JPH0515494B2 - - Google Patents
Info
- Publication number
- JPH0515494B2 JPH0515494B2 JP403587A JP403587A JPH0515494B2 JP H0515494 B2 JPH0515494 B2 JP H0515494B2 JP 403587 A JP403587 A JP 403587A JP 403587 A JP403587 A JP 403587A JP H0515494 B2 JPH0515494 B2 JP H0515494B2
- Authority
- JP
- Japan
- Prior art keywords
- membrane
- aqueous solution
- polyvinylidene fluoride
- coated
- organic liquid
- 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
- 239000012528 membrane Substances 0.000 claims description 116
- 239000007788 liquid Substances 0.000 claims description 55
- 239000007864 aqueous solution Substances 0.000 claims description 35
- 239000012510 hollow fiber Substances 0.000 claims description 33
- 239000002033 PVDF binder Substances 0.000 claims description 28
- 238000000576 coating method Methods 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 28
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 28
- 239000011248 coating agent Substances 0.000 claims description 27
- 239000002904 solvent Substances 0.000 claims description 27
- 229920005573 silicon-containing polymer Polymers 0.000 claims description 26
- 239000000243 solution Substances 0.000 claims description 19
- 239000011148 porous material Substances 0.000 claims description 17
- 229920000642 polymer Polymers 0.000 claims description 13
- -1 dimethylsiloxane Chemical class 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 230000000903 blocking effect Effects 0.000 claims description 4
- 229920001296 polysiloxane Polymers 0.000 claims description 4
- 239000002131 composite material Substances 0.000 claims description 2
- 239000008187 granular material Substances 0.000 claims description 2
- 239000006193 liquid solution Substances 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 60
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 33
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 23
- 238000000926 separation method Methods 0.000 description 22
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 238000002474 experimental method Methods 0.000 description 12
- 239000000126 substance Substances 0.000 description 12
- 230000035699 permeability Effects 0.000 description 11
- 239000012466 permeate Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 9
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000000835 fiber Substances 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 238000009792 diffusion process Methods 0.000 description 4
- 229910001873 dinitrogen Inorganic materials 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 229920006332 epoxy adhesive Polymers 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- 101150092509 Actn gene Proteins 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- PQPVPZTVJLXQAS-UHFFFAOYSA-N hydroxy-methyl-phenylsilicon Chemical class C[Si](O)C1=CC=CC=C1 PQPVPZTVJLXQAS-UHFFFAOYSA-N 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000005373 pervaporation Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 238000009987 spinning Methods 0.000 description 2
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 2
- AJDIZQLSFPQPEY-UHFFFAOYSA-N 1,1,2-Trichlorotrifluoroethane Chemical compound FC(F)(Cl)C(F)(Cl)Cl AJDIZQLSFPQPEY-UHFFFAOYSA-N 0.000 description 1
- MIZLGWKEZAPEFJ-UHFFFAOYSA-N 1,1,2-trifluoroethene Chemical compound FC=C(F)F MIZLGWKEZAPEFJ-UHFFFAOYSA-N 0.000 description 1
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- 229920010177 Kynar® 460 Polymers 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 1
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 1
- TVJPBVNWVPUZBM-UHFFFAOYSA-N [diacetyloxy(methyl)silyl] acetate Chemical compound CC(=O)O[Si](C)(OC(C)=O)OC(C)=O TVJPBVNWVPUZBM-UHFFFAOYSA-N 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000000502 dialysis Methods 0.000 description 1
- 238000000909 electrodialysis Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000001631 haemodialysis Methods 0.000 description 1
- 230000000322 hemodialysis Effects 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 229920001600 hydrophobic polymer Polymers 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 229960004592 isopropanol Drugs 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 238000004382 potting Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000002940 repellent Effects 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 238000005211 surface analysis Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
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
- B01D71/30—Polyalkenyl halides
- B01D71/32—Polyalkenyl halides containing fluorine atoms
- B01D71/34—Polyvinylidene fluoride
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は、揮発性有機液体成分をその水溶液か
ら濃縮して分離する膜分離法に使用する分離膜と
その使用方法およびその製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a separation membrane used in a membrane separation method for concentrating and separating a volatile organic liquid component from an aqueous solution thereof, a method for using the same, and a method for producing the same.
［従来の技術］
近年、膜分離法に関する技術は、逆浸透法、限
外ろ過法、拡散透析法、血液透析法、電気透析
法、ガス分離法、およびパーベーパレーシヨン法
等の技術として目覚ましく発展している。[Conventional technology] In recent years, technologies related to membrane separation methods have made remarkable progress, such as reverse osmosis, ultrafiltration, diffusion dialysis, hemodialysis, electrodialysis, gas separation, and pervaporation. It is developing.
一般に、反応系あるいは種々のプロセス内で生
成あるいは蓄積してくる有機液体の水溶液を濃縮
しつつ系外に分離して取出すニーズは非常に多
い。しかし、従来の分離技術では低濃度の水溶液
からこの様な成分を効率よく省エネルギー的に分
離することが困難であつた。 Generally, there is a great need to concentrate and separate an aqueous solution of an organic liquid that is generated or accumulated in a reaction system or various processes and take it out of the system. However, with conventional separation techniques, it has been difficult to efficiently separate such components from low-concentration aqueous solutions in an energy-saving manner.
現在注目されているパーベーパレーシヨン法に
おいても、有機液体の水溶液から分離を試みると
ほとんどすべての膜素材は水を選択的に透過さ
せ、また、大容量の装置を高い真空度に保つ、ト
ラツプを低温に保つ等といつたエネルギー多消費
型プロセスが必要であるといつた問題点があつ
た。 Even in pervaporation methods, which are currently attracting attention, when trying to separate organic liquids from aqueous solutions, almost all membrane materials allow water to permeate selectively. The problem was that it required an energy-intensive process, such as keeping it at a low temperature.
そこで、温度差を主たる駆動力とする。液−液
系の揮発性有機液体成分を濃縮する疎水性高分子
の多孔性膜を用いたアツプヒル輸送型膜分離方法
が特願昭60−038810号公報により提案されてい
る。 Therefore, the temperature difference is used as the main driving force. An uphill transport membrane separation method using a porous hydrophobic polymer membrane for concentrating volatile organic liquid components in a liquid-liquid system has been proposed in Japanese Patent Application No. 60-038810.
［発明が解決しようとする問題点］
しかしながら、特願昭60−038810号公報に提案
する方法においても、その分離性能は、充分満足
の得られるものではなかつた。[Problems to be Solved by the Invention] However, even in the method proposed in Japanese Patent Application No. 60-038810, the separation performance was not fully satisfactory.
本発明は高い分離性能を持つ、揮発性有機液体
水溶液濃縮膜とその使用方法およびその製造方法
を提供することを目的とする。 An object of the present invention is to provide a volatile organic liquid aqueous solution concentration membrane having high separation performance, a method for using the same, and a method for producing the same.
［問題点を解決するための手段］
本発明は、かかる従来技術の欠点を解消するた
めに下記の構成を有する。[Means for Solving the Problems] The present invention has the following configuration in order to eliminate the drawbacks of the prior art.
