JPS62250906A - Membrane for separating water-alcohol - Google Patents
Membrane for separating water-alcoholInfo
- Publication number
- JPS62250906A JPS62250906A JP9595086A JP9595086A JPS62250906A JP S62250906 A JPS62250906 A JP S62250906A JP 9595086 A JP9595086 A JP 9595086A JP 9595086 A JP9595086 A JP 9595086A JP S62250906 A JPS62250906 A JP S62250906A
- Authority
- JP
- Japan
- Prior art keywords
- water
- membrane
- alcohol
- separation
- graft
- 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 67
- 238000000926 separation method Methods 0.000 claims abstract description 60
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 14
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 14
- 239000000178 monomer Substances 0.000 claims abstract description 11
- 238000010559 graft polymerization reaction Methods 0.000 claims abstract description 9
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 48
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 33
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 abstract description 12
- 238000000034 method Methods 0.000 abstract description 11
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 abstract description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 abstract description 7
- 239000003513 alkali Substances 0.000 abstract description 6
- 239000000758 substrate Substances 0.000 abstract description 6
- 239000003054 catalyst Substances 0.000 abstract description 4
- XMPZTFVPEKAKFH-UHFFFAOYSA-P ceric ammonium nitrate Chemical compound [NH4+].[NH4+].[Ce+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O XMPZTFVPEKAKFH-UHFFFAOYSA-P 0.000 abstract description 4
- 239000012466 permeate Substances 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 3
- 238000006116 polymerization reaction Methods 0.000 abstract description 3
- 150000001735 carboxylic acids Chemical class 0.000 abstract 2
- 238000002309 gasification Methods 0.000 abstract 1
- 230000003472 neutralizing effect Effects 0.000 abstract 1
- 230000003204 osmotic effect Effects 0.000 abstract 1
- 239000007864 aqueous solution Substances 0.000 description 14
- 238000005373 pervaporation Methods 0.000 description 11
- 238000002474 experimental method Methods 0.000 description 8
- 239000011259 mixed solution Substances 0.000 description 7
- 229920001577 copolymer Polymers 0.000 description 4
- 229920000578 graft copolymer Polymers 0.000 description 4
- 125000003010 ionic group Chemical group 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000003014 ion exchange membrane Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000006386 neutralization reaction Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- 229920000557 Nafion® Polymers 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005371 permeation separation Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- -1 (p. 401) Substances 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 150000000703 Cerium Chemical class 0.000 description 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 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
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000000502 dialysis Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920005597 polymer membrane Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000004627 regenerated cellulose Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
本発明は水とアルコールの混合溶液から水を効率良く透
過分離してアルコールを濃縮するための新規な分離膜に
関するものである。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a novel separation membrane for efficiently permeating and separating water from a mixed solution of water and alcohol to concentrate alcohol.
従来の技術
分離精製工程への膜の利用に対する関心が最近一層高ま
っている。これは省資源・省エネルギーに対応する技術
であるためであるばかりでな（。BACKGROUND OF THE INVENTION There has recently been increased interest in the use of membranes in conventional technology separation and purification processes. This is not only because it is a technology that saves resources and energy (.
膜を用いることによって熱で変性し易い物質の分離精製
や蒸留のみでは分離の困難°な異性体の分離°５の適用
の可能性が期待されるためである。This is because the use of a membrane is expected to be applicable to the separation and purification of substances that are easily denatured by heat and the separation of isomers that are difficult to separate by distillation alone.
膜分離が実用化されている例としては、現在のところ逆
浸透膜を用いた海水の淡水化や半導体製造用に用いられ
る超純水の製造、限外濾過膜を用いた人工透析や血液の
成分への分離環、ガス分離膜による空気からの酸素の富
化等が挙げられる。Examples of practical applications of membrane separation include seawater desalination using reverse osmosis membranes, ultrapure water production for semiconductor manufacturing, and artificial dialysis and blood treatment using ultrafiltration membranes. Examples include separating rings into components and enriching oxygen from air using a gas separation membrane.
これに対して、水−アルコール分離など液体分離は現在
のところ実用の域には至っていない。これは分離に好適
な膜の開発が出来ていないためである。On the other hand, liquid separation such as water-alcohol separation has not yet reached the practical level. This is because membranes suitable for separation have not been developed.
