JPH0817917B2 - Diffusion dialysis method - Google Patents
Diffusion dialysis methodInfo
- Publication number
- JPH0817917B2 JPH0817917B2 JP62310868A JP31086887A JPH0817917B2 JP H0817917 B2 JPH0817917 B2 JP H0817917B2 JP 62310868 A JP62310868 A JP 62310868A JP 31086887 A JP31086887 A JP 31086887A JP H0817917 B2 JPH0817917 B2 JP H0817917B2
- Authority
- JP
- Japan
- Prior art keywords
- diffusion
- liquid
- dialysis
- acid
- diffusion dialysis
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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- Separation Using Semi-Permeable Membranes (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は、イオン交換膜を用いる拡散透析法に関し、
詳しくはイオン交換膜を介して拡散用液と透析用液を存
在させて拡散透析を行なうにあたり、該拡散用液を予め
脱気して供給することを特徴とする拡散透析法である。TECHNICAL FIELD The present invention relates to a diffusion dialysis method using an ion exchange membrane,
More specifically, the diffusion dialysis method is characterized in that the diffusion liquid is preliminarily degassed before the diffusion dialysis is performed in the presence of the diffusion liquid and the dialysis liquid through the ion exchange membrane.
イオン交換膜を用いた拡散透析法は、特別な試薬や加
熱あるいは電気エネルギーを用いることなく、簡単な装
置で効率的に酸または金属塩水溶液を分離，回収でき
る。さらに、中空糸状のイオン交換膜を用いる場合に
は、フィルタープレス型イオン交換膜に比べて大きい膜
面積を必要としない特徴を有し、巾広い分野に利用され
ている。The diffusion dialysis method using an ion exchange membrane can efficiently separate and recover an acid or metal salt aqueous solution with a simple device without using a special reagent, heating, or electric energy. Further, when the hollow fiber-shaped ion exchange membrane is used, it has a feature that it does not require a large membrane area as compared with a filter press type ion exchange membrane, and is used in a wide range of fields.
これら拡散透析法による酸または金属塩の分離，回収
においては、濃度勾配による回収率を高めるため、種々
の方法が提案なされているがその代表的なものは例えば
酸を含む水溶液と水とが向流接触するよう供給する方法
である。Various methods have been proposed for separating and recovering an acid or a metal salt by the diffusion dialysis method in order to enhance the recovery rate by a concentration gradient. Typical examples are, for example, an aqueous solution containing an acid and water. It is a method of supplying so as to make a flow contact.
しかしながら、かかるイオン交換膜による向流接触式
の拡散透析法においても、特に中空糸状膜を用いる場合
には、長時間の拡散透析を続けていくにつれて、酸の回
収率および金属塩の分離効率が低下してくるという欠点
がある。However, even in the countercurrent contact type diffusion dialysis method using such an ion exchange membrane, particularly when a hollow fiber membrane is used, as the diffusion dialysis is continued for a long time, the recovery rate of the acid and the separation efficiency of the metal salt are improved. It has the drawback of decreasing.
本発明者らは上記した問題点を解決するために、イオ
ン交換膜を用いる拡散透析法について鋭意研究，開発を
重ねた。その結果、特に中空糸状のイオン交換膜を用い
る拡散透析法においては、拡散液中に含まれる空気など
の溶存気体が温度変化により、該中空糸状膜の上部ある
いは内部に滞留して該拡散液の流れを阻害するため、酸
の回収率および金属塩の分離効率の低下を招くという知
見を得た。本発明はかかる知見に基づき開発したもので
あり、イオン交換膜を介してそれぞれ拡散用液と透析用
液を存在させて拡散透析を行うにあたり、該拡散用液を
予め脱気して供給することを特徴とする拡散透析する方
法により、高い酸の回収率および金属塩の分離効率を達
成することが出来る。In order to solve the above-mentioned problems, the present inventors have conducted extensive research and development on a diffusion dialysis method using an ion exchange membrane. As a result, particularly in the diffusion dialysis method using a hollow fiber-shaped ion exchange membrane, the dissolved gas such as air contained in the diffusion liquid is retained at the upper part or inside of the hollow fiber-shaped membrane due to the temperature change and It was found that the recovery of acid and the separation efficiency of metal salts are reduced because the flow is obstructed. The present invention was developed on the basis of such knowledge, and in carrying out diffusion dialysis in the presence of a diffusion liquid and a dialysis liquid respectively through an ion exchange membrane, the diffusion liquid should be degassed and supplied in advance. With the method of diffusion dialysis characterized by, it is possible to achieve a high acid recovery rate and a high metal salt separation efficiency.
