JPH0490833A - Separation membrane for water-soluble organic matter - Google Patents
Separation membrane for water-soluble organic matterInfo
- Publication number
- JPH0490833A JPH0490833A JP20904290A JP20904290A JPH0490833A JP H0490833 A JPH0490833 A JP H0490833A JP 20904290 A JP20904290 A JP 20904290A JP 20904290 A JP20904290 A JP 20904290A JP H0490833 A JPH0490833 A JP H0490833A
- Authority
- JP
- Japan
- Prior art keywords
- water
- separation
- layer
- membrane
- polyvinyl alcohol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000012528 membrane Substances 0.000 title claims abstract description 73
- 238000000926 separation method Methods 0.000 title claims abstract description 62
- 239000005416 organic matter Substances 0.000 title claims description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 43
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 43
- 239000004627 regenerated cellulose Substances 0.000 claims description 34
- 238000000576 coating method Methods 0.000 claims description 7
- 239000011248 coating agent Substances 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 36
- 238000000034 method Methods 0.000 abstract description 33
- 229920002678 cellulose Polymers 0.000 abstract description 9
- 239000001913 cellulose Substances 0.000 abstract description 9
- 230000005540 biological transmission Effects 0.000 abstract description 6
- 230000008929 regeneration Effects 0.000 abstract description 3
- 238000011069 regeneration method Methods 0.000 abstract description 3
- 238000005373 pervaporation Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 20
- 238000002474 experimental method Methods 0.000 description 12
- 239000000203 mixture Substances 0.000 description 12
- 239000007788 liquid Substances 0.000 description 10
- 239000000126 substance Substances 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 7
- 239000003431 cross linking reagent Substances 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 6
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 5
- 229920000297 Rayon Polymers 0.000 description 4
- 229920000298 Cellophane Polymers 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000011976 maleic acid Substances 0.000 description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid group Chemical group C(\C=C/C(=O)O)(=O)O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 3
- 230000035699 permeability Effects 0.000 description 3
- 229920002239 polyacrylonitrile Polymers 0.000 description 3
- 229920005597 polymer membrane Polymers 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000012466 permeate Substances 0.000 description 2
- -1 polyethylene Polymers 0.000 description 2
- 238000007127 saponification reaction Methods 0.000 description 2
- 229920001661 Chitosan Polymers 0.000 description 1
- 229920001353 Dextrin Polymers 0.000 description 1
- 239000004375 Dextrin Substances 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229920002873 Polyethylenimine Polymers 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- PQLVXDKIJBQVDF-UHFFFAOYSA-N acetic acid;hydrate Chemical compound O.CC(O)=O PQLVXDKIJBQVDF-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- QKSIFUGZHOUETI-UHFFFAOYSA-N copper;azane Chemical compound N.N.N.N.[Cu+2] QKSIFUGZHOUETI-UHFFFAOYSA-N 0.000 description 1
- FDADMSDCHGXBHS-UHFFFAOYSA-N copper;ethene Chemical group [Cu].C=C FDADMSDCHGXBHS-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 235000019425 dextrin Nutrition 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- ZOOODBUHSVUZEM-UHFFFAOYSA-N ethoxymethanedithioic acid Chemical compound CCOC(S)=S ZOOODBUHSVUZEM-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000012510 hollow fiber Substances 0.000 description 1
- 238000007602 hot air drying Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- XTUSEBKMEQERQV-UHFFFAOYSA-N propan-2-ol;hydrate Chemical compound O.CC(C)O XTUSEBKMEQERQV-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000012991 xanthate Substances 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〕
本発明は水溶性有機物分離膜に関する。更に詳しくはパ
ーベーパレーション法（以下ＰＶ法と略す）分離及び蒸
気透過性分離に極めて好適な水選択透過性の分離膜に関
する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a water-soluble organic substance separation membrane. More specifically, the present invention relates to a water selectively permeable separation membrane that is extremely suitable for pervaporation (hereinafter abbreviated as PV method) separation and vapor permeable separation.
