JP2529478B2 - Separation method of mixed solution - Google Patents
Separation method of mixed solutionInfo
- Publication number
- JP2529478B2 JP2529478B2 JP3059863A JP5986391A JP2529478B2 JP 2529478 B2 JP2529478 B2 JP 2529478B2 JP 3059863 A JP3059863 A JP 3059863A JP 5986391 A JP5986391 A JP 5986391A JP 2529478 B2 JP2529478 B2 JP 2529478B2
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- JP
- Japan
- Prior art keywords
- permeable membrane
- mixed solution
- surface tension
- liquid
- liquid component
- 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.)
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- Separation Using Semi-Permeable Membranes (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は、気化浸透法とも称すべ
き透過膜を用いた混合溶液の分離方法に関するものであ
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for separating a mixed solution using a permeable membrane, which is also called vaporization permeation method.
【０００２】[0002]
【従来の技術】水とアルコールとの混合溶液など、２以
上の液成分が混合された混合溶液からアルコールなど特
定の液成分を透過膜を用いて分離する工法として、浸透
気化法と称される方法が従来から知られている。この浸
透気化法は、槽内を透過膜で上側の溶液室と下側の減圧
室とに仕切り、上側の溶液室内に混合溶液を導入して透
過膜に溶液を接触させた状態で減圧室内を減圧すること
によって、混合溶液中の特定の液成分を透過膜に優先的
に浸透拡散させると共に透過膜を透過したこの液成分を
透過膜の表面から減圧室に気化させるようにしたもので
あり、このようにして透過膜を浸透透過させた減圧室の
成分を捕集することによって混合溶液から特定の液成分
を分離採取することができるのである。しかし、この浸
透気化法においては混合溶液が透過膜に直接接触する状
態にあり、一般に高分子材料で形成される透過膜は混合
溶液によって膨潤されることが多い。そしてこのように
透過膜が膨潤されると透過膜の膜機能が低下し、透過膜
による混合溶液の分離性能は著しく損なわれることにな
る。2. Description of the Related Art A method for separating a specific liquid component such as alcohol from a mixed solution in which two or more liquid components such as a mixed solution of water and alcohol are mixed by using a permeable membrane is called a pervaporation method. Methods are conventionally known. In this pervaporation method, the inside of the tank is partitioned by a permeable membrane into an upper solution chamber and a lower decompression chamber, and a mixed solution is introduced into the upper solution chamber, and the decompression chamber is brought into contact with the solution to the permeable membrane. By reducing the pressure, a specific liquid component in the mixed solution is preferentially permeated and diffused into the permeable membrane, and the liquid component that has passed through the permeable membrane is vaporized from the surface of the permeable membrane to the decompression chamber, In this way, by collecting the components in the decompression chamber that have been permeated through the permeable membrane, a specific liquid component can be separated and collected from the mixed solution. However, in this pervaporation method, the mixed solution is in direct contact with the permeable membrane, and generally the permeable membrane formed of a polymer material is often swollen by the mixed solution. When the permeable membrane is swollen in this way, the membrane function of the permeable membrane deteriorates, and the separation performance of the mixed solution by the permeable membrane is significantly impaired.
【０００３】このために本発明者等によって気化浸透法
とも称すべき手法が開発されており、この気化浸透法を
用いた混合溶液の分離方法は特開昭６３−１６２００３
号公報等で既に提供されている。すなわちこの方法は図
１にその原理を示すように、減圧室１と混合溶液２が導
入される溶液室３とを混合溶液２に接触させないように
透過膜４で仕切り、減圧室１を減圧して溶液室３内で発
生する混合溶液２の蒸気を透過膜４に浸透透過させるよ
うにしたものである。この方法では透過膜４は混合溶液
２に接しないために透過膜４の膨潤による膜機能の低下
という問題がなく、透過膜４による混合溶液２の分離性
能を高く得ることができるのである。[0003] For this purpose, the present inventors have developed a technique which can also be referred to as a vaporization and infiltration method. A method for separating a mixed solution using the vaporization and infiltration method is disclosed in Japanese Patent Application Laid-Open No. 63-162003.
It is already provided in Japanese Patent Publication No. That is, in this method, as shown in the principle of FIG. 1, the decompression chamber 1 and the solution chamber 3 into which the mixed solution 2 is introduced are partitioned by a permeable membrane 4 so as not to contact the mixed solution 2, and the decompression chamber 1 is decompressed. The vapor of the mixed solution 2 generated in the solution chamber 3 is permeated through the permeable membrane 4. In this method, since the permeable membrane 4 does not come into contact with the mixed solution 2, there is no problem that the membrane function is deteriorated due to the swelling of the permeable membrane 4, and the separation performance of the mixed solution 2 by the permeable membrane 4 can be improved.
【０００４】[0004]
【発明が解決しようとする課題】上記のように気化浸透
法においては浸透気化法よりも高い分離性能で混合溶液
２を分離することができるのであるが、この方法は浸透
気化法と同様に液成分を透過膜４内に拡散させて浸透透
過させることによって分離をおこなうようにしているた
めに、液成分が透過膜４を透過する速度が遅く、十分な
透過速度で透過膜４に液を透過させて液分離をおこなう
ことが困難であり、液分離の生産性の上で問題があって
実用が難しいものであった。As described above, in the vaporization permeation method, the mixed solution 2 can be separated with higher separation performance than the permeation vaporization method. Since the components are separated by diffusing into the permeable membrane 4 and permeating and permeating, the liquid component permeates the permeable membrane 4 at a slow rate, and the liquid permeates into the permeable membrane 4 at a sufficient permeation rate. It was difficult to perform liquid separation by doing so, and there was a problem in productivity of liquid separation, which was difficult to put into practical use.