しかしながら膜を用いた溶液分離への期待は太き（９例
えば水−アルコール分離が可能となれば従来の蒸留に代
り、より効率的にアルコールの生産が出来ると期待され
る。すなわち、膜分離は低温プロセスであるために、省
エネルギー的に、かつ、アルコールの連続生産も可能と
なるはずである。この様な目的を達成するためには９分
離性能の優れた分離膜が必要なことは言うまでもない。However, there are high expectations for solution separation using membranes (9 For example, if water-alcohol separation becomes possible, it is expected that alcohol can be produced more efficiently instead of conventional distillation. In other words, membrane separation is Because it is a low-temperature process, it should save energy and enable continuous production of alcohol.It goes without saying that in order to achieve these goals, a separation membrane with excellent separation performance is required. .
こうした膜の開発が急がれている。The development of such membranes is urgently needed.
水−アルコール混合溶液から水を選択的に透過分離させ
るには、水と親和性の高い膜素材を用いれはよい。モし
て、これまでに再生セルロース膜。In order to selectively permeate and separate water from a water-alcohol mixed solution, a membrane material with high affinity for water may be used. So far, regenerated cellulose membranes have been developed.
ポリヒニルアルコール膜、セルロースアセテート膜、ナ
フィオン膜、ポリアクリロニトリル−ポリビニルピロリ
ドンブレンド膜、マレイミド−アクリロニトリル共重合
膜、アクリル酸−アクリロニトリル共重合膜などで水−
アルコール分離が検討され、水が優先的に透過分離する
ことが確認されている。Polyhinyl alcohol membrane, cellulose acetate membrane, Nafion membrane, polyacrylonitrile-polyvinylpyrrolidone blend membrane, maleimide-acrylonitrile copolymer membrane, acrylic acid-acrylonitrile copolymer membrane, etc.
Alcohol separation has been investigated and it has been confirmed that water is preferentially permeated and separated.
水との親和性を更に高めるためには膜をイオン化した構
造にすることが一層効果的である。こうして検討された
膜として、ナフィオン膜（ジャーナルｅオブ・、メンプ
ラン・サイエンス誌、 第２４巻。In order to further increase the affinity with water, it is more effective to form the membrane into an ionized structure. The membrane studied in this way is the Nafion membrane (Journal of Memplan Science, Vol. 24).
第１０１頁（１９８５））、ＣＭＶ膜およびＡＭＶ膜（
同上誌、第２２巻、第３３３頁（１９８５））などのイ
オン交換膜、コポリ （１−ブチル−４−ビニルピリジ
ニウムアイオグイドーアクリロニトリル）膜（高分子予
稿集、第３４巻、第３号、第４０１頁）などの共重合膜
、あるいは多孔性高分子膜へ“アクリル酸等をグラフト
重合させたのち、アルカリ処理によりイオン化した構成
の膜（１、ｆｆ願昭６０−２６９９５１号）があり、水
の選択透過性が認められている。101 (1985)), CMV membranes and AMV membranes (
Ion-exchange membranes such as the above-mentioned magazine, Vol. 22, p. 333 (1985); There are copolymer membranes such as (p. 401), or membranes in which acrylic acid, etc. is graft-polymerized to a porous polymer membrane and then ionized by alkali treatment (1, FF Application No. 60-269951). Permselectivity for water is recognized.
しかしなから実用的にはこれらの膜はそれぞれ以下の様
な欠点を有し、必ずしも満足し得るものとは言えない。However, in practical use, these films each have the following drawbacks and cannot be said to be necessarily satisfactory.
まず、イオン交換膜は架橋の密度が高（、また膜が比較
的厚いために一般に透過の速度が遅い。First, ion exchange membranes have a high density of crosslinks (and are relatively thick, so the rate of permeation is generally slow).
通常のイオン交換膜は本来分子径の小さい無＋３ （オ
ンや金属イオンへ適用出来るように構造設計が為されて
おり、水−アルコール分離膜としては必ずしも適してい
るものではない。Ordinary ion exchange membranes are structurally designed so that they can be applied to ions and metal ions, which have small molecular diameters, and are not necessarily suitable as water-alcohol separation membranes.