尚ＰＶ法及び蒸気透過法とは適当な高分子膜を境として
膜の一方の供給側（又は１次側ともいう）に有機系混合
物（９通は水と有機物の混合物）の液体又は蒸気を導き
、膜の他方（透過側又は２次側）を減圧にするか、又は
不活性ガスを流すことにより高分子膜の両面に目的成分
の分圧差を設け、この分圧差によって目的成分を１次側
から２次側へ透過させて気化状態で取り出す分離方法で
ある。本発明の場合は水を高分子膜を通して１次側から
２次側へ透過させるものである。そしてこの方法に於い
て１次側へ混合蒸気を供給する方法が蒸気透過法であり
、混合液体を供給する方法がＰＶ法である。The PV method and the vapor permeation method are methods in which liquid or vapor of an organic mixture (9 cases is a mixture of water and organic substances) is supplied to one supply side (or also called the primary side) of the membrane with a suitable polymer membrane as the boundary. A partial pressure difference of the target component is created on both sides of the polymer membrane by reducing the pressure on the other side of the membrane (permeation side or secondary side) or flowing an inert gas, and this partial pressure difference causes the target component to become primary. This is a separation method in which the gas permeates from the side to the secondary side and is taken out in a vaporized state. In the case of the present invention, water is permeated from the primary side to the secondary side through a polymer membrane. In this method, the method for supplying the mixed vapor to the primary side is the vapor permeation method, and the method for supplying the mixed liquid is the PV method.
ＰＶ法、蒸気透過法は通常の蒸留法では分離が困難な有
機系混合物を分離・濃縮する方法として注目を集めてい
る。このような有機系混合物とは、共沸混合物を形成す
るもの、成分の沸点が近似しているもの、また熱にて変
性し易い化合物を含んでいるものであり、具体的には、
メタノール−水系、エタノール−水系、イソプロパノ−
ルー水系のようなアルコール−水系混合物、アセトン−
水系のようなケトン−水系混合物、酢酸−水系のような
を機酸−水系混合物などがある。通常の蒸留法では分離
できないこのような水−有機物混合物もＰＶ法や蒸気透
過法を用いれば選択的に水又は有機物を透過させ、有機
物を分離することが可能となる。The PV method and vapor permeation method are attracting attention as methods for separating and concentrating organic mixtures that are difficult to separate using ordinary distillation methods. Such organic mixtures are those that form an azeotrope, those whose components have similar boiling points, and those that contain compounds that are easily denatured by heat. Specifically,
Methanol-water system, ethanol-water system, isopropano-
Alcohol-water-based mixtures such as roux-based, acetone-
Examples include ketone-water mixtures such as water-based mixtures, organic acid-water mixtures such as acetic acid-water systems, and the like. By using the PV method or the vapor permeation method, it becomes possible to selectively permeate water or organic matter and separate the organic matter from such a water-organic mixture that cannot be separated by ordinary distillation methods.
ＰＶ法や蒸気透過法による水溶性有機物の分離に使用す
る水選択透過性の膜については、従来米国特許にてポリ
ビニルアルコール系膜及びポリアクリロニトリル系膜が
開示され、それ以来国内特許でも数多くの膜が開示され
てきた。それらの膜の代表的なものを挙げると、再生セ
ルロース系、ポリビニルアルコール系、酢酸セルロース
系、デキストリン系、キトサン系、ポリエチレンイミン
系及びこれらの高分子化合物にスルホン酸基やカルボン
酸基などのイオン交換基を導入した膜などである。Regarding water-selective permeable membranes used for the separation of water-soluble organic substances by the PV method and vapor permeation method, polyvinyl alcohol-based membranes and polyacrylonitrile-based membranes have been previously disclosed in US patents, and since then, numerous membranes have been disclosed in domestic patents. has been disclosed. Representative membranes include regenerated cellulose, polyvinyl alcohol, cellulose acetate, dextrin, chitosan, polyethyleneimine, and polymer compounds containing ions such as sulfonic acid groups and carboxylic acid groups. These include membranes with exchange groups introduced.
この種の膜には第１に水に対する選択透過性が大きいこ
とと、第２には液の透過量が大きいことが要請される。This type of membrane is required, firstly, to have a high selective permeability to water, and secondly, to have a large amount of liquid permeation.
水に対する選択透過性は下記式で表される分離係数α■
０によって評価され、これが大きい稚仔離性が良い。The selective permselectivity for water is expressed by the following formula: separation coefficient α■
It is evaluated by 0, and the higher this value, the better the separation from young children.
液の透過量は透過速度＝ｆ（ｋｇ／ボ・ｈ）によって膜
面積１留当たり１時間に透過した液量（ｋｇ）で表され
る。ｆも大きい膜性能の良い膜となる。The amount of liquid permeated is expressed as the amount (kg) of liquid permeated in one hour per one column of membrane area using the permeation rate = f (kg/boh). The film has a large f and has good film performance.
分離係数も透過速度も１次側の濃度と温度及び２次側圧
力によって大きく影響されるので、それらの条件は一定
にして膜性能の評価を行わなければならない。Since the separation coefficient and permeation rate are greatly affected by the concentration and temperature on the primary side and the pressure on the secondary side, membrane performance must be evaluated while keeping these conditions constant.