【０００５】本発明は上記の点に鑑みてなされたもので
あり、気化浸透法による工法で分離性能高く液分離をす
ることができると共に、分離液の透過速度を実用レベル
まで高めることができるようにすることを目的とするも
のである。The present invention has been made in view of the above points, and it is possible to perform liquid separation with a high separation performance by the method of vaporization and permeation and to increase the permeation rate of the separated liquid to a practical level. The purpose is to
【０００６】[0006]
【課題を解決するための手段】本発明に係る混合溶液の
分離方法は、複数の液成分が混合された混合溶液２が導
入される溶液室３と減圧室１との間に混合溶液２が接触
されない状態で透過膜４を設け、減圧室１を減圧して溶
液室３内で発生する混合溶液２の蒸気を溶液室３側から
減圧室１側へと透過膜４を透過させることによって、混
合溶液２中の特定の液成分を分離するにあたって、透過
膜４として、混合溶液２中の成分のうち他の液成分より
も分離する特定の液成分の表面張力に近い臨界表面張力
を有すると共に、分離する特定の液成分の表面張力より
大きく且つ他の液成分の表面張力より小さい臨界表面張
力を有する多孔質膜を用いることを特徴とするものであ
る。In the method for separating a mixed solution according to the present invention, a mixed solution 2 is introduced between a decompression chamber 1 and a solution chamber 3 into which a mixed solution 2 in which a plurality of liquid components are mixed is introduced. By providing the permeable membrane 4 in a state where the permeable membrane 4 is not contacted, decompressing the decompression chamber 1 to allow the vapor of the mixed solution 2 generated in the solution chamber 3 to permeate the permeable membrane 4 from the solution chamber 3 side to the decompression chamber 1 side, When separating a specific liquid component in the mixed solution 2, the permeable membrane 4 is used as the permeable membrane 4 from other liquid components among the components in the mixed solution 2.
Critical surface tension close to the surface tension of a specific liquid component that also separates
And has a surface tension of a specific liquid component that separates
Critical surface tension that is large and smaller than the surface tension of other liquid components
It is characterized by using a porous film having strength .
【０００７】以下本発明を詳細に説明する。図１は既述
のように気化浸透法による液分離の原理装置の一例を示
すものであって、透過膜４で分離槽５を上側の減圧室１
と下側の溶液室３とに仕切り、溶液室３内に導入される
混合溶液２の液面と透過膜４の下面との間に空間を形成
させて透過膜４には混合溶液２が接触しないようにして
あり、減圧室１には真空ポンプなどを接続して減圧する
ようにしてある。また混合溶液２としては、例えば醗酵
アルコールからアルコールを濃縮分離する場合における
水とアルコールとの混合溶液など、２以上の液成分が混
合されたものが用いられる。The present invention will be described in detail below. FIG. 1 shows an example of the principle device of liquid separation by the vaporization and permeation method as described above, in which the separation tank 5 is connected to the upper decompression chamber 1 by the permeable membrane 4.
And the lower solution chamber 3, and a space is formed between the liquid surface of the mixed solution 2 introduced into the solution chamber 3 and the lower surface of the permeable membrane 4 so that the mixed solution 2 contacts the permeable membrane 4. A vacuum pump or the like is connected to the decompression chamber 1 to reduce the pressure. Further, as the mixed solution 2, for example, a mixed solution of two or more liquid components such as a mixed solution of water and alcohol in the case of concentrating and separating alcohol from fermentation alcohol is used.
【０００８】そして本発明において上記透過膜４として
は多数の連通する細孔を有する多孔質膜が用いられる。
この多孔質膜は細孔の大きさが、その平均直径が１×１
０-3μ〜５μの範囲のものを用いるのが好ましい。細孔
の大きさがこれよりも大きいと、透過膜４によって液分
離の作用を受けないで細孔を通過してしまう成分が多く
なって、液の分離性能を高く得ることができなくなるも
のであり、また逆に細孔の大きさがこれよりも小さい
と、液成分は細孔を容易に通過することができなくなっ
て、分離液の透過速度を実用レベルにまで高めることが
できなくなるものである。ここで本出願において細孔の
直径は、細孔の面積と同じ面積の円を想定したときのこ
の円の直径として定義されるものであり、平均直径は各
細孔の直径の平均値として定義されるものである。また
この多孔質膜の表面積に占める細孔の面積の割合、すな
わち空孔率は５％以上のものを用いるのが好ましい。空
孔率がこれより低いと、液成分の透過量が少なくなって
分離液の透過速度を実用レベルにまで高めることが難し
くなる。In the present invention, the permeable membrane 4 is a porous membrane having a large number of communicating pores.
