JP3331808B2 - Liquid separation membrane - Google Patents
Liquid separation membraneInfo
- Publication number
- JP3331808B2 JP3331808B2 JP06494595A JP6494595A JP3331808B2 JP 3331808 B2 JP3331808 B2 JP 3331808B2 JP 06494595 A JP06494595 A JP 06494595A JP 6494595 A JP6494595 A JP 6494595A JP 3331808 B2 JP3331808 B2 JP 3331808B2
- Authority
- JP
- Japan
- Prior art keywords
- pmsp
- membrane
- organic solvent
- paraffin
- separation
- 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
- 238000000926 separation method Methods 0.000 title claims description 26
- 239000012528 membrane Substances 0.000 title claims description 23
- 239000007788 liquid Substances 0.000 title claims description 13
- 229920003242 poly[1-(trimethylsilyl)-1-propyne] Polymers 0.000 claims description 27
- 239000003960 organic solvent Substances 0.000 claims description 20
- 239000012188 paraffin wax Substances 0.000 claims description 16
- 238000005373 pervaporation Methods 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- 239000010408 film Substances 0.000 description 7
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 150000004045 organic chlorine compounds Chemical class 0.000 description 5
- 238000002156 mixing Methods 0.000 description 4
- 239000012466 permeate Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 230000035699 permeability Effects 0.000 description 3
- 229920002379 silicone rubber Polymers 0.000 description 3
- 239000004945 silicone rubber Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 150000002605 large molecules Chemical class 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 206010007269 Carcinogenicity Diseases 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000007670 carcinogenicity Effects 0.000 description 1
- 231100000260 carcinogenicity Toxicity 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012527 feed solution Substances 0.000 description 1
- 229920001002 functional polymer Polymers 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- -1 polyethylene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920005597 polymer membrane Polymers 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は、液体分離膜に関する。
更に詳しくは、浸透気化法による分離などに有効に用い
られる液体分離膜に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a liquid separation membrane.
More specifically, the present invention relates to a liquid separation membrane effectively used for separation by a pervaporation method.
【０００２】[0002]
【従来の技術】高分子膜を用いて有機溶媒と水とを分離
する場合、用いられた高分子物質に対する有機溶媒と水
の溶解性の違いが主な原因となって分離を可能とさせ
る。そのため、有機溶媒分子を選択的に透過させるに
は、用いられる高分子物質は極性基を持たず、できるだ
け疎水性であることが好ましい。また、水よりも大きな
有機溶媒分子が高分子物質中を拡散するので、拡散性も
良好であることが好ましい。一方、低分子化合物の拡散
が良好であるためには、高分子鎖の密度が小さく、分子
鎖の運動性が良好であることが好ましい。その上、薄膜
として用いるため強度が良好であることも必要である。2. Description of the Related Art When a polymer membrane is used to separate an organic solvent and water, the separation is made possible mainly due to the difference in the solubility of the organic solvent and water in the used polymer substance. Therefore, in order to selectively allow organic solvent molecules to permeate, it is preferable that the polymer substance used has no polar group and is as hydrophobic as possible. In addition, since organic solvent molecules larger than water diffuse in the polymer substance, it is preferable that the diffusibility is good. On the other hand, in order for the low molecular compound to diffuse well, it is preferable that the density of the polymer chain is low and the mobility of the molecular chain is good. In addition, it must have good strength because it is used as a thin film.
【０００３】疎水性で高分子鎖の密度が小さく、しかも
強度の良好な材料としては、ポリ[1-(トリメチルシリ
ル)-1-プロピン] (ＰＭＳＰ) があり、この膜状物は低
分子化合物の透過性にすぐれているため、酸素富化膜、
有機溶媒選択透過性浸透気化膜などとしての用途が注目
されている。[0003] Poly [1- (trimethylsilyl) -1-propyne] (PMSP) is a material which is hydrophobic, has a low density of polymer chains, and has good strength. Because of its excellent permeability, oxygen-enriched membrane,
Attention has been focused on its use as an organic solvent selectively permeable pervaporation membrane.