共重合膜は各種のイオン性基を持つ単量体を用いて種々
の割合で作成した高分子を構成出来るという特徴がある
。しかしながら、このようなイオン性の基は水との親和
性が高いために、イオン性基の密度を高くすると溶解し
たり、あるいは膜が破損するといったことが生じる恐れ
がある。すなわち、イオン性基を導入出来る密度はせい
ぜい数パーセント止まりである。このために水−アルコ
ール分離の性能向上には限界がある。Copolymer membranes are characterized in that they can consist of polymers made using monomers with various ionic groups in various ratios. However, since such ionic groups have a high affinity for water, increasing the density of ionic groups may cause dissolution or damage to the membrane. That is, the density at which ionic groups can be introduced is at most a few percent. For this reason, there is a limit to the performance improvement of water-alcohol separation.
多孔膜上へ親水性単量体をグラフト重合させた構造の分
離膜は、力学的強度を基質多孔膜に、また分離性をグラ
フト重合層に持たせた所にその特徴がある。しかしなが
ら多孔膜上の孔がすべてグラフト重合層で被覆されてい
ないと混合溶液が素通りして成分への分離は出来ない。A separation membrane having a structure in which a hydrophilic monomer is graft-polymerized onto a porous membrane is characterized in that the mechanical strength is imparted to the substrate porous membrane, and the separability is imparted to the graft-polymerized layer. However, unless all the pores on the porous membrane are covered with the graft polymer layer, the mixed solution will pass through and separation into components will not be possible.
すなわち、グラフト重合過程での処理の制御が十分に為
されなければならない。このことは実験室的には比較的
容易であっても、より大規模の処理は簡単ではない。That is, the treatment during the graft polymerization process must be sufficiently controlled. Although this is relatively easy in the laboratory, it is not easy to process on a larger scale.
本発明が改良しようとする問題点 本発明はこの様な従来方法が持つ欠点を克服し。Problems that the present invention seeks to improve The present invention overcomes the drawbacks of such conventional methods.
水とアルコールの混合溶液から水を選択的に透過分離す
る新規分離膜を提供することを目的としている。The purpose of this invention is to provide a new separation membrane that selectively permeates and separates water from a mixed solution of water and alcohol.
問題点を解決するための手段
本発明者は、上記の目的を達成するために、鋭意研究を
重ねた結果、架橋ポリビニルアルコール膜に不飽和カル
ボン酸単量体をグラフト重合せしめたのち、このグラフ
ト重合層をアルカリ処理により中和イオン化した膜が、
水−アルコール混合溶液からより効率的に水を透過分離
することを見出した。すなわち２本発明は基質ポリビニ
ルアルコールの持つ力学的安定性に加え、グラフト層に
よる分離性の向上せしめられた新しい分離膜を提供する
ものである。Means for Solving the Problems In order to achieve the above object, the inventor of the present invention, as a result of extensive research, graft-polymerized an unsaturated carboxylic acid monomer onto a crosslinked polyvinyl alcohol film, and then A membrane whose polymerized layer is neutralized and ionized by alkali treatment is
We have discovered that water can be more efficiently permeated and separated from a water-alcohol mixed solution. In other words, the present invention provides a new separation membrane that has not only the mechanical stability of the polyvinyl alcohol substrate but also improved separation properties due to the graft layer.
本発明の分離膜作成に用いられるカルボン酸単量体とし
ては、アクリル酸、メタクリル酸を挙げることが出来る
。さらに、これらの不飽和カルボン酸単量体は、アクリ
ルアミド、メタクリルアミド等水溶性単量体とグラフト
共重合させるととも可能である。Examples of the carboxylic acid monomer used to prepare the separation membrane of the present invention include acrylic acid and methacrylic acid. Furthermore, these unsaturated carboxylic acid monomers can be graft copolymerized with water-soluble monomers such as acrylamide and methacrylamide.
グラフト重合の方法としてはこれまでに多くの方法が知
られている（例えば、大津、木下著「高分子実験法」化
学同人９等）が２本発明においてはこれらの中から任意
に選択して用いることが出来る。Many graft polymerization methods have been known so far (for example, Otsu and Kinoshita, "Polymer Experiment Method" Kagaku Doujin 9, etc.), but in the present invention, two methods can be arbitrarily selected from these. It can be used.
本発明の水−アルコール分離膜作成に際しては。When producing the water-alcohol separation membrane of the present invention.
不飽和カルボン酸単量体を２〜１０９６水溶液としてグ
ラフト重合を行うことが適当である。グラフト重合開始
用触媒としてはレドックス触媒が用いられる。レドック
ス触媒であればいずれでも構わないが。It is appropriate to carry out the graft polymerization using an aqueous solution of 2 to 1096 unsaturated carboxylic acid monomers. A redox catalyst is used as a catalyst for initiating graft polymerization. Any redox catalyst may be used.