The size of the pores of this porous membrane is 1 × 1
It is preferable to use one having a range of 0 −3 μ to 5 μ. If the size of the pores is larger than this, a large amount of components pass through the pores without being affected by the liquid separation by the permeable membrane 4, and it becomes impossible to obtain a high liquid separation performance. If the size of the pores is smaller than this, on the contrary, the liquid component cannot easily pass through the pores, and the permeation rate of the separated liquid cannot be increased to a practical level. is there. Here, in the present application, the diameter of the pore is defined as the diameter of this circle assuming a circle having the same area as the area of the pore, and the average diameter is defined as the average value of the diameter of each pore. Is what is done. Further, it is preferable to use a porous membrane having a ratio of pore area to the surface area, that is, a porosity of 5% or more. When the porosity is lower than this, the amount of permeation of the liquid component decreases, and it becomes difficult to increase the permeation rate of the separated liquid to a practical level.
【０００９】そしてこの多孔質の透過膜４として本発明
では、その臨界表面張力が混合溶液２中の各液成分のう
ち透過膜４を透過させて分離する液成分の表面張力に近
いものを用いるものである。すなわち、混合溶液がＡ，
Ｂ，Ｃ…の各液成分が混合したものである場合、Ａの液
成分を透過膜４を透過させて他の液成分Ｂ，Ｃ…から分
離するときには、液成分Ｂ，Ｃ…の表面張力よりもＡの
液成分の表面張力に近い臨界表面張力を有する透過膜４
を用いるのである。この場合、透過膜４の臨界表面張力
は、透過膜４を透過させて分離する液成分の表面張力よ
りも大きく且つ混合溶液２中の他の液成分の表面張力よ
りも小さいもの、すなわち透過膜４を透過させる液成分
Ａの表面張力より大きく、且つ混合溶液２中の他のＢ，
Ｃ…の液成分の表面張力より小さいものが好ましい。例
えば各種液体の表面張力は「表１」に示す通りであり、
水の表面張力よりも「表１」中の他の液体の表面張力に
近い臨界表面張力を有する透過膜４を用いれば、水と
「表１」中の他の液体との混合溶液２から「表１」中の
他の液体を分離することができるものであり、さらに水
の表面張力と「表１」中の他の液体の表面張力との間の
臨界表面張力を有する透過膜４を用いれば、水と「表
１」中の他の液体との混合溶液２から「表１」中の他の
液体を一層効率良く分離することができるのである。こ
こで、固体の臨界表面張力は次のように定義さている。
すなわち、固体面上で液体炭化水素その他の有機液体化
合物の同族列が示す接触角をθ、その液体の表面張力を
γとすると、ｃｏｓθ〜γは同族体の種類に関せず一定
の直線となることが多く、この際のθ＝０に相当するγ
値が固体の臨界表面張力として定義されるものである。In the present invention, as the porous permeable membrane 4, one having a critical surface tension close to the surface tension of the liquid component of each liquid component in the mixed solution 2 which is separated by permeating the permeable membrane 4 is used. It is a thing. That is, the mixed solution is A,
When the liquid components B, C ... Are mixed and the liquid component A is permeated through the permeable membrane 4 and separated from the other liquid components B, C ..., the surface tension of the liquid components B, C. Permeable membrane 4 having a critical surface tension closer to the surface tension of the liquid component of A than
Is used. In this case, the critical surface tension of the permeable membrane 4 is larger than the surface tension of the liquid component that permeates and separates the permeable membrane 4 and is smaller than the surface tension of other liquid components in the mixed solution 2, that is, the permeable membrane. 4, which is larger than the surface tension of the liquid component A which allows the other component B to pass through,
Those having a surface tension smaller than that of the liquid component of C ... are preferable. For example, the surface tensions of various liquids are as shown in "Table 1",
If the permeable membrane 4 having a critical surface tension closer to the surface tension of other liquids in "Table 1" than the surface tension of water is used, the mixed solution 2 of water and other liquids in "Table 1" will be A permeable membrane 4 is used which is capable of separating the other liquids in Table 1 and which has a critical surface tension between the surface tension of water and the surface tension of the other liquids in Table 1. For example, the other liquid in "Table 1" can be more efficiently separated from the mixed solution 2 of water and the other liquid in "Table 1". Here, the critical surface tension of a solid is defined as follows.
That is, assuming that the contact angle of a homologous series of liquid hydrocarbons and other organic liquid compounds on the solid surface is θ and the surface tension of the liquid is γ, cos θ to γ are constant straight lines regardless of the type of homologue. In many cases, γ corresponding to θ = 0 in this case
The value is defined as the critical surface tension of the solid.
【００１０】[0010]
【表１】 [Table 1]
【００１１】このような多孔質の透過膜４としては特定
のものに限定されるものではないが、ポリプロピレンの
多孔質膜、ポリテトラフルオロエチレンの多孔質膜、ポ
リカーボネートの多孔質膜などを用いることができる。
ポリプロピレンの多孔質膜としてはヘキスト社製の「セ
ルガード」などが、ポリテトラフルオロエチレンの多孔
質膜としては住友電工社製の「フロロポア」などが、ポ
リカーボネートの多孔質膜としてはニュクリポア社製の
「ニュクリポア」などがそれぞれ入手して使用可能であ
る。The porous permeable membrane 4 is not limited to a particular one, but a polypropylene porous membrane, a polytetrafluoroethylene porous membrane, a polycarbonate porous membrane, or the like is used. You can
As a porous film of polypropylene, "Celgard" manufactured by Hoechst, etc., as a porous film of polytetrafluoroethylene, "Fluoropore" manufactured by Sumitomo Electric Co., Ltd., etc., as a porous film of polycarbonate manufactured by Nuclepore. Nikuripoi "etc. can be obtained and used respectively.