すなわち本発明は、
１ ポリフツ化ビニリデン系多孔性膜の表面に該
膜表面の少なくとも一部の開孔部が閉塞される
ことなく、ジメチルシロキサンを主成分とする
シリコーン系ポリマがコートされていることを
特徴とする揮発性有機液体水溶液濃縮膜。 That is, the present invention provides the following features: 1. The surface of a polyvinylidene fluoride porous membrane is coated with a silicone polymer mainly composed of dimethylsiloxane without blocking at least some of the pores on the surface of the membrane. A volatile organic liquid aqueous solution concentration membrane characterized by:
２ ポリフツ化ビニリデン系多孔性膜の表面に、
該膜表面の少なくとも一部の開孔部が閉塞され
ることなくジメチルシロキサンを主成分とする
シリコーン系ポリマがコートされている複合膜
において、該膜の一次側に該膜の平均微細孔半
径の１／15以下のストークス半径を持ち、かつ
該膜に対して実質的に不透性を示す揮発性有機
液体水溶液を供給し、気化した状態で膜を透過
させることを特徴とする揮発性有機液体水溶液
濃縮膜の使用方法。2 On the surface of the polyvinylidene fluoride porous membrane,
In a composite membrane coated with a silicone polymer mainly composed of dimethylsiloxane without blocking at least some of the pores on the surface of the membrane, the primary side of the membrane has an average micropore radius of A volatile organic liquid characterized by supplying an aqueous volatile organic liquid solution having a Stokes radius of 1/15 or less and being substantially impermeable to the membrane, and allowing the liquid to permeate through the membrane in a vaporized state. How to use an aqueous solution concentration membrane.
３ シリコーン系ポリマのコーテイング液の溶媒
と相溶性を示すポリフツ化ビニリデンの非溶媒
を、ポリフツ化ビニリデン系多孔性膜に含浸さ
せ、該膜の表面にシリコーン系ポリマの溶液を
コートし、溶媒を蒸発・揮散させたのちキユア
リングして、ポリフツ化ビニリデンの表面の開
孔部を閉塞させることなくシリコーン系ポリマ
をコートしたことを特徴とする揮発性有機液体
水溶液濃縮膜の製造方法。3. A polyvinylidene fluoride porous membrane is impregnated with a polyvinylidene fluoride non-solvent that is compatible with the solvent of the silicone polymer coating solution, the silicone polymer solution is coated on the surface of the membrane, and the solvent is evaporated. - A method for producing a volatile organic liquid aqueous solution concentration membrane, characterized in that it is cured after volatilization and coated with a silicone polymer without clogging the pores on the surface of polyvinylidene fluoride.
に関する。Regarding.
本発明で用いるポリフツ化ビニリデン系多孔性
膜としては、フツ化ビニリデン単独重合体、また
は少なくとも70重量％のフツ化ビニリデンと、ト
リもしくはテトラフルオロエチレンとの共重合体
からなる多孔性膜である。 The polyvinylidene fluoride porous membrane used in the present invention is a porous membrane made of a vinylidene fluoride homopolymer or a copolymer of at least 70% by weight of vinylidene fluoride and tri- or tetrafluoroethylene.
本願発明に用いるポリフツ化ビニリデン系多孔
性膜の微細孔半径は平均半径で20Å以上、1000Å
以下であることが好ましい。平均半径が20Åより
小さい場合、気体の状態であつても揮発性有機液
体成分が優先的に透過せず、1000Åより大きい場
合、膜の一次側に供給する揮発性有機液体水溶液
は、液体の状態でも膜を透過し膜分離を実施する
ことができない。 The micropore radius of the polyvinylidene fluoride porous membrane used in the present invention is 20 Å or more and 1000 Å in average radius.
It is preferable that it is below. If the average radius is smaller than 20 Å, volatile organic liquid components will not preferentially permeate even in a gaseous state, and if it is larger than 1000 Å, the volatile organic liquid aqueous solution supplied to the primary side of the membrane will be in a liquid state. However, it cannot pass through a membrane and perform membrane separation.
本願発明の膜は、該膜の平均微細孔径に対し
て、１／15以下のストークス半径を持ち、かつ該
膜に対して実質的に不透性を示す物質の分離に好
ましく用いられる。平均微細孔径に対してストー
クス半径の比が、１／15より大きい場合は、分離
対象物質である揮発性有機液体成分が水に対して
優先的に透過しない。該膜に対して実質的に不透
性を示す分離対象物の孔径は、操作条件に於ける
該膜の表面張力、分離対象物質水溶液の表面張
力、１次側と２次側との圧力差等によつて変化
し、一概に規定することが困難である。ただし、
多孔性膜は、その孔径が、膜の表面の開孔部は比
較的小さく内部になると拡大しているなど全体的
に不均一であるので、それらの平均的な孔径から
考えられる水溶液に対する不透性よりも、実際の
水溶液に対する不透性は大きいと考えられる。 The membrane of the present invention has a Stokes radius of 1/15 or less of the average micropore diameter of the membrane and is preferably used for separating substances that are substantially impermeable to the membrane. When the ratio of the Stokes radius to the average micropore diameter is larger than 1/15, the volatile organic liquid component, which is the substance to be separated, does not preferentially permeate water. The pore size of the substance to be separated that is substantially impermeable to the membrane is determined by the surface tension of the membrane under operating conditions, the surface tension of the aqueous solution of the substance to be separated, and the pressure difference between the primary and secondary sides. etc., and it is difficult to define it unambiguously. however,
Porous membranes are generally non-uniform in pore size, with the openings on the surface of the membrane being relatively small and expanding inside. It is thought that the impermeability to an actual aqueous solution is greater than the property.
また、本発明において、「実質的に不透性であ
る」とは、液体の状態では膜に対して不透性であ
り、気体の状態では透過することをいう。本発明
では、分離対象物質は気化した状態で膜を透過す
る方法に使用するため膜は濡れることなく分離対
象物質を分離する。 Furthermore, in the present invention, "substantially impermeable" means that the membrane is impermeable in a liquid state, but permeable in a gaseous state. In the present invention, since the substance to be separated is used in the method of permeating the membrane in a vaporized state, the substance to be separated is separated without the membrane getting wet.
膜の分離性能を有利に発現するためには、平均
孔径のほかに体積空孔率がより大きく、膜の内部
に比較的大きい空孔を有することが好ましい。体
積空孔率は通常20％以上、好ましくは40％以上で
膜の機械的特性を損なわぬ範囲で高い程有利であ
る。 In order to advantageously exhibit the separation performance of the membrane, it is preferable that the membrane has a larger volume porosity in addition to the average pore diameter, and has relatively large pores inside the membrane. The volumetric porosity is usually 20% or more, preferably 40% or more, and it is advantageous to have a higher volume porosity within a range that does not impair the mechanical properties of the membrane.
この様な多孔構造のポリフツ化ビニリデン系多
孔性膜は湿式系、または乾湿式系または、乾式系
等の従来公知の製膜法で作製することができる。 A polyvinylidene fluoride porous membrane having such a porous structure can be produced by a conventionally known film forming method such as a wet system, a wet-dry system, or a dry system.
