JPH01288305A - Modifying method for sulfonic multi-layered membrane - Google Patents
Modifying method for sulfonic multi-layered membraneInfo
- Publication number
- JPH01288305A JPH01288305A JP11695188A JP11695188A JPH01288305A JP H01288305 A JPH01288305 A JP H01288305A JP 11695188 A JP11695188 A JP 11695188A JP 11695188 A JP11695188 A JP 11695188A JP H01288305 A JPH01288305 A JP H01288305A
- Authority
- JP
- Japan
- Prior art keywords
- membrane
- sulfonic acid
- sulfonated
- heat
- aqueous solution
- 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
- 239000012528 membrane Substances 0.000 title claims abstract description 73
- 238000000034 method Methods 0.000 title claims description 9
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000007864 aqueous solution Substances 0.000 claims abstract description 22
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229920002492 poly(sulfone) Polymers 0.000 claims abstract description 11
- 229920000642 polymer Polymers 0.000 claims abstract description 11
- 125000000542 sulfonic acid group Chemical group 0.000 claims abstract description 9
- 239000004697 Polyetherimide Substances 0.000 claims abstract description 6
- 229920001601 polyetherimide Polymers 0.000 claims abstract description 6
- 239000002131 composite material Substances 0.000 claims description 27
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 8
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 6
- 229920006380 polyphenylene oxide Polymers 0.000 claims description 6
- 238000010030 laminating Methods 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 23
- 239000000243 solution Substances 0.000 abstract description 8
- 150000001875 compounds Chemical class 0.000 abstract description 5
- 230000007935 neutral effect Effects 0.000 abstract description 5
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 abstract 2
- 239000000126 substance Substances 0.000 abstract 1
- 230000035699 permeability Effects 0.000 description 14
- 239000005720 sucrose Substances 0.000 description 12
- 229930006000 Sucrose Natural products 0.000 description 11
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 11
- 230000007717 exclusion Effects 0.000 description 9
- 239000010408 film Substances 0.000 description 9
- 239000012510 hollow fiber Substances 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 238000001223 reverse osmosis Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229920000368 omega-hydroxypoly(furan-2,5-diylmethylene) polymer Polymers 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 150000003384 small molecules Chemical class 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N Tetraethylene glycol, Natural products OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- -1 alkali metal salt Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- VAOCPAMSLUNLGC-UHFFFAOYSA-N metronidazole Chemical compound CC1=NC=C([N+]([O-])=O)N1CCO VAOCPAMSLUNLGC-UHFFFAOYSA-N 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
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、溶液系におけるイオンや低分子化合物の分離
に有用なスルホン酸型複合膜の溶質排除率を向上させる
方法に関するもので、本発明によって改質された膜は耐
熱性を有する低圧型逆浸透膜として利用できる。Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a method for improving the solute exclusion rate of a sulfonic acid type composite membrane useful for separating ions and low molecular weight compounds in a solution system. The modified membrane can be used as a heat-resistant, low-pressure reverse osmosis membrane.
（従来の技術）
近年、その操作性と経済性の観点から、耐熱性を持ち、
しかも低い圧力で操作できる逆浸透膜の研究が盛んに行
われているが、耐熱性エンジニアリングプラスチックを
スルホン化したポリマーは、その要求を満たす膜素材と
して利用することができる。その中でもスルホン化ポリ
スルホン（例えば、特開昭６１−４５０６など）、スル
ホン化ポリフェニレンオキサイド（例えば、特公昭４３
−１３１３１など）はそのまま製膜したり、あるいは適
当な支持膜上に積層させたりして複合膜として利用でき
ることが報告されている。一般に逆浸透膜では、従来の
酢酸セルロースに代表されるような、イオンや低分子化
合物に対して高い排除率を示すものは耐熱性に乏しい。(Conventional technology) In recent years, from the viewpoint of operability and economic efficiency,
Moreover, research into reverse osmosis membranes that can be operated at low pressures is being actively conducted, and sulfonated heat-resistant engineering plastics can be used as membrane materials that meet these requirements. Among them, sulfonated polysulfone (for example, JP-A-61-4506), sulfonated polyphenylene oxide (for example, JP-A-43
-13131, etc.) can be used as a composite film by forming a film as it is or by laminating it on a suitable support film. In general, reverse osmosis membranes that exhibit a high rejection rate for ions and low-molecular compounds, such as conventional cellulose acetate, have poor heat resistance.