【００１２】しかして図１の装置において、減圧室１内
を減圧すると透過膜４の孔を通して溶液室３内も減圧状
態になり、溶液室３内において混合溶液２から各液成分
の蒸気が発生し、各液成分の蒸気が多孔質の透過膜４に
至る。ここで、混合溶液２の各成分のうち透過膜４の臨
界表面張力に表面張力が近い液成分は透過膜４に対して
濡れ易くて親和性が高く、表面張力が近くない液成分は
逆に透過膜４に対して濡れ難くて親和性がない。さらに
特に透過膜４の臨界表面張力よりも表面張力が小さい液
成分は透過膜４に対して濡れ易くて親和性があり、逆に
透過膜４の臨界表面張力よりも表面張力が大きい液成分
は透過膜４に対して濡れ難くて親和性がない。従って、
多孔質の透過膜４に至った各液成分の蒸気のうち、透過
膜４の臨界表面張力に表面張力が近く、また透過膜４の
臨界表面張力よりも表面張力が小さい液成分は透過膜４
の表面に親和して細孔を容易に通過し、透過膜４を溶液
室３側から減圧室１側へと容易に透過するが、透過膜４
の臨界表面張力に表面張力が近くなく、また透過膜４の
臨界表面張力よりも表面張力が大きい液成分は透過膜４
の表面にはじかれて細孔を通過し難く、透過膜４を溶液
室３側から減圧室１側へと容易に透過することができな
い。このようにして、混合溶液２中の各液成分のうち透
過膜４の臨界表面張力に表面張力が近く、また透過膜４
の臨界表面張力よりも表面張力が小さい液成分を優先的
に透過膜４を透過させて、混合溶液２から所定の液成分
を分離してこの液成分の濃度が高い液を得ることができ
るものである。このとき、必要とする液成分を透過膜４
を透過させて液分離する場合には減圧室１に至った液を
回収すればよく、逆に不要な液成分を透過膜４を透過さ
せて液分離することによって必要とする液を溶液室３内
に残す場合にはこの液を溶液室３内から回収すればよ
い。In the apparatus of FIG. 1, however, when the pressure inside the decompression chamber 1 is reduced, the inside of the solution chamber 3 is also depressurized through the holes of the permeable membrane 4, and the vapor of each liquid component is generated from the mixed solution 2 in the solution chamber 3. Then, vapor of each liquid component reaches the porous permeable membrane 4. Here, of the components of the mixed solution 2, a liquid component having a surface tension close to the critical surface tension of the permeable membrane 4 easily wets the permeable membrane 4 and has a high affinity. It is difficult to wet the permeable membrane 4 and has no affinity. Further, in particular, a liquid component having a surface tension smaller than the critical surface tension of the permeable membrane 4 is easily wetted and has an affinity for the permeable membrane 4, and conversely, a liquid component having a surface tension larger than the critical surface tension of the permeable membrane 4 is It is difficult to wet the permeable membrane 4 and has no affinity. Therefore,
Of the vapor of each liquid component reaching the porous permeable membrane 4, the liquid component having a surface tension close to the critical surface tension of the permeable membrane 4 and a surface tension smaller than the critical surface tension of the permeable membrane 4 is the permeable membrane 4.
Of the permeable membrane 4 easily passing through the pores and easily passing through the permeable membrane 4 from the solution chamber 3 side to the decompression chamber 1 side.
The liquid component whose surface tension is not close to the critical surface tension of the permeable membrane 4 and whose surface tension is larger than the critical surface tension of the permeable membrane 4 is
It is difficult to pass through the fine pores due to being repelled by the surface of the membrane, and the permeable membrane 4 cannot easily permeate from the solution chamber 3 side to the decompression chamber 1 side. In this way, the surface tension of each liquid component in the mixed solution 2 is close to the critical surface tension of the permeable membrane 4, and the permeable membrane 4
A liquid component having a surface tension lower than the critical surface tension is preferentially permeated through the permeable membrane 4 to separate a predetermined liquid component from the mixed solution 2 to obtain a liquid having a high concentration of this liquid component. Is. At this time, the necessary liquid component is added to the permeable membrane 4
When liquid is separated by permeating the liquid, it is sufficient to collect the liquid that has reached the decompression chamber 1. On the contrary, the liquid that is needed is obtained by permeating the unnecessary liquid component through the permeable membrane 4 and separating the liquid. When the solution is left inside, the solution may be recovered from the solution chamber 3.
【００１３】そしてこのように気化浸透法の工法におい
て多孔質の透過膜４を用いて液分離をおこなうにあたっ
て、分離される液成分は透過膜４の細孔を通過して溶液
室３側から減圧室１側に透過される。従って既述の特開
昭６３−１６２００３号公報等において気化浸透法で用
いる非多孔質の透過膜のように液成分を透過膜中に拡散
させて浸透させることによって透過させる場合に比べ
て、分離される液成分が透過膜４を透過する速度は極め
て速くなり、実用的なレベルの透過速度を得ることが可
能になるのである。When liquid separation is performed using the porous permeable membrane 4 in the vaporization and permeation method as described above, the separated liquid component passes through the pores of the permeable membrane 4 and is decompressed from the solution chamber 3 side. It is transmitted to the chamber 1 side. Therefore, as compared with the case of permeating a liquid component by diffusing and permeating into the permeable membrane as in the non-porous permeable membrane used in the vaporization permeation method described in JP-A-63-162003 and the like, separation The speed of the liquid component to be transmitted through the permeable membrane 4 becomes extremely high, and it becomes possible to obtain a practical level of the transmission speed.
