JPS61249505A - Method for preserving fluid separator - Google Patents
Method for preserving fluid separatorInfo
- Publication number
- JPS61249505A JPS61249505A JP9210485A JP9210485A JPS61249505A JP S61249505 A JPS61249505 A JP S61249505A JP 9210485 A JP9210485 A JP 9210485A JP 9210485 A JP9210485 A JP 9210485A JP S61249505 A JPS61249505 A JP S61249505A
- Authority
- JP
- Japan
- Prior art keywords
- fluid separation
- separation device
- preserving
- cellulose ester
- membrane
- 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.)
- Granted
Links
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
Description
【発明の詳細な説明】
(産業上の利用分野)
本発明は、セルロースエステルからなる選択透過性の中
空糸膜、スパイラル型膜、チューブラ−型膜等から構成
される流体分離装置の性能を保持した状態で保存するた
めの保存方法に関するものである。Detailed Description of the Invention (Industrial Application Field) The present invention maintains the performance of a fluid separation device composed of a permselective hollow fiber membrane, a spiral type membrane, a tubular type membrane, etc. made of cellulose ester. This relates to a preservation method for preserving the material in a preserved state.
(従来の技術)
従来のセルローズエステルからなる選択性透過膜で構成
された流体分離装置を保存する方法としチ一般に0.1
%以上かつ5%以下の濃度のホルマリンを含む水溶波を
流体分離装置に充填する方法がとられている。0.1%
以上かつ3%以下のホルマリンを使ったセルロースエス
テルからなる選択性透過膜で構成される流体分離装置の
保存方法は流体分離装置の性能保持という面では非常に
良い方法である。また、ホルマリンによる流体分離装置
内の無菌性の保持という面でも、ホルマリンによる殺菌
能力が十分に強力であるということから非常に優れた流
体分離装置の保存剤である。しかしながら、同時に、流
体分離装置内に充填されているホルマリンを水洗操作す
ることにより、流体分離装置内から排除するには、ホル
マリン濃度が低濃度になるまで洗浄しなければならない
ので、数時間乃至24時間という長い洗浄時間を必要と
するという欠点を合わせ持っていた。(Prior Art) As a conventional method for preserving a fluid separation device configured with a selectively permeable membrane made of cellulose ester,
A method has been adopted in which a fluid separation device is filled with an aqueous wave containing formalin at a concentration of 5% or more and 5% or less. 0.1%
The method of preserving a fluid separation device constituted by a selectively permeable membrane made of cellulose ester using formalin of 3% or less is a very good method in terms of maintaining the performance of the fluid separation device. Furthermore, in terms of maintaining sterility within the fluid separation device using formalin, formalin is an extremely excellent preservative for fluid separation devices because its sterilizing ability is sufficiently strong. However, at the same time, in order to remove the formalin filled in the fluid separation device from the fluid separation device by washing with water, it is necessary to wash the formalin until the concentration of formalin becomes low, which takes several hours to 24 hours. It also had the disadvantage of requiring a long cleaning time.
(発明が解決しようとする問題点)
本発明者らは、セルロースエステルからなる選択性透過
膜の性能保持性が良く、かつ殺菌性を持った保存液で、
流体分離装置を水洗により洗浄する時に排除効率性が良
い流体分離装置の保存液について鋭意研究した結果、本
発明に至った。(Problems to be Solved by the Invention) The present inventors have developed a storage solution that has good performance retention for a selectively permeable membrane made of cellulose ester and has bactericidal properties.
The present invention was achieved as a result of intensive research into a storage solution for a fluid separation device that has good removal efficiency when the fluid separation device is washed with water.
(問題を解決するための手段)
即ち、本発明は、セルローズエステルからなる選択性透
過膜で構成される流体分離装置を保存するに際し、流体
分離装置内に101!9/A以上かつ14000岬/を
以下の亜硫酸水素ナトリウムおよび0.5%以上かつ2
5%以下の多価アルコール水溶液を流体分離装置の保存
剤として流体分離装置内に充填する流体分離装置の保存
方法である。(Means for Solving the Problem) That is, the present invention provides, when storing a fluid separation device constituted by a selectively permeable membrane made of cellulose ester, a fluid separation device containing 101!9/A or more and 14000 cape/A. Sodium bisulfite and not less than 0.5% and 2
This is a method for preserving a fluid separation device in which a 5% or less polyhydric alcohol aqueous solution is filled into the fluid separation device as a preservative for the fluid separation device.