その中で特にセリウム塩が適当である。グラフト重合に
おける処理温度、処理時間は特に限定されるものではな
いが、基質の架橋ポリビニルアルコール膜への影響や、
不飽和カルボン酸単量体のホモポリマー化を出来るだけ
抑制するためには、３０℃〜６０°Ｃの温度で０．５〜
６時間処理することが適当である。Among them, cerium salts are particularly suitable. The treatment temperature and treatment time in graft polymerization are not particularly limited, but are subject to the influence of the substrate on the crosslinked polyvinyl alcohol film,
In order to suppress homopolymerization of unsaturated carboxylic acid monomers as much as possible, at a temperature of 30°C to 60°C,
A treatment time of 6 hours is appropriate.
十１
要は水−アルコール選択分離に活古な一定景以上のグラ
フト重合層を形成せしめることにあり、このためには基
質ポリビニルアルコール膜の単位面積当りのグラフト層
の重量で１．０〜１０■／ｃｌ、より好ましくは２．０
〜６．０ ＩＩＩｇ／ ｃｄのグラフト重合層を形成せ
しめてやれば良い。グラフト重合層の中和イオン化は９
通常良く行われるアルカリ処理により容易に行うことが
出来る。例えば、水酸化ナトリウムないしは水酸化カリ
ウムの２〜５９６水溶液に室温で３０〜６０分間浸漬し
ておくことによってイオン化が出来る。これより以上の
アルカリ濃度、あるいは高温での処理は１分離膜を劣化
させる恐れがあり、これを避けた方が俳難である。以上
の様にして本発明の水−アルコール分離膜妻作成するこ
とが出来る。11. The key point is to form a graft polymer layer of a certain amount or more that is effective for water-alcohol selective separation. ■/cl, more preferably 2.0
A graft polymer layer of ~6.0 IIIg/cd may be formed. The neutralization ionization of the graft polymerization layer is 9
This can be easily carried out by a commonly used alkali treatment. For example, ionization can be achieved by immersing the material in a 2-596 aqueous solution of sodium hydroxide or potassium hydroxide at room temperature for 30-60 minutes. Processing at a higher alkali concentration or at a higher temperature may deteriorate the separation membrane, and it is better to avoid this. The water-alcohol separation membrane of the present invention can be produced in the manner described above.
水−アルコール分離操作には浸透気化法が用いられる。A pervaporation method is used for the water-alcohol separation operation.
浸透気化法は公知であって１例えば沸点の近接した液体
混合物の分離、蒸留では困難な異性体混合物の分離に有
効である。この方法は、膜を介して一方に分離対象物を
溶液として供給し、他方を真空に吸引して、透過してき
た成分を冷却トラップして分離するものである。The pervaporation method is well known and is effective, for example, for separating liquid mixtures with close boiling points and isomer mixtures that are difficult to separate by distillation. In this method, the substance to be separated is supplied as a solution to one membrane through the membrane, the other membrane is vacuumed, and the components that permeate are separated by cold trapping.
物質の分離の程度は２分離係数（α）を用いて示される
。この分離係数は、以下の様な方法で求められる指標で
ある。The degree of separation of substances is indicated using the 2 separation factor (α). This separation coefficient is an index obtained by the following method.
今、２つの成分Ａ、Ｂの混合物から、一方の成分Ｂの透
過分離を考えることにする。膜を介して供給側のＡ、
Ｂ各成分の濃度をＸＡ、ＸＢ、また、透過側のＡ、 Ｂ
各成分の濃度をＹＡ、ＹＢとすれば、Ｂの分離係数α［
３／Ａは、つぎの式で与えられる。Let us now consider the permeation separation of one component B from a mixture of two components A and B. A on the supply side via the membrane;
B The concentration of each component is XA, XB, and the transmission side A, B
If the concentrations of each component are YA and YB, the separation coefficient α[
3/A is given by the following formula.
ａ Ｂ／Ａ＝（Ｙｓ ／ ＹＡ） ／ （Ｘ［ｌ／ Ｘ
Ａ ）このαの値が大きければ大きいほど選択分離性が
優れていることを示す。a B/A=(Ys/YA)/(X[l/X
A) The larger the value of α, the better the selective separation property is.