【００１４】図２は気化浸透法による液分離の原理装置
の改良された一例を示すものであり、このものでは溶液
室３内の混合溶液２を加熱すると共に透過膜４を冷却す
るようにしてある。混合溶液２の加熱は溶液室３を加熱
浴７に浸漬しておこなう他、溶液室３の外周に加熱ジャ
ケットを取り付けたり、溶液室３内にヒータを取り付け
たり、さらには分離槽５の全体を加熱したり、任意の方
法でおこなうことができる。この加熱は、少なくとも分
離槽５が置かれている雰囲気温度よりも高い温度に混合
溶液２を昇温させるようにすればよく、加熱の温度は何
等規制されない。透過膜４の冷却は、例えば透過膜４の
周囲にジャケット８を取り付けてジャケット８に冷媒を
通すことによっておこなうことができる。この冷却は透
過膜４の温度が溶液室３の混合溶液２の液温より低く保
つことができるものであればよい。また、この図２の装
置で液分離をおこなう場合には、混合溶液２として沸点
の異なる２以上の液成分が混合されたもの、例えば水と
エタノール(沸点７８. ３℃) との混合溶液２や水とメ
タノール( 沸点６４. １℃) との混合溶液２などを使用
するものであり、さらに多孔質の透過膜４として混合溶
液２中の沸点の低い液成分と親和性が高くこの沸点の低
い液成分を選択的に優先して透過させるもの、すなわち
混合溶液２中の沸点の低い液成分の表面張力に臨界表面
張力が近く、また沸点の低い液成分の表面張力よりも臨
界表面張力が大きく、且つ混合溶液２中の他の沸点の高
い液成分の表面張力に臨界表面張力が近くなく、またこ
の沸点の高い液成分の表面張力よりも臨界表面張力が小
さい透過膜４を用いるものである。FIG. 2 shows an improved example of the principle of liquid separation by the vaporization and permeation method, in which the mixed solution 2 in the solution chamber 3 is heated and the permeable membrane 4 is cooled. is there. The heating of the mixed solution 2 is performed by immersing the solution chamber 3 in the heating bath 7, a heating jacket is attached to the outer periphery of the solution chamber 3, a heater is attached in the solution chamber 3, and the entire separation tank 5 is It can be heated or performed by any method. This heating may be performed by raising the temperature of the mixed solution 2 to a temperature higher than at least the ambient temperature in which the separation tank 5 is placed, and the heating temperature is not regulated at all. The permeable membrane 4 can be cooled by, for example, attaching a jacket 8 around the permeable membrane 4 and passing a coolant through the jacket 8. This cooling may be performed as long as the temperature of the permeable membrane 4 can be kept lower than the liquid temperature of the mixed solution 2 in the solution chamber 3. When liquid separation is performed with the apparatus of FIG. 2, a mixed solution 2 in which two or more liquid components having different boiling points are mixed, for example, a mixed solution 2 of water and ethanol (boiling point 78.3 ° C.) Or a mixed solution 2 of water and methanol (boiling point 64.1 ° C.) is used, and the porous permeable membrane 4 has a high affinity with a liquid component having a low boiling point in the mixed solution 2 A material that selectively preferentially permeates a low liquid component, that is, the critical surface tension is close to the surface tension of the liquid component having a low boiling point in the mixed solution 2, and the critical surface tension is higher than that of the liquid component having a low boiling point. The permeable membrane 4 is large and has a critical surface tension not close to the surface tension of other liquid components having a high boiling point in the mixed solution 2 and a critical surface tension smaller than the surface tension of the liquid components having a high boiling point. is there.