また、本発明の好適態様としてアルカリ土類金属塩を前
記の亜硫酸水素す) IJウムおよび多価アルコールを
含む保存液に更に添加することにより、選択性透過膜の
膜性能の保持性を更に高めることができる。In addition, as a preferred embodiment of the present invention, by further adding an alkaline earth metal salt to the storage solution containing hydrogen sulfite and polyhydric alcohol, the retention of membrane performance of the selectively permeable membrane can be further enhanced. be able to.
セルローズエステルからなる選択性透過膜で構成される
流体分離装置の保存液として、亜硫酸水素ナトリウムを
多価アルコールと混合せず、亜硫酸水素す) IJウム
単独の水溶液を流体分離装置に充填する場合には、亜硫
酸水素す) IJウムが分解することにより充填した水
溶液のpHが低下し、セルローズエステルが加水分解さ
れることにより選択性透過膜の膜性能が低下する結果に
なってしまう。また、セルロースエステルからなる選択
性透過膜で構成された流体分離装置の保存液として多価
アルコールを亜硫酸水素ナトリウムと混合せず、多価ア
ルコール単独の水溶液を流体分離装置に充填する場合に
は多価アルコールによる殺菌効果が小さいために長期間
保存すると流体分離装置内に細菌が繁殖する結果になる
。セルロースエステルは特定の細菌の栄養源にもなりう
ろことから、選択性透過膜が特定の細菌に蚕食され、選
択性透過膜の膜性能が低下することもある。When filling a fluid separation device with an aqueous solution of sodium hydrogen sulfite (without mixing sodium bisulfite with polyhydric alcohol and using hydrogen sulfite instead of mixing it with a polyhydric alcohol) as a storage solution for a fluid separation device consisting of a selectively permeable membrane made of cellulose ester. (Hydrogen sulfite) The decomposition of IJium lowers the pH of the filled aqueous solution, and the hydrolysis of cellulose ester results in a decrease in the membrane performance of the selectively permeable membrane. In addition, when filling an aqueous solution of polyhydric alcohol alone as a storage solution in a fluid separation device configured with a selectively permeable membrane made of cellulose ester without mixing polyhydric alcohol with sodium bisulfite, it is possible to Since the sterilizing effect of alcohol is low, long-term storage will result in bacterial growth within the fluid separation device. Since cellulose ester can also serve as a nutrient source for certain bacteria, the selectively permeable membrane may be eaten by certain bacteria, resulting in a decrease in the membrane performance of the selectively permeable membrane.
本発明では亜硫酸水素ナトリウムと多価アルコールを混
合した水溶液を使用することが必須である。In the present invention, it is essential to use an aqueous solution containing a mixture of sodium bisulfite and polyhydric alcohol.
本線纂で用いる亜硫酸水素す) IJウムは重亜硫醗ナ
トリウムとも言われる。また、市販の亜硫酸水素ナトリ
ウムには、一般にピロ亜硫酸ナトリウムが多く含まれて
おり、ピロ亜硫酸ナトリウムも亜硫酸水素す) IJウ
ムと同じ物質と本各論では考えるO
また、多価アルコールとは、同一分子内に水酸基を2個
以上もつアルコールをいう。二価アルコール、三価アル
コール、グリセリン等が挙げられ透過膜(逆浸透膜、限
外濾過膜、精密濾過膜等を含む)を主構成要素とする一
般的に言うエレメントを意味すると同時に、エレメント
および外筒等み替えることができる。また流体分離装置
内に保存剤を充填するということは、流体分離装置内の
空間部に1%乃至100%の割合で充填することを意味
する。モジュールを保存する方法として、水を選択性分
離膜により精製する装置等を停台する場合には、モジュ
ールを装置に取付けた状態のまま保存することもある。Hydrogen sulfite (IJum) used in the main line is also called sodium bisulfite. In addition, commercially available sodium bisulfite generally contains a large amount of sodium pyrosulfite, and sodium pyrosulfite is also hydrogen sulfite).In this article, it is considered to be the same substance as IJium. An alcohol that has two or more hydroxyl groups within it. Dihydric alcohol, trihydric alcohol, glycerin, etc. are mentioned, and at the same time it means an element that has a permeable membrane (including reverse osmosis membrane, ultrafiltration membrane, precision filtration membrane, etc.) as its main component, and also refers to an element and The outer cylinder etc. can be replaced. Furthermore, filling the fluid separation device with a preservative means filling the space within the fluid separation device at a rate of 1% to 100%. When a device for purifying water using a selective separation membrane or the like is stopped, the module may be stored while attached to the device.