水選択透過性膜として、前記の如く多種類のものが現在
までに開示されて来ている。しかしそれらの膜は一般的
に分離係数が小さすぎるか、若しくは透過速度が小さい
ため実用的でないという欠点を有する。As mentioned above, many types of water selectively permeable membranes have been disclosed to date. However, these membranes generally have the disadvantage that their separation coefficients are too small or their permeation rates are too low to be practical.
本発明が解決しようとする課題は、ＰＶ法・蒸気透過法
により水溶性有機物の水を選択的に透過させるに際し使
用される分離膜として、分離係数が大きくて且つ透過速
度も充分大きい分離膜を開発することである。The problem to be solved by the present invention is to provide a separation membrane that has a large separation coefficient and a sufficiently high permeation rate as a separation membrane used when selectively permeating water of water-soluble organic substances by the PV method/vapor permeation method. It is to develop.
本発明者らは上記課題を解決するため鋭意研究を重ねた
結果、再生セルロース層とポリビニルアルコール層を有
効に組み合わせた分離膜が、水溶性有機物の系に於いて
水の分離係数を著しく向上せしめ得られると共に、且つ
透過速度も充分高く維持できることを見出し本発明を完
成するに至った。即ち、本発明は分離層が再生セルロー
ス層とポリビニルアルコール層の２層からなることを特
徴とする水選択透過性の水溶性有機物用の分離膜に係る
。The present inventors have conducted extensive research to solve the above problems, and have found that a separation membrane that effectively combines a regenerated cellulose layer and a polyvinyl alcohol layer significantly improves the separation coefficient of water in a system of water-soluble organic substances. The present inventors have discovered that it is possible to obtain the desired results and maintain a sufficiently high permeation rate, leading to the completion of the present invention. That is, the present invention relates to a water-selective permeable separation membrane for water-soluble organic substances, characterized in that the separation layer consists of two layers: a regenerated cellulose layer and a polyvinyl alcohol layer.
〔発明の作用並びに構成］
本発明による膜はＰＶ法又は蒸気透過法でアルコール−
水混合物、ケトン−水混合物、有機酸−水混合物から水
を分離するのに極めて適している。[Function and structure of the invention] The membrane according to the present invention can
It is highly suitable for separating water from water mixtures, ketone-water mixtures, organic acid-water mixtures.
本発明の分離層は再生セルロース層とポリビニルアルコ
ール層からなることを基本としている。The separation layer of the present invention basically consists of a regenerated cellulose layer and a polyvinyl alcohol layer.
ここで用いる再生セルロース層はセルロースザントゲン
酸ソーダ溶液（ビスコース溶液）やその他ノセルロース
溶液、例えば銅アンモニア、銅エチレンジアミン等゛の
金属錯体の水溶液にセルロースを溶解した溶液、各種ア
ミン系溶媒にセルロースを熔解した溶液などから得るこ
とができるが、−船釣にはビスコース溶液から得る方法
が好ましい。分離膜はその構成材料が水によっても対象
とする有機物によっても熔解したり、変質しないことが
必要であるが、再生セルロース膜は化学的に安定で、水
に不溶であり、また通常の有機溶剤にも不溶である上、
高い水選択透過性を有しているので分離層に適している
。The regenerated cellulose layer used here includes cellulose xanthate sodium solution (viscose solution) and other cellulose solutions, such as solutions in which cellulose is dissolved in aqueous solutions of metal complexes such as copper ammonia and copper ethylene diamine, and cellulose in various amine-based solvents. Although it can be obtained from a solution obtained by melting , it is preferable for boat fishing to obtain it from a viscose solution. Separation membranes require that their constituent materials do not dissolve or deteriorate in water or in the presence of target organic substances, but regenerated cellulose membranes are chemically stable, insoluble in water, and compatible with ordinary organic solvents. In addition to being insoluble in
It has high water selective permeability, making it suitable for separation layers.
本発明の再生セルロース層は上記溶液をダイから押し出
し適当な処理を行うことにより膜状に成形したものでも
構わないし、支持膜としての多孔性フィルム例えばポリ
アクリロニトリルやポリスルホン、ポリエチレン等の多
孔性フィルム上へ塗布して形成したものでも構わない。The regenerated cellulose layer of the present invention may be formed into a membrane by extruding the above solution through a die and performing appropriate treatment, or may be formed on a porous film such as polyacrylonitrile, polysulfone, polyethylene, etc. as a support membrane. It may also be formed by applying it to the surface.