本発明の分離膜では、水の選択分離性が基質の架橋ポリ
ビニルアルコール膜に比し、αで最高３０倍程度まで向
上することが認められ、水とアルコールの分離に有効な
ことを示している。アルカリ処理により中和イオン化す
る前の単なるグラフト重合処理膜では分離性に顕著な差
は見られず、中和イオン化が、水の選択分離に強（利い
ていることを示している。すなわち、グラフト重合層の
イオン化したーＣＯ〇−基が一〇〇〇Ｈ基よりも水との
親和性がはるかに高く、膜内に水を取り込み易くなって
透過分離の効率を上げていると考えられる。The separation membrane of the present invention was found to have improved selective separation of water by up to 30 times at α compared to the crosslinked polyvinyl alcohol membrane used as the substrate, indicating that it is effective in separating water and alcohol. . There was no noticeable difference in separation performance between membranes that had been simply graft polymerized before being neutralized and ionized by alkali treatment, indicating that neutralization ionization is effective in selectively separating water. It is thought that the ionized -CO〇- group in the polymerization layer has a much higher affinity for water than the 1000H group, making it easier to take water into the membrane and increasing the efficiency of permeation separation.
本発明の分離膜の水−アルコール分離性能は。What is the water-alcohol separation performance of the separation membrane of the present invention?
既存の分離膜と比較して遜色がないと共に、特にアルコ
ールの低濃度域での高い透過速度を示すところに特色が
ある。It is comparable to existing separation membranes and is unique in that it exhibits a high permeation rate, especially in the low alcohol concentration range.
発明の効果 本発明の分離膜は以下に示すような特徴を有する。Effect of the invention The separation membrane of the present invention has the following characteristics.
１）基質膜として架橋性ポリビニルアルコール膜を用い
ているために力学的強度が有ること。1) It has mechanical strength because a crosslinkable polyvinyl alcohol film is used as the substrate film.
２）架橋性ポリビニルアルコール膜が、既に一定の水−
アルコール分離性を保持しており、これを加工している
ために重合の程度にかかわらず、水−アルコール混合溶
液が分離することな（素通りするといった欠陥の生じる
恐れが全（ないこと。2) The crosslinkable polyvinyl alcohol film is already coated with a certain amount of water.
It maintains alcohol separability, and because it is processed, there is no risk of the water-alcohol mixed solution separating (passing through) regardless of the degree of polymerization.
３）中和イオン化したグラフト層により高い水−アルコ
ール選択分離性が得られていること。3) High water-alcohol selective separation property is obtained by the neutralized and ionized graft layer.
４）特にアルコールの低濃度領域で高い透過速度が得ら
れること。4) A high permeation rate can be obtained, especially in the low alcohol concentration range.
従って９本発明の水−アルコール用分離膜は。Therefore, the water-alcohol separation membrane of the present invention is as follows.
例えば発酵液からあらかじめ水を透過分離してアルコー
ルを効率的に濃縮する目的等で使用することが出来る。For example, it can be used for the purpose of efficiently concentrating alcohol by permeating and separating water from fermentation liquid in advance.
実施例 次に、実施例によって本発明を更に詳細に説明する。Example Next, the present invention will be explained in more detail with reference to Examples.
実施例１
架橋性ホリビニルアルコールフィルム（６Ｘ６ｃｎｔ）
を、５％アクリル酸水溶液２０ｍ１に浸し、これに硝酸
セリウムアンモニウム０．１モル／１３水溶液Ｑ、 ５
ｖｉｌを加λ、１７°Ｃの室温下に２時間処理した。Example 1 Crosslinkable polyvinyl alcohol film (6X6cnt)
was soaked in 20 ml of 5% acrylic acid aqueous solution, and cerium ammonium nitrate 0.1 mol/13 aqueous solution Q, 5
vil was heated at room temperature of 17°C for 2 hours.
水洗、乾燥後、００９１ｇの重量増加が認められた。こ
れはフィルム面積当り２．５２１１１ｇ／ｃｒＪのグラ
フト率に当たる。このフィルムを２９６の水酸化す）
ＩＪウム水溶液２０プに室温で３０分間浸漬処理してグ
ラフト重合層の中和イオン化を行った。After washing with water and drying, an increase in weight of 0,091 g was observed. This corresponds to a grafting rate of 2.52111 g/crJ per film area. This film is hydroxylated with 296)
The graft polymer layer was neutralized and ionized by immersion treatment in 20 μl of IJum aqueous solution at room temperature for 30 minutes.