また高い排除率を示し、かつ９０℃近い高温にも耐える
といわれているスルホン化ポリフルフリルアルコール膜
（例えば、１．Ｃａｂａｓｓｏ、Ａ、Ｐ、Ｔａｍｖａｋ
ｉｓ、Ｊ、Ａｐｐｌ、Ｐｏｌｙｍ、Ｓｃｉ、、１９７９
，２３．１５０９−１５２５など）は、４０ ｋ ｇ
／ ｃ ｍ ”以上の使用圧力を必要とし透水性も低い
（圧力１０ｋｇ／ａｍ２に換算しておよそ０，１〜０．
２ｍ３７ｍ” ・日）といった、操作上・経済上の難点
を持っている。−方、１５ｋｇ／ｃｍ２程度の低い圧力
で使用でき、イオンおよびアルコールのような低分子化
合物に対しても高い排除率を示すポリアミド系の複合膜
（例えば、特開昭６２−１２１６０３など）も報告され
ているが、ポリアミド系の膜は一般に膜の殺菌や洗浄に
必要な塩素に対する耐久性に乏しく、かつ耐熱性がない
ため、その使用範囲は限定されてしまう。これに対して
、上記のスルホン化された耐熱性ポリマーを利用すると
、これらの欠点をカバーした、耐熱性を持ち１０ ｋ
ｇ ／ ｃｍ２程度の低い圧力で操作できる複合膜を提
供することができる。しかしながら、これらの膜はその
排除率において、一般の逆浸透膜に対して劣る。とりわ
け、電気的に中正な低分子化合物に対しては高い排除率
を期待できず、例えばスルホン化ポリフェニレンオキサ
イド複合膜における、分子量３４２のショ糖の排除率は
４０％程度である（例えば、特願昭６２−５９９２８な
ど）。これは、膜中のスルホン酸基の水和による膜の膨
潤により膜の緻密性が減少するのに加え、電気的に中性
な化合物は膜中のスルホン酸基の持つ陰電荷によるドナ
ン排除の影響を受けないためだと解釈される。In addition, sulfonated polyfurfuryl alcohol membranes (for example, 1.Cabasso, A, P, Tamvak
is, J. Appl, Polym, Sci., 1979
, 23.1509-1525, etc.) is 40 kg
/ cm" or more, and the water permeability is low.
However, it has operational and economical drawbacks, such as 2m37m"/day). On the other hand, it can be used at a low pressure of about 15kg/cm2, and has a high rejection rate even for ions and low-molecular compounds such as alcohol. Polyamide-based composite membranes (e.g., JP-A-62-121603) have also been reported, but polyamide-based membranes generally have poor durability against chlorine, which is necessary for sterilizing and cleaning the membrane, and lack heat resistance. Therefore, its range of use is limited.On the other hand, the use of the above-mentioned sulfonated heat-resistant polymer overcomes these drawbacks and has heat resistance of 10K.
Composite membranes can be provided that can be operated at pressures as low as g/cm2. However, these membranes are inferior to general reverse osmosis membranes in their rejection rates. In particular, a high rejection rate cannot be expected for electrically neutral low-molecular compounds; for example, the rejection rate of sucrose with a molecular weight of 342 in a sulfonated polyphenylene oxide composite membrane is about 40% (for example, in the patent application (Sho 62-59928, etc.) This is because the density of the membrane decreases due to swelling of the membrane due to hydration of the sulfonic acid groups in the membrane, and electrically neutral compounds are more susceptible to Donnan exclusion due to the negative charge of the sulfonic acid groups in the membrane. It is interpreted that this is to avoid being affected.
（発明が解決しようとする問題点）
本発明は、耐熱性を有したスルホン酸型複合膜の溶質排
除性を向上させる方法を提供せんとするものである。(Problems to be Solved by the Invention) The present invention aims to provide a method for improving the solute exclusion properties of a heat-resistant sulfonic acid type composite membrane.