またその他ビスコース法から得られる汎用再生セルロー
スフィルムであるセロハンをそのまま利用することも可
能である。In addition, it is also possible to use cellophane, which is a general-purpose regenerated cellulose film obtained by the viscose method, as it is.
再生セルロース層の厚みは２〜２５μｍ、好ましくは３
〜１０μｍである。２μｍに達しないと膜の均一性が損
なわれ、ピンホール等の欠陥が生じやすく、膜性能が不
安定になる。しかも低粘度低濃度液から作成されるため
機械的にも弱い膜となる。The thickness of the regenerated cellulose layer is 2 to 25 μm, preferably 3 μm.
~10 μm. If the thickness does not reach 2 μm, the uniformity of the film is impaired, defects such as pinholes are likely to occur, and the film performance becomes unstable. Moreover, since it is made from a low-viscosity, low-concentration liquid, the film is also mechanically weak.
２５μｍより大きくなると透過速度が小さくなりすぎ実
用的ではない。セルロースの重合度は特に限定しないが
、通常は１００〜５００程度である。If it is larger than 25 μm, the transmission rate becomes too low to be practical. The degree of polymerization of cellulose is not particularly limited, but is usually about 100 to 500.
１００未満の場合膜の機械的強度が弱くなる傾向があり
、また５００より大きくなると高粘度溶液となりすぎ、
作成した膜厚の均一性が悪くなることがあり、惹いては
性能が変動し易くなることがある。If it is less than 100, the mechanical strength of the membrane tends to be weak, and if it is more than 500, the solution becomes too viscous.
The uniformity of the formed film thickness may deteriorate, which in turn may make the performance more likely to fluctuate.
本発明のポリビニルアルコール層はポリビニルアルコー
ル溶液、−船釣には水溶液を前記再生セルロース膜上べ
塗布することによって得られる。The polyvinyl alcohol layer of the present invention is obtained by coating the regenerated cellulose membrane with a polyvinyl alcohol solution, or an aqueous solution for boat fishing.
ポリビニルアルコール層も再生セルロース層と同様に化
学的に安定であり、通常の有機溶剤には不溶である。し
かしポリビニルアルコール層は徐々に水に溶解していく
ため何らかの架橋処理を施して水に不溶とする必要があ
る。Like the regenerated cellulose layer, the polyvinyl alcohol layer is also chemically stable and insoluble in ordinary organic solvents. However, since the polyvinyl alcohol layer gradually dissolves in water, it is necessary to perform some kind of crosslinking treatment to make it insoluble in water.
この架橋処理はポリビニルアルコール水溶液中に架橋剤
を添加することによって行われ、架橋剤が添加された水
溶液を再生セルロース膜上へ塗布し、比較的高温で加熱
乾燥・熱処理を行うことによってなされる。この用途に
使われる架橋剤としては、従来から使用されてきたもの
が使用され、例えばジカルボン酸、ジハロゲン化物、ア
ルデヒド′又はジアルデヒドなどが挙げられるが、これ
らＣζ限定されるものではない。代表例としてはマレイ
ン酸を例示でき、ポリビニルアルコールに対してマレイ
ン酸を数重量％添加したポリビニルアルコール水溶液を
再生セルロース膜上に塗布し、１５０”Ｃにて乾燥熱処
理を行えばこの膜は水に不溶性となる。また本発明に於
いては架橋剤を使用せず、架橋効果のあるモノマーとの
共重合体である変性ポリビニルアルコールを使用するこ
ともでき、この水溶液を再生セルロース膜に塗布し、乾
燥熱処理しても水不溶性のポリビニルアルコール膜が得
られる。この種の変性ポリビニルアルコールとしては無
水マレイン酸などの共重合体も使用することができる。This crosslinking treatment is performed by adding a crosslinking agent to an aqueous polyvinyl alcohol solution, applying the aqueous solution to which the crosslinking agent has been added onto the regenerated cellulose membrane, and performing drying and heat treatment at a relatively high temperature. As the crosslinking agent used for this purpose, those conventionally used include dicarboxylic acids, dihalides, aldehydes and dialdehydes, but are not limited to these Cζ. A typical example is maleic acid; if a polyvinyl alcohol aqueous solution containing several weight percent of maleic acid added to polyvinyl alcohol is applied onto a regenerated cellulose membrane and then subjected to a dry heat treatment at 150"C, this membrane becomes water resistant. In the present invention, it is also possible to use modified polyvinyl alcohol, which is a copolymer with a monomer that has a crosslinking effect, without using a crosslinking agent, and this aqueous solution is applied to the regenerated cellulose membrane. Even after dry heat treatment, a water-insoluble polyvinyl alcohol film can be obtained. Copolymers such as maleic anhydride can also be used as this type of modified polyvinyl alcohol.