【０００４】ＰＭＳＰ膜を用いて、有機溶媒を含む水か
ら有機溶媒を選択的に透過分離する浸透気化法に用いる
場合、極性の大きい分子の分離係数が小さく、実用性の
点で問題となっている。即ち、ＰＭＳＰ膜による分離の
原理は、ＰＭＳＰとそれに溶解する分子との親和性に基
づいているため、極性の大きい溶媒の場合には親和性の
差は小さくなり、しかもその分子が大きいとＰＭＳＰ膜
内での分子の拡散が抑制され易く、従って分離性が阻害
されるようになる。浸透気化法での分離対象の有機溶媒
は、低分子アルコール、有機塩素化合物、ケトン、芳香
族化合物等であり、この内有機塩素化合物は、分子が大
きくかつ極性も大きいため分離性が阻害されるものの、
オゾン層を破壊したり、発ガン性を示すなどの問題がみ
られるため、水中に溶解している有機塩素化合物を膜に
よって分離することが検討されている。When a PMSP membrane is used in a pervaporation method in which an organic solvent is selectively permeated and separated from water containing an organic solvent, the separation coefficient of a molecule having a large polarity is small, which poses a problem in practicality. I have. That is, since the principle of separation by the PMSP membrane is based on the affinity between PMSP and molecules dissolved in the PMSP membrane, the difference in affinity is small in the case of a solvent having a large polarity. Diffusion of molecules in the inside is easily suppressed, and therefore, the separability is impaired. Organic solvents to be separated by pervaporation are low molecular alcohols, organic chlorine compounds, ketones, aromatic compounds, etc. Among them, the organic chlorine compounds have large molecules and large polarities, which impair the separation. Although,
Since problems such as destruction of the ozone layer and carcinogenicity are observed, separation of an organic chlorine compound dissolved in water by a membrane has been studied.
【０００５】かかる目的でＰＭＳＰ膜を用いると、有機
塩素化合物は水に対して優先的に透過・分離除去される
ことが知られており、その際トリクロロエチレンやテト
ラクロロエチレン等の極性の小さい有機塩素化合物の水
に対する分離係数は数100程度と大きいものの、1,1,1-
トリクロロエタン等の極性の大きい有機塩素化合物の分
離係数は小さい。このような分子量が比較的大きくしか
も極性の大きな有機溶媒分子の場合には、ＰＭＳＰに対
する有機溶媒および水のそれぞれ親和性の差が小さくな
り、その上その有機溶媒分子が大きい場合には、ＰＭＳ
Ｐ膜内での分子の拡散性が抑制され易くなり、それによ
り分離性が阻害されるために分離係数が大きくはなら
ず、その点での改善が望まれている。It is known that when a PMSP membrane is used for such a purpose, an organic chlorine compound is preferentially permeated / separated and removed from water. The separation coefficient for water is as large as several hundreds, but 1,1,1-
The separation coefficient of a highly polar organic chlorine compound such as trichloroethane is small. In the case of such an organic solvent molecule having a relatively large molecular weight and a large polarity, the difference in the affinity between the organic solvent and water for PMSP is small, and when the organic solvent molecule is large, the PMS
Since the diffusivity of the molecules in the P film is easily suppressed, and thereby the separability is hindered, the separation coefficient does not increase, and an improvement in that respect is desired.