（問題を解決するための手段）
本発明は、スルホン酸型複合膜の表面に、フルフリルア
ルコールと硫酸を含む水溶液を含浸させ、次いで加熱す
ることによって、１０ ｋ ｇ ／ ｃｍ２程度の低い
圧力で操作でき、耐熱性と高い溶質排除率を持った複合
膜が得られることを見出し、これに基すいてなされたも
のである。この原因についての詳細はあきらかではない
が、スルホン酸基を含んだポリマーより成る複合膜の活
性層が、硫酸存在下におけるフルフリルアルコールの重
合によって生成するスルホン化ポリフルフリルアルコー
ルによって、ポリマー鎖同士が複雑にからみあった状態
で固定化され、その結果として水分子の浸透による膨潤
が妨げられるためと推定される。(Means for Solving the Problems) The present invention impregnates the surface of a sulfonic acid type composite membrane with an aqueous solution containing furfuryl alcohol and sulfuric acid, and then heats the membrane to produce a membrane with a pressure as low as 10 kg/cm2. This work was carried out based on the discovery that a composite membrane that can be manipulated, has heat resistance, and a high solute exclusion rate can be obtained. The details of the cause of this are not clear, but the active layer of the composite membrane made of a polymer containing sulfonic acid groups is caused by sulfonated polyfurfuryl alcohol produced by polymerization of furfuryl alcohol in the presence of sulfuric acid. It is presumed that this is because they are immobilized in a complexly entangled state, which prevents them from swelling due to the penetration of water molecules.
本発明におけるスルホン酸型複合膜とは、スルホン酸基
を含む耐熱性高分子を支持膜上に活性層として積層させ
た複合膜を指し、スルホン酸基を含む耐熱性高分子とし
てはスルホン化ポリスルホン、スルホン化ポリフェニレ
ンオキサイド又は、スルホン化ポリエーテルイミドなど
が好ましく用いられる。スルホン酸基の状態としては水
素型あるいはアルカリ金属塩いずれの型になっていても
良い。これら複合膜の製法は一般に知られているもので
良く（例えば、Ｒ，Ｙ、Ｍ、Ｈｕａｎｇ。The sulfonic acid type composite membrane in the present invention refers to a composite membrane in which a heat-resistant polymer containing sulfonic acid groups is laminated as an active layer on a support membrane. , sulfonated polyphenylene oxide, or sulfonated polyetherimide are preferably used. The state of the sulfonic acid group may be either hydrogen type or alkali metal salt type. The manufacturing method of these composite membranes may be generally known (for example, R, Y, M, Huang.
Ｊ、Ｊ、にｉｍ、Ｊ、Ａｐｐｌ、Ｐｏｌｙｍ、Ｓｃｉ、
、１９８４，２９．４０２９〜４０３５など）、スルホ
ン酸型ポリマーを、支持膜を溶解しない溶剤に適当な濃
度で溶解し、支持膜上に塗付した後、溶剤を蒸発させて
製膜することができる。支持膜としては特に限定される
ものではないが、上記スルホン酸型ポリマーを溶解する
ような溶剤に対して溶解することのない高分子としてポ
リスルホンやポリエーテルイミドなどがあげられ、とり
わけすぐれた耐熱性、耐塩素性、広範な使用ｐＨ範囲を
持つという点からポリスルホンを用いるのが好ましい。J, J, im, J, Appl, Polym, Sci,
, 1984, 29. 4029-4035, etc.), a sulfonic acid type polymer can be dissolved at an appropriate concentration in a solvent that does not dissolve the support film, applied onto the support film, and then the solvent can be evaporated to form a film. can. The support membrane is not particularly limited, but examples of polymers that do not dissolve in solvents that dissolve the sulfonic acid type polymers include polysulfone and polyetherimide, which have particularly excellent heat resistance. It is preferable to use polysulfone because of its chlorine resistance and wide usable pH range.
また、膜形態としては平服、中空糸等、どのようなもの
でもよく、特に限定されない。Furthermore, the membrane form may be of any type, such as plain clothes or hollow fibers, and is not particularly limited.