再生セルロース膜上ヘポリビニルアルコール水溶液を塗
布する際に塗布液の粘度が低すぎる場合、再生セルロー
ス膜が水で膨潤し、均一な厚みの膜とならず、その分離
性能に悪影響を及ぼすことがあるので、塗布液の粘度は
塗布液が再生セルロース膜中へ全面的には浸透していか
ず、表面近傍に留まって膜を形成する程度となし、且つ
塗布後は素早く乾燥を仕上げるようにするのが好ましい
。When applying a polyvinyl alcohol aqueous solution onto a regenerated cellulose membrane, if the viscosity of the coating solution is too low, the regenerated cellulose membrane may swell with water, resulting in an unevenly thick membrane, which may adversely affect its separation performance. Therefore, the viscosity of the coating solution should be set so that the coating solution does not completely penetrate into the regenerated cellulose membrane, but remains near the surface and forms a film, and it should be dried quickly after application. preferable.
また予め再生セルロース膜を水で充分膨潤させておきそ
の上へポリビニルアルコール水溶液を塗布し、その後乾
燥・熱処理する手段も均一な分離性能を出すには有効で
ある。Furthermore, it is also effective to sufficiently swell the regenerated cellulose membrane with water in advance, apply an aqueous polyvinyl alcohol solution thereon, and then dry and heat-treat the membrane to achieve uniform separation performance.
ポリビニルアルコール層の厚みは、０．５〜１５μｍで
、好ましくは１〜６μｍである。０．５μｍ未満では再
生セルロース層の場合と同様な理由で均一性がなくなり
、機械的強度も低下する。１５μｍより大きくなると透
過速度が小さくなりすぎて実用的でない。用いるポリビ
ニルアルコールの重合度は適当な膜形成能と膜強度があ
るものであれば特に限定されない。ケン化度は耐水性を
少しでも上げる意味からできるだけ高いケン化度のもの
が好ましいが特に限定されない。The thickness of the polyvinyl alcohol layer is 0.5 to 15 μm, preferably 1 to 6 μm. If the thickness is less than 0.5 μm, uniformity will be lost for the same reason as in the case of the regenerated cellulose layer, and mechanical strength will also decrease. If it is larger than 15 μm, the transmission rate becomes too low to be practical. The degree of polymerization of the polyvinyl alcohol used is not particularly limited as long as it has suitable film-forming ability and film strength. The degree of saponification is not particularly limited, although it is preferably as high as possible in order to improve water resistance as much as possible.
次に本発明の分＃膜の全体の構成を図面に基づいて説明
する。第１図の分Ｈ膜はセロハンのようす再生セルロー
ス層（２）上にポリビニルアルコール又は変性ポリビニ
ルアルコールの水溶液を塗布し、乾燥・熱処理し形成し
た層（１）である。Next, the overall structure of the separation membrane of the present invention will be explained based on the drawings. The membrane shown in FIG. 1 is a layer (1) formed by applying an aqueous solution of polyvinyl alcohol or modified polyvinyl alcohol to a regenerated cellulose layer (2) resembling cellophane, followed by drying and heat treatment.
第２図は第１図の膜をポリアクリロニトリル等の機械的
強度の優れた多孔性支持膜（３）上にラミネ−トシた形
態の分離膜であり、ポリビニルアルコールを塗布した再
生セルロース層（２）を多孔性支持膜（３）にラミネー
トしても構わないし、再生セルロース層（２）を多孔性
支持膜（３）にラミネートしてから、再生セルロース層
（２）上に塗布法にてポリビニルアルコール層（１）を
形成しても構わない。Figure 2 shows a separation membrane in which the membrane in Figure 1 is laminated on a porous support membrane (3) with excellent mechanical strength such as polyacrylonitrile, and a regenerated cellulose layer (2) coated with polyvinyl alcohol. ) may be laminated on the porous support membrane (3), or the regenerated cellulose layer (2) may be laminated on the porous support membrane (3), and then polyvinyl is coated on the regenerated cellulose layer (2) by a coating method. An alcohol layer (1) may also be formed.
第３図はセルロース溶液を多孔性支持膜（３）上に塗布
し、その後適当な処理を行い、再生セルロース膜を形成
し、その上へ塗布法にてポリビニルアルコール層（１）
を重ねた形の分離膜である。本発明は第１〜３図のどの
構成となっても構わない。また形態も平膜状、中空糸状
、スパイラル状等いかなるものでも構わない。Figure 3 shows that a cellulose solution is coated on a porous support membrane (3), then an appropriate treatment is performed to form a regenerated cellulose membrane, and a polyvinyl alcohol layer (1) is applied on top of it by a coating method.
