JPH0824829B2 - Hollow fiber ultrafiltration membrane with improved oxidation resistance - Google Patents
Hollow fiber ultrafiltration membrane with improved oxidation resistanceInfo
- Publication number
- JPH0824829B2 JPH0824829B2 JP16137188A JP16137188A JPH0824829B2 JP H0824829 B2 JPH0824829 B2 JP H0824829B2 JP 16137188 A JP16137188 A JP 16137188A JP 16137188 A JP16137188 A JP 16137188A JP H0824829 B2 JPH0824829 B2 JP H0824829B2
- Authority
- JP
- Japan
- Prior art keywords
- hollow fiber
- ultrafiltration membrane
- fiber ultrafiltration
- membrane
- oxidation resistance
- 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 - Lifetime
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
- B01D71/68—Polysulfones; Polyethersulfones
Description
【発明の詳細な説明】 （イ）産業上の利用分野 本発明は、中空糸限外瀘過膜に関し、さらに詳しく
は、耐酸化性が改良された中空糸限外瀘過膜に関するも
のである。TECHNICAL FIELD The present invention relates to a hollow fiber ultrafiltration membrane, and more particularly, to a hollow fiber ultrafiltration membrane having improved oxidation resistance. .
（ロ）従来の技術 中空糸限外瀘過膜は、通常、200μｍ〜2000μｍの外
径を有し、10μｍ〜500μｍ程度の膜厚を有するさまざ
まな大きさのものがある。これらを数千〜数万本束ね
て、中空糸モジュールが作製される。これは、コンパク
トであることなどから、さまざまな分野に利用されてお
り、酸化作用を有する薬品に接触する機会も増えてい
る。(B) Conventional Technology Hollow fiber ultrafiltration membranes are usually of various sizes having an outer diameter of 200 μm to 2000 μm and a film thickness of about 10 μm to 500 μm. Thousands to tens of thousands are bundled to produce a hollow fiber module. Since it is compact, it is used in various fields, and the chances of contact with chemicals having an oxidizing action are increasing.
たとえば、１〜５％程度の過酸化水素水による中空糸
膜の殺菌が挙げられる。For example, sterilization of the hollow fiber membrane with about 1 to 5% hydrogen peroxide solution can be mentioned.
（ハ）発明が解決しようとする課題 ところが、一般に中空糸限外瀘過膜は、多孔質で単位
重量当りの接液部分が非常に大きく、酸化作用を有する
薬品と接触した場合、中空糸限外瀘過膜は少なからず影
響を受ける。(C) Problems to be Solved by the Invention However, in general, a hollow fiber ultrafiltration membrane is porous and has a very large wetted portion per unit weight, and when contacted with a chemical having an oxidizing action, the hollow fiber ultrafiltration membrane is The epileptic membrane is affected in no small way.
そして、これが繰り返し行なわれると、膜の機械強度
が低下すると共に分画性能も低下する。さらに劣化が進
むと膜素材の欠落により透過水中のTOC（全有機炭素
量）や微粒子数が増す。Then, when this is repeated, the mechanical strength of the membrane decreases and the fractionation performance also decreases. As the deterioration progresses further, TOC (total organic carbon content) and the number of fine particles in the permeate will increase due to the lack of membrane material.
このように膜の透過特性が変化すると、膜を使用した
製品に不良を生ずることになる。また、中空糸限外瀘過
膜モジュールは非常に高価であるため、膜の寿命の短縮
はコスト的にもかなり不利である。This change in the transmission characteristics of the membrane causes a defect in the product using the membrane. In addition, since the hollow fiber ultrafiltration membrane module is very expensive, shortening the life of the membrane is considerably disadvantageous in terms of cost.
この発明は耐酸化性を向上できる中空糸限外瀘過膜を
提供することを目的の一つとするものである。An object of the present invention is to provide a hollow fiber ultrafiltration membrane which can improve oxidation resistance.
（ニ）課題を解決するための手段 本発明は、鉄の含有量が1ppm以下である耐酸化性が改
良された中空糸限外瀘過膜である。(D) Means for Solving the Problem The present invention is a hollow fiber ultrafiltration membrane having an iron content of 1 ppm or less and having improved oxidation resistance.
すなわち、本発明は耐酸化性を改良した中空糸限外瀘
過膜を提供するものである。That is, the present invention provides a hollow fiber ultrafiltration membrane having improved oxidation resistance.
本発明者らは、酸化作用のある薬品と中空糸限外瀘過
膜とが繰り返し接触した場合の膜性能の劣化について、
膜表面あるいは膜中に存在する鉄が関係していることを
突き止めた。すなわち、まず、膜の鉄含有量の多いもの
は、酸化作用のある薬品と接触すると性能の劣化が大き
いことを突き止めた。これは、鉄成分が酸化作用のある
薬品の触媒として働いたためであると考えられる。The present inventors, regarding the deterioration of the membrane performance when the chemical having an oxidizing action and the hollow fiber ultrafiltration membrane are repeatedly contacted,
We have found that the iron present on or in the film is involved. That is, first, it was found that a film having a high iron content deteriorates greatly in performance when it is brought into contact with a chemical having an oxidizing action. It is considered that this is because the iron component worked as a catalyst for a chemical having an oxidizing action.
さらに、本発明者らは鉄の含有量を少なくした中空糸
限外瀘過膜が、酸化作用のある薬品との繰り返しの接触
に対し、性能の劣化が少ないことを見い出した。その結
果、鉄の含有量は1ppm以下が好ましく、この程度になる
と一般的な中空糸限外瀘過膜の使用に対し、ほとんど膜
性能の劣化を招くおそれがない。Furthermore, the present inventors have found that the hollow fiber ultrafiltration membrane having a reduced iron content shows less deterioration in performance upon repeated contact with a chemical having an oxidizing action. As a result, the iron content is preferably 1 ppm or less, and when it is about this level, there is almost no risk of deterioration of the membrane performance in the use of a general hollow fiber ultrafiltration membrane.
また、膜の材質はどの様なものでも本発明の効果は得
られるが、ポリスルホン系樹脂、ポリエーテルスルホン
系樹脂の場合には、これらは耐薬品性の高いとされる樹
脂であることから、薬品処理される場合が多く、特に本
発明の効果が大きい。そして、膜の構造は特定されず、
これらは、目的に合せて適宜選択して作られる。Further, the effect of the present invention can be obtained with any material of the film, but in the case of polysulfone-based resin, polyethersulfone-based resin, since these are resins that are considered to have high chemical resistance, It is often treated with chemicals, and the effect of the present invention is particularly great. And the structure of the membrane is not specified,
These are appropriately selected and made according to the purpose.
本発明による鉄の含有量が1ppm以下である中空糸限外
瀘過膜は、一旦成型された中空糸限外瀘過膜を、pH3以
下の酸性水溶液、好ましくは塩酸、硫酸などの鉱酸の希
釈水溶液と、室温乃至若干高められた温度で接触さすこ
とによって得ることができる。接触時間は、使用する酸
性水溶液の酸の濃度と種類、接触温度などによって影響
される。たとえば、0.6規定程度の希塩酸水溶液中、室
温では１時間程度で十分目的が達せられる。酸性水溶液
と接触させた後の中空糸限外瀘過膜は、純水で十分に洗
浄することが好ましい。The hollow fiber ultrafiltration membrane having an iron content of 1 ppm or less according to the present invention is a hollow fiber ultrafiltration membrane once molded, and an acidic aqueous solution having a pH of 3 or less, preferably hydrochloric acid, or a mineral acid such as sulfuric acid. It can be obtained by contacting with a dilute aqueous solution at room temperature or slightly elevated temperature. The contact time is affected by the concentration and type of acid in the acidic aqueous solution used, the contact temperature, and the like. For example, in a dilute hydrochloric acid aqueous solution of about 0.6 N, at room temperature, the purpose can be sufficiently achieved in about 1 hour. The hollow fiber ultrafiltration membrane after contact with the acidic aqueous solution is preferably thoroughly washed with pure water.
（ホ）実施例 以下、実施例により本発明を詳細に説明するが本発明
はこれらに何等限定されない。(E) Examples Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited thereto.
以下の実施例および比較例で使用する中空糸限外瀘過
膜を次のようにして製造した。Hollow fiber ultrafiltration membranes used in the following Examples and Comparative Examples were produced as follows.