この複合膜表面に含浸させる水溶液は、フルフリルアル
コール０．３〜１．５重量％、硫酸０．３〜１．５ｆｆ
ｉ量％の組成より成る。フルフリルアルコールと硫酸の
重量％は、多すぎると重合が進みすぎ、より強固な活性
層を形成するため膜の透水性が低下する。また、少なす
ぎると重合が不十分なために排除率の向上性が小さくな
る。得られる膜性能から見て上記の範囲が適当である。The aqueous solution impregnated on the surface of this composite membrane contains 0.3 to 1.5% by weight of furfuryl alcohol and 0.3 to 1.5ff of sulfuric acid.
It consists of a composition of i amount %. If the weight percentages of furfuryl alcohol and sulfuric acid are too large, polymerization will proceed too much and a stronger active layer will be formed, resulting in a decrease in water permeability of the membrane. On the other hand, if the amount is too small, polymerization will be insufficient and the improvement in rejection rate will be reduced. The above range is appropriate in view of the membrane performance obtained.
なお、上記範囲内で重量％を調整することによって、膜
性能を変化させることができる。また、この水溶液は、
ドデシル硫酸ナトリウム０〜１．０重量％、イソプロパ
ツール０〜２０．０重量％を含んでいても良い。ここで
、ドデシル硫酸ナトリウムはこの水溶液を含浸させる複
合膜表面との親和性を向上させるために、また、イソプ
ロパツールは溶液中でフルフリルアルコールが重合する
のを防ぐために加えられる。なお、ここでいう複合膜表
面とはスルホン酸型ポリマーが積層している活性層側を
指す。Note that the membrane performance can be changed by adjusting the weight % within the above range. In addition, this aqueous solution is
It may contain 0 to 1.0% by weight of sodium dodecyl sulfate and 0 to 20.0% by weight of isopropanol. Here, sodium dodecyl sulfate is added to improve the affinity with the composite membrane surface impregnated with this aqueous solution, and isopropanol is added to prevent furfuryl alcohol from polymerizing in the solution. Note that the composite membrane surface herein refers to the active layer side on which the sulfonic acid type polymer is laminated.
次に、この水溶液をこの複合膜表面に含浸させる。これ
にはどのような方法を用いても良いが、複合膜表面をこ
の溶液に１分程度接触させた後、過剰に付着した溶液を
除去するために膜を数分間垂直に保持する方法が簡便で
ある。その後、この膜を加熱する。この時、加熱温度が
高く、加熱時間が長いほどフルフリルアルコールの重合
は促進され、膜の透水性は低下する。また加熱温度が低
く、加熱時間が短いと重合がなかなか進行せず、排除率
の向上が不十分になる。このように加熱時間と加熱温度
を調整することにより膜性能を変化させることができる
が、得られる膜性能から判断して温度としては１００〜
１３０℃、時間としては１０〜１５分間が適当である。Next, the surface of this composite membrane is impregnated with this aqueous solution. Any method can be used for this, but a convenient method is to contact the composite membrane surface with this solution for about 1 minute and then hold the membrane vertically for several minutes to remove excess solution. It is. This film is then heated. At this time, the higher the heating temperature and the longer the heating time, the more the polymerization of furfuryl alcohol is promoted and the water permeability of the membrane decreases. Furthermore, if the heating temperature is low and the heating time is short, polymerization will not proceed easily and the rejection rate will not be improved sufficiently. The membrane performance can be changed by adjusting the heating time and heating temperature in this way, but judging from the membrane performance obtained, the temperature should be 100~
A temperature of 130° C. for 10 to 15 minutes is appropriate.
以下、実施例によって本発明を具体的に説明する。Hereinafter, the present invention will be specifically explained with reference to Examples.