It is a separation membrane in the form of stacked layers. The present invention may have any of the configurations shown in FIGS. 1 to 3. Further, the shape may be any shape such as a flat membrane, a hollow fiber, or a spiral.
以下実施例により本発明を更に詳しく説明するが、本発
明はこれらの実施例に限定されるものではない。The present invention will be explained in more detail below with reference to Examples, but the present invention is not limited to these Examples.
く分離実験の説明〉
第４図に示す実験装置を用い、エタノール−水系とイソ
プロパノ−ルー水系にて蒸気透過法とＰＶ法の膜分離実
験を行った。ＰＶ法では１次側を混合液で満たし、蒸気
透過法では混合液の平衡謂気で満たし、夫々ファン又は
ポンプにて撹拌した。Description of Separation Experiment> Using the experimental apparatus shown in FIG. 4, membrane separation experiments using the vapor permeation method and the PV method were conducted in an ethanol-water system and an isopropanol-water system. In the PV method, the primary side was filled with a mixed liquid, and in the vapor permeation method, it was filled with equilibrium air of the mixed liquid and stirred by a fan or pump, respectively.
実験条件は１次側への供給アルコール濃度を９０重量％
、温度を５０°Ｃとし、２次側圧力を２ Ｔｏｒｒとし
た。膜の取り付けはポリビニルアルコール層が２次側に
なるようにした。膜の有効面積は約９０ｃｓｆｌである
。この条件で水選択透過型のアルコール−水分離実験を
行い、結果を、分離係数及び透過速であり、また透過速
度＝ｆ（ｋｇ／ｎ（・ｈ）である。The experimental conditions were that the alcohol concentration supplied to the primary side was 90% by weight.
, the temperature was 50°C, and the secondary pressure was 2 Torr. The membrane was attached so that the polyvinyl alcohol layer was on the secondary side. The effective area of the membrane is approximately 90 csfl. A selective water permeation type alcohol-water separation experiment was conducted under these conditions, and the results are the separation coefficient and permeation rate, and permeation rate = f (kg/n (·h)).
但し第４図中００）は分離膜、（１１）はファン、０２
）はモーター、０３）はクーラー、０４１！よポンプ、
０■はクーラ、０６）はトラップ、（＋７）はポンプを
示す。However, 00) in Figure 4 is the separation membrane, (11) is the fan, and 02
) is the motor, 03) is the cooler, 041! Yo pump,
0■ indicates a cooler, 06) indicates a trap, and (+7) indicates a pump.
実施例１
熔解バルブを原料としてセルロース濃度９．０％、苛性
ソーダ濃度６．１％（いずれも重量％）で粘度力２０°
Ｃニテ５０００ ｃ ｐのビスコース液を調製した。Example 1 Using a melting valve as a raw material, the cellulose concentration was 9.0%, the caustic soda concentration was 6.1% (both weight%), and the viscosity was 20°.
A viscose liquid of 5000 cp of C.Nite was prepared.
該ヒスコース液を長さ４０ｃｍの２枚のステンレス板を
約８０μｍの空隙を有するように組合わせて作成したス
リットより、硫酸濃度１５０ｇ／ ｌ、硫酸ナトリウム
濃度２００ｇ／ ｊｌ！、温度４５°Ｃの凝固浴中へ押
し出し、その後セロハン製造工程と同じ再生浴、温水洗
浴、水洗浴の処理浴を順次通過させ、薬品処理及び洗浄
を行い、その後多筒式乾燥器にて乾燥させ、厚さ約６μ
ｍの再生セルロース膜を得た。The hiscose liquid was passed through a slit made by combining two 40 cm long stainless steel plates with a gap of approximately 80 μm to obtain a sulfuric acid concentration of 150 g/l and a sodium sulfate concentration of 200 g/jl! , extruded into a coagulation bath at a temperature of 45°C, then sequentially passed through the same treatment baths as in the cellophane manufacturing process: a regeneration bath, a warm water washing bath, and a water washing bath, chemical treatment and washing, and then dried in a multi-tube dryer. about 6μ thick
A regenerated cellulose membrane of m was obtained.