多孔構造を好適な状態に保持した乾燥状態のポ
リフツ化ビニリデン系多孔性膜を調製するには、
水と混和する有機溶媒でフツ化ビニリデン系ポリ
マの非溶媒に置換してから乾燥する方法が好まし
い。 To prepare a dry polyvinylidene fluoride porous membrane that maintains a suitable porous structure,
A preferred method is to replace the non-solvent of the vinylidene fluoride polymer with an organic solvent that is miscible with water and then dry it.
膜の形状は、どのような形状であつても本発明
の効果を何等制約するものではないが、実質的見
地からは中空糸膜が有利である。 Any shape of the membrane does not limit the effects of the present invention in any way, but hollow fiber membranes are advantageous from a practical standpoint.
コートする表面は平膜の場合には表面の状態に
よつて分離性能の発現に影響が出ることが考えら
れるが、ポリフツ化ビニリデン系ポリマ単独の膜
であればいずれの面でもよい。不織布またはタフ
タ等の基材膜上に製膜されたポリフツ化ビニリデ
ン系多孔性膜の場合には勿論ポリフツ化ビニリデ
ン膜表面にコートする。中空糸膜の場合には、中
空糸の内表面と外表面と２つの場合が考えられ
る。この場合は中空糸膜の使用方法によつていず
れかの面にコートすれば良いが、液−液系の温度
差を駆動力とする揮発性有機液体水溶液濃縮方法
に使用する場合、シリコーン系ポリマをコートし
た面を１次側（供給液側）に向けるのが分離性能
を改善するのに効果的である。とくに、実質的見
地からと性能改善効果とから中空糸の内表面にコ
ートする方法がよい。 If the surface to be coated is a flat membrane, the state of the surface may affect the separation performance, but any surface may be used as long as it is a membrane made solely of vinylidene fluoride polymer. In the case of a polyvinylidene fluoride porous film formed on a base film such as nonwoven fabric or taffeta, the surface of the polyvinylidene fluoride film is of course coated. In the case of a hollow fiber membrane, there are two possible cases: the inner surface and the outer surface of the hollow fiber. In this case, depending on how the hollow fiber membrane is used, either side may be coated, but when used in a volatile organic liquid aqueous solution concentration method in which the driving force is the temperature difference between the liquid and liquid systems, silicone-based polymers may be used. Directing the coated surface toward the primary side (supply liquid side) is effective for improving separation performance. In particular, a method of coating the inner surface of the hollow fiber is preferred from a practical standpoint and performance improvement effect.
コーテイングに用いるシリコーン系ポリマとし
ては、ジメチルシロキサン残基を主成分とし、ア
ルキルメチルシロキサン、フエニルメチルシロキ
サンなどを共重合成分とするシロキサンポリマを
使用することができる。アルキルメチルシロキサ
ンの場合にはアルキル基にさらに他の官能基やフ
ツ素原子を有する基が導入されていてもよい。本
発明の効果を発現する機構は明らかでないが、要
するに水分子に対して反発し揮発性有機液体成分
の分子に対しては親和性を有する事がひとつの必
要条件のようである。 As the silicone polymer used for coating, a siloxane polymer containing dimethylsiloxane residue as a main component and copolymerizing components such as alkylmethylsiloxane and phenylmethylsiloxane can be used. In the case of alkylmethylsiloxane, another functional group or a group having a fluorine atom may be further introduced into the alkyl group. Although the mechanism by which the effects of the present invention are exerted is not clear, one necessary condition seems to be that it is repellent to water molecules and has affinity for molecules of volatile organic liquid components.
ポリフツ化ビニリデン系多孔性膜の膜表面の開
孔部を閉塞させずに顆粒状でシリコーン系ポリマ
をコートする方法は以下のような方法で実施する
ことができる。すなわち、ポリフツ化ビニリデン
系多孔膜にコーテイング溶液の溶媒と相溶性を示
すポリフツ化ビニリデンの非溶媒を含浸させ、し
かるのちシリコーン系ポリマのコーテイング液を
所定量コートし、溶媒を蒸発・揮散させる。ポリ
フツ化ビニリデンの多孔膜に含浸させる溶媒は極
性の強い溶媒が好ましく、しかもコーテイングに
用いるシリコーン系ポリマの非溶媒がさらによ
い。特に好ましくはメタノール、エタノール、プ
ロパノールなどの１価の低級アルコール、アセト
ニトリル、エチレングリコールジメチルエーテ
ル、エチレングリコールジエチルエーテルおよび
それらの混合溶媒などがよい。該含浸溶媒が沸点
が高く揮発性が低い場合にはコーテイング液の溶
媒を蒸発させたのち、含浸溶媒と混和する該シリ
コーン系ポリマの非溶媒にコーテイング後蒸発・
揮散させた膜を浸漬してもよい。シリコーン系ポ
リマのコーテイング液に用いる溶媒としては、通
常のシリコーン系ポリマの溶媒が好ましく用いら
れるが、フツ化ビニリデン系ポリマの性状、含浸
溶媒の性質、シリコーン系ポリマの性質等を良く
考慮して選定することが必要である。中空糸膜の
内表面にコートする場合には中空糸の内側およ
び／または外側から含浸溶媒を含浸させたのち、
中空糸の内側に窒素気流または空気流などの不活
性気体を通じて過剰の含浸溶媒を除いてから、コ
ーテイング液を中空糸の内部に充填し数秒から数
分後に、上述と同様に不活性気体を通じてコーテ
イング液の溶媒を蒸発・揮散させることにより本
願発明の揮発性有機液体濃縮膜を作製することが
できる。 A method for coating a silicone polymer in granular form without clogging the openings on the membrane surface of a polyvinylidene fluoride porous membrane can be carried out by the following method. That is, a polyvinylidene fluoride porous membrane is impregnated with a polyvinylidene fluoride non-solvent that is compatible with the solvent of the coating solution, and then a predetermined amount of a silicone polymer coating solution is coated, and the solvent is evaporated and volatilized. The solvent with which the polyvinylidene fluoride porous membrane is impregnated is preferably a highly polar solvent, and more preferably a non-solvent for the silicone polymer used for coating. Particularly preferred are monohydric lower alcohols such as methanol, ethanol, and propanol, acetonitrile, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and mixed solvents thereof. If the impregnating solvent has a high boiling point and low volatility, the solvent of the coating liquid is evaporated and then coated with the non-solvent of the silicone polymer that is miscible with the impregnating solvent.
The volatilized membrane may be immersed. The solvent used in the silicone polymer coating solution is preferably a normal silicone polymer solvent, but it should be selected with careful consideration of the properties of the vinylidene fluoride polymer, the properties of the impregnating solvent, the properties of the silicone polymer, etc. It is necessary to. When coating the inner surface of a hollow fiber membrane, after impregnating the hollow fiber with an impregnating solvent from the inside and/or outside,
Excess impregnating solvent is removed by passing an inert gas such as a nitrogen stream or air stream inside the hollow fiber, and then the coating liquid is filled inside the hollow fiber, and after a few seconds to several minutes, the coating is carried out by passing an inert gas in the same manner as described above. The volatile organic liquid concentration membrane of the present invention can be produced by evaporating and volatilizing the solvent of the liquid.