【０００６】また、ＰＭＳＰにシリコーンゴムをブレン
ドした膜を浸透気化膜として用いることも行われている
が[第9回次世代産業基盤技術シンポジウム-高機能性高
分子材料-予稿集(II)第793〜837頁]、この場合にはＰＭ
ＳＰ単独膜と比べて分離係数、透過速度が共に小さくな
っており、シリコーンゴムの割合が多い程、分離係数、
透過速度は小さくなっている。即ち、ＰＭＳＰとシリコ
ーンゴムとは相溶性がいいので、ＰＭＳＰ膜のポリマー
粒子の隙間にシリコーンゴムが入り込み、そのため液体
としてアルコールを用いた場合でも、その透過速度が小
さくなることがその原因と考えられている。[0006] A membrane obtained by blending silicone rubber with PMSP has also been used as a pervaporation membrane. [Ninth Symposium on Next-Generation Industrial Technology-Highly Functional Polymer Materials-Proceedings (II) 793-837], in this case PM
Both the separation coefficient and the permeation rate are smaller than those of the SP alone membrane.
The transmission speed is small. That is, since PMSP and silicone rubber have good compatibility, silicone rubber enters into the gaps between the polymer particles of the PMSP film, and therefore, even when alcohol is used as the liquid, the permeation speed is considered to be low. ing.
【０００７】[0007]
【発明が解決しようとする課題】本発明の目的は、浸透
気化法による分離などに有効に用いられるポリ[1-(トリ
メチルシリル)-1-プロピン]系液体分離膜であって、極
性の大きい有機塩素化合物等の分子の大きい有機溶媒を
水から分離するのに用いた場合にあっても、分離係数を
大きく改善されたものを提供することにある。SUMMARY OF THE INVENTION An object of the present invention is to provide a poly [1- (trimethylsilyl) -1-propyne] -based liquid separation membrane effectively used for separation by a pervaporation method and the like. An object of the present invention is to provide an organic solvent having a large separation coefficient even when an organic solvent having a large molecule such as a chlorine compound is used for separating water from water.
【０００８】[0008]
【課題を解決するための手段】かかる本発明の目的は、
ポリ[1-(トリメチルシリル)-1-プロピン]99.8〜60重量%
およびこれと共通の有機溶媒に溶解し得るパラフィン0.
2〜40重量%のブレンド物から成膜された液体分離膜によ
って達成される。SUMMARY OF THE INVENTION The object of the present invention is as follows.
Poly [1- (trimethylsilyl) -1-propyne] 99.8-60% by weight
And paraffin soluble in common organic solvents.
Achieved by liquid separation membranes formed from 2-40% by weight of the blend.
【０００９】ＰＭＳＰにブレンドされるパラフィンとし
ては、一般に融点が約20℃以上であり、ＰＭＳＰ共通の
有機溶媒に溶解し得るものが用いられる。パラフィン
は、高分子量になるとポリエチレンとなり、機械的強度
が強くしかも薄膜化も可能であるが、結晶性が良く、緻
密であるため、透過性が著しく悪く、このため分離透過
材料としては実用性に欠けている。これに対して、本発
明で用いられるパラフィンはＰＭＳＰと共通の有機溶媒
に溶解可能な低分子量のものであって、このようなパラ
フィンをブレンドして用いることにより、ＰＭＳＰが本
来有する透過速度を実質的に殆んど低下させることな
く、揮発性有機溶媒の水からの分離性を向上させること
ができる。As the paraffin to be blended with PMSP, those having a melting point of about 20 ° C. or higher and which can be dissolved in an organic solvent common to PMSP are used. Paraffin becomes polyethylene when its molecular weight becomes high, and has high mechanical strength and can be made into a thin film.However, it has good crystallinity and is dense, so its permeability is extremely poor. Missing. On the other hand, the paraffin used in the present invention has a low molecular weight that can be dissolved in the same organic solvent as PMSP, and by blending such a paraffin, the permeation speed inherent to PMSP can be substantially reduced. The separability of the volatile organic solvent from water can be improved without any substantial reduction.