次に重合度２０００、ケン化度９９〜１００％のポリビ
ニルアルコールを８５°Ｃの温水へ溶解し、ａ 度７０
ｇ／ｌのポリビニルアルコール溶液を作成し、冷却後績
ポリビニルアルコール溶液中にポリビニルアルコール当
たり５重量％のマレイン酸を熔解し、架橋剤入りポリビ
ニルアルコール溶液を得た。Next, polyvinyl alcohol with a degree of polymerization of 2000 and a degree of saponification of 99 to 100% was dissolved in warm water at 85°C, and
A polyvinyl alcohol solution of g/l was prepared, and after cooling, 5% by weight of maleic acid per polyvinyl alcohol was dissolved in the polyvinyl alcohol solution to obtain a polyvinyl alcohol solution containing a crosslinking agent.
該架橋剤入りポリビニルアルコール溶液をマイヤーバー
を用いて上記再生セルロース股上へ塗布し、その後１５
０°Ｃの熱風乾燥品中で１時間乾燥・熱処理して再生セ
ルロース膜厚６μｍ、架橋ポリビニルアルコール膜厚約
３μｍの合計的９μｍの厚みを持った再生セルロース層
とポリビニルアルコール層の２層からなる分離膜を得た
。この膜を用いて前記分離実験を行った。結果を以下に
記す。The crosslinking agent-containing polyvinyl alcohol solution was applied to the regenerated cellulose crotch using a Mayer bar, and then
It consists of two layers: a regenerated cellulose layer and a polyvinyl alcohol layer, with a total thickness of 9 μm, with a regenerated cellulose film thickness of 6 μm and a crosslinked polyvinyl alcohol film thickness of approximately 3 μm after drying and heat treatment for 1 hour in a hot air drying product at 0°C. A separation membrane was obtained. The separation experiment described above was conducted using this membrane. The results are described below.
■蒸気透過法による実験
（イ）エタノール−水系
分離係数：
透過速度： ｆ ＝０．０８ （ｋｇ／ボ・ｈ）（ロ
）イソプロパノ−ルー水系
分離係数：
透過速度： ｆ ＝０．０５ （ｋｇ／ｎ（−ｈ ）
■ＰＶ法による実験
イソプロパノ−ルー水系
分離係数：
透過速度： ｆ ＝０．１５ （ｋｇ／ボ・ｈ）比較
例１
実施例１と同様な操作で約９μｍ厚の再生セルロース膜
を作成した。この膜を用いて分離実験を行い以下のデー
タを得た。■Experiment using vapor permeation method (a) Ethanol-water separation coefficient: Permeation rate: f = 0.08 (kg/bo・h) (b) Isopropanol-aqueous separation coefficient: Permeation rate: f = 0.05 (kg) /n(-h)
(2) Experiment using PV method Isopropanol-aqueous separation coefficient: Permeation rate: f = 0.15 (kg/boh) Comparative Example 1 A regenerated cellulose membrane with a thickness of approximately 9 μm was prepared in the same manner as in Example 1. Separation experiments were conducted using this membrane and the following data were obtained.
■蒸気透過法による実験
（イ）エタノール−水系
分離係数：
透過速度： ｆ ＝０．１３ （ｋｇ／ボ・ｈ）（ロ
）イソプロパノ−ルー水系
分離係数：
１００ｇ／ ｉの架橋剤入りポリビニルアルコール溶液
をガラス板上に流延し、直ちに熱風乾燥器中で１５０°
Ｃで１時間乾燥熱処理した。その後冷却してガラス板よ
り剥がし、厚さ約９μｍのポリビニルアルコール膜を得
た。この膜を用い分離実験を行い以下のデータを得た。■Experiment using vapor permeation method (a) Ethanol-water separation coefficient: Permeation rate: f = 0.13 (kg/bo・h) (b) Isopropanol-aqueous separation coefficient: 100 g/i polyvinyl alcohol solution containing crosslinking agent was cast onto a glass plate and immediately heated at 150° in a hot air dryer.
A dry heat treatment was performed at C for 1 hour. Thereafter, it was cooled and peeled off from the glass plate to obtain a polyvinyl alcohol film with a thickness of about 9 μm. Separation experiments were conducted using this membrane and the following data were obtained.