この場合には、モジュールを含めた装置全体に本発明の
保存液を充填させる。流体分離装置の性能保持という面
では逆浸透膜の場合に高い塩除去率が要求されるので、
本発明は逆浸透膜の保存に対し特に有効なものである。In this case, the entire device including the module is filled with the preservation solution of the present invention. In order to maintain the performance of fluid separation equipment, reverse osmosis membranes require a high salt removal rate.
The present invention is particularly effective for preserving reverse osmosis membranes.
尚、本発明に係るセルローズエステルとはセルロースジ
アセテート、セルローストリアセテート、硝酸セルロー
ス等が挙げられる。Note that the cellulose ester according to the present invention includes cellulose diacetate, cellulose triacetate, cellulose nitrate, and the like.
(発明の効果)
セルローズエステルからなる選択性透過膜で構成される
流体分離装置の保存液としては、選択性透過膜の膜性能
の保持、殺菌性および保存剤の洗浄除去性が良いものが
望まれる。本発明は前記の3つの特性を十分に満足した
セルロースエステルからなる選択性透過膜の保存液であ
り、セルロースエステルからなる選択性透過膜で構成さ
れるエレメントおよびモジエール等の流体分離装置の保
管、運搬等の時に利用することができる。また、セルミ
ーXエステルからなる前記のモジュールを組み込んだ水
の精製装置、および海水またはカン水から飲料水または
純水を製造するための装置を停台するときおよび装置を
建設または改造してから運転するまでの間の選択性透過
膜の効果的保存液として有効に使用することができる。(Effect of the invention) As a storage solution for a fluid separation device composed of a selectively permeable membrane made of cellulose ester, it is desirable to have a solution that maintains the membrane performance of the selectively permeable membrane, has good sterilization properties, and has good washing and removal properties of the preservative. It will be done. The present invention is a storage solution for a selectively permeable membrane made of cellulose ester that fully satisfies the above three characteristics, and is a storage solution for a fluid separation device such as an element and a module made of a selectively permeable membrane made of cellulose ester. It can be used for transportation, etc. Also, when shutting down a water purification device incorporating the above-mentioned module made of Selmy It can be effectively used as an effective preservation solution for selectively permeable membranes until the time of use.
(実施例)
以下本発明の実施例を記載するが、本発明はこれら実施
例に限定されるものではない。(Examples) Examples of the present invention will be described below, but the present invention is not limited to these Examples.
実施例1及び実施例2
実施例および比較例として、セルローズトリアセテート
からなる選択性透過膜により逆浸透膜を作製し、以下に
記載する成分を含み水溶液を保存液として使用した場合
の膜性能保持率、殺菌能力を第1表に示す。Example 1 and Example 2 As an example and a comparative example, a reverse osmosis membrane was prepared using a selective permeation membrane made of cellulose triacetate, and the membrane performance retention rate was obtained when an aqueous solution containing the components listed below was used as a storage solution. Table 1 shows the bactericidal ability.
膜性能保持率としては逆浸透膜を1500ppmi1度
、25℃、30Kf/32Qで運転した時の塩除去率〔
%〕および水透過性能Crt//klr )を測定し、
評価開始時の値と保存液に1ケ月間浸漬した後、同様に
測定した値の比率を示す。The membrane performance retention rate is the salt removal rate when the reverse osmosis membrane is operated at 1500ppmi at 1 degree, 25℃, and 30Kf/32Q.
%] and water permeability Crt//klr),
The ratio between the value at the start of evaluation and the value similarly measured after being immersed in the storage solution for one month is shown.
殺菌能力は、大腸菌を指標菌として使用し評価開始時に
流体分離装置内に約10”個/−の菌濃度になる様に充
填液中に添加し、更に保存剤を添加してから24時間後
の充填液中の菌濃度を初期の値との比率で示す。The bactericidal ability is determined by using Escherichia coli as an indicator bacterium and adding it to the filling liquid at the beginning of the evaluation to a concentration of approximately 10" bacteria/- in the fluid separation device, and 24 hours after adding a preservative. The bacterial concentration in the filling liquid is expressed as a ratio to the initial value.
第 1 表
#11表の結果から実施例(瀧1)は膜性能の保持率が
良く、殺菌能力も高いことを示しているが、Nllの比
較例に示したように亜硫酸水素ナトリウム単独の場合に
は、十分な殺菌能力が得られず膜性能の保持率も低下し
ている。The results in Table 1 #11 show that Example (Taki 1) has a good membrane performance retention rate and high sterilizing ability, but as shown in the comparative example of Nll, when using sodium bisulfite alone, However, sufficient sterilizing ability cannot be obtained and the retention rate of membrane performance is also decreasing.
