JPS61204009A - Membrane for separating liquid mixture - Google Patents
Membrane for separating liquid mixtureInfo
- Publication number
- JPS61204009A JPS61204009A JP4487585A JP4487585A JPS61204009A JP S61204009 A JPS61204009 A JP S61204009A JP 4487585 A JP4487585 A JP 4487585A JP 4487585 A JP4487585 A JP 4487585A JP S61204009 A JPS61204009 A JP S61204009A
- Authority
- JP
- Japan
- Prior art keywords
- membrane
- pervaporation
- water
- tertiary amine
- mixture
- 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 32
- 239000007788 liquid Substances 0.000 title claims description 15
- 239000000203 mixture Substances 0.000 title abstract description 20
- 150000003512 tertiary amines Chemical class 0.000 claims abstract description 12
- 239000005062 Polybutadiene Substances 0.000 claims abstract description 8
- 229920002857 polybutadiene Polymers 0.000 claims abstract description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 2
- 238000000926 separation method Methods 0.000 abstract description 18
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 abstract description 15
- 238000005373 pervaporation Methods 0.000 abstract description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 7
- 239000002253 acid Substances 0.000 abstract description 4
- 238000002156 mixing Methods 0.000 abstract description 4
- SWZDQOUHBYYPJD-UHFFFAOYSA-N tridodecylamine Chemical compound CCCCCCCCCCCCN(CCCCCCCCCCCC)CCCCCCCCCCCC SWZDQOUHBYYPJD-UHFFFAOYSA-N 0.000 abstract description 3
- 229920000642 polymer Polymers 0.000 abstract description 2
- 239000011521 glass Substances 0.000 abstract 1
- 230000035699 permeability Effects 0.000 abstract 1
- 239000012466 permeate Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 3
- 150000007524 organic acids Chemical class 0.000 description 3
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- PQLVXDKIJBQVDF-UHFFFAOYSA-N acetic acid;hydrate Chemical compound O.CC(O)=O PQLVXDKIJBQVDF-UHFFFAOYSA-N 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 229920005597 polymer membrane Polymers 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- ZENZJGDPWWLORF-UHFFFAOYSA-N (Z)-9-Octadecenal Natural products CCCCCCCCC=CCCCCCCCC=O ZENZJGDPWWLORF-UHFFFAOYSA-N 0.000 description 1
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 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
- 239000000470 constituent Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 description 1
- DIAIBWNEUYXDNL-UHFFFAOYSA-N n,n-dihexylhexan-1-amine Chemical compound CCCCCCN(CCCCCC)CCCCCC DIAIBWNEUYXDNL-UHFFFAOYSA-N 0.000 description 1
- XTAZYLNFDRKIHJ-UHFFFAOYSA-N n,n-dioctyloctan-1-amine Chemical compound CCCCCCCCN(CCCCCCCC)CCCCCCCC XTAZYLNFDRKIHJ-UHFFFAOYSA-N 0.000 description 1
- 230000003204 osmotic effect Effects 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000002904 solvent 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５発明は、ポリブタジェンに三級アミンをブレンド
してなる水−有機酸混合物を分離するための分−膜に関
する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a separation membrane for separating a water-organic acid mixture made of polybutadiene blended with a tertiary amine.
一毛°従来の技術〕
従来、分離膜で区割された二つの室の供給液側（−次側
）に分離されるべき液体混合物を供給し透過液側（二次
側）を減圧にするが、又は不活性ガスを流すことによっ
て低蒸気圧に保ち、膜との酬１）で水−有機液体混合物
を分離する方法が実施されており、このようなパーベー
パレーション法によ多水−有機液体混合物を分離した実
験例が種々報告されている。具体的には、米国特許第２
、９５３．５０２ 号にはセルロースアセテート膜やポ
リビニルアルコール系膜を用いて共沸混合液体を分離し
た実験例、Ｊｏｕｒｎａｌ ｏｆ Ａｐｐｌｉｅｄ Ｐ
ｏｌｙｍｅｒ ５ｃｉｅｎｃｅｖｏｌ、２６（１９８１
）の３２２３ページにはグラフト化ポリビニルアルコー
ル膜を用いて水−メタノール混合液体を分離した実験例
などが報告されているる
〔発Ｆ！Ａが解決しようとする問題点〕パーベーパレー
ション法は、従来の逆浸透法のように浸透圧による濃度
的な制限がないため低濃こと、また従来の蒸留法では分
離の困難な共沸混合物や沸点の接近した溶媒異性体（た
とえばオル渭ミと 異性体 スとト ／ス異性体）
の分離可能などの特徴を有しているため、非常に有用分
離方法であると考えられている。Ichimo ° Conventional technology] Conventionally, a liquid mixture to be separated is supplied to the feed liquid side (-side) of two chambers separated by a separation membrane, and the pressure is reduced on the permeate side (secondary side). However, methods have been implemented in which water-organic liquid mixtures are separated using a membrane (1) by keeping the vapor pressure low by flowing an inert gas or by flowing an inert gas. Various experimental examples have been reported in which organic liquid mixtures were separated. Specifically, U.S. Patent No.