このフィルムを用い、４０°Ｃのもとて水−エタノール
混合溶液を供給して浸透気化法による分離を試み９次の
様な結果を得た。Using this film and supplying a mixed solution of water and ethanol at 40 DEG C., separation by pervaporation was attempted and the following results were obtained.
エタノール濃度がそれぞれ７．９． １６．８，４４．
７゜６３．８．８４．９％のとき、透過速度は１．５５
．１．３９゜０．８８． ０．３３． ０．１５ ｋｇ
／ｍ”−ｈｒであり、またエタノールに対する水の分離
係数は３７．０．２５．５，３０．１゜３０．０．１０
．９であった。The ethanol concentration was 7.9. 16.8,44.
At 7°63.8.84.9%, the permeation rate is 1.55
．． 1.39°0.88. 0.33. 0.15 kg
/m”-hr, and the separation coefficient of water for ethanol is 37.0.25.5, 30.1°30.0.10
．． It was 9.
実施例２
架橋性ホＩＪビニルアルコールフィルムを、５％アクリ
ル酸水溶液２Ｑｒｎｌに浸し、これに硝酸セリウムアン
モニウム０．１モル／ｌ水溶液０．５ｒＬｌヲ加え、１
７°Ｃの室温下に４時間処理した。水洗、乾燥後、秤ｔ
ｉｉ Ｌ／、 ５．２１ ［Ｑｇ／ｃｎｌのグラフト
収率が認められた。このフィルムを２９６の水酸化ナト
リウム水溶液で中和イオン化を行った。Example 2 A crosslinkable vinyl alcohol film was immersed in 2 Qrnl of a 5% acrylic acid aqueous solution, and 0.5 rLl of a 0.1 mol/l aqueous solution of cerium ammonium nitrate was added thereto.
It was treated at room temperature of 7°C for 4 hours. After washing with water and drying, weigh the
ii A grafting yield of 5.21 [Qg/cnl was observed. This film was neutralized and ionized with a 296 aqueous sodium hydroxide solution.
このフィルムを用いて３０°Ｃのもとて浸透気化法によ
る分離を行い２次の様な結果を得た。Using this film, separation was carried out by pervaporation at 30°C, and the following results were obtained.
エタノール濃度がそれぞれ１６．７．４８．６．６９．
２゜８８．３９６の水溶液を供給したとき、透過速度は
４．１４゜１．４０．０．６２． ０．０４ｋｇ／ｒｎ
”・ｈｒであり、またエタノールに対する水の分離係数
αは８．７． ３７．１゜９０．５，１２０．３であっ
た。Ethanol concentration is 16.7.48.6.69.
When an aqueous solution of 2°88.396 was supplied, the permeation rate was 4.14°1.40.0.62. 0.04kg/rn
”·hr, and the separation coefficient α of water to ethanol was 8.7.37.1°90.5.120.3.
実施例３
実施例２で用いた分離膜で３５°Ｃのもとて浸透気化実
験を行い、以下の結果を得た。Example 3 A pervaporation experiment was conducted at 35°C using the separation membrane used in Example 2, and the following results were obtained.
エタノール濃度がそれぞれ１６．７ 、 ４８．６ 、
６９．２％の水溶液を供給したとき、透過速度は４．２
４゜１、４７ 、０．６９ ｋｇ／ｍ’−ｈｒであり、
またエタノール濃度する水の分離係数は３０．１ 、２
７９．７ 、８４９．７であった。Ethanol concentration was 16.7, 48.6, respectively.
When feeding a 69.2% aqueous solution, the permeation rate was 4.2
4゜1,47,0.69 kg/m'-hr,
Also, the separation coefficient of water with ethanol concentration is 30.1, 2
They were 79.7 and 849.7.
実施例４
実施例２で用いた分離膜で４０°Ｃのもとて浸透気化実
験を行い、以下の結果を得た。Example 4 A pervaporation experiment was conducted at 40°C using the separation membrane used in Example 2, and the following results were obtained.
エタノール濃度がそれぞれ１６．７，４８゜６゜６９、
２ 、 ８８．３９６のとき、透過速度は４．６３，１
．８３゜０、７６、０．０６ ｋｇ／ｒｒｆ −ｈｒで
あり、エタノールに対する水の分離係数は１４．６．３
２４．０．２３０．３．３７８．６であった。Ethanol concentration is 16.7, 48°6°69, respectively.
