JP3241855B2 - Porous membrane filled with inorganic salts - Google Patents
Porous membrane filled with inorganic saltsInfo
- Publication number
- JP3241855B2 JP3241855B2 JP07017193A JP7017193A JP3241855B2 JP 3241855 B2 JP3241855 B2 JP 3241855B2 JP 07017193 A JP07017193 A JP 07017193A JP 7017193 A JP7017193 A JP 7017193A JP 3241855 B2 JP3241855 B2 JP 3241855B2
- Authority
- JP
- Japan
- Prior art keywords
- membrane
- porous membrane
- plugging
- inorganic salt
- polysulfone
- 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.)
- Expired - Fee Related
Links
- 239000012528 membrane Substances 0.000 title claims description 48
- 150000003839 salts Chemical class 0.000 title description 2
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 12
- 229920002492 poly(sulfone) Polymers 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 21
- 230000035699 permeability Effects 0.000 description 15
- 238000001035 drying Methods 0.000 description 11
- 239000003795 chemical substances by application Substances 0.000 description 10
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 7
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- 239000001110 calcium chloride Substances 0.000 description 6
- 229910001628 calcium chloride Inorganic materials 0.000 description 6
- 239000003153 chemical reaction reagent Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 238000001914 filtration Methods 0.000 description 4
- 235000011187 glycerol Nutrition 0.000 description 4
- 239000012510 hollow fiber Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 241000894006 Bacteria Species 0.000 description 3
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000001632 sodium acetate Substances 0.000 description 3
- 235000017281 sodium acetate Nutrition 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- 238000000108 ultra-filtration Methods 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229920002307 Dextran Polymers 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 235000011148 calcium chloride Nutrition 0.000 description 1
- 238000000502 dialysis Methods 0.000 description 1
- 230000003670 easy-to-clean Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 235000011147 magnesium chloride Nutrition 0.000 description 1
- 238000001471 micro-filtration Methods 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 235000002639 sodium chloride Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0081—After-treatment of organic or inorganic membranes
- B01D67/0097—Storing or preservation
Description
【０００１】[0001]
【産業上の利用分野】本発明は、種々の分離プロセスに
用いられる多孔膜及びその製法に関し、さらに詳しく
は、乾燥しても膜性能が変わらない多孔膜及びその製法
に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a porous membrane used for various separation processes and a method for producing the same, and more particularly to a porous membrane whose membrane performance does not change even when dried, and a method for producing the same.
【０００２】[0002]
【従来の技術】有機高分子よりなる多孔膜、中でも限外
濾過膜は、製膜後に乾燥させると乾燥前に比べて著しく
透水率が低下することが知られている。そのため膜は常
に湿潤状態か、水に浸漬させた状態で取り扱う必要があ
った。なお透水率とは一定温度、一定圧力で単位時間、
単位面積当りの透水量のことである。2. Description of the Related Art It is known that a porous membrane made of an organic polymer, particularly an ultrafiltration membrane, has a significantly lower water permeability when dried after film formation than before drying. Therefore, it was necessary to always handle the membrane in a wet state or in a state of being immersed in water. Note that the water permeability is a constant temperature, a constant pressure, a unit time,
It is the amount of water per unit area.
【０００３】この対策として従来よりとられてきた方法
は製膜後、乾燥前にグリセリン等の低揮発性有機液体を
多孔膜中の空孔部分に詰めておく事であった。このよう
に多孔膜の空孔部分に詰めておく物質のことを“目詰め
剤”、膜中に目詰め剤を詰める操作を“目詰め処理”と
呼ぶことにする。このようにグリセリン等の低揮発性有
機液体で目詰めすることにより、多孔膜は乾燥後も、膜
内に詰めたグリセリン等の低揮発性有機液体を洗い流し
さえすれば、ほぼ乾燥前の透水率が保持されるのであ
る。しかしながら、グリセリン等の低揮発性有機液体に
よる目詰め処理を行った場合には、低揮発性有機液体は
一般に高粘度なため、目詰め剤の洗浄除去に時間がかか
ったり、膜を保存中に細菌やカビが繁殖するという欠点
があった。[0003] As a countermeasure against this, a method which has heretofore been taken is to fill a pore portion of a porous film with a low-volatile organic liquid such as glycerin after film formation and before drying. The substance to be filled in the pores of the porous membrane as described above is referred to as “plugging agent”, and the operation of filling the plugging agent in the membrane is referred to as “plugging treatment”. By filling the porous membrane with a low-volatile organic liquid such as glycerin in this manner, even after the porous membrane has been dried, if the low-volatile organic liquid such as glycerin packed in the membrane is only washed out, the water permeability before the drying is almost complete. Is maintained. However, when a plugging treatment with a low-volatile organic liquid such as glycerin is performed, since the low-volatile organic liquid generally has a high viscosity, it takes time to wash and remove the plugging agent, or during storage of the film. There was a drawback that bacteria and mold proliferated.
【０００４】[0004]
【発明が解決しようとする課題】本発明は、膜を保存中
に細菌やカビが繁殖することなく、また目詰め処理後の
目詰め剤の洗浄が容易であるような新規な目詰め剤で目
詰めされた多孔膜及びその製造方法を提供することを課
題とする。DISCLOSURE OF THE INVENTION The present invention relates to a novel plugging agent which does not allow bacteria and mold to grow during storage of a membrane and which is easy to clean after plugging. It is an object to provide a clogged porous membrane and a method for producing the same.
【０００５】[0005]
【課題を解決するための手段】本発明者らは、上記の課
題を解決するため、鋭意研究の結果、本発明を完成する
に至った。すなわち、本発明は、その骨子が無機塩をポ
リスルホン製多孔膜の目詰め剤に用いるというものであ
り、本発明の第１は、無機塩で目詰め処理させた後、膜
の重量変化がなくなるまで乾燥させたポリスルホン製多
孔膜であり、本発明の第２は、無機塩の溶液中にポリス
ルホン製多孔膜を浸漬させ、膜中に無機塩を含浸させた
後に膜の重量変化がなくなるまで乾燥させることを特徴
とする、ポリスルホン製多孔膜の製造法である。Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, completed the present invention. That is, the present invention, port its gist is an inorganic salt
Are those that use in clogged agents Risuruhon made porous film, a first invention, after clogged treated with an inorganic salt, film
A polysulfone multi <br/> porous membrane was dried until the weight change of disappears, the second invention, Police in a solution of an inorganic salt
A method for producing a polysulfone porous membrane, characterized by immersing a porous membrane made of Rufon , impregnating the membrane with an inorganic salt, and then drying the membrane until there is no change in weight of the membrane .
【０００６】無機塩としては特に限定はされないが、塩
化ナトリウム、塩化カルシウム、炭酸ナトリウム、酢酸
ナトリウム、塩化マグネシウム、硫酸カリウム、塩化ア
ンモニウム、硝酸ナトリウムなど通常市販の無機塩が用
いることができる。中でも塩化カルシウムが最も好まし
い効果を発揮する。処理を施すポリスルホン製多孔膜の
形態としては、平膜、中空糸膜、管状膜などあるが、い
ずれの形態であってもよい。なおここで言う多孔膜とは
精密濾過膜（ＭＦ）、限外濾過膜（ＵＦ）、逆浸透膜
（ＲＯ）、透析膜等の濾過膜のことを示す。The inorganic salt is not particularly limited, but commercially available inorganic salts such as sodium chloride, calcium chloride, sodium carbonate, sodium acetate, magnesium chloride, potassium sulfate, ammonium chloride and sodium nitrate can be used. Among them, calcium chloride exerts the most preferable effect. Examples of the form of the polysulfone porous membrane to be treated include a flat membrane, a hollow fiber membrane, and a tubular membrane, and any form may be used. The porous membrane mentioned here refers to a filtration membrane such as a microfiltration membrane (MF), an ultrafiltration membrane (UF), a reverse osmosis membrane (RO), and a dialysis membrane.