, No. 953.502, there is an experimental example of separating azeotropic liquids using a cellulose acetate membrane or a polyvinyl alcohol membrane, Journal of Applied P
olymer 5sciencevol, 26 (1981
), page 3223 reports an experimental example in which a water-methanol mixed liquid was separated using a grafted polyvinyl alcohol membrane [F! [Problem that A aims to solve] Pervaporation method does not have concentration limitations due to osmotic pressure like conventional reverse osmosis method, so it has low concentration, and it also avoids azeotropic mixtures that are difficult to separate using conventional distillation method. and solvent isomers with similar boiling points (e.g., oleamine and isomer, s and t /s isomer)
It is considered to be a very useful separation method because of its characteristics such as the ability to separate.
しかしながら、従来のパーベーパレーション用、Ｊを水
−有機酸混合物の分離に用いることは、酸已よる膜の劣
化等により、事実上困難である。又、ツ１リコン、ポリ
オレフィン、ポリテトラフルオロ冨
一エチレン等の耐薬品性に優れた素材を膜に用いても、
混合液体が高分子膜を一回通過することによる分離の割
合、すなわち、分離係数が小さいため、目的とする濃度
まで分離または濃縮するには、非常に多数の膜を透過さ
せる必要があり、又、とくに、高分子膜を透過する透過
速度〔一般に、単位膜表面積及び単位時間当シの透過量
、すなわちＱ（ｋｐ７．１’ｈｒ ’）で表示する〕が
実用性のある高い値となったとき、分離係数αが非常に
低くなってしまうため、やはり実用化は困難である。However, it is practically difficult to use the conventional J for pervaporation to separate a water-organic acid mixture due to the deterioration of the membrane due to acid exposure. In addition, even if materials with excellent chemical resistance such as tricon, polyolefin, and polytetrafluorofuichiethylene are used for the membrane,
Because the rate of separation when a mixed liquid passes through a polymer membrane once, that is, the separation coefficient, is small, it is necessary to pass through a very large number of membranes in order to separate or concentrate the mixed liquid to the desired concentration. In particular, the permeation rate through the polymer membrane [generally expressed as the amount of permeation per unit membrane surface area and unit time, that is, Q (kp7.1'hr')] has reached a high value that is practical. In this case, the separation coefficient α becomes very low, making it difficult to put it into practical use.
分離係数αＢは、膜透過後のＡ成分のＢ成分に対する重
量比ＷＡ／ＷＢを膜透過前のＡ成分のＢ成分に対する重
量比ＷＡ／ＷＢで除した値、で定義されるが、本発明の
目的は水−有機液体混合物をパーベーパレーション法で
分離するにあた有機酸と親和性のある三級アミンをブレ
ンドしてレンドしてなる混合液分離用の膜である。The separation coefficient αB is defined as the value obtained by dividing the weight ratio WA/WB of component A to component B after permeation through the membrane by the weight ratio WA/WB of component A to component B before permeation through the membrane. The object of the present invention is a membrane for separating a water-organic liquid mixture by a pervaporation method, which is made by blending and blending a tertiary amine with an affinity for an organic acid.
本発明の膜は、ポリブタジェンに第三級アミン（（Ｒ１
）ｓＮ、 Ｒ１二次化水素基〕をブレンドして得られる
が、このような第三級アミンとしては、炭素数が４〜１
８の炭化水素基をもつものが好ましく、炭素数６〜１２
の炭化水素基をもつものがさらに好ましい。具体的には
、トリヘキシルアミン、トリオクチルアミン、トリラウ
リルアミン等があげられる。The membrane of the present invention has polybutadiene with a tertiary amine ((R1
)sN, R1 secondary hydrogen group], but such tertiary amines have 4 to 1 carbon atoms.
Those having 8 hydrocarbon groups are preferable, and have 6 to 12 carbon atoms.