【００１０】ＰＭＳＰとパラフィンとは、前者が99.8〜
60重量%、好ましくは99.5〜95重量%の割合で、また後者
が0.2〜40重量%、好ましくは0.5〜5重量%の割合でそれ
ぞれ用いられる。パラフィンのブレンド割合がこれ以下
では、ＰＭＳＰ単独膜の分離透過性能と殆んど変わら
ず、一方これ以上の割合でブレンドして用いると、低分
子量のパラフィンによる機械的強度および透過特性の低
下がみられるようになる。[0010] PMSP and paraffin are 99.8-
It is used in a proportion of 60% by weight, preferably 99.5 to 95% by weight, and the latter is used in a proportion of 0.2 to 40% by weight, preferably 0.5 to 5% by weight. When the blending ratio of paraffin is less than this, it is almost the same as the separation and permeation performance of the PMSP single membrane, but when blended at a higher ratio, the mechanical strength and the permeation characteristics are deteriorated by low molecular weight paraffin. Will be able to
【００１１】ブレンド膜の製膜は、ＰＭＳＰとパラフィ
ンとを両者の共通の溶媒、例えばn-ヘキサン、n-ヘプタ
ン、ベンゼン、トルエン、更には蒸気圧が0.1〜30mmHg/
25℃の脂肪族炭化水素(n-パラフィン)、具体的にはC8〜
C12の脂肪族炭化水素(n-パラフィン)等に溶解し、その
溶液をガラス板、テフロンシート等の平坦なあるいは多
孔質の基質上に流延し、溶媒を蒸発させるキャスティン
グ法によって一般には行われるが、水面展開法によって
も製膜が行われる。In forming a blend film, PMSP and paraffin are used in a solvent common to both, for example, n-hexane, n-heptane, benzene, toluene, and a vapor pressure of 0.1 to 30 mmHg /.
Aliphatic hydrocarbon (n-paraffin) at 25 ° C, specifically C 8 ~
Was dissolved in aliphatic hydrocarbons (n- paraffins) and the like C 12, glass plates and the solution was cast on a substrate of a flat or porous Teflon sheet or the like, generally in a row by a casting method in which the solvent is evaporated However, film formation is also performed by a water surface spreading method.
【００１２】得られたブレンド膜は、浸透気化法などに
用いられるため、約0.1〜100μm、好ましくは約1〜50μ
m程度の厚さに製膜される。Since the obtained blend membrane is used for a pervaporation method or the like, it is about 0.1 to 100 μm, preferably about 1 to 50 μm.
The film is formed to a thickness of about m.
【００１３】[0013]
【発明の効果】ポリ[1-(トリメチルシリル)-1-プロピ
ン]に少量の低分子量パラフィンをブレンドして製膜す
ることにより、機械的強度にすぐれた液体分離膜が得ら
れ、これを有機塩素化合物、低分子アルコール、ケトン
等の極性および分子量の大きい揮発性有機溶媒を水から
分離する浸透気化法に使用した場合には、ポリ[1-(トリ
メチルシリル)-1-プロピン]が本来有する透過速度を実
質的に低下させることなく、分離係数が高められるとい
う効果が得られる。According to the present invention, a liquid separation membrane having excellent mechanical strength can be obtained by blending poly [1- (trimethylsilyl) -1-propyne] with a small amount of low-molecular-weight paraffin to form a liquid separation membrane. When volatile organic solvents with high polarity and molecular weight such as compounds, low molecular weight alcohols and ketones are used for pervaporation to separate water from water, the permeation rate inherent to poly [1- (trimethylsilyl) -1-propyne] Without substantially lowering the separation coefficient.
【００１４】[0014]
【実施例】次に、実施例について本発明を説明する。Next, the present invention will be described with reference to examples.