（実施例１）
ポリスルホン（ＵＣＣ社製のＵｄｅｌ、Ｐ−３５００）
２０重量％、Ｎ、Ｎ−ジメチルアセトアミド７１重量％
、テトラエチレングリコール９重量％を用いて製膜用原
液を作製し、特開昭５８−１５６０１８、実施例１の方
法に準じて、外径１．３５ｍｍ、内径０．７２ｍｍの中
空糸状限外濾過膜を作製した。この膜を含水状態のまま
２５重量％のグリセリン水溶液に６０℃で５時間浸漬し
、次いで、５０℃の乾燥機中で２４時間乾燥させること
により、グリセリンが内部に目詰めされた中空糸状乾燥
限外濾過膜を得た。以下これを支持膜として用いた。次
に、イオン交換容量１．５０ミリ当ｆｆｉ／ｇのスルホ
ン化ポリスルホンを２．０重量％エチレグリコールモノ
ーｎ−ブチルエーテル溶液とし、ポリスルホン中空糸状
支持膜外表面にこの溶液を塗付した後、中空糸を垂直に
保フたまま室温で２日間風乾させ、複合膜を作製した。(Example 1) Polysulfone (Udel, P-3500 manufactured by UCC)
20% by weight, N,N-dimethylacetamide 71% by weight
A stock solution for membrane formation was prepared using 9% by weight of tetraethylene glycol, and a hollow fiber ultrafiltration film having an outer diameter of 1.35 mm and an inner diameter of 0.72 mm was prepared according to the method of JP-A-58-156018, Example 1. A membrane was prepared. This membrane was immersed in a 25% by weight glycerin aqueous solution at 60°C for 5 hours in a water-containing state, and then dried in a dryer at 50°C for 24 hours. An outer filtration membrane was obtained. This was used as a support membrane hereinafter. Next, sulfonated polysulfone with an ion exchange capacity of 1.50 mm/ffi/g was made into a 2.0% by weight ethylene glycol monon-butyl ether solution, and this solution was applied to the outer surface of the polysulfone hollow fiber support membrane. A composite membrane was prepared by air-drying the yarn at room temperature for 2 days while keeping it vertical.
次に、フルフリルアルコール０．３重量％、硫酸０．３
重量％、ドデシル硫酸ナトリウム０．３重量％、インプ
ロパツール２０重量％の水溶液を調整し、上記複合膜の
外表面にこの水溶液を塗付した後、１０分間垂直に保持
し、次いで１００℃の熱風乾燥機中で１０分間加熱した
。この膜を５００ｐｐｍシヨ糖水溶液を評価溶液として
外圧式１０ｋｇ／ｃｍ２の圧力で評価したところ、透水
率０．９５ｍ’／ｍ” ・日、排除率５５．２％であっ
た。Next, furfuryl alcohol 0.3% by weight, sulfuric acid 0.3%
After preparing an aqueous solution containing 0.3% by weight of sodium dodecyl sulfate and 20% by weight of Improper Tool, this aqueous solution was applied to the outer surface of the composite membrane, held vertically for 10 minutes, and then heated at 100°C. It was heated in a hot air dryer for 10 minutes. When this membrane was evaluated using a 500 ppm sucrose aqueous solution as an evaluation solution under an external pressure of 10 kg/cm2, the water permeability was 0.95 m'/m''·day and the rejection rate was 55.2%.
（実施例２）
スルホン化ポリスルホンの代りにイオン交換容３１．９
８ミリ当量／ｇのスルホン化ポリフェニレンオキサイド
を用いた以外は、実施例１と同様の方法で膜を処理し評
価したところ、５００ｐｐｍシヨ糖水溶液の透水率０
、８７ ｍ ’ ／ ｍ ２ ・日、排除率５９．７％
であった。(Example 2) Ion exchange volume 31.9 instead of sulfonated polysulfone
When the membrane was treated and evaluated in the same manner as in Example 1 except that 8 meq/g of sulfonated polyphenylene oxide was used, the water permeability of a 500 ppm sucrose aqueous solution was 0.
, 87 m'/m2 day, exclusion rate 59.7%
Met.
（実施例３）
スルホン化ポリスルホンの代りにイオン交換容ｊｉ３．
９３ミリ当１ｔ／ｇのスルホン化ポリエーテルイミドを
用い、溶剤としてエチレングリコールモノ−ｎ−ブチル
エーテルの代りにジメチルスルホキシドと水（重量比９
：１）の混合溶剤を用いた以外は、実施例１と同様の方
法で膜を処理し評価したところ、５００ｐｐｍシヨ糖水
溶液の透水率１゜１５ｍ３／ｍ２・日、排除率４５．８
％であった。(Example 3) Ion exchange volume ji3. instead of sulfonated polysulfone.
Using 1 t/g of sulfonated polyetherimide per 93 mmol, dimethyl sulfoxide and water (weight ratio 9) were used instead of ethylene glycol mono-n-butyl ether as a solvent.
: When the membrane was treated and evaluated in the same manner as in Example 1 except for using the mixed solvent of 1), the water permeability of 500 ppm sucrose aqueous solution was 1°15 m3/m2·day, and the rejection rate was 45.8.
%Met.
（実施例４）
複合膜へ含浸させる水溶液の組成をフルフリルアルコー
ル１．５重量％、硫酸１．５重量％とじた以外は、実施
例２と同様の方法で膜を処理し評価したところ、５００
ｐｐｍシヨ糖水溶液の透水率０．７０ｍ３／ｍ２ ・日
、排除率６２．０％であった。(Example 4) The membrane was treated and evaluated in the same manner as in Example 2, except that the composition of the aqueous solution impregnated into the composite membrane was 1.5% by weight of furfuryl alcohol and 1.5% by weight of sulfuric acid. 500
The water permeability of the ppm sucrose aqueous solution was 0.70 m3/m2·day, and the rejection rate was 62.0%.
（実施例５）
加熱条件を１３０℃で１５分とした以外は、実施例２と
同様の方法で膜を処理し評価したところ、５００ｐｐｍ
シヨ糖水溶液の透水率０．５３ｍ ’ ／ ｍ ” ・
日、排除率７５．５％であった。(Example 5) A film was treated and evaluated in the same manner as in Example 2, except that the heating conditions were 130°C for 15 minutes.
Water permeability of sucrose aqueous solution 0.53m'/m''・
On day one, the exclusion rate was 75.5%.
（実施例６）
実施例１で処理した膜を８０℃熱水に４時間浸漬した後
、実施例１と同様の方法で評価したところ、５００ｐｐ
ｍシヨ糖水溶液の透水率０．９８ｍ ３／ ｍ ” ・
日、排除率５６．０％であり、熱水浸漬後の膜性能の低
下はみられなかった。(Example 6) After the membrane treated in Example 1 was immersed in 80°C hot water for 4 hours, it was evaluated in the same manner as in Example 1.
Water permeability of m-sucrose aqueous solution: 0.98 m 3/m ”・
The rejection rate was 56.0%, and no deterioration in membrane performance was observed after immersion in hot water.
（実施例７）
実施例２で処理した膜を８０℃熱水に４時間浸漬した後
、実施例２と同様の方法で評価したところ、５００ｐｐ
ｍシヨ糖水溶液の透水率０．８８ｍ ３／ ｍ ２ ・
日、排除率６０．０％であり、熱水浸漬後の膜性能の低
下はみられなかった。(Example 7) After the membrane treated in Example 2 was immersed in 80°C hot water for 4 hours, it was evaluated in the same manner as in Example 2.
Water permeability of sucrose aqueous solution 0.88 m 3 / m 2 ・
The rejection rate was 60.0%, and no deterioration in membrane performance was observed after immersion in hot water.
（実施例８）
実施例３で処理した膜を８０℃熱水に４時間浸漬した後
、実施例３と同様の方法で評価したところ、５００ｐｐ
ｍシヨ糖水溶液の透水率１．１５ｍ’ ／ｍ２・Ｅｌ、
排除率４６．０％であり、熱水浸漬後の膜性能の低下は
みられなかった。(Example 8) After the membrane treated in Example 3 was immersed in 80°C hot water for 4 hours, it was evaluated in the same manner as in Example 3.
mWater permeability of sucrose aqueous solution 1.15 m'/m2・El,
The rejection rate was 46.0%, and no decrease in membrane performance was observed after immersion in hot water.