コーテイング液の濃度は、通常0.1〜20.0％位
の範囲に好適な条件がある。ポリマ溶液の粘性は
ポリマの分子量、溶媒との組合わせによつて非常
に大きく変わり、コーテイングしたときの付着量
は溶液の粘性、表面張力、あるいは溶媒の蒸発速
度等に依存するので、この様な要因を考慮して決
めるべきである。また、コーテイングを繰返し重
ね塗りする方法も顕著な効果を示すことがあるの
で、コーテイングの条件と方法も考慮する必要が
ある。 A suitable concentration of the coating liquid is usually in the range of about 0.1 to 20.0%. The viscosity of a polymer solution varies greatly depending on the molecular weight of the polymer and the combination with the solvent, and the amount of coating applied depends on the viscosity of the solution, surface tension, evaporation rate of the solvent, etc. The decision should be made taking into account the following factors. In addition, coating conditions and methods must also be considered, as methods of repeatedly applying coatings may also have a significant effect.
蒸発・揮散後のコートされたシリコーン系ポリ
マのキユアリングは、該ポリマのキユアリング条
件に応じて室温または所定の温度において実施す
る。ただし、ポリフツ化ビニリデン系多孔性膜の
細孔構造が著しく変化し、分離対象物質の透過性
が低下するような高い温度の処理は避けるべきで
ある。 Curing of the coated silicone polymer after evaporation and volatilization is carried out at room temperature or a predetermined temperature depending on the curing conditions of the polymer. However, treatment at high temperatures that would significantly change the pore structure of the polyvinylidene fluoride porous membrane and reduce the permeability of the substance to be separated should be avoided.
第１図は本発明に使用し得る多孔性のポリフツ
化ビニリデン系の膜の断面の写真である。第２図
は該ポリフツ化ビニリデン系膜の表面の形態の写
真である。表面に製膜方向に並んだスリツト状の
開孔部が多数存在する。第３Ａ図、第３Ｂ図はシ
リコーン系ポリマをコートした膜の表面の写真で
ある。コートされたシリコーン系ポリマは、ポリ
フツ化ビニリデン系膜の表面の細孔の回りのフイ
ブリル状のフツ化ビニリデン系ポリマの上に微少
な顆粒状となつて累積しており、表面の細孔を閉
塞していない。このような形態は高分解能の走査
型電子顕微鏡によつて観察することができる。第
１図、第２図、第３Ａ図、第３Ｂ図は、該顕微鏡
によるものであるが、第１図は、約500倍の倍率
に、第２図と第３Ａ図とは約2000倍の倍率に相当
する。第３Ｂ図は約50000倍に相当する。また、
膜表面のコートされたシリコーン系ポリマの存在
は、ESCAまたはSIMS等の表面分析法で確認で
きる。簡単にはコーテイング前後の膜の重量変化
を測定することによつても確認できる。あるい
は、シリコーン系ポリマをコートした膜の表面の
開孔部が閉塞されていないことは、該膜の通気性
を測定することによつて確認される。この方法に
よれば通気性の低下の度合いから膜表面にポリマ
がコートされていることが確められる。本願発明
で好適な性能を示したシリコーン系ポリマのコー
ト膜の窒素の通気性は、ほぼ0.1〜3.5×10-2cm2
（STP）cm-2S-1cmHg-1の範囲にあり、とくに高
い性能を示したコーテイング膜は0.15〜3.0×10-2
cm2（STP）cm-2S-1cmHg-1の範囲にあつた。 FIG. 1 is a photograph of a cross section of a porous polyvinylidene fluoride membrane that can be used in the present invention. FIG. 2 is a photograph of the surface morphology of the polyvinylidene fluoride film. There are many slit-like openings arranged in the film forming direction on the surface. FIGS. 3A and 3B are photographs of the surface of a film coated with a silicone polymer. The coated silicone polymer accumulates in the form of minute granules on the fibrillar vinylidene fluoride polymer around the pores on the surface of the polyvinylidene fluoride membrane, blocking the surface pores. I haven't. Such morphology can be observed using a high-resolution scanning electron microscope. Figures 1, 2, 3A, and 3B are taken using the microscope; Figure 1 has a magnification of about 500 times, and Figures 2 and 3A have a magnification of about 2000 times. Corresponds to magnification. Figure 3B corresponds to approximately 50,000 times. Also,
The presence of silicone polymer coated on the membrane surface can be confirmed by surface analysis methods such as ESCA or SIMS. This can be easily confirmed by measuring the change in weight of the film before and after coating. Alternatively, it is confirmed that the pores on the surface of the membrane coated with a silicone polymer are not blocked by measuring the air permeability of the membrane. According to this method, it can be confirmed that the membrane surface is coated with a polymer based on the degree of decrease in air permeability. The nitrogen permeability of the silicone polymer coating film that showed suitable performance in the present invention is approximately 0.1 to 3.5 × 10 -2 cm 2
(STP) cm -2 S -1 cmHg -1 , and the coating film that showed particularly high performance was 0.15 to 3.0×10 -2
cm 2 (STP) was in the range of cm -2 S -1 cmHg -1 .
ポリフツ化ビニリデン系多孔性膜の平均微細孔
半径は以下に述べる方法で測定する。膜の透水性
（Lp）と、溶質の拡散透過性（Pm）を分離対象
物質であるメタノール、エタノール、プロパノー
ル、ブタノール、アセトン、等について測定し、
次式の関係を使つて計算して求める。 The average micropore radius of the polyvinylidene fluoride porous membrane is measured by the method described below. Membrane water permeability (Lp) and solute diffusion permeability (Pm) are measured for the substances to be separated, such as methanol, ethanol, propanol, butanol, acetone, etc.
It is calculated using the following relationship.
Pm＝（Ｄ／Ｌ）・（Ｈ／ts2） (1)
Lp＝（Ｈ／Ｌ）・（Rp2／8η） (2)
ここで、Ｄ：溶質の拡散係数、Ｌ：膜厚、Ｈ：
含水率、ts：溶質の曲路率、Rp：平均微細孔半
径、η：水の粘性、である。tsは次の式から計算
する。 Pm=(D/L)・(H/ts 2 ) (1) Lp=(H/L)・(Rp 2 /8η) (2) Here, D: Solute diffusion coefficient, L: Film thickness, H :
water content, ts: tortuosity of solute, Rp: average micropore radius, η: viscosity of water. ts is calculated from the following formula.
fsw＝RT／Ｄ (3)
fsw＝（RT／Pm−Vs／Lp）・（Ｈ／Ｌ） (4)
ts＝fsw／f°sw (5)
Ｒは気体定数、Ｔは測定時の温度(K)、Vsは溶
質の部分モル容積である。 fsw=RT/D (3) fsw=(RT/Pm-Vs/Lp)・(H/L) (4) ts=fsw/f°sw (5) R is the gas constant, T is the temperature at the time of measurement ( K), Vs is the partial molar volume of the solute.
コーテイング層の形成は上述の平均孔径と曲路
率の測定でも確めることができる。すなわち、コ
ーテイングにより膜表面の開孔部が狭められると
平均孔径の変化は小さくとも、曲路率は大きく変
化する。 Formation of the coating layer can also be confirmed by measuring the average pore diameter and tortuosity described above. That is, when the pores on the membrane surface are narrowed by coating, the curvature ratio changes greatly even if the change in the average pore diameter is small.
本発明を適用しうる揮発性有機液体水溶液は、
当該水溶液の気液平衡における気相中の有機液体
物質の組成が液相中の組成より大きい物質に対し
ては、基本的に適用することができる。この様な
物質の例としては、メタノール、エタノール、ｎ
−プロパノール、iso−プロパノール、ｎ−ブタ
ノール、ｔ−ブタノール、アセトン、テトラハイ
ドロフラン、１，４−ジオキサン、メチルアミ
ン、エチルアミン、アセトニトリル、エチルメチ
ルケトン、酢酸メチル、酢酸エチル等がある。 The volatile organic liquid aqueous solution to which the present invention can be applied is
This method can basically be applied to substances in which the composition of the organic liquid substance in the gas phase in the vapor-liquid equilibrium of the aqueous solution is greater than the composition in the liquid phase. Examples of such substances include methanol, ethanol, n
-propanol, iso-propanol, n-butanol, t-butanol, acetone, tetrahydrofuran, 1,4-dioxane, methylamine, ethylamine, acetonitrile, ethyl methyl ketone, methyl acetate, ethyl acetate and the like.
本発明を適用しうるこれらの物質の水溶液の濃
度は、本発明の方法の特徴を生かす観点からは比
較的低濃度の領域が好ましく、0.5〜20重量％が
適当である。水溶液濃度の上限は、主として分離
対象の水溶液が膜を濡らさない濃度で決まる。こ
れは膜素材ポリマの物理化学的性質、膜の微細孔
径、分離対象溶液の表面張力等が関係し、更に操
作圧の影響もあるので一概に限定することができ
ない。 The concentration of the aqueous solution of these substances to which the present invention can be applied is preferably in a relatively low concentration range from the viewpoint of taking advantage of the characteristics of the method of the present invention, and is suitably in the range of 0.5 to 20% by weight. The upper limit of the aqueous solution concentration is mainly determined by the concentration at which the aqueous solution to be separated does not wet the membrane. This is related to the physicochemical properties of the membrane material polymer, the micropore diameter of the membrane, the surface tension of the solution to be separated, etc., and is also affected by the operating pressure, so it cannot be definitively determined.
［実施例］
実施例によつて更に詳細に説明するが、本発明
はこれらに限定されるものではない。[Example] The present invention will be explained in more detail with reference to Examples, but the present invention is not limited thereto.
なお液−液系の揮発性有機液体水溶液の濃縮法
の実験は、第４図に模式的に示した方法で行つ
た。即ち、供給液槽１から５％のエタノール水溶
液を50℃に調節して膜モジユール４に供給し、循
環する。一方、膜の２次側には15℃に調節した５
％のエタノール水溶液を透過液槽から循環供給す
る。実験の開始後、所定時間毎に供給液槽（高温
側）と透過液槽（低温側）からサンプル液を採り
その濃度をガスクロマトグラフイまたは示差屈折
計で測定する。実験終了後、供給液槽および透過
液槽の液重量を測定する。高温側の濃度は低下
し、低温側の濃度は増加する。これらの高温側お
よび低温側の濃度の経時的変化と液の透過量とか
ら実験初期のエタノールの分離係数および水およ
びエタノールの透過速度を算出した。すなわち、
CH(t)＝｛EH(o)−Qe(t)−ΣcH(n)・SH(n)｝／EHT(t)(
6)
CL(t)＝｛EL(o)＋Qe(t)−ΣcL(n)・SL(n)｝／ELT(t)(
7)
ここで、Ｃ(t)は実験開始後、ｔ時間後のエタノ
ールの濃度で、添字Ｈは高温側を、Ｌは低温側を
示す。Ｃ(n)はｎ回目のサンプリングの濃度を表
す。Ｓ(n)はｎ回目のサンプリングの量を示してい
る。Ｅ(o)、Ｅ(t)はそれぞれ実験開始前と開始ｔ時
間後のエタノールの量を表す。EHT(t)、ELT(t)は実
験開始ｔ時間後のそれぞれ高温側と低温側の溶液
の全量である。上の式を利用し、次の関係を考慮
してエタノール透過速度Jeおよび水の透過速度
Jwをカーブフイツテイング法で算出し、下記の
(10)式でエタノールに対する分離係数αを求める。
Qe(t)はｔ時間後のエタノールの透過量である。 The experiment for concentrating a liquid-liquid volatile organic liquid aqueous solution was carried out by the method schematically shown in FIG. That is, a 5% aqueous ethanol solution is adjusted to 50° C. from the supply liquid tank 1 and supplied to the membrane module 4, where it is circulated. On the other hand, on the secondary side of the membrane,
% ethanol aqueous solution is circulated and supplied from the permeate tank. After the start of the experiment, sample liquids are taken from the supply liquid tank (high temperature side) and the permeate liquid tank (low temperature side) at predetermined intervals, and their concentrations are measured using gas chromatography or a differential refractometer. After the experiment is completed, measure the weight of the liquid in the feed liquid tank and permeate liquid tank. The concentration on the high temperature side decreases and the concentration on the low temperature side increases. The separation coefficient of ethanol and the permeation rate of water and ethanol at the initial stage of the experiment were calculated from the changes over time in the concentrations on the high temperature side and the low temperature side and the permeation amount of the liquid. That is, C H (t)={E H (o)−Qe(t)−Σc H (n)・S H (n)}/E HT (t)(
6) C L (t)＝{E L (o)＋Qe(t)−Σc L (n)・S L (n)}／E LT (t)(
7) Here, C(t) is the concentration of ethanol t hours after the start of the experiment, the subscript H indicates the high temperature side, and L indicates the low temperature side. C(n) represents the concentration of the nth sampling. S(n) indicates the amount of n-th sampling. E(o) and E(t) represent the amount of ethanol before the start of the experiment and at time t after the start of the experiment, respectively. E HT (t) and E LT (t) are the total amounts of solution on the high temperature side and low temperature side, respectively, after t hours from the start of the experiment. Using the above formula and considering the following relationships, calculate the ethanol permeation rate Je and the water permeation rate.
Calculate Jw using the curve fitting method and use the following method.
Find the separation coefficient α for ethanol using equation (10).
Qe(t) is the amount of ethanol permeated after t time.
Qe(t)＝A∫tJedt (8)
Qw(t)＝A∫tJwdt (9)
αEtOH＝（Je／Jw）／CH(t)／｛１−cH(t)｝ (10)
実施例 １
ペンウオルト社製ポリフツ化ビニリデン
KYNAR460と740とを混合してポリマ濃度29％、
110℃での溶液粘度1000ポイズになるように調整
したジメチルスルホキサイド（DMSO）を主溶
媒とする紡糸原液を、DMSO80％の水溶液を中
空部に注入して、環状中空糸紡糸用口金から紡出
し、45℃の水中で凝固させ、しかるのち水で洗浄
して、含水状態のポリフツ化ビニリデン中空糸膜
を得た。この膜を試薬１級のメタノールに浸せき
し１昼夜放置後、風乾した。中空糸膜の外径は
1037μm、内径は738μm体積空孔率は0.717であつ
た。乾燥後の中空糸膜をメタノールを介して水に
置換した後、透水性とメタノール、エタノール、
ｎ−ブタノール、アセトン等の拡散透過性を測定
し、平均孔径（Rp）とそれぞれの曲路率（ts）
を求めた。Rpは230Å、tsはそれぞれ2.75、2.88、
2.66、2.63、で、Rpとストークス半径との比はそ
れぞれ160、119、94、120であつた。 Qe(t)＝A∫ t Jedt (8) Qw(t)＝A∫ t Jwdt (9) α EtOH = (Je／Jw)／C H (t)／{1−c H (t)} (10 ) Example 1 Polyvinylidene fluoride manufactured by Pennwalt Co., Ltd.