【００１５】実施例 ＰＭＳＰ(ポリスチレン換算の重量平均分子量約150万) 0.194g パラフィン(関東化学製品、融点40〜42℃) 0.006g n-ヘプタン 19.800g を用い、ＰＭＳＰおよびパラフィンを48時間かけて室温
下で溶解させた。この溶液をガラス板上に流延し、一昼
夜風乾した後、水中でガラス板から剥がし、２日間真空
乾燥して、厚さ約30μmのブレンド膜を得た。Example PMSP (polystyrene-equivalent weight average molecular weight: about 1.5 million) 0.194 g paraffin (Kanto Chemical, melting point: 40 to 42 ° C.) 0.006 g n-heptane 19.800 g, PMSP and paraffin were added at room temperature for 48 hours. Dissolved below. This solution was cast on a glass plate, air-dried all day and night, peeled off from the glass plate in water, and vacuum-dried for 2 days to obtain a blend film having a thickness of about 30 μm.
【００１６】比較例１〜２ 実施例において、ＰＭＳＰ量およびパラフィン量がそれ
ぞれ次のように変更された。比較例 ＰＭＳＰ(g) パラフィン(g) １ 0.200 - ２ 0.100 0.100Comparative Examples 1-2 In the examples, the amounts of PMSP and paraffin were changed as follows. Comparative Example PMSP (g) Paraffin (g) 1 0.200-2 0.100 0.100
【００１７】以上の実施例および比較例１で得られたブ
レンド膜について、供給液濃度約6ppmの1,1,1-トリクロ
ロエタン(TCE)水溶液のパーベーパレーションによる分
離実験を、常法に従って操作温度25℃、膜の透過側圧力
約0.5Torrの条件下で行い、分離係数α(TCE/H2O)を求め
た。 α(TCE/H2O)＝(X2/Y2)／(X1/Y1) X1：供給液側のTCEの質量分率 X2：透過液側のTCEの質量分率 Y1：供給液側の水の質量分率 Y2：透過液側の水の質量分率 また、単位時間当りトラップに採取された液体の重量か
ら透過係数を算出した。なお、比較例２で得られた膜
は、不均質で機械的強度も著しく小さいため、測定を行
わなかった。With respect to the blend membranes obtained in the above Examples and Comparative Example 1, a separation experiment by pervaporation of a 1,1,1-trichloroethane (TCE) aqueous solution having a feed solution concentration of about 6 ppm was conducted according to a conventional method at an operating temperature. Separation coefficient α (TCE / H 2 O) was determined at 25 ° C. under a pressure of about 0.5 Torr on the permeate side of the membrane. α (TCE / H 2 O) = (X 2 / Y 2 ) / (X 1 / Y 1 ) X 1 : Mass fraction of TCE on the feed side X 2 : Mass fraction of TCE on the permeate side Y 1 : Mass fraction of water on the supply liquid side Y 2 : Mass fraction of water on the permeate liquid side The permeation coefficient was calculated from the weight of the liquid collected in the trap per unit time. Note that the film obtained in Comparative Example 2 was not measured because it was heterogeneous and had extremely low mechanical strength.
【００１８】得られた結果は、次の表に示される。 表例 分離係数α 透過係数(kg・m/m2・hr) 実施例 290 2.7×10-6 比較例１ 160 3.9×10-6 The results obtained are shown in the following table. tableAn example Separation coefficient α Permeability coefficient (kg ・ m / m 2・ hr) Example 290 2.7 × 10-6 Comparative Example 1 160 3.9 × 10-6
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 平６−339618（ＪＰ，Ａ) 特開 平２−222715（ＪＰ，Ａ) 特開 平３−221129（ＪＰ，Ａ) 特開 昭61−101212（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) B01D 61/00 - 71/82 510 C02F 1/44 ──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-6-339618 (JP, A) JP-A-2-222715 (JP, A) JP-A-3-221129 (JP, A) JP-A-61- 101212 (JP, A) (58) Fields investigated (Int. Cl. 7 , DB name) B01D 61/00-71/82 510 C02F 1/44
Claims (2)
ン]99.8〜60重量%およびこれと共通の有機溶媒に溶解し
得るパラフィン0.2〜40重量%のブレンド物から成膜され
た液体分離膜。1. A liquid separation membrane formed from a blend of 99.8-60% by weight of poly [1- (trimethylsilyl) -1-propyne] and 0.2-40% by weight of paraffin soluble in a common organic solvent. .