（比較例１）
実施例１における中空糸状スルホン化ポリスルホン複合
膜を、本発明による改質処理を施さずに実施例１と同様
の方法で評価したところ、５００ｐｐｍシヨ糖水溶液の
透水率１．３０ｍ３７ｍ２・日、排除率２５．０％であ
った。(Comparative Example 1) When the hollow fiber sulfonated polysulfone composite membrane in Example 1 was evaluated in the same manner as in Example 1 without being subjected to the modification treatment according to the present invention, the water permeability of a 500 ppm sucrose aqueous solution was 1.30 m37 m2.・On Sunday, the exclusion rate was 25.0%.
（比較例２）
実施例２における中空糸状スルホン化ポリフェニレンオ
キサイド複合膜を、本発明による改質処理を施さずに実
施例２と同様の方法で評価したところ、５００ｐｐｍシ
ヨ糖水溶液の透水率１．０３ｍ３／ｍ２ ・日、排除率
３９．８％であった。(Comparative Example 2) When the hollow fiber sulfonated polyphenylene oxide composite membrane in Example 2 was evaluated in the same manner as in Example 2 without being subjected to the modification treatment according to the present invention, the water permeability of a 500 ppm sucrose aqueous solution was 1. 03 m3/m2 ·day, the exclusion rate was 39.8%.
（比較例３）
実施例３における中空糸状スルホン化ポリエーテルイミ
ド複合膜を、本発明による改質処理を施さずに実施例３
と同様の方法で評価したところ、５００ｐｐｍシヨ糖水
溶液の透水率１．７０ｍ３／ｍ２・日、排除率５．０％
であった。(Comparative Example 3) The hollow fiber sulfonated polyetherimide composite membrane in Example 3 was prepared in Example 3 without being subjected to the modification treatment according to the present invention.
When evaluated using the same method as above, the water permeability of 500 ppm sucrose aqueous solution was 1.70 m3/m2・day, and the rejection rate was 5.0%.
Met.
（発明の効果）
耐熱性を持ち、１０ｋｇ／Ｃｍ２程度の低い圧力で操作
できるというスルホン酸型複合膜の利点を著しく損なわ
ずに、電気的に中性な低分子化合物の溶質排除率を向上
させた膜を得ることができる。(Effect of the invention) The solute exclusion rate of electrically neutral low molecular weight compounds can be improved without significantly impairing the advantages of the sulfonic acid type composite membrane, which is heat resistance and can be operated at a low pressure of about 10 kg/Cm2. A thin film can be obtained.
Claims (2)
層させて成る複合膜の表面に、フルフリルアルコールと
硫酸を含む水溶液を含浸させ、次いで加熱することを特
徴とするスルホン酸型複合膜の改質方法。(1) A sulfonic acid type characterized by impregnating the surface of a composite membrane formed by laminating a heat-resistant polymer containing a sulfonic acid group on a support membrane with an aqueous solution containing furfuryl alcohol and sulfuric acid, and then heating it. Method for modifying composite membranes.
ポリスルホン、スルホン化ポリフェニレンオキサイド又
は、スルホン化ポリエーテルイミドである請求項１記載
のスルホン酸型複合膜の改質方法。(2) The method for modifying a sulfonic acid type composite membrane according to claim 1, wherein the heat-resistant polymer containing sulfonic acid groups is sulfonated polysulfone, sulfonated polyphenylene oxide, or sulfonated polyetherimide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11695188A JPH01288305A (en) | 1988-05-16 | 1988-05-16 | Modifying method for sulfonic multi-layered membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11695188A JPH01288305A (en) | 1988-05-16 | 1988-05-16 | Modifying method for sulfonic multi-layered membrane |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01288305A true JPH01288305A (en) | 1989-11-20 |
Family
ID=14699774
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11695188A Pending JPH01288305A (en) | 1988-05-16 | 1988-05-16 | Modifying method for sulfonic multi-layered membrane |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01288305A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2015143348A (en) * | 2013-12-26 | 2015-08-06 | フタムラ化学株式会社 | Resin solid acid and method for producing the same |
-
1988
- 1988-05-16 JP JP11695188A patent/JPH01288305A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2015143348A (en) * | 2013-12-26 | 2015-08-06 | フタムラ化学株式会社 | Resin solid acid and method for producing the same |
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