1@2の比較例の場合には、グリセリンのみでは殺菌能
力が全く無いばかりか、細菌によるセルローズエステル
膜の蚕食が原因でFR保持率が100%以上になってし
まった。この現象は、大巾なRJ保持率の低下を伴なう
ので膜性能は悪くなってしまう。In the case of Comparative Example 1@2, glycerin alone had no bactericidal ability at all, and the FR retention rate was over 100% due to the phagocytosis of the cellulose ester film by bacteria. This phenomenon is accompanied by a large decrease in RJ retention, resulting in poor membrane performance.
実施例のN12で示すようにアルカリ土類金属塩である
1J01zを、実施例のNIILIの液に添加すると膜
性能の保持率が実施例のNllの場合よりも更に良くな
ることがわかる。It can be seen that when the alkaline earth metal salt 1J01z, as shown by N12 in the example, is added to the NIILI solution in the example, the membrane performance retention rate becomes even better than in the case of Nll in the example.
実施例3
保存剤としてのグリセリンの添加は、セ・ルローズエス
テルの選択透過性膜に対して使用される場合には、グリ
セリン自身の影響による膜性能の保持と亜硫酸水素す)
IJウムが分解するのを防ぐことにより亜硫酸水素ナ
トリウムの分解により保存剤のpHが下がり、これが原
因でセルローズエステルが分解するという反応を防ぐと
いう効果も合わせ持っている。そこで、第2表にセルロ
ーズエステルに対するグリセリン濃度と亜硫酸水素ナト
リウム濃度の保持率との関係を示す。Example 3 When the addition of glycerin as a preservative is used for a cellulose ester permselective membrane, the membrane performance is maintained due to the influence of glycerin itself and hydrogen sulfite (hydrogen sulfite) is maintained.
By preventing the decomposition of IJum, the pH of the preservative is lowered by the decomposition of sodium bisulfite, which also has the effect of preventing the reaction in which cellulose ester decomposes. Therefore, Table 2 shows the relationship between the retention rate of glycerin concentration and sodium bisulfite concentration for cellulose ester.
第2表かられかるように亜硫酸水素ナトリウムとグリセ
リンとの混合液等では、グリセリン濃度が0.5%未満
では亜硫酸水素す)9ウムの保持率が悪く、またこの時
のpHが3以下になるのでセルローズエステルからなる
選択性分m11Mの保存剤としては適さない。また、グ
リセリンの濃度が25%を越えるとグリセリンの保存剤
中での分散が悪いので適さない。As can be seen from Table 2, when the glycerin concentration is less than 0.5%, the retention rate of hydrogen sulfite (9um) is poor in a mixed solution of sodium hydrogen sulfite and glycerin, and the pH at this time is 3 or less. Therefore, it is not suitable as a preservative for selective fraction m11M consisting of cellulose ester. Furthermore, if the concentration of glycerin exceeds 25%, it is not suitable because the glycerin will be poorly dispersed in the preservative.
実施例4
第3表にセルロースエステルに対する亜硫酸水素す)
IJウム濃度と殺菌能力との関係を示す。第3表の比較
テストでは保存液中に10%のグリセリンを添加した状
態で行なった。ここで言う殺菌能力の意味およびテスト
法は第1表の場合と同じである。Example 4 Table 3 shows hydrogen sulfite for cellulose ester)
The relationship between IJum concentration and bactericidal ability is shown. The comparative tests shown in Table 3 were conducted with 10% glycerin added to the storage solution. The meaning and test method of sterilizing ability here are the same as in Table 1.
第3表の結果から、保存液中の亜硫酸水素ナトリウム濃
度が5■/を以下の場合には保存液による殺菌能力が著
しく低下することがわかる。また、保存液中の亜硫酸水
素す) IJウム濃度が14000my/lを越えると
亜硫酸水素ナトリウムが分解して発生する亜硫酸ガスの
臭いが強くなり取り扱いが難しくなる。 ″
実施例5
@4表に本発明による保存液の水洗による洗浄除去性を
1%ホルマリンを使用した場合と比較して示す。From the results in Table 3, it can be seen that when the concentration of sodium bisulfite in the storage solution is less than 5 ml, the bactericidal ability of the storage solution is significantly reduced. In addition, if the concentration of hydrogen sulfite in the storage solution exceeds 14,000 my/l, the odor of sulfur dioxide gas generated by decomposition of sodium hydrogen sulfite becomes strong and handling becomes difficult. ``Example 5 @Table 4 shows the washing removability of the preservation solution according to the present invention by washing with water in comparison with the case where 1% formalin was used.