に用いられる請求項１記載の液体分離膜。2. The liquid separation membrane according to claim 1, which is used for separating a volatile organic solvent by a pervaporation method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP06494595A JP3331808B2 (en) | 1995-02-28 | 1995-02-28 | Liquid separation membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP06494595A JP3331808B2 (en) | 1995-02-28 | 1995-02-28 | Liquid separation membrane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH08229368A JPH08229368A (en) | 1996-09-10 |
| JP3331808B2 true JP3331808B2 (en) | 2002-10-07 |
Family
ID=13272693
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP06494595A Expired - Fee Related JP3331808B2 (en) | 1995-02-28 | 1995-02-28 | Liquid separation membrane |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3331808B2 (en) |
-
1995
- 1995-02-28 JP JP06494595A patent/JP3331808B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH08229368A (en) | 1996-09-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5387378A (en) | Integral asymmetric fluoropolymer pervaporation membranes and method of making the same | |
| Namboodiri et al. | High permeability membranes for the dehydration of low water content ethanol by pervaporation | |
| US5733663A (en) | Composite membrane and process for its production | |
| Chang et al. | Preparation of multi-layer silicone/PVDF composite membranes for pervaporation of ethanol aqueous solutions | |
| US4871378A (en) | Ultrathin ethylcellulose/poly(4-methylpentene-1) permselective membranes | |
| JPH031056B2 (en) | ||
| US6316684B1 (en) | Filled superglassy membrane | |
| Cao et al. | Incorporating ZIF-71 into poly (ether-block-amide)(PEBA) to form mixed matrix membranes for enhanced separation of aromatic compounds from aqueous solutions by pervaporation | |
| Zuo et al. | Dehydration of industrial isopropanol (IPA) waste by pervaporation and vapor permeation membranes | |
| CA1294093C (en) | Polyphosphazene fluid separation membranes | |
| Ying et al. | pH effect of coagulation bath on the characteristics of poly (acrylic acid)-grafted and poly (4-vinylpyridine)-grafted poly (vinylidene fluoride) microfiltration membranes | |
| JPH0798947B2 (en) | Method for separating a solvent from a hydrocarbon dissolved in the solvent | |
| US5707423A (en) | Substituted polyacetylene separation membrane | |
| JP3331808B2 (en) | Liquid separation membrane | |
| US20120132590A1 (en) | Method for fabrication of elastomeric asymmetric membranes from hydrophobic polymers | |
| KR100531129B1 (en) | A method for preparing ionic liquid supported liquid membrane | |
| Kittur et al. | Preparation of zeolite‐incorporated poly (dimethyl siloxane) membranes for the pervaporation separation of isopropyl alcohol/water mixtures | |
| JP3314518B2 (en) | Liquid separation membrane | |
| JP3429093B2 (en) | Liquid separation membrane | |
| CN112337324B (en) | A bilayer membrane with controllable hydrophilicity and hydrophobicity, preparation method and application thereof in filtration of non-polar solvent system | |
| Sun et al. | Membranes of block copolymer-poly (divinylbenzene) blends for the pervaporation of alcohol/water mixtures | |
| Roualdes et al. | Comparative performance of various plasma polysiloxane films for the pervaporative recovery of organics from aqueous streams | |
| US4810366A (en) | Process for separating a fluid feed mixture containing hydrocarbon oil and an organic solvent | |
| JPS6125606A (en) | Impregnated liquid film | |
| Nomura et al. | Permselectivities of various polymer membranes toward some aromatic compounds in organic media in the reverse osmosis process |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20080726 Year of fee payment: 6 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20080726 Year of fee payment: 6 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090726 Year of fee payment: 7 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090726 Year of fee payment: 7 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100726 Year of fee payment: 8 |
|
| LAPS | Cancellation because of no payment of annual fees |