【０００７】次に本発明の目詰め処理の方法について説
明する。まず目詰め剤とする無機塩の溶液を作る。濃度
は目詰めによる透水率保持効果を高めるために１ｗｔ％
以上あることが望ましい。無機塩の溶剤としては無機塩
を所定濃度溶かし、ポリスルホン製多孔膜を劣化させな
いものであればなんでもよいが、通常は水を用いる。次
に処理を施すポリスルホン製多孔膜を目詰め剤の溶液中
に浸漬する。温度は膜が劣化をきたさない範囲で行い、
時間はあまり短すぎると十分な目詰めが困難になるので
最低一分は行うのが好ましい。次に目詰め処理を施した
ポリスルホン製多孔膜を乾燥する。乾燥条件は特に限定
されないが、膜の重量変化がほぼなくなった時点で乾燥
が終了したと判断する。Next, the method of the clogging process of the present invention will be described. First, a solution of an inorganic salt to be used as a filler is prepared. The concentration is 1 wt% to enhance the effect of maintaining water permeability by plugging.
It is desirable to have the above. As the solvent for the inorganic salt, any solvent may be used as long as it dissolves the inorganic salt at a predetermined concentration and does not deteriorate the polysulfone porous membrane. Usually, water is used. Next, the polysulfone porous membrane to be treated is immersed in a solution of a plugging agent. The temperature is set within the range where the film does not deteriorate,
If the time is too short, sufficient clogging becomes difficult, so it is preferable to perform the treatment for at least one minute. Next, it was clogged
The polysulfone porous membrane is dried. The drying conditions are not particularly limited, but it is determined that the drying is completed when the change in the weight of the film is almost eliminated.
【０００８】[0008]
【実施例】以下、実施例、比較例等により本発明をさら
に詳細にかつ具体的に説明する。なおこの中で用いられ
ている“T ー70 ”とは、Pharmacia 社製の試薬デキスト
ランT ー70 （平均分子量70000）のことを示す。The present invention will be described below in more detail with reference to examples and comparative examples. The term "T-70" used herein refers to the reagent Dextran T-70 (average molecular weight 70,000) manufactured by Pharmacia.
【０００９】[0009]
【多孔膜製造例】特開昭58-156018号の実施例1の方法に
準じて、ポリスルホン（ＵＣＣ社製のUdel，Pー3500）20
重量部、Ｎ，Ｎージメチルアセトアミド71重量部、テト
ラエチレングリコール9重量部を用いて製膜用原液を作
成し、外径1.35mm、内径0.72mmのポリスルホン製中空繊
維状限外濾過膜を作成し、水中で保存した。[Example of porous membrane production] Polysulfone (Udel, P-3500 manufactured by UCC) 20 according to the method of Example 1 of JP-A-58-156018.
Part weight solution, 71 parts by weight of N, N-dimethylacetamide and 9 parts by weight of tetraethylene glycol were used to prepare a stock solution for membrane formation, and a hollow fiber ultrafiltration membrane made of polysulfone with an outer diameter of 1.35 mm and an inner diameter of 0.72 mm was prepared. And stored in water.
【００１０】得られた中空糸を、純水及び1000ppm のT-
70水溶液で内圧式、25℃、濾過圧1.0kg/cm2 、線速1.0m
/secにて評価したところ、純水の透水率は6.35m3/m2 da
y 、T-70の阻止率は55.9% となった。[0010] The obtained hollow fiber is purified water and 1000 ppm of T-
70 aqueous solution, internal pressure type, 25 ° C, filtration pressure 1.0kg / cm 2 , linear velocity 1.0m
/ sec, the permeability of pure water is 6.35m 3 / m 2 da
y, the rejection of T-70 was 55.9%.
【００１１】[0011]
【実施例１】目詰め剤として塩化カルシウム（和光純薬
（株）試薬特級）の23wt%水溶液を用い、該水溶液中に
多孔膜製造例で作ったポリスルホン中空糸を60℃で5時
間浸漬した後、乾燥を行った。乾燥条件は重量変化がほ
ぼなくなるまで、すなわち、50℃の乾燥器中で１時間乾
燥させた。乾燥後、膜を水中に約半日浸漬し、純水及び
1000ppm のT-70水溶液を用いて、25℃、内圧式、濾過圧
1.0kg/cm2 、線速1.0m/secにて評価したところ、純水の
透水率は5.77m3/m2 day 、T-70の阻止率は55.1% となっ
た。従って透水率及び阻止性能も塩化カルシウムによる
目詰め処理でほぼ完全に保持されていた。Example 1 A 23 wt% aqueous solution of calcium chloride (special grade reagent, Wako Pure Chemical Industries, Ltd.) was used as a filler, and the polysulfone hollow fiber prepared in the porous membrane production example was immersed in the aqueous solution at 60 ° C. for 5 hours. Thereafter, drying was performed. The drying conditions were such that the weight change was almost eliminated, that is, drying was performed in a dryer at 50 ° C. for 1 hour. After drying, immerse the membrane in water for about half a day,
25 ℃, internal pressure type, filtration pressure using 1000ppm T-70 aqueous solution
When evaluated at 1.0 kg / cm 2 and a linear velocity of 1.0 m / sec, the permeability of pure water was 5.77 m 3 / m 2 day, and the rejection of T-70 was 55.1%. Therefore, the water permeability and the inhibition performance were almost completely maintained by the clogging treatment with calcium chloride.
【００１２】[0012]
【比較例１】多孔膜製造例で作った膜を50℃で１時間乾
燥させた膜を内圧式、25℃、濾過圧1.0kg/cm2 、線速1.
0m/secにて評価したところ、純水の透水率は1.28 m3 /m
2 ・day 、T ー70 の阻止率は95.5% であった。[Comparative Example 1] membrane pressure equation 1 hour dried film membrane 50 ° C. made in Production Example, 25 ° C., filtration pressure 1.0 kg / cm 2, linear velocity 1.
When evaluated at 0 m / sec, the permeability of pure water is 1.28 m 3 / m
Two days, the rejection of T-70 was 95.5%.
【００１３】[0013]
【実施例２】目詰め剤として塩化カルシウム（和光純薬
（株）試薬特級）の1wt%水溶液を用いた事以外は、実施
例１で示した条件と同様の方法で目詰め処理及び測定を
行った。純水の透水率は5.15m3/m2 day となり、透水率
は塩化カルシウムによる目詰めでほぼ完全に保持されて
いた。Example 2 A plugging treatment and measurement were performed in the same manner as in Example 1 except that a 1 wt% aqueous solution of calcium chloride (Wako Pure Chemical Industries, Ltd. reagent grade) was used as a plugging agent. Was. The permeability of pure water was 5.15 m 3 / m 2 day, and the permeability was almost completely maintained by the clogging with calcium chloride.
【００１４】[0014]
【実施例３】目詰め剤として炭酸ナトリウム（和光純薬
（株）試薬特級）の30wt% 水溶液を用いた事以外は実施
例１で示した条件と同様の方法で目詰め処理及び測定を
行ったところ、純水の透水率は3.56m3/m2 day となり、
透水率は炭酸ナトリウムによる目詰めで高く保持されて
いた。Example 3 A plugging treatment and measurement were performed in the same manner as in Example 1 except that a 30 wt% aqueous solution of sodium carbonate (special grade of reagent of Wako Pure Chemical Industries, Ltd.) was used as a plugging agent. However, the permeability of pure water is 3.56m 3 / m 2 day,
Permeability was kept high by plugging with sodium carbonate.
【００１５】[0015]
【実施例４】目詰め剤として塩化ナトリウム（和光純薬
（株）試薬特級）の30wt% 溶液を用いた事以外は実施例
１で示した条件と同様の方法で目詰め処理及び測定を行
ったところ、純水の透過率は6.30m3/m2 day となり、透
水率は塩化ナトリウムによる目詰めでほぼ完全に保持さ
れていた。Example 4 A plugging treatment and measurement were performed in the same manner as in Example 1 except that a 30 wt% solution of sodium chloride (special grade of reagent, Wako Pure Chemical Industries, Ltd.) was used as a plugging agent. However, the transmittance of pure water was 6.30 m 3 / m 2 day, and the water permeability was almost completely maintained by plugging with sodium chloride.
【００１６】[0016]
【実施例５】目詰め剤として酢酸ナトリウム（和光純薬
（株）試薬特級）の30wt% 水溶液を用いて実施例１で示
した条件と同様の方法で目詰め処理及び測定を行ったと
ころ、純水の透水率は4.00m3/m2 day となり、透水率は
酢酸ナトリウムによる目詰めで高く保持されていた。Example 5 When a 30 wt% aqueous solution of sodium acetate (special grade of reagent of Wako Pure Chemical Industries, Ltd.) was used as a plugging agent, plugging treatment and measurement were carried out in the same manner as in Example 1, and The water permeability of pure water was 4.00 m 3 / m 2 day, and the water permeability was kept high by clogging with sodium acetate.
【００１７】[0017]
【発明の効果】本発明による無機塩による目詰め処理は
乾燥後も多孔膜の膜性能を保持し、細菌やカビの繁殖が
なく、また洗浄しやすいことから、従来の目詰め処理に
は見られなかった効果を発揮することができる。The plugging treatment with an inorganic salt according to the present invention maintains the membrane performance of the porous membrane even after drying, has no growth of bacteria and mold, and is easy to wash. Unexpected effects can be exhibited.
Claims (2)
なくなるまで乾燥させたことを特徴とするポリスルホン
製多孔膜。1. After the plugging treatment with an inorganic salt, the weight change of the membrane is reduced.
Polysulfone characterized by being dried until it disappears
Manufacturing porous membrane.
中に無機塩を含浸させた後、膜の重量変化がなくなるま
で乾燥させることを特徴とする、ポリスルホン製多孔膜
の製造法。2. After the porous membrane is immersed in a solution of an inorganic salt to impregnate the inorganic salt into the membrane, the change in weight of the membrane is eliminated.
And producing the polysulfone porous membrane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP07017193A JP3241855B2 (en) | 1993-03-29 | 1993-03-29 | Porous membrane filled with inorganic salts |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP07017193A JP3241855B2 (en) | 1993-03-29 | 1993-03-29 | Porous membrane filled with inorganic salts |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06277470A JPH06277470A (en) | 1994-10-04 |
| JP3241855B2 true JP3241855B2 (en) | 2001-12-25 |
Family
ID=13423825
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP07017193A Expired - Fee Related JP3241855B2 (en) | 1993-03-29 | 1993-03-29 | Porous membrane filled with inorganic salts |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3241855B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4503117B2 (en) * | 1999-08-03 | 2010-07-14 | 旭化成ケミカルズ株式会社 | Hydrophilic porous membrane |
| DE60333161D1 (en) * | 2003-04-10 | 2010-08-12 | X Flow Bv | Process for drying a wet porous membrane structure |
| CN108211808B (en) * | 2017-12-13 | 2020-12-08 | 浙江长兴求是膜技术有限公司 | Food-grade polyvinylidene fluoride membrane and manufacturing method thereof |
-
1993
- 1993-03-29 JP JP07017193A patent/JP3241855B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH06277470A (en) | 1994-10-04 |
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