この洗浄テストは、セルローストリアセテートからなる
選択性透過膜により逆浸透膜を作成し、流体分離装置に
組み込み、この流体分離装置に保存液を前もって充填し
た後、流体分離装置を水洗洗浄した時に流体分離装置の
排出口から出てくる液をサンプリングして、亜流酸水素
ナトリウムの濃度またはホルマリンの濃度を測定した。In this cleaning test, a reverse osmosis membrane was created using a selective permeation membrane made of cellulose triacetate, was incorporated into a fluid separation device, and after the fluid separation device was filled with a storage solution in advance, fluid separation occurred when the fluid separation device was washed with water. The liquid coming out of the outlet of the device was sampled to measure the concentration of sodium hydrogen sulfite or formalin.
そして各々の濃度が一定値以下になるまでの所要時間を
測定した。Then, the time required for each concentration to fall below a certain value was measured.
第 4 表
実施例5は亜硫酸水素ナトリウムを2000 W/lお
よびグリセリンを20%含む水溶液を保存液として使用
した。In Example 5 of Table 4, an aqueous solution containing 2000 W/l of sodium bisulfite and 20% glycerin was used as a storage solution.
また、比較例3はxray/lのホルマリン水溶液を保
存液として使用した。Furthermore, in Comparative Example 3, xray/l formalin aqueous solution was used as the storage solution.
第4表から、実施例5の方が比較例3よりも水洗洗浄に
よる保存剤の排除性がはるかに優れていることがわかる
。From Table 4, it can be seen that Example 5 is far superior to Comparative Example 3 in removing the preservative by washing with water.
Claims (2)
される流体分離装置を保存するに際し、流体分離装置内
に10mg/l以上かつ1400mg/を以下の亜硫酸
水素ナトリウムおよび0.5%以上かつ25%以下の多
価アルコールを含む水溶液を流体分離装置の保存液とし
て充填することを特徴とする流体分離装置の保存方法。(1) When storing a fluid separation device composed of a selectively permeable membrane made of cellulose ester, the fluid separation device must contain at least 10 mg/l and 1400 mg/l of sodium bisulfite and at least 0.5% and 25% A method for preserving a fluid separation device, comprising filling the following aqueous solution containing a polyhydric alcohol as a storage solution for the fluid separation device.
る特許請求の範囲第(1)項記載の流体分離装置の保存
方法。(2) A method for preserving a fluid separation device according to claim (1), which uses an aqueous solution to which an alkaline earth metal salt is further added.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP9210485A JPS61249505A (en) | 1985-04-27 | 1985-04-27 | Method for preserving fluid separator |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP9210485A JPS61249505A (en) | 1985-04-27 | 1985-04-27 | Method for preserving fluid separator |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS61249505A true JPS61249505A (en) | 1986-11-06 |
JPH0472569B2 JPH0472569B2 (en) | 1992-11-18 |
Family
ID=14045131
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP9210485A Granted JPS61249505A (en) | 1985-04-27 | 1985-04-27 | Method for preserving fluid separator |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS61249505A (en) |
Cited By (24)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1312408A2 (en) * | 2001-11-16 | 2003-05-21 | US Filter Wastewater Group, Inc. | Method of cleaning membranes |
WO2005123233A1 (en) * | 2004-06-22 | 2005-12-29 | Toyo Boseki Kabushiki Kaisha | Storage solution for fluid separator and/or membrane element, fluid separator and membrane element, and method of storing the same |
JP2007063222A (en) * | 2005-09-01 | 2007-03-15 | Mitsubishi Rayon Eng Co Ltd | Preservation liquid for separation membrane, separation membrane module and method for preservation of separation membrane |
JP2011131173A (en) * | 2009-12-25 | 2011-07-07 | Sepa Sigma Inc | Flat membrane set for filtration separation, module, and method for preserving the same |
US8268176B2 (en) | 2003-08-29 | 2012-09-18 | Siemens Industry, Inc. | Backwash |
US8287743B2 (en) | 2007-05-29 | 2012-10-16 | Siemens Industry, Inc. | Membrane cleaning with pulsed airlift pump |
US8293098B2 (en) | 2006-10-24 | 2012-10-23 | Siemens Industry, Inc. | Infiltration/inflow control for membrane bioreactor |
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JP2011131173A (en) * | 2009-12-25 | 2011-07-07 | Sepa Sigma Inc | Flat membrane set for filtration separation, module, and method for preserving the same |
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