More preferred are those having a hydrocarbon group of Specific examples include trihexylamine, trioctylamine, trilaurylamine, and the like.
又、本発明の膜は、ポリブタジェンに三級アミンを１〜
５０重量％ブレンドして得ることができるが、三級アミ
ンの量が少なすぎると本発明の効果が小さく、又多すぎ
ると機械的強度に劣るので２０〜４０重量％の範囲でブ
レンドするのが好ましい０
本発明の膜は、ポリブタジェンをトルエン等の状（平膜
形状）で用いられるが、その細円筒状あ有機酸混合物と
しては、液状であればいかなる水−有機酸混合物でもよ
いが、具体的には水／ギ酸、水／酢酸、水／プロピオン
酸、水／酪酸等をあげることができる。In addition, the membrane of the present invention contains polybutadiene with 1 to 3 tertiary amines.
It can be obtained by blending 50% by weight, but if the amount of tertiary amine is too small, the effect of the present invention will be small, and if it is too large, the mechanical strength will be poor, so it is recommended to blend in the range of 20 to 40% by weight. Preferable 0 In the membrane of the present invention, polybutadiene is used in the form of toluene or the like (flat membrane shape), but the organic acid mixture may be any water-organic acid mixture as long as it is in a liquid state. Specific examples include water/formic acid, water/acetic acid, water/propionic acid, and water/butyric acid.
本発明に用いられるパーベーパレーション装置は特に限
定されることな〈従来公知の装置が用いられ、かかる装
置を常法の条件で運転して液体混合物を分離することが
できる。パーベーパレーションを行なうにあ六シ、供給
液側と透過液側の圧力差については大きければ大きいほ
ど効果的であるが、工業的に実施するには、０．５〜１
気圧の圧力差を設けることが好適である。また供給液側
の圧力は大気圧あるいはその近傍の圧力が好ましく、透
過液側の圧力は透過成分の蒸気圧以下の減圧に保つこと
が好ましい。透過液側を減圧に保つ方法としては真空に
引いて減圧にするか、構成成分と反応しないガスを流し
て低蒸気圧に保つなどの方させたり、蒸留と組み合せた
りして目的の濃度にまで濃縮分離することができる。The pervaporation device used in the present invention is not particularly limited; any conventionally known device can be used, and such a device can be operated under conventional conditions to separate a liquid mixture. For pervaporation, the larger the pressure difference between the feed liquid side and the permeate side, the more effective it is, but for industrial implementation, the pressure difference between 0.5 and 1
It is preferable to provide an atmospheric pressure difference. The pressure on the feed liquid side is preferably at or near atmospheric pressure, and the pressure on the permeate side is preferably maintained at a reduced pressure below the vapor pressure of the permeate component. The method of keeping the permeate side at reduced pressure is to reduce the pressure by drawing a vacuum, or by flowing a gas that does not react with the constituent components to maintain a low vapor pressure, or by combining it with distillation to reach the desired concentration. Can be concentrated and separated.
本発明の膜ヲ用いてパーベーパレーションで水−有機酸
混合物を分離することにより、高い分離係数を維持しつ
つ、大きい透過速度で効率よく処理することができるが
、かかる効果は従来の知見からは全く予想しがたいこと
である。かかる効果を生ずる理由は必らずしも明らかで
はないが、膜中の三級アミンが有機酸と錯体を作ること
にあるが、不発明はこれらにより何ら制限されるもので
はない。By separating a water-organic acid mixture by pervaporation using the membrane of the present invention, it is possible to efficiently treat the mixture at a high permeation rate while maintaining a high separation coefficient. is completely unpredictable. Although the reason for such an effect is not necessarily clear, it is that the tertiary amine in the film forms a complex with the organic acid, but the invention is not limited to this in any way.
実施例
ポリブタジェン１０Ｆをトルエン９０ｆに溶解したポリ
ブタジェンのトルエン溶液に、トリラウリルアミンをポ
リマーに対して４０重量％加え、厚９６／Ｊｍの均質ブ
レンド膜を得た。該嘆をパーベーパレーション装置（有
効膜面積７．Ｏｃ！Ａ）に装着し、酢酸濃度２．６重量
％の水−酢酸混合液を６０℃で供給し、透過液側を真空
ポンプにてｌ ｗＨｆに吸引シ、パーベーパレーション
法によ膜分離を行った。膜を透過した成分の酢酸濃度（
酢酸が優先透過）はガスクロマトグラフにて分析し、透
過した成分の量は、透過成分を凝縮させて定量した。Example To a toluene solution of polybutadiene 10F dissolved in toluene 90f, trilaurylamine was added in an amount of 40% by weight based on the polymer to obtain a homogeneous blend film having a thickness of 96/Jm. The tube was attached to a pervaporation device (effective membrane area 7.Oc!A), a water-acetic acid mixture with an acetic acid concentration of 2.6% by weight was supplied at 60°C, and the permeate side was pumped with a vacuum pump. The wHf was suctioned and membrane separation was performed by pervaporation method. Concentration of acetic acid in the components that permeated the membrane (
(acetic acid permeates preferentially) was analyzed using a gas chromatograph, and the amount of permeated components was determined by condensing the permeated components.