中空糸限外瀘過膜の製造例１ ポリエーテルスルホン（ICI社製 300Pパウダー）20重
量％、ポリエチレングリコール（平均分子量 200）20重
量％、ジメチルスルホキシド（以下DMSOと略す）60重量
％の組成の紡糸原液を、内部凝固液としてDMSO50重量％
および水50重量％の混合液を用いて二重環状ノズルより
水中に押し出した。この際、原液及び内部凝固液の温度
を25℃に、外部凝固液の温度を40℃にそれぞれ調整し
た。こうして得られた中空糸は内径500μｍ、外径800μ
ｍであり、純水に浸漬しておいた。Hollow fiber ultrafiltration membrane production example 1 Polyethersulfone (ICP 300P powder) 20% by weight, polyethylene glycol (average molecular weight 200) 20% by weight, dimethyl sulfoxide (hereinafter abbreviated as DMSO) 60% by weight 50% by weight DMSO as an internal coagulating liquid for the spinning dope
And a 50% by weight water mixture were used to extrude into water through a double annular nozzle. At this time, the temperature of the stock solution and the internal coagulating solution was adjusted to 25 ° C, and the temperature of the external coagulating solution was adjusted to 40 ° C. The hollow fiber thus obtained has an inner diameter of 500 μm and an outer diameter of 800 μm.
m and was immersed in pure water.
中空糸限外瀘過膜の製造例２ ポリスルホン（UCC社製、ユーデルポリサルポンＰ−1
700）を溶媒である２−ピロリドン:N−メチル−２−ピ
ロリドン（重量比1:2）混合溶媒に溶解し、さらに非溶
媒としてポリエチレングリコール（PFG 200;三洋化成
製）を30重量％になるように加えてポリスルホンが20重
量％の中空糸紡糸原液を調製した。この紡糸原液を瀘過
及び脱泡することにより原液中に含まれるゴミ、気体を
除去した後、チューブインオリフィスタイプの２重環ノ
ズルより水中に吐出して中空糸を紡糸した。内部凝固液
としては精製水を用い、空中走行距離10cm、外部凝固液
は70℃の温水を用いて20m/minで紡糸した。次いで、得
られた中空糸を完全に脱溶剤ができるまで60℃の温水で
洗浄した。Production Example 2 of Hollow Fiber Ultrafiltration Membrane Polysulfone (UCC, Udel Polysarpon P-1
700) is dissolved in a solvent 2-pyrrolidone: N-methyl-2-pyrrolidone (weight ratio 1: 2) mixed solvent, and polyethylene glycol (PFG 200; Sanyo Kasei) is added as a non-solvent to 30% by weight. Thus, a hollow fiber spinning solution containing 20% by weight of polysulfone was prepared. The spinning stock solution was filtered and defoamed to remove dust and gas contained in the stock solution, and then discharged into water from a tube-in-orifice type double ring nozzle to spin a hollow fiber. Purified water was used as the internal coagulating liquid, the running distance was 10 cm in the air, and the external coagulating liquid was hot water at 70 ° C. and spun at 20 m / min. Then, the obtained hollow fiber was washed with warm water at 60 ° C. until the solvent was completely removed.
こうして得られた中空糸は内径500μｍ、外径800μｍ
であり、純水に浸漬しておいた。The hollow fiber thus obtained has an inner diameter of 500 μm and an outer diameter of 800 μm.
And was immersed in pure water.
以下の実施例および比較例における鉄の含有量は測定
したい中空糸膜10gを電気炉で550℃で強熱し灰化させた
後、1mlの35％塩酸水と19mlの超純水を加え、原子吸光
光度法によって鉄の濃度を測定することによって得た。The iron content in the following examples and comparative examples was ignited by igniting 10 g of the hollow fiber membranes to be measured at 550 ° C. in an electric furnace, and 1 ml of 35% hydrochloric acid water and 19 ml of ultrapure water were added, and atomic Obtained by measuring the concentration of iron by absorptiometry.
実施例１ 製造例１で得られた中空糸膜を0.6Nの塩酸水溶液に室
温で１時間浸漬した。その後、超純水で十分に洗浄して
塩酸を除去した。この中空糸の鉄の含有量は0.9ppmであ
った。Example 1 The hollow fiber membrane obtained in Production Example 1 was immersed in a 0.6N aqueous hydrochloric acid solution at room temperature for 1 hour. Then, it was sufficiently washed with ultrapure water to remove hydrochloric acid. The iron content of this hollow fiber was 0.9 ppm.
この中空糸を５％H2O2水溶液に140時間浸漬した。こ
うして酸化された中空糸膜10本につき破断強度を測定し
た結果を第１表に示す。This hollow fiber was immersed in a 5% H 2 O 2 aqueous solution for 140 hours. The results of measuring the breaking strength of 10 hollow fiber membranes thus oxidized are shown in Table 1.