Mix KYNAR460 and 740 to obtain a polymer concentration of 29%.
A spinning stock solution containing dimethyl sulfoxide (DMSO) as the main solvent, adjusted to have a solution viscosity of 1000 poise at 110°C, is injected into the hollow part with an aqueous solution of 80% DMSO, and then spun from a circular hollow fiber spinning nozzle. The membrane was taken out, coagulated in water at 45°C, and then washed with water to obtain a polyvinylidene fluoride hollow fiber membrane in a water-containing state. This membrane was immersed in reagent grade 1 methanol, left for one day and night, and then air-dried. The outer diameter of the hollow fiber membrane is
The inner diameter was 1037 μm, the inner diameter was 738 μm, and the volume porosity was 0.717. After replacing the dried hollow fiber membrane with water via methanol, the water permeability and methanol, ethanol,
Measure the diffusion permeability of n-butanol, acetone, etc., and calculate the average pore diameter (Rp) and each tortuosity (ts).
I asked for Rp is 230Å, ts is 2.75 and 2.88, respectively.
2.66, 2.63, and the ratios of Rp and Stokes radius were 160, 119, 94, and 120, respectively.
この乾燥した中空糸膜を約40cmの長さに切り、
十数本を束ねて両端をエポキシ接着剤でポツテイ
ングし、硬化後中空糸束の開口端を作製するため
切断し、両端がエポキシ接着剤でポツテイングさ
れた中空糸束を作製した。この中空糸束の内側に
メタノールを充填し再びメタノールで含浸させ
た。含浸後、中空糸内部の過剰のメタノールを窒
素ガスで押出し、約数秒から数分窒素ガスを通じ
て余分のメタノールを蒸発させて除いた。次い
で、トーレ・シリコーン(株)製SE6721をフレオン
−113に２重量％になるように溶かしたコーテイ
ング液を中空糸の内側に充填し、約数秒から数分
放置した後窒素ガスを通じて溶媒を蒸発させ、し
かるのち、70℃、４時間キユアリングした。この
コーテイング処理をした中空糸を14本、アクリル
製のパイプで作製した低温側溶液の入口ノズルと
出口ノズルを有するケースに挿入し、ケース両端
でポテイングして実験用膜モジユールを作製し
た。同様に、コーテイング処理をしていない中空
糸の膜モジユールも作製して比較例の実験に供し
た。液−液系の揮発性有機液体水溶液の濃縮法の
実験は、エタノールの５％水溶液を用いて前述の
方法で行なつた。 Cut this dried hollow fiber membrane into a length of about 40 cm.
Ten or more fibers were bundled and both ends potted with epoxy adhesive, and after curing, the hollow fiber bundle was cut to create an open end of the hollow fiber bundle, and both ends were potted with epoxy adhesive to produce a hollow fiber bundle. The inside of this hollow fiber bundle was filled with methanol and impregnated with methanol again. After impregnation, excess methanol inside the hollow fiber was extruded with nitrogen gas, and the excess methanol was removed by evaporating the nitrogen gas through the fiber for about several seconds to several minutes. Next, a coating solution prepared by dissolving SE6721 manufactured by Toray Silicone Co., Ltd. in Freon-113 at a concentration of 2% by weight was filled inside the hollow fibers, and after being left for several seconds to several minutes, the solvent was evaporated by passing nitrogen gas. , and then cured at 70°C for 4 hours. Fourteen coated hollow fibers were inserted into a case made of acrylic pipes that had an inlet nozzle and an outlet nozzle for the low-temperature solution, and potted at both ends of the case to create an experimental membrane module. Similarly, a hollow fiber membrane module that had not been coated was also produced and used in comparative experiments. Experiments on the method for concentrating a liquid-liquid volatile organic liquid aqueous solution were carried out using a 5% aqueous solution of ethanol in the manner described above.
本実施例の場合、モジユール入口の高温側溶液
温度は51.0℃、低温側の入口の溶液温度は17.0℃
で、実験初期のエタノールの透過速度は0.24Kg
m-2h-1で、水の透過速度は0.28Kgm-2h-1、エタ
ノールに対する分離係数αEtOHは16.3であつた。こ
れに対して比較例では同一の条件に対して実験初
期のエタノールの透過速度は0.24Kgm-2h-1で、水
の透過速度は0.88Kgm-2h-1、エタノールに対する
分離係数αは5.1であつた。比較例に対して、本
実験例の方が同一の濃度の供給液に対して２次側
をより高い濃度にすることができる。 In the case of this example, the solution temperature on the high temperature side at the module inlet is 51.0°C, and the solution temperature at the low temperature side inlet is 17.0°C.
So, the permeation rate of ethanol at the beginning of the experiment was 0.24Kg.
m -2 h -1 , the water permeation rate was 0.28 Kgm -2 h -1 and the separation coefficient α EtOH for ethanol was 16.3. On the other hand, in the comparative example, under the same conditions, the ethanol permeation rate at the initial stage of the experiment was 0.24 Kgm -2 h -1 , the water permeation rate was 0.88 Kgm -2 h -1 , and the separation coefficient α for ethanol was 5.1. It was hot. Compared to the comparative example, in this experimental example, the secondary side can be made to have a higher concentration with respect to the supply liquid having the same concentration.
なお、未処理の比較例の中空糸膜の窒素ガスの
通気性は2.40×10-2ml（STP）cm-2S-1cmHgで、
実施例の中空糸膜では1.97（単位同上）であり、
コーテイングにより膜表面の開孔部が閉塞されて
いないことが確められた。また、この膜の内表面
のシリコーンの存在の確認はSIMSの測定によつ
て膜表面から3000〜4500Åの厚さでSiとＯ原子が
ほぼ同濃度で検出されたことで確められた。 The nitrogen gas permeability of the untreated comparative hollow fiber membrane was 2.40×10 -2 ml (STP) cm -2 S -1 cmHg.
In the hollow fiber membrane of the example, it is 1.97 (units same as above),
It was confirmed that the openings on the membrane surface were not blocked by the coating. The presence of silicone on the inner surface of this film was confirmed by SIMS measurement, where Si and O atoms were detected at approximately the same concentration at a thickness of 3000 to 4500 Å from the film surface.
実施例 ２
実施例１と同様に紡糸したテトラフルオロエチ
レン30重量％を含むフツ化ビニリデン共重合体か
らなる、外径1040μm、内径729μm、体積空孔率
0.733、Rp＝180Å、エタノールのtsが3.07の中空
糸14本を用いて膜モジユールを作製した。一方は
メタノールを含浸させずにそれ以外の条件は実施
例１と同じコーテイング液を前述と同様の方法・
条件で膜モジユールでコートし、比較例とした。
他方はエタノールを含浸させた後、全く同様にコ
ートした。実施例１と同一の条件で膜の性能を評
価したところ本実施例では、エタノールの透過速
度が0.19Kgm-2h-1、水の透過速度が0.18Kgm-2
h-1、αEtOHは22.0であるのにたいして、比較例で
はそれぞれ、0.16、0.43、6.4であり、シリコーン
ポリマのコーテイングの効果は認められたが、本
実施例で推奨する方法・条件でコートした方が、
より優れた結果が得られることが分つた。なお、
本実施例に用いた基膜のRpとストークス半径と
の比は93で、実施例の窒素の通気性は1.97、比較
例のそれは0.44であつた。単位は前述と同じであ
る。Example 2 Made of vinylidene fluoride copolymer containing 30% by weight of tetrafluoroethylene spun in the same manner as in Example 1, outer diameter 1040 μm, inner diameter 729 μm, volume porosity.
A membrane module was fabricated using 14 hollow fibers with 0.733, Rp = 180 Å, and ethanol ts of 3.07. One side was coated with the same coating solution as in Example 1 without being impregnated with methanol, but in the same manner as described above.
It was coated with the membrane module under the following conditions and used as a comparative example.
The other was impregnated with ethanol and then coated in exactly the same manner. The performance of the membrane was evaluated under the same conditions as in Example 1. In this example, the permeation rate of ethanol was 0.19Kgm -2 h -1 and the permeation rate of water was 0.18Kgm -2
h -1 and α EtOH were 22.0, whereas in the comparative example they were 0.16, 0.43, and 6.4, respectively, and the effect of silicone polymer coating was recognized, but it was coated using the method and conditions recommended in this example. Better,
It was found that better results were obtained. In addition,
The ratio of Rp to the Stokes radius of the base film used in this example was 93, the nitrogen permeability of the example was 1.97, and that of the comparative example was 0.44. The units are the same as above.
実施例 ３
実施例１に使用した中空糸を実施例１と同様に
ただし一端だけをエポキシ接着剤でポツテイング
した中空糸束を作製し、中空糸の部分をガラス管
に挿入したアセトニトリル中に浸漬して含浸させ
た。次いで、中空糸の内部の過剰のアセトニトリ
ルを窒素気流で除き、室温硬化型ジメチルシロキ
サンの２％フレオン溶液を中空糸内部に充填し、
窒素気流を約１時間通じて溶媒を蒸発させ、70
℃、４時間キユアリングした。この中空糸14本を
膜モジユールに組立て、エタノール５％の水溶液
で膜性能を評価した。室温硬化型ジメチルシロキ
サンとしては、プレポリマの両未端が水酸基のシ
ロキサンプレポリマを使い、架橋剤メチルトリア
セトキシシランと触媒ジブチルスズジアセテート
を加えてコーテイング液とした。Example 3 A hollow fiber bundle was prepared by potting only one end of the hollow fibers used in Example 1 with epoxy adhesive in the same manner as in Example 1, and the hollow fiber portion was inserted into a glass tube and immersed in acetonitrile. and impregnated it. Next, excess acetonitrile inside the hollow fiber was removed with a nitrogen stream, and a 2% Freon solution of room temperature curing dimethylsiloxane was filled inside the hollow fiber.
Evaporate the solvent by passing a nitrogen stream for about 1 hour,
Cure for 4 hours. Fourteen of these hollow fibers were assembled into a membrane module, and membrane performance was evaluated using a 5% ethanol aqueous solution. A siloxane prepolymer having hydroxyl groups at both ends of the prepolymer was used as the room temperature-curable dimethylsiloxane, and a crosslinking agent methyltriacetoxysilane and a catalyst dibutyltin diacetate were added to form a coating liquid.
その結果、エタノールの透過速度が0.16Kgm-2
h-1、水の透過速度が0.42Kgm-2h-1、αEtOHは7.3で
性能の向上効果が認められた。本実施例のコーテ
イング膜の通気性は1.47であつた。 As a result, the permeation rate of ethanol was 0.16Kgm -2
h -1 , water permeation rate was 0.42 Kgm -2 h -1 , and α EtOH was 7.3, indicating an improvement in performance. The air permeability of the coating film of this example was 1.47.
実施例 ４
実施例１に使用した膜モジユールを使つて、２
％のアセトン水溶液で膜の分離性能を上述と同様
の温度条件で評価した。その結果、本実施例では
アセトンの透過速度が0.41Kgm-2h-1、水の透過速
度が0.29Kgm-2h-1、αACTNは70.4であつたが、比較
例の膜モジユールではアセトンの透過速度が0.47
Kgm-2h-1、水の透過速度が0.41Kgm-2h-1、αACTN
は55.7で、本実施例がアセトン水溶液に対しても
有効であつた。Example 4 Using the membrane module used in Example 1, 2
% acetone aqueous solution under the same temperature conditions as described above. As a result, in this example, the acetone permeation rate was 0.41Kgm -2 h -1 , the water permeation rate was 0.29Kgm -2 h -1 , and α ACTN was 70.4, but in the membrane module of the comparative example, acetone Transmission rate is 0.47
Kgm -2 h -1 , water permeation rate is 0.41Kgm -2 h -1 , α ACTN
was 55.7, indicating that this example was also effective for acetone aqueous solutions.
実施例 ５
実施例４と同様に、実施例１に使用した膜モジ
ユールを使つて、２％のアセトニトリル水溶液で
膜の分離性能を上述と同様に温度条件で評価し
た。その結果、本実施例ではアセトニトリルの透
過速度が0.18Kgm-2h-1、水の透過速度が0.21Kg
m-2h-1、αACNRは40.5であつたが、比較例の膜モ
ジユールではアセトンの透過速度が0.25Kgm-2
h-1、水の透過速度が0.43Kgm-2h-1、αACNRは27.3
で、本実施例がアセトニトリル水溶液に対しても
有効であつた。Example 5 Similarly to Example 4, using the membrane module used in Example 1, the separation performance of the membrane was evaluated using a 2% acetonitrile aqueous solution under the same temperature conditions as described above. As a result, in this example, the permeation rate of acetonitrile was 0.18Kgm -2 h -1 and the permeation rate of water was 0.21Kgm
m -2 h -1 and α ACNR was 40.5, but the membrane module of the comparative example had an acetone permeation rate of 0.25 Kgm -2
h -1 , water permeation rate is 0.43Kgm -2 h -1 , α ACNR is 27.3
This example was also effective for acetonitrile aqueous solutions.
実施例 ６
実施例１に使用したのと同じ中空糸で膜モジユ
ールを作製し、アセトニトリルを含浸させ、フエ
ニルメチルシロキサン（20モル％）ジメチルシロ
キサンコポリマを実施例３と同様にしてコートし
た。エタノール水溶液で膜の分離性能を測定した
結果、エタノールの透過速度が0.12Kgm-2h-1、水
の透過速度が0.31Kgm-2h-1、αEtOHは7.6以上で、
コーテイングの条件を最適化すればさらに優れた
性能を示す可能性があることが分つた。Example 6 A membrane module was made from the same hollow fibers used in Example 1, impregnated with acetonitrile, and coated with phenylmethylsiloxane (20 mole %) dimethylsiloxane copolymer as in Example 3. As a result of measuring the separation performance of the membrane with an ethanol aqueous solution, the permeation rate of ethanol was 0.12Kgm -2 h -1 , the permeation rate of water was 0.31Kgm -2 h -1 , and α EtOH was 7.6 or higher.
