8468392A patent/JPH05245351A/en active Pending
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1996039246A1 (en) * | 1995-06-06 | 1996-12-12 | Millipore Investment Holdings Limited | Ion exchange polyethylene membrane and process |
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