実施例２ 製造例２で得られた中空糸膜を0.6Nの塩酸水溶液に室
温で１時間浸漬した。その後、超純水で十分に洗浄して
塩酸を除去した。この中空糸の鉄の含有量は0.8ppmであ
った。Example 2 The hollow fiber membrane obtained in Production Example 2 was immersed in a 0.6N aqueous hydrochloric acid solution at room temperature for 1 hour. Then, it was sufficiently washed with ultrapure water to remove hydrochloric acid. The iron content of this hollow fiber was 0.8 ppm.
この中空糸を５％H2O2水溶液に140時間浸漬した。こ
うして酸化された中空糸膜10本につき破断強度を測定し
た結果を第１表に示す。This hollow fiber was immersed in a 5% H 2 O 2 aqueous solution for 140 hours. The results of measuring the breaking strength of 10 hollow fiber membranes thus oxidized are shown in Table 1.
比較例１ 塩酸水溶液に浸漬しなかった以外は実施例１と同様に
して酸化し、破断強度を測定した。結果を第１表に示
す。また、この中空糸膜の酸化する前の鉄の含有量は3.
0ppmであった。Comparative Example 1 Oxidation was performed in the same manner as in Example 1 except that the sample was not immersed in an aqueous hydrochloric acid solution, and the breaking strength was measured. The results are shown in Table 1. The iron content of the hollow fiber membrane before oxidation was 3.
It was 0 ppm.
比較例２ 塩酸水溶液に浸漬しなかった以外は実施例２と同様に
して酸化し、破断強度を測定した。結果を第１表に示
す。また、この中空糸膜の酸化する前の鉄の含有量は2.
6ppmであった。Comparative Example 2 Oxidation was performed in the same manner as in Example 2 except that the sample was not immersed in a hydrochloric acid aqueous solution, and the breaking strength was measured. The results are shown in Table 1. The iron content of the hollow fiber membrane before oxidation was 2.
It was 6 ppm.
（ヘ）発明の効果 以上説明してきたように、本発明の中空糸限外瀘過膜
は、鉄の含有量を1ppm以下に構成したので、酸化作用に
よる膜の劣化を防止することができる。従って、中空糸
限外瀘過膜の寿命を延長でき、経済的にも有利である。 (F) Effects of the Invention As described above, the hollow fiber ultrafiltration membrane of the present invention has an iron content of 1 ppm or less, and therefore can prevent deterioration of the membrane due to oxidation. Therefore, the life of the hollow fiber ultrafiltration membrane can be extended, which is economically advantageous.
Claims (2)
良された中空糸限外瀘過膜。1. A hollow fiber ultrafiltration membrane having an iron content of 1 ppm or less and having improved oxidation resistance.
テルスルホン系樹脂である請求項１記載の中空糸限外瀘
過膜。2. The hollow fiber ultrafiltration membrane according to claim 1, wherein the material is a polysulfone resin or a polyethersulfone resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16137188A JPH0824829B2 (en) | 1988-06-29 | 1988-06-29 | Hollow fiber ultrafiltration membrane with improved oxidation resistance |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16137188A JPH0824829B2 (en) | 1988-06-29 | 1988-06-29 | Hollow fiber ultrafiltration membrane with improved oxidation resistance |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH029426A JPH029426A (en) | 1990-01-12 |
| JPH0824829B2 true JPH0824829B2 (en) | 1996-03-13 |
Family
ID=15733817
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP16137188A Expired - Lifetime JPH0824829B2 (en) | 1988-06-29 | 1988-06-29 | Hollow fiber ultrafiltration membrane with improved oxidation resistance |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0824829B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109109035A (en) * | 2018-06-27 | 2019-01-01 | 湖州科滤膜技术有限公司 | A kind of hollow fiber ultrafiltration membrane processing unit (plant) |
-
1988
- 1988-06-29 JP JP16137188A patent/JPH0824829B2/en not_active Expired - Lifetime
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109109035A (en) * | 2018-06-27 | 2019-01-01 | 湖州科滤膜技术有限公司 | A kind of hollow fiber ultrafiltration membrane processing unit (plant) |
| CN109109035B (en) * | 2018-06-27 | 2020-11-10 | 淮北智行信息科技有限公司 | Processing device for hollow fiber ultrafiltration membrane |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH029426A (en) | 1990-01-12 |
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