It was found that even better performance could be achieved by optimizing the coating conditions.
［発明の効果］
本発明によれば、揮発性有機液体水溶液から該
有機液体を選択的に濃縮分離する液−液系の膜分
離法において使用しうる、分離性能の改善された
分離膜とその使用方法およびその製造方法を提供
することができる。[Effects of the Invention] According to the present invention, there is provided a separation membrane with improved separation performance that can be used in a liquid-liquid membrane separation method for selectively concentrating and separating an organic liquid from an aqueous solution of a volatile organic liquid. Methods of use and methods of manufacturing the same can be provided.
第１図は本願発明に好適に使用しうる、繊維の
断面形状の写真である。第２図は第１図の繊維の
表面形状を示す写真である。第３Ａ図は、本発明
の実施例１の繊維の表面形状の写真である。第３
Ｂ図は、第３Ａ図を更に高倍率で示した繊維の表
面形状の写真である。第４図は、本発明の実施例
に使用した膜分離実験装置を模式的に示した図で
ある。１は供給（または１次）液槽、２は供給液
側循環ポンプ、３は供給液側熱交換器、４は膜モ
ジユール、９および１０はそれぞれ供給液側膜モ
ジユールの入口と出口である。５は透過（または
２次）液槽、６は透過液側熱交換器、７は調圧
弁、８は透過液側循環ポンプ、１１および１２は
それぞれ透過液側膜モジユールの入口と出口であ
る。
FIG. 1 is a photograph of the cross-sectional shape of a fiber that can be suitably used in the present invention. FIG. 2 is a photograph showing the surface shape of the fiber shown in FIG. FIG. 3A is a photograph of the surface shape of the fiber of Example 1 of the present invention. Third
Figure B is a photograph of the surface shape of the fiber showing Figure 3A at a higher magnification. FIG. 4 is a diagram schematically showing a membrane separation experimental apparatus used in an example of the present invention. 1 is a feed (or primary) liquid tank, 2 is a circulation pump on the feed liquid side, 3 is a heat exchanger on the feed liquid side, 4 is a membrane module, and 9 and 10 are the inlet and outlet of the membrane module on the feed liquid side, respectively. 5 is a permeate (or secondary) liquid tank, 6 is a permeate side heat exchanger, 7 is a pressure regulating valve, 8 is a permeate side circulation pump, and 11 and 12 are the inlet and outlet of the permeate side membrane module, respectively.
Claims (1)
該膜表面の少なくとも一部の開孔部が閉塞される
ことなく、ジメチルシロキサンを主成分とするシ
リコーン系ポリマがコートされていることを特徴
とする揮発性有機液体水溶液濃縮膜。 ２ ポリフツ化ビニリデン系多孔性膜が、中空糸
膜であり、その内表面にジメチルシロキサンを主
成分とするシリコーン系ポリマがコートされてい
ることを特徴とする特許請求の範囲第１項記載の
揮発性有機液体水溶液濃縮膜。 ３ シリコーン系ポリマが顆粒状でコーテイング
されていることを特徴とする特許請求の範囲第１
項記載の揮発性有機液体水溶液濃縮膜。 ４ ポリフツ化ビニリデン系多孔性膜の表面に、
該膜表面の少なくとも一部の開孔部が閉塞される
ことなくジメチルシロキサンを主成分とするシリ
コーン系ポリマがコートされている複合膜におい
て、該膜の一次側に該膜の平均微細孔半径の１／
15以下のストークス半径を持ち、かつ該膜に対し
て実質的に不透性を示す揮発性有機液体水溶液を
供給し、気化した状態で膜を透過させることを特
徴とする揮発性有機液体水溶液濃縮膜の使用方
法。 ５ シリコーン系ポリマのコーテイング液の溶媒
と相溶性を示すポリフツ化ビニリデンの非溶媒
を、ポリフツ化ビニリデン系多孔性膜に含浸さ
せ、該膜の表面にシリコーン系ポリマの溶液をコ
ートし、溶媒を蒸発・揮散させたのちキユアリン
グして、ポリフツ化ビニリデンの表面の開孔部を
閉塞することなくシリコーン系ポリマをコートし
たことを特徴とする揮発性有機液体水溶液濃縮膜
の製造方法。[Claims] 1. On the surface of a polyvinylidene fluoride porous membrane,
A volatile organic liquid aqueous solution concentration membrane characterized in that at least some of the openings on the surface of the membrane are coated with a silicone polymer containing dimethylsiloxane as a main component without being blocked. 2. The volatilization method according to claim 1, wherein the polyvinylidene fluoride porous membrane is a hollow fiber membrane, the inner surface of which is coated with a silicone polymer whose main component is dimethylsiloxane. organic liquid aqueous solution concentration membrane. 3 Claim 1 characterized in that the silicone-based polymer is coated in the form of granules.
Volatile organic liquid aqueous solution concentration membrane described in . 4 On the surface of the polyvinylidene fluoride porous membrane,
In a composite membrane coated with a silicone polymer mainly composed of dimethylsiloxane without blocking at least some of the pores on the surface of the membrane, the primary side of the membrane has an average micropore radius of 1/
A volatile organic liquid aqueous solution concentration characterized by supplying an aqueous volatile organic liquid solution having a Stokes radius of 15 or less and showing substantially impermeability to the membrane, and allowing the aqueous solution to pass through the membrane in a vaporized state. How to use the membrane. 5. Impregnate a polyvinylidene fluoride porous membrane with a polyvinylidene fluoride non-solvent that is compatible with the solvent of the silicone polymer coating solution, coat the surface of the membrane with the silicone polymer solution, and evaporate the solvent. - A method for producing a volatile organic liquid aqueous solution concentration membrane, which is characterized in that it is cured after volatilization and coated with a silicone polymer without clogging the pores on the surface of polyvinylidene fluoride.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP403587A JPS63175606A (en) | 1987-01-13 | 1987-01-13 | Membrane for concentrating aqueous solution of volatile organic liquid, use and preparation thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP403587A JPS63175606A (en) | 1987-01-13 | 1987-01-13 | Membrane for concentrating aqueous solution of volatile organic liquid, use and preparation thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63175606A JPS63175606A (en) | 1988-07-20 |
| JPH0515494B2 true JPH0515494B2 (en) | 1993-03-01 |
Family
ID=11573706
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP403587A Granted JPS63175606A (en) | 1987-01-13 | 1987-01-13 | Membrane for concentrating aqueous solution of volatile organic liquid, use and preparation thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63175606A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0671532B2 (en) * | 1989-09-18 | 1994-09-14 | 東レ株式会社 | Fluid separation module and manufacturing method thereof |
| JP2953454B2 (en) | 1998-02-18 | 1999-09-27 | 日本電気株式会社 | Bag breaking device |
-
1987
- 1987-01-13 JP JP403587A patent/JPS63175606A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63175606A (en) | 1988-07-20 |
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