■蒸気透過法による実験
（イ）エタノール−水系
分離係数：
透過速度： ｆ ＝０．１０ （ｋｇ／ボ・ｈ）■Ｐ
Ｖ法による実験
イソプロパノ−ルー水系
分離係数：
α８２０ ＝＝ １ ００
透過速度： ｆ ＝０．２４ （ｋｇ／ボ・ｈ）比較
例２
透過速度： ｆ ＝０．０８ （ｋｇ／イ・ｈ）（ロ
）イソプロパノ−ルー水系
分離係数：
透過速度： ｆ ＝０．０７ （ｋｇ／ボ・ｈ）■ｐ
ｖ法による実験
イソプロパノ−ルー水系
分離係数：
α”’＝２００
透過速度： ｆ ＝０．２０ （ｋｇ／イ・ｈ）〔効
果〕
以上の例から再生セルロース単独膜やポリビニルアルコ
ール単独膜に比較して再生セルロース層とポリビニルア
ルコール層の２層の組合わせからなる分離膜はその相乗
効果により極めて高い水選択透過性を有し、且つ透過速
度も充分大きく保持されていることがわかる。従って本
発明の分離膜がアルコール・水系に代表される水溶性有
機物の分離に高い性能を発揮することは明らかである。■Experiment using vapor permeation method (a) Ethanol-water separation coefficient: Permeation rate: f = 0.10 (kg/bo・h) ■P
Experiment by V method Isopropanol-aqueous separation coefficient: α820 == 1 00 Permeation rate: f = 0.24 (kg/Ih) Comparative example 2 Permeation rate: f = 0.08 (kg/Ih) ( b) Isopropanol-aqueous separation coefficient: Permeation rate: f = 0.07 (kg/bo・h)■p
Experiment using v method Isopropanol-aqueous separation coefficient: α”' = 200 Permeation rate: f = 0.20 (kg/Ih) [Effect] Based on the above examples, comparison with regenerated cellulose-only membrane and polyvinyl alcohol-only membrane It can be seen that a separation membrane consisting of a two-layer combination of a regenerated cellulose layer and a polyvinyl alcohol layer has an extremely high water selective permeability due to the synergistic effect, and the permeation rate is also maintained sufficiently high. It is clear that the separation membrane of the invention exhibits high performance in separating water-soluble organic substances such as alcohol/water systems.
第１〜３図はいずれも本発明の分離膜の一例を示す説明
図である。また第４図は分離膜の特性を測定する際に使
用した装置の概略説明図である。
（］） ・・・ ポリビニルアルコール層（２）・・
・ 再生セルロース層
（３）・・・ 多孔質支持膜
第１図
第２図
第３図
第４図1 to 3 are explanatory diagrams showing an example of the separation membrane of the present invention. Moreover, FIG. 4 is a schematic explanatory diagram of the apparatus used when measuring the characteristics of the separation membrane. (]) ... Polyvinyl alcohol layer (2) ...
- Regenerated cellulose layer (3)... Porous support membrane Figure 1 Figure 2 Figure 3 Figure 4
Claims (4)
ル層の２層からなることを特徴とする水溶性有機物分離
膜。(1) A water-soluble organic matter separation membrane characterized in that the separation layer consists of two layers: a regenerated cellulose layer and a polyvinyl alcohol layer.
ルコール溶液を塗布して作成した層である請求項（１）
に記載の分離膜。(2) Claim (1), wherein the separation layer is a layer created by coating a polyvinyl alcohol solution on a regenerated cellulose membrane.
Separation membrane described in.
された架橋ポリビニルアルコール層である請求項（１）
〜（２）に記載の分離膜。(3) Claim (1) wherein the polyvinyl alcohol layer of the separation layer is a water-insolubilized crosslinked polyvinyl alcohol layer.
- The separation membrane described in (2).
項（１）〜（３）のいずれかに記載の分離膜。(4) The separation membrane according to any one of claims (1) to (3), wherein the separation layer is supported by a porous support membrane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP02209042A JP3114985B2 (en) | 1990-08-06 | 1990-08-06 | Separation membrane for water-soluble organic substances |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP02209042A JP3114985B2 (en) | 1990-08-06 | 1990-08-06 | Separation membrane for water-soluble organic substances |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0490833A true JPH0490833A (en) | 1992-03-24 |
| JP3114985B2 JP3114985B2 (en) | 2000-12-04 |
Family
ID=16566298
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP02209042A Expired - Fee Related JP3114985B2 (en) | 1990-08-06 | 1990-08-06 | Separation membrane for water-soluble organic substances |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3114985B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117482765A (en) * | 2023-12-18 | 2024-02-02 | 上海乐纯生物技术股份有限公司 | Novel functional separation membrane and preparation method thereof |
-
1990
- 1990-08-06 JP JP02209042A patent/JP3114985B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117482765A (en) * | 2023-12-18 | 2024-02-02 | 上海乐纯生物技术股份有限公司 | Novel functional separation membrane and preparation method thereof |
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| Publication number | Publication date |
|---|---|
| JP3114985B2 (en) | 2000-12-04 |
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