【００１５】このものにあって、減圧室１を減圧すると
共に溶液室３内の混合溶液２を加熱すると、混合溶液２
の各成分のうち沸点の低い液成分が蒸発され易いため
に、透過膜４に達する蒸気は沸点の低い液成分の濃度が
高くなっており、そしてこの沸点の低い液成分が選択的
に透過膜４を優先して透過されるために、透過膜４を透
過させて分離する液成分の濃度を高めることができ、混
合溶液２の分離性能を高めることができるのである。し
かもこのとき、上記のように透過膜４を冷却することに
よって、混合溶液２の分離性能を一層高めることができ
る。その理由は明らかではないが、溶液室３において混
合溶液２から蒸発した蒸気がこの透過膜４に至ると、透
過膜４による冷却作用で蒸気中の沸点の高い液成分は沸
点の低い液成分よりも凝縮され易く、従って沸点の高い
液成分は会合され易くなって分子の集合形態が大きくな
り、この結果、沸点の高い液成分は透過膜４の細孔をよ
り透過し難くなると共に、これに伴って沸点の低い液成
分が透過膜４の細孔をより優先して透過されることにな
るためであると予想される。このように混合溶液２を加
熱すると共に透過膜４を冷却することによって、透過膜
４を透過させて分離する液成分の濃度を高めることがで
きることになるのである。In this case, when the decompression chamber 1 is decompressed and the mixed solution 2 in the solution chamber 3 is heated, the mixed solution 2
The liquid component having a low boiling point has a high concentration in the vapor reaching the permeable membrane 4, and the liquid component having a low boiling point is selectively evaporated in the vapor reaching the permeable membrane 4. 4 is preferentially permeated, so that the concentration of the liquid component that permeates the permeable membrane 4 to be separated can be increased, and the separation performance of the mixed solution 2 can be improved. Moreover, at this time, the separation performance of the mixed solution 2 can be further enhanced by cooling the permeable membrane 4 as described above. Although the reason is not clear, when the vapor evaporated from the mixed solution 2 in the solution chamber 3 reaches the permeable membrane 4, the liquid component having a high boiling point in the vapor is cooled more than the liquid component having a lower boiling point by the cooling action of the permeable membrane 4. Are also easily condensed, and therefore the liquid components having a high boiling point are easily associated with each other to increase the aggregated form of molecules. As a result, the liquid components having a high boiling point are more difficult to permeate through the pores of the permeable membrane 4, and Accordingly, it is expected that the liquid component having a low boiling point is more preferentially permeated through the pores of the permeable membrane 4. By thus heating the mixed solution 2 and cooling the permeable membrane 4, it is possible to increase the concentration of the liquid component that permeates the permeable membrane 4 and separates.
【００１６】[0016]
【実施例】次に、本発明を実施例によって例証する。実施例 １ 多孔質の透過膜４としてヘキスト社製「セルガード＃２
４００」を用いた。この「セルガード＃２４００」は厚
みが２５μ、臨界表面張力が３５ｄｙｎｅ／ｃｍの多孔
質ポリプロピレンフィルムであり、細孔は長径×短径＝
０．１２５×０．０５μの平均の大きさの長孔（平均直
径０．０７９μ）として形成されており、空孔率は３８
％である。そして混合溶液２として１０重量％のエタノ
ールを含む水−エタノール溶液を用い、図２の装置で、
溶液室３内の混合溶液２を４０℃の加熱浴７で加熱する
と共に透過膜４を０℃のジャケット８で冷却し、減圧室
１を１０-1Ｔｏｒｒの条件で減圧することによって、液
の分離操作をおこなった。エタノールは表面張力が２
２．６ｄｙｎｅ／ｃｍ、沸点が７８．３℃であるのに対
して、水は表面張力が７２．８ｄｙｎｅ／ｃｍ、沸点が
１００℃であるために、エタノールが透過膜４を優先的
に透過し、減圧室１においてエタノールの濃度が高めら
れた液を捕集して回収した。The invention will now be illustrated by the examples. Example 1 As the porous permeable membrane 4, “Celguard # 2” manufactured by Hoechst Co., Ltd.
400 ”was used. This “Celguard # 2400” is a porous polypropylene film having a thickness of 25 μ and a critical surface tension of 35 dyne / cm, and the pores have a major axis × minor axis =
It is formed as a long hole having an average size of 0.125 × 0.05μ (average diameter 0.079μ) and has a porosity of 38.
%. Then, using a water-ethanol solution containing 10% by weight of ethanol as the mixed solution 2, the apparatus of FIG.
The mixed solution 2 in the solution chamber 3 is heated in a heating bath 7 at 40 ° C., the permeable membrane 4 is cooled by a jacket 8 at 0 ° C., and the decompression chamber 1 is decompressed under the condition of 10 −1 Torr to remove the liquid. A separation operation was performed. The surface tension of ethanol is 2
While water has a surface tension of 72.8 dyne / cm and a boiling point of 100 ° C., ethanol preferentially permeates the permeable membrane 4 while 2.6 dyne / cm and a boiling point of 78.3 ° C. Then, in the decompression chamber 1, a liquid having an increased concentration of ethanol was collected and collected.
【００１７】実施例２ 多孔質の透過膜４として住友電工社製の「フロロポアＦ
Ｐ−０１０」を用いた。この「フロロポアＦＰ−０１
０」は厚みが６０μ、臨界表面張力が２８．５ｄｙｎｅ
／ｃｍの多孔質ポリテトラフルオロエチレンフィルムで
あり、細孔は平均直径が０．１０μの丸孔として形成さ
れており、空孔率は７０％である。あとは実施例１と同
様にして液分離操作をおこない、減圧室１においてエタ
ノールの濃度が高められた液を捕集して回収した。 Example 2 "Fluorophore F" manufactured by Sumitomo Electric Industries, Ltd. was used as the porous permeable membrane 4.
P-010 ”was used. This "Fluorophore FP-01
0 ”has a thickness of 60 μ and a critical surface tension of 28.5 dyne.
/ Cm porous polytetrafluoroethylene film, the pores are formed as round pores having an average diameter of 0.10 μ, and the porosity is 70%. After that, the liquid separation operation was performed in the same manner as in Example 1 to collect and collect the liquid in which the concentration of ethanol was increased in the decompression chamber 1.