パーベーパレーションを開始して６時間後の分離膜を用
いた以外は実施例と全く同様にして、水−酢酸混合液の
パーベーパレーション分離を行った。Pervaporation separation of a water-acetic acid mixture was carried out in exactly the same manner as in the example except that a separation membrane was used 6 hours after starting pervaporation.
ｃＯＨ 分離係数α （水が優先透過）は０．４２、透過ｚＯ らかでおる。cOH Separation coefficient α (water preferentially permeates) is 0.42, permeation zO It's bright.
本発明の膜を用いれば、酸による劣化を生ずることなく
、従来の膜を用いた分離方法にくらべて高い分離係数を
維持しつつ、大きい透過速度で水−有機酸混合物を効率
よく処理することができる〇このため、分離システムの
コンパクト化、処理能力の増大、低コスト化が図られ、
本発明は化学工業などの分離精製プロセスの短縮化や省
エネルギー化への膜分離方法の実用化に有効であり、産
業上の有用性が極めて大きいものである。By using the membrane of the present invention, it is possible to efficiently treat a water-organic acid mixture at a high permeation rate while maintaining a higher separation coefficient than separation methods using conventional membranes without causing deterioration due to acid. 〇This makes the separation system more compact, increases processing capacity, and lowers costs.
The present invention is effective for shortening separation and purification processes in the chemical industry and for practical application of membrane separation methods for energy saving, and has extremely great industrial utility.
Claims (1)
レンドしてなる混合液分離用の膜。 （２）該三級アミンが（Ｒ＿１）＿３Ｎ（Ｒ＿１：炭素
数が４〜１８の炭化水素基）である特許請求の範囲第（
１）項記載の膜。 （８）該三級アミンが（Ｒ＿１）＿３Ｎ（Ｒ＿１：炭素
数が６〜１２の炭化水素基）である特許請求の範囲第（
１）項記載の膜。[Scope of Claims] (1) A membrane for separating mixed liquids made of polybutadiene blended with 1 to 50% by weight of tertiary amine. (2) The tertiary amine is (R_1)_3N (R_1: a hydrocarbon group having 4 to 18 carbon atoms).
The membrane described in section 1). (8) The tertiary amine is (R_1)_3N (R_1: a hydrocarbon group having 6 to 12 carbon atoms).
The membrane described in section 1).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4487585A JPS61204009A (en) | 1985-03-08 | 1985-03-08 | Membrane for separating liquid mixture |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4487585A JPS61204009A (en) | 1985-03-08 | 1985-03-08 | Membrane for separating liquid mixture |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61204009A true JPS61204009A (en) | 1986-09-10 |
| JPH0224575B2 JPH0224575B2 (en) | 1990-05-30 |
Family
ID=12703666
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4487585A Granted JPS61204009A (en) | 1985-03-08 | 1985-03-08 | Membrane for separating liquid mixture |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61204009A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2855000A4 (en) * | 2012-05-25 | 2016-03-09 | Pbi Performance Products Inc | ACID-RESISTANT PBI MEMBRANE FOR PERVAPORATION DEHYDRATION OF ACID SOLVENTS |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0446572U (en) * | 1990-08-23 | 1992-04-21 |
-
1985
- 1985-03-08 JP JP4487585A patent/JPS61204009A/en active Granted
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2855000A4 (en) * | 2012-05-25 | 2016-03-09 | Pbi Performance Products Inc | ACID-RESISTANT PBI MEMBRANE FOR PERVAPORATION DEHYDRATION OF ACID SOLVENTS |
| EP3653286A1 (en) * | 2012-05-25 | 2020-05-20 | PBI Performance Products, Inc. | Acid resistant pbi membrane for pervaporation dehydration of acidic solvents |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0224575B2 (en) | 1990-05-30 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |