JP2851371B2 - Ultrafiltration membrane fractionation performance evaluation method - Google Patents
Ultrafiltration membrane fractionation performance evaluation methodInfo
- Publication number
- JP2851371B2 JP2851371B2 JP11653590A JP11653590A JP2851371B2 JP 2851371 B2 JP2851371 B2 JP 2851371B2 JP 11653590 A JP11653590 A JP 11653590A JP 11653590 A JP11653590 A JP 11653590A JP 2851371 B2 JP2851371 B2 JP 2851371B2
- Authority
- JP
- Japan
- Prior art keywords
- colloidal silica
- ultrafiltration membrane
- fractionation performance
- rejection
- evaluation method
- 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
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- Separation Using Semi-Permeable Membranes (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は、限外濾過膜の分画性能の設計、品質管理、
仕様説明等に用いるための分画性能評価方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to the design of ultrafiltration membrane fractionation performance, quality control,
The present invention relates to a method for evaluating fractionation performance for use in explanation of specifications and the like.
一般に、限外濾過膜の分画性能は、予めサイズのわか
っている指標物質を用い、これをクリーンな純水に溶か
した溶液を膜濾過し、指標物質の阻止率を測定すること
によって評価されている。Generally, the fractionation performance of an ultrafiltration membrane is evaluated by using an indicator substance of which size is known in advance, filtering the solution obtained by dissolving it in clean pure water, and measuring the rejection of the indicator substance. ing.
ここで阻止率とは、 の意味である。Here, the rejection rate is Is the meaning of
また分画分子量とは、ある分子量のわかっている指標
物質（例えば、分子量20,000のポリエチレングリコー
ル）を、90％阻止する膜を「ポリエチレングリコール基
準の分画分子量20,000」と呼ぶ、分画性能の表現方法の
ことである。Also, the molecular weight cutoff refers to a membrane that blocks 90% of an indicator substance with a known molecular weight (eg, polyethylene glycol with a molecular weight of 20,000) by 90%. That's how.
従来より分画性能評価に用いられる指標物質として
は、デキストランやポリエチレングリコール等の高分
子、あるいは酵素等の球状タンパク質等が挙げられる。Indicator substances conventionally used for evaluation of fractionation performance include polymers such as dextran and polyethylene glycol, and globular proteins such as enzymes.
しかし、デキストランやポリエチレングリコール等の
高分子は鎖状形状であるため、圧力条件や流れ（膜面流
速）による剪断力条件が変化した場合、形状や向きが自
由に変化し、膜の透過しやすさが変化する。従って膜の
分画性能評価における阻止率が上記条件の影響を大きく
受けるため、膜自体の真の分画性能を評価することが難
しかった。However, since polymers such as dextran and polyethylene glycol have a chain shape, when the pressure conditions and the shearing force conditions due to the flow (membrane surface flow rate) change, the shape and direction change freely, and the membrane easily permeates. Changes. Therefore, since the rejection rate in the evaluation of the fractionation performance of the film is greatly affected by the above conditions, it has been difficult to evaluate the true fractionation performance of the film itself.
一方、酵素等のタンパク質は、非常に高価であるた
め多量かつ頻繁に使用できない、タンパク質同士の化
学的相互作用による結合の影響を避けるために、特定の
pHでかつ電解質を含む溶媒を用いなければならない、
タンパク質と膜材質間の化学的相互作用によって阻止率
が影響を受ける、タンパク質の種類によって、の
性質が大きく異なる、タンパク質が変形しやすいので
阻止率が圧力条件や流れによる剪断力条件の影響を受け
る、ポンプ等で強く撹拌した場合、分解や変形を起こ
す、等の種々の問題を有するため、前記高分子物質以上
に取り扱いが難しい。On the other hand, proteins such as enzymes are very expensive and cannot be used in large quantities and frequently.To avoid the effects of binding due to chemical interaction between proteins,
must use a solvent at pH and containing electrolytes,
The rejection rate is affected by the chemical interaction between the protein and the membrane material. The properties vary greatly depending on the type of protein. The protein is easily deformed, so the rejection rate is affected by the pressure conditions and shearing conditions due to flow. If the mixture is strongly stirred by a pump or the like, it causes various problems such as decomposition and deformation, and is more difficult to handle than the above-mentioned polymer substance.
従って、かかる圧力条件、流れによる剪断力条件、そ
の他の化学的物理的な条件の影響を受けずに安定して分
画性能評価を行うことができる指標物質は今まで見いだ
されていなかった。Therefore, an index substance capable of stably evaluating the fractionation performance without being affected by such pressure conditions, shear force conditions due to flow, and other chemical and physical conditions has not been found so far.
本発明では、コロイダルシリカ粒子を用いることによ
り上記問題点を解決できることを見いだした。In the present invention, it has been found that the above problems can be solved by using colloidal silica particles.
即ち本発明は、コロイダルシリカ粒子を用いることを
特徴とする限外濾過膜の分画性能評価方法を提供する。That is, the present invention provides a method for evaluating the fractionation performance of an ultrafiltration membrane, characterized by using colloidal silica particles.
本発明におけるコロイダルシリカ粒子とは、無機珪酸
の超微粒子のことで、水を分散媒として無水珪酸の超微
粒子を水中に分散せしめてなるコロイド溶液である。か
かるコロイダルシリカ粒子の平均粒子径は、1mμｍ〜10
0mμｍが好ましい。かかるコロイダルシリカ粒子は、安
価で入手しやすく、安定した性質を有するので取り扱い
も容易である。また、粒径分布範囲が狭いのでシャープ
な分画性能評価が可能である。市販のものとしては、例
えば、日産化学（株）製の商品名「スノーテックス」等
を好適に用いることができるが、これに限定されるもの
ではない。。The colloidal silica particles in the present invention are ultrafine particles of inorganic silicic acid, and are a colloid solution obtained by dispersing ultrafine particles of silicic anhydride in water using water as a dispersion medium. The average particle diameter of the colloidal silica particles is 1 mμm to 10
0 μm is preferred. Such colloidal silica particles are inexpensive, easily available, and have stable properties, so that they are easy to handle. Further, since the particle size distribution range is narrow, sharp evaluation of fractionation performance is possible. As a commercially available product, for example, “Snowtex” (trade name, manufactured by Nissan Chemical Industries, Ltd.) can be preferably used, but it is not limited thereto. .
一般に、球状タンパク質の粒子径ｒと分子量Mwとの関
係は、一般に、 （Ferryの式）で表される。「スノーテックス」のコロ
イダルシリカ粒子の粒子サイズには、粒径４〜6mμｍ、
７〜9mμｍ、10〜20mμｍ等があるため、上記式を用い
ればこれらの分子量は、順に8,000〜27,000、43,000〜9
1,000、125,000〜1,000,000に相当する。また、コロイ
ダルシリカ粒子の粒子径は、BET法（表面吸着法の一
種）によって測定することができる。Generally, the relationship between the particle diameter r of a globular protein and the molecular weight Mw is (Ferry's formula). The particle size of the “Snowtex” colloidal silica particles is 4-6 μm,
Since there are 7 to 9 mμm, 10 to 20 mμm, etc., using the above formula, these molecular weights are 8,000 to 27,000, 43,000 to 9
1,000, equivalent to 125,000-1,000,000. The particle size of the colloidal silica particles can be measured by a BET method (a type of surface adsorption method).
コロイダルシリカ粒子の表面には、−SiOH基及び−OH
-イオンが存在し、アルカリイオンによって電気二重層
が形成され、粒子間の反発により安定化されている。こ
の電荷バランスがくずれると、粒子同士が結合し凝集が
おこるため好ましくない。On the surface of the colloidal silica particles, -SiOH groups and -OH
- ion present, the electric double layer is formed by alkali ions, are stabilized by repulsion between particles. If the charge balance is lost, the particles are undesirably bonded and aggregate.
コロイダルシリカ粒子のpHに対する影響は、pH10.5以
上で溶解し、pHが酸性域になると凝集しやすくなる。ま
たコロイダルシリカ粒子濃度が高いほど凝集しやすくな
る。The effect of colloidal silica particles on pH is such that the particles are dissolved at pH 10.5 or higher, and are easily aggregated when the pH is in an acidic range. Also, the higher the colloidal silica particle concentration, the more easily the particles are aggregated.
本発明においては、かかるコロイダルシリカ粒子溶液
（市販の溶液濃度は20〜30重量％）を、純水で10〜10,0
00ppm、好ましくは100〜2,000ppmとなるように希釈し、
塩酸及び水酸化ナトリウムでpH6〜10、好ましくはpH7〜
９に調整して、限外濾過膜の分画性能評価に用いる。In the present invention, such a colloidal silica particle solution (commercially available solution concentration is 20 to 30% by weight) is mixed with pure water at 10 to 10.0%.
00 ppm, preferably diluted to 100 to 2,000 ppm,
PH 6 ~ 10, preferably pH7 ~ with hydrochloric acid and sodium hydroxide
Adjusted to 9 and used for evaluation of fractionation performance of ultrafiltration membrane.
なお、原液及び透過液中に含まれるコロイダルシリカ
濃度の定量は、ICP（Inductively Coupled Plasma Atom
ic Emission Spectrometer）法あるいは蒸発乾固法によ
って行うことができる。The concentration of colloidal silica contained in the undiluted solution and the permeate was determined by ICP (Inductively Coupled Plasma Atom).
ic emission spectrometer) or evaporation to dryness.
次に実施例により、本発明をより具体的に説明する。 Next, the present invention will be described more specifically with reference to examples.
限外濾過膜として、日東電工（株）製、中空糸状限外
濾過膜を使用した。かかる分画分子量はポリエチレング
リコール基準で20,000（タンパク質基準で6,000）相当
である。この限外濾過膜をポリプロピレン製チューブ内
に注型し、長さ20cmの膜モジュールを作製した。As the ultrafiltration membrane, a hollow fiber ultrafiltration membrane manufactured by Nitto Denko Corporation was used. Such a molecular weight cutoff is equivalent to 20,000 based on polyethylene glycol (6,000 based on protein). This ultrafiltration membrane was cast in a polypropylene tube to produce a membrane module having a length of 20 cm.
評価用原液のコロイダルシリカ溶液には、日産化学
（株）製のスノーテックスXS（粒子径４〜6mμｍ）を用
い、適宜クリーン水で希釈し、塩酸及び水酸化ナトリウ
ムにてpH調整を行い評価を行った。For the colloidal silica solution of the stock solution for evaluation, use Snowtex XS (particle size: 4-6 mμm) manufactured by Nissan Chemical Industries, Ltd., appropriately dilute with clean water, adjust the pH with hydrochloric acid and sodium hydroxide, and evaluate. went.
阻止率は、セイコー電子工業（株）製プラズマ発光分
析装置SPS−7000を用い、IPC法にて原液及び透過液のケ
イ素濃度を測定し、次式により算出して求めた。The rejection was determined by measuring the silicon concentration of the undiluted solution and the permeate by the IPC method using a plasma emission analyzer SPS-7000 manufactured by Seiko Denshi Kogyo KK and calculating by the following formula.
また、比較例で用いたポリエチレングリコール（分子
量20,000）については、クリーンな純水に溶解して評価
原液とし、阻止率は屈折計にて濃度を測定し求めた。 The polyethylene glycol (molecular weight 20,000) used in the comparative example was dissolved in clean pure water to prepare an evaluation stock solution, and the rejection was determined by measuring the concentration with a refractometer.
実施例１ コロイダルシリカ（平均粒径50Å（換算分子量15,00
0））溶液を、濃度1,000ppm、pH8に調整し、これを膜面
線速0.6m/sec、平均圧力0.5、1.0、1.5kgf/cm2の各条件
で、膜モジュールの内側より濾過させた時のコロイダル
シリカ粒子の阻止率を第１図に示す。Example 1 Colloidal silica (average particle size: 50Å (converted molecular weight: 15,00
0)) The solution was adjusted to a concentration of 1,000 ppm and a pH of 8, and was filtered from the inside of the membrane module under the conditions of a linear velocity of the membrane surface of 0.6 m / sec, an average pressure of 0.5, 1.0 and 1.5 kgf / cm 2 . FIG. 1 shows the rejection of colloidal silica particles at the time.
比較例１ ポリエチレングリコール（分子量20,000）溶液を濃度
5,000ppmに調整し、これを実施例１と同様の条件下で濾
過させた時のポリエチレングリコールの阻止率を第１図
に併せて示す。Comparative Example 1 Concentration of polyethylene glycol (molecular weight 20,000) solution
FIG. 1 also shows the rejection of polyethylene glycol when adjusted to 5,000 ppm and filtered under the same conditions as in Example 1.
実施例２ コロイダルシリカ（平均粒径50Å（換算分子量15,00
0））溶液を、濃度1,000ppm、pH8に調整し、これを平均
圧力1.0kgf/cm2、膜面線速0.2、0.6、1m/secの各条件
で、膜モジュールの内側より濾過させた時のコロイダル
シリカ粒子の阻止率を第２図に示す。Example 2 Colloidal silica (average particle size: 50Å (converted molecular weight: 15,00
0)) When the solution was adjusted to a concentration of 1,000 ppm and a pH of 8, and was filtered from the inside of the membrane module under the conditions of an average pressure of 1.0 kgf / cm 2 , a linear velocity of the membrane surface of 0.2, 0.6, and 1 m / sec. FIG. 2 shows the rejection of the colloidal silica particles.
比較例２ ポリエチレングリコール（分子量20,000）溶液を濃度
5,000ppmに調整し、これを実施例２と同様の条件下で濾
過させた時のポリエチレングリコールの阻止率を第２図
に併せて示す。Comparative Example 2 Concentration of Polyethylene Glycol (Molecular Weight 20,000) Solution
FIG. 2 also shows the rejection of polyethylene glycol when adjusted to 5,000 ppm and filtered under the same conditions as in Example 2.
実施例３ pH6、８、10の３種類のコロイダルシリカ（平均粒径5
0Å（換算分子量15,000））1,000ppm溶液を用い、平均
圧力1.0kgf/cm2、膜面線速0.6m/secの条件で、膜モジュ
ールの内側より濾過させた時のコロイダルシリカ粒子の
阻止率を第３図に示す。Example 3 Three types of colloidal silica having an average particle size of 5 (pH 6, 8, 10)
0Å (converted molecular weight 15,000)) The rejection of colloidal silica particles when filtered from the inside of the membrane module using a 1,000 ppm solution at an average pressure of 1.0 kgf / cm 2 and a membrane surface linear velocity of 0.6 m / sec. As shown in FIG.
上記実施例より明らかな如く、限外濾過膜のコロイダ
ルシリカの阻止率は、圧力条件及び流れによる剪断力条
件の影響をほとんど受けなかった。As is clear from the above examples, the rejection of colloidal silica in the ultrafiltration membrane was hardly affected by the pressure condition and the shear force condition due to the flow.
また、コロイダルシリカ溶液のpHに対しても、pH6〜1
0の中性域ではほとんど影響を受けなかった。Also, with respect to the pH of the colloidal silica solution, pH 6-1
In the neutral region of 0, it was hardly affected.
本発明によれば、圧力条件や流れによる剪断力条件の
影響をほとんど受けず、かつpH条件についても、pH6〜1
0の中性域でほとんど影響を受けることなく、限外濾過
膜の分画性能評価を行うことができる。According to the present invention, it is hardly influenced by the pressure condition and the shearing force condition due to the flow, and the pH condition is pH 6-1.
The fractionation performance of the ultrafiltration membrane can be evaluated with little effect in the neutral region of 0.
第１〜３図は、実施例及び比較例で得られた阻止率の測
定結果を表すグラフである。FIGS. 1 to 3 are graphs showing the measurement results of the rejection obtained in the examples and comparative examples.
Claims (1)
とする限外濾過膜の分画性能評価方法。1. A method for evaluating the fractionation performance of an ultrafiltration membrane, comprising using colloidal silica particles.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11653590A JP2851371B2 (en) | 1990-05-02 | 1990-05-02 | Ultrafiltration membrane fractionation performance evaluation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11653590A JP2851371B2 (en) | 1990-05-02 | 1990-05-02 | Ultrafiltration membrane fractionation performance evaluation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0416217A JPH0416217A (en) | 1992-01-21 |
| JP2851371B2 true JP2851371B2 (en) | 1999-01-27 |
Family
ID=14689534
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11653590A Expired - Lifetime JP2851371B2 (en) | 1990-05-02 | 1990-05-02 | Ultrafiltration membrane fractionation performance evaluation method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2851371B2 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4985904B2 (en) * | 2005-03-18 | 2012-07-25 | 栗田工業株式会社 | Membrane evaluation method in membrane separator |
| JP4874179B2 (en) * | 2007-07-04 | 2012-02-15 | 国立大学法人東北大学 | Ultrafiltration membrane, method for producing the same, and method for size separation of nanoparticles |
| JP4903756B2 (en) * | 2008-07-10 | 2012-03-28 | メタウォーター株式会社 | Membrane inspection method |
| JP2010253334A (en) * | 2009-04-21 | 2010-11-11 | Sepa Sigma Inc | Aqueous solution with distributed ferric hydroxide colloidal particles for nondestructive membrane performance and integrity test, and method of manufacturing the aqueous solution |
-
1990
- 1990-05-02 JP JP11653590A patent/JP2851371B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0416217A (en) | 1992-01-21 |
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