【００１８】比較例 透過膜４として非多孔質のポリジ
メチルシロキサンフィルム（東レダウコーニング社製
「ＳＥ−９５２０」）を用いた。あとは実施例１と同様
にして液分離操作をおこない、減圧室１においてエタノ
ールの濃度が高められた液を捕集して回収した。実施例
１、２及び比較例において減圧室１から回収した液のエ
タノールの濃度を透過液濃度として測定すると共にこの
液が透過膜４を透過する速度を透過速度として測定し、
さらにエタノールの分離係数αを測定した。この分離係
数αは次式で定義されるものである。 α＝（Ｙ1 ／Ｙ2 ）／（Ｘ1 ／Ｘ2 ） 式中Ｘ1 とＸ2 は溶液室３に導入される混合溶液２のエ
タノールの重量分率と水の重量分率を、Ｙ1 とＹ2 は減
圧室１で捕集された溶液のエタノールの重量分率と水の
重量分率をそれぞれ示すものであり、従ってαが１以上
の数値であると、透過膜４を透過する液はエタノールの
分量が水の分量よりも大きいということになり、αの数
値が大きい程エタノールが優先的に透過膜４を透過する
ということを意味する。これらの測定結果を「表２」に
示す。 Comparative Example As the permeable membrane 4, a non-porous polydimethylsiloxane film (“SE-9520” manufactured by Toray Dow Corning) was used. After that, the liquid separation operation was performed in the same manner as in Example 1 to collect and collect the liquid in which the concentration of ethanol was increased in the decompression chamber 1. In Examples 1 and 2 and Comparative Example, the concentration of ethanol in the liquid recovered from the decompression chamber 1 was measured as the permeate concentration, and the rate at which this liquid permeated through the permeable membrane 4 was measured as the permeation rate.
Further, the separation coefficient α of ethanol was measured. The separation coefficient α is defined by the following equation. α = (Y 1 / Y 2 ) / (X 1 / X 2 ) where X 1 and X 2 are the weight fraction of ethanol and the weight fraction of water of the mixed solution 2 introduced into the solution chamber 3, respectively. 1 and Y 2 represent the weight fraction of ethanol and the weight fraction of water of the solution collected in the decompression chamber 1, respectively. Therefore, when α is a numerical value of 1 or more, it permeates the permeable membrane 4. The liquid means that the amount of ethanol is larger than the amount of water, and the larger the value of α, the more preferentially the ethanol permeates the permeable membrane 4. The results of these measurements are shown in Table 2.
【００１９】[0019]
【表２】 [Table 2]
【００２０】「表２」にみられるように、非多孔質の透
過膜を用いた比較例のものでは、透過液濃度や分離係数
は高いレベルであるが、透過速度は低いために実用化は
困難である。これに対して多孔質の透過膜を用いた実施
例１及び実施例２のものでは透過液濃度や分離係数とし
て所定のレベルを得ることができると共に、透過速度が
極めて速くなっているために、実用化が可能である。As can be seen from "Table 2", in the case of the comparative example using the non-porous permeable membrane, the permeated liquid concentration and the separation coefficient are at a high level, but the permeation rate is low, so that it is not practically used. Have difficulty. On the other hand, in Examples 1 and 2 using the porous permeable membrane, a predetermined level can be obtained as the concentration of the permeate and the separation coefficient, and the permeation rate is extremely high, Practical application is possible.
【００２１】[0021]
【発明の効果】上記のように本発明は、分離される液成
分は多孔質の透過膜の細孔を通過して減圧室側から溶液
室側に透過されるようにしたので、非多孔質の透過膜の
ように液成分を透過膜中に拡散させて浸透させることに
よって透過させる場合に比べて、分離される液成分が透
過膜を透過する速度が極めて速くなり、実用的なレベル
の透過速度を得ることができるものである。しかもこの
透過膜として、混合溶液中の成分のうち他の液成分より
も分離する特定の液成分の表面張力に近い臨界表面張力
を有すると共に、分離する特定の液成分の表面張力より
大きく且つ他の液成分の表面張力より小さい臨界表面張
力を有する多孔質膜を用いるようにしているので、透過
膜に至った混合溶液の各液成分の蒸気のうち、透過膜の
臨界表面張力に表面張力が近く、また透過膜の臨界表面
張力よりも表面張力が小さい液成分は透過膜の表面に親
和して細孔を容易に透過するが、透過膜の臨界表面張力
に表面張力が近くなく、また透過膜の臨界表面張力より
も表面張力が大きい液成分は透過膜の表面にはじかれて
細孔を透過し難いものであって、混合溶液中の各液成分
のうち透過膜の臨界表面張力に表面張力が近く、また透
過膜の臨界表面張力よりも表面張力が小さい液成分を優
先的に透過膜を透過させて、混合溶液から所定の液成分
を効率良く分離することができるものであり、実用的な
レベルの透過速度を得ながら、分離性能を実用レベルに
高めることができるものである。 As described above, according to the present invention, the liquid phase separation is performed.
The solution passes through the pores of the porous permeable membrane from the decompression chamber side to the solution
Since it is made to permeate to the chamber side, a non-porous permeable membrane
To diffuse and permeate liquid components into the permeable membrane.
Therefore, compared with the case of permeation, the liquid component to be separated is transparent.
The permeation rate through the membrane is extremely high, which is a practical level.
It is possible to obtain the transmission rate of Moreover, this permeable membrane has a critical surface tension closer to the surface tension of the specific liquid component to be separated than the other liquid components among the components in the mixed solution, and the surface tension of the specific liquid component to be separated. Since a porous membrane having a larger critical surface tension than the surface tension of other liquid components is used, the critical surface tension of the permeable membrane in the vapor of each liquid component of the mixed solution reaching the permeable membrane is used. The surface tension is close to that of the permeable membrane, and the liquid component whose surface tension is smaller than the critical surface tension of the permeable membrane has an affinity for the surface of the permeable membrane and easily permeates through the pores, but the surface tension is close to the critical surface tension of the permeable membrane. Liquid components with a surface tension greater than the critical surface tension of the permeable membrane are repelled by the surface of the permeable membrane and are difficult to permeate through the pores. Surface tension is close to that of surface tension Of the surface tension is less liquid component is transmitted through the preferentially permeable membrane than the critical surface tension, which a predetermined liquid component from a mixed solution can be efficiently separated, practical
Separation performance at a practical level while achieving a level of permeation speed
It can be raised.
【図１】気化浸透法による液分離の原理装置を示す断面
図である。FIG. 1 is a sectional view showing a principle device of liquid separation by a vaporization and permeation method.
【図２】気化浸透法による液分離の原理装置の改良例を
示す断面図である。FIG. 2 is a cross-sectional view showing an improved example of the principle device for liquid separation by the vaporization and permeation method.
１ 減圧室 ２ 混合溶液 ３ 溶液室 ４ 透過膜 1 decompression chamber 2 mixed solution 3 solution chamber 4 permeable membrane
Claims (3)
入される溶液室と減圧室との間に混合溶液に接触されな
い状態で透過膜を設け、減圧室を減圧して溶液室内で発
生する混合溶液の蒸気を溶液室側から減圧室側へと透過
膜を透過させることによって、混合溶液中から特定の液
成分を分離するにあたって、透過膜として、混合溶液中
の成分のうち他の液成分よりも分離する特定の液成分の
表面張力に近い臨界表面張力を有すると共に、分離する
特定の液成分の表面張力より大きく且つ他の液成分の表
面張力より小さい臨界表面張力を有する多孔質膜を用い
ることを特徴とする混合溶液の分離方法。1. A permeable membrane is provided between a decompression chamber and a solution chamber into which a mixed solution in which a plurality of liquid components are mixed is introduced, and the decompression chamber is decompressed to generate a permeable membrane inside the solution chamber. When a specific liquid component is separated from the mixed solution by allowing the vapor of the mixed solution to pass through the permeable membrane from the solution chamber side to the decompression chamber side, it is used as a permeable membrane in the mixed solution.
Of certain liquid components that are separated from other liquid components
It has a critical surface tension close to the surface tension and separates
Table of other liquid components that are higher than the surface tension of a specific liquid component
A method for separating a mixed solution, which comprises using a porous membrane having a critical surface tension smaller than the surface tension .
径が１×１０ -3 〜５μであり、空孔率が５％以上である
ことを特徴とする請求項１に記載の混合溶液の分離方
法。2. The porous membrane constituting the permeable membrane has an average straightness of pores.
The diameter is 1 × 10 −3 to 5 μ, and the porosity is 5% or more.
The method for separating a mixed solution according to claim 1 , wherein:
点よりも低い混合溶液を用い、溶液室内の混合溶液を加
熱すると共に透過膜をこの加熱温度よりも低い温度に冷
却することを特徴とする請求項１又は２に記載の混合溶
液の分離方法。3. The boiling point of the liquid component to be separated is the boiling point of the other liquid component.
Use a mixed solution lower than the point and add the mixed solution in the solution chamber.
Heat and cool the permeable membrane to a temperature below this heating temperature.
The method for separating a mixed solution according to claim 1 or 2 , wherein the method is separated.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3059863A JP2529478B2 (en) | 1991-03-25 | 1991-03-25 | Separation method of mixed solution |
| US07/856,797 US5271846A (en) | 1986-12-25 | 1992-03-24 | Method for separating a liquid component from a solution containing two or more liquid components |
| EP19920105130 EP0506010B1 (en) | 1991-03-25 | 1992-03-25 | Method for separating a liquid component from a solution containing two or more liquid components |
| BR929201042A BR9201042A (en) | 1991-03-25 | 1992-03-25 | PROCESS TO SEPARATE A SPECIFIC LIQUID COMPONENT FROM A SOLUTION CONTAINING TWO OR MORE LIQUID COMPONENTS |
| DE1992604511 DE69204511T2 (en) | 1991-03-25 | 1992-03-25 | Process for separating a liquid component from a solution containing two or more liquid components. |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3059863A JP2529478B2 (en) | 1991-03-25 | 1991-03-25 | Separation method of mixed solution |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04293524A JPH04293524A (en) | 1992-10-19 |
| JP2529478B2 true JP2529478B2 (en) | 1996-08-28 |
Family
ID=13125440
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|---|---|---|---|
| JP3059863A Expired - Lifetime JP2529478B2 (en) | 1986-12-25 | 1991-03-25 | Separation method of mixed solution |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63126521A (en) * | 1986-11-14 | 1988-05-30 | Mitsubishi Heavy Ind Ltd | Dehydrating method for triethylene glycol |
| JPH0634900B2 (en) * | 1988-06-15 | 1994-05-11 | リグナイト株式会社 | Separation method of mixed solution |
-
1991
- 1991-03-25 JP JP3059863A patent/JP2529478B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH04293524A (en) | 1992-10-19 |
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