2, 88.396, the permeation rate is 4.63,1
．． 83°0, 76, 0.06 kg/rrf -hr, and the separation coefficient of water to ethanol is 14.6.3
It was 24.0.230.3.378.6.
実施例５
実施例２で用いた分離膜で５０’Ｃのもとて浸透気化実
験を行い、以下の結果を得た。Example 5 A pervaporation experiment was conducted at 50'C using the separation membrane used in Example 2, and the following results were obtained.
エタノール濃度がそれぞれ１６．７． ４８．６゜６９
、２． ８８． ３９６のとき、透過速度は ５．５４
゜２．０８，０．８８，０．０９ｋｇ／ｍ”−ｈｒ、
分離係数αは１８．３．３２４．０．９３７．４．
３１４．８であった。The ethanol concentration was 16.7. 48.6°69
, 2. 88. 396, the permeation rate is 5.54
゜2.08, 0.88, 0.09kg/m"-hr,
The separation coefficient α is 18.3.324.0.937.4.
It was 314.8.
実施例６
架ａ性ボリビニルアルコールフィルムヲ、５９！６メタ
クリル酸水溶液２０ｍ１に浸し、これに硝酸セリウムア
ンモニウム０．１モル／ｌ水溶液０．５ ｍを加えて４
０゛Ｃの恒温槽で４時間処理しグラフト重合を行った。Example 6 A cross-linkable polyvinyl alcohol film was soaked in 20 ml of a 59!6 methacrylic acid aqueous solution, and 0.5 ml of a cerium ammonium nitrate 0.1 mol/l aqueous solution was added thereto.
Graft polymerization was carried out by treating in a constant temperature bath at 0°C for 4 hours.
水洗、乾燥後、秤量して２．２０ｍｇ／ｃｎ（のグラフ
ト収率が得られた。このフィルムを２％の水酸化ナトリ
ウム水溶液で処理し、中和イオン化を行った。After washing with water, drying, and weighing, a grafting yield of 2.20 mg/cn was obtained. This film was treated with a 2% aqueous sodium hydroxide solution to perform neutralization and ionization.
この〕、ｆルムを用い、４０″Ｃのもとて浸透気化実験
を行い２次の結果を得た。Using this], a pervaporation experiment was conducted at 40''C using the f lum, and the following results were obtained.
エタノール濃度がそれぞれ１９．２． ４８．０，７２
．０゜８８．８％の水溶液を用いたとき、透過速度は３
．４８゜１．２０．０．５０．０．１０ ｋｇ／ｍ”−
ｈｒであり、エタノールに対する水の分離係数αは１３
．０．３２．０．４５．２゜２７．０であった。The ethanol concentration was 19.2. 48.0,72
．． When using an aqueous solution of 0°88.8%, the permeation rate is 3
．． 48゜1.20.0.50.0.10 kg/m"-
hr, and the separation coefficient α of water for ethanol is 13
．． It was 0.32.0.45.2°27.0.
比較例１
架４Ｂ！＝ポリビニルアルコールフィルムヲ用いて４０
°Ｃのもとて浸透気化実験を行い、以下の結果を得た。Comparative example 1 Shelf 4B! =40 using polyvinyl alcohol film
A pervaporation experiment was conducted at °C, and the following results were obtained.
エタノール濃度がそれぞれ１４．２． ４４．４，６６
．１８４．０９６のとき、透過速度は０．９８． ０．
（３４，０，２９゜ｏ、 ０９ ｋｇ／ ｍ’・ｈｒ、
エタノールに対する水の分離係数αは、 ２２．４．
２１．８．２９．４．１８．９であった。The ethanol concentration is 14.2. 44.4,66
．． 184.096, the permeation rate is 0.98. 0.
(34,0,29°o, 09 kg/m'・hr,
The separation coefficient α of water to ethanol is: 22.4.
It was 21.8.29.4.18.9.
比較例２
架橋性ポリビニルアルコールフィルムにアクリル酸を２
，５２■Ｉｇ／ｃｎｌグラフト重合させた分離１良を用
い、 ４０℃で浸透気化実験を行い、以下を得た。Comparative Example 2 Acrylic acid was added to a crosslinkable polyvinyl alcohol film.
A pervaporation experiment was conducted at 40°C using Separation 1, which had been graft-polymerized with 52 Ig/cnl, and the following was obtained.
エタノール濃度がそれぞれ８．５． １５．８．４４．
６゜６６．３． ８６．７％の水溶液を供給したとき、
透過速度は１．４２． １．２６． ０．８１． ０．
４１． ０．１３ｋｇ／ｍ”ｈｒであり、水の分離係数
αは２０．４．１２．２．１９．８゜３２．０，２１．
２であった。The ethanol concentration is 8.5. 15.8.44.
6°66.3. When an 86.7% aqueous solution was supplied,
The permeation rate is 1.42. 1.26. 0.81. 0.
41. 0.13 kg/m"hr, and the water separation coefficient α is 20.4.12.2.19.8°32.0,21.
It was 2.
比較例３
架橋性ポリビニルアルコールフィルムにアクリル酸を５
．２１１ｆ１ｇ／ＣｒＡグラフト重合させた分離膜を用
い、５０°Ｃのもとて浸透気化実験を行った結果。Comparative Example 3 Acrylic acid was added to a crosslinkable polyvinyl alcohol film for 50 minutes.
．． The results of a pervaporation experiment at 50°C using a separation membrane graft-polymerized with 211f1g/CrA.
以下を得た。I got the following.
エタノール濃度が１８．４． ４９．３． ６７．３，
９１．３％の水溶液を供給したとき、透過速度は２．５
６゜１、４３ 、 ０．９０ 、 ０．７４ ｋｇ／ｒ
ｎ” ｅ ｈｒであり、エタノールに対する水の分離係
数αは、 １４．８． １４．４゜１０．３． ４．
８であった。Ethanol concentration is 18.4. 49.3. 67.3,
When feeding 91.3% aqueous solution, the permeation rate was 2.5
6゜1, 43, 0.90, 0.74 kg/r
n” e hr, and the separation coefficient α of water for ethanol is 14.8. 14.4°10.3. 4.
It was 8.
Claims (1)
橋性ポリビニルアルコール膜の中和物から成る水−アル
コール用分離膜。(1) A water-alcohol separation membrane comprising a neutralized crosslinkable polyvinyl alcohol membrane obtained by graft polymerization of an unsaturated carboxylic acid monomer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9595086A JPS62250906A (en) | 1986-04-25 | 1986-04-25 | Membrane for separating water-alcohol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9595086A JPS62250906A (en) | 1986-04-25 | 1986-04-25 | Membrane for separating water-alcohol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62250906A true JPS62250906A (en) | 1987-10-31 |
| JPH046411B2 JPH046411B2 (en) | 1992-02-05 |
Family
ID=14151537
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9595086A Granted JPS62250906A (en) | 1986-04-25 | 1986-04-25 | Membrane for separating water-alcohol |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62250906A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5015268A (en) * | 1988-10-13 | 1991-05-14 | Exxon Research And Engineering Co. | Polymeric membrane and process for separating aliphatically unsaturated hydrocarbons |
| WO1999064129A2 (en) * | 1998-06-10 | 1999-12-16 | Korea Research Institute Of Chemical Technology | Process for preparing hydroxylated aromatics by hydrogen and oxygen |
| JP2014113522A (en) * | 2012-12-06 | 2014-06-26 | Molecular Gate Membrane Module Technology Research Association | Gas separation membrane |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5840104A (en) * | 1981-08-31 | 1983-03-09 | Kuraray Co Ltd | Separation of mixed liquid |
-
1986
- 1986-04-25 JP JP9595086A patent/JPS62250906A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5840104A (en) * | 1981-08-31 | 1983-03-09 | Kuraray Co Ltd | Separation of mixed liquid |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5015268A (en) * | 1988-10-13 | 1991-05-14 | Exxon Research And Engineering Co. | Polymeric membrane and process for separating aliphatically unsaturated hydrocarbons |
| WO1999064129A2 (en) * | 1998-06-10 | 1999-12-16 | Korea Research Institute Of Chemical Technology | Process for preparing hydroxylated aromatics by hydrogen and oxygen |
| WO1999064129A3 (en) * | 1998-06-10 | 2000-04-13 | Korea Res Inst Chem Tech | Process for preparing hydroxylated aromatics by hydrogen and oxygen |
| JP2014113522A (en) * | 2012-12-06 | 2014-06-26 | Molecular Gate Membrane Module Technology Research Association | Gas separation membrane |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH046411B2 (en) | 1992-02-05 |
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