即ち、本発明は、イオン交換膜を介してそれぞれ拡散
用液と透析用液を存在させて拡散透析を行うにあたり、
該拡散用液中に存在する酸素を5ppm以下となるように、
予め脱気して供給することを特徴とする拡散透析法であ
る。That is, the present invention, when performing diffusion dialysis in the presence of a diffusion liquid and a dialysis liquid respectively through the ion exchange membrane,
Oxygen existing in the diffusion liquid is 5 ppm or less,
The diffusion dialysis method is characterized by supplying gas after degassing in advance.
本発明において用いるイオン交換膜は、従来公知の拡
散透析用の陰イオン交換膜または陽イオン交換膜であれ
ば特に制限されず、拡散透析の目的（用途）に応じて適
宜選択される。例えば酸を回収する場合には陰イオン交
換膜、また塩基を回収する場合には陽イオン交換膜が採
用される。しかして、本発明の方法は特に陰イオン交換
基を有する重合体から形成された中空糸状膜を用いる場
合に有効である。拡散用液としては、主に水であり、ま
た透析用液としては、一般に酸を含有する金属塩水溶液
が多く適用され、それら酸の回収および金属塩の分離，
回収が行われる。上記の酸としては、例えば硫酸，塩
酸，硝酸，リン酸，酢酸，弗化水素酸などであり、また
金属塩としては、例えばアルミニウム，銅，鉄，マグネ
シゥム，ニッケル，鉛，亜鉛，ウランなどの塩である。The ion exchange membrane used in the present invention is not particularly limited as long as it is a conventionally known anion exchange membrane or cation exchange membrane for diffusion dialysis, and is appropriately selected according to the purpose (use) of diffusion dialysis. For example, an anion exchange membrane is used to recover an acid, and a cation exchange membrane is used to recover a base. Therefore, the method of the present invention is particularly effective when using a hollow fiber membrane formed from a polymer having an anion exchange group. The diffusion liquid is mainly water, and the dialysis liquid is generally an acid-containing metal salt aqueous solution, which is often used to recover the acids and separate the metal salts.
Collection is done. The above-mentioned acid is, for example, sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, acetic acid, hydrofluoric acid, etc., and the metal salt is, for example, aluminum, copper, iron, magnesium, nickel, lead, zinc, uranium, etc. It is salt.
本発明における拡散用液の脱気は、その脱気手段など
特に制限されないが、該拡散液に含有される溶存気体を
溶存酸素の濃度として一般に5ppm以下、特に2ppmに脱気
することが、長時間の拡散透析においても酸または金属
塩を高い回収率を維持できるために極めて好ましい。即
ち、溶存酸素が特に5ppmより多く含有されている拡散用
液を供した場合には、長時間の拡散透析において、次第
に酸または金属塩の低下を来たす。The degassing of the diffusion liquid in the present invention is not particularly limited such as degassing means, but the dissolved gas contained in the diffusion liquid is generally degassed to a concentration of dissolved oxygen of 5 ppm or less, particularly 2 ppm. It is extremely preferable because a high recovery rate of the acid or metal salt can be maintained even in diffusion dialysis for a long time. That is, when a diffusion liquid containing dissolved oxygen in an amount of more than 5 ppm is provided, the acid or metal salt gradually decreases in the diffusion dialysis for a long time.
拡散用液の脱気手段としては、例えば通常の加熱によ
る煮沸する方法や超音波加熱法なども用いられるが、多
量の熱エネルギーが必要であること、連続的に脱気する
場合に装置が大型化するなど経済的および工業的に不利
である。したがって、本発明においては特に真空チャン
バー内に設けた中空状高分子膜に拡散用液を通過させて
減圧脱気する簡便な方法が好ましく採用され、真空度を
調節することにより、該拡散液中に含有の溶存気体を溶
存酸素として一般に2ppm以下まで容易に脱気することが
出来る。このような真空チャンバー内に設ける中空糸状
高分子膜は、例えばポリ四フッ化エチレン，四フッ化エ
チレン−パーフロロアルキルビニルエーテル共重合体な
どのフッ素系高分子膜やポリスルホン，ポリエーテルイ
ミド，シリコンなど酸素透過性の材質も用いられてい
る。As a degassing means for the diffusion liquid, for example, a method of boiling by ordinary heating or an ultrasonic heating method is also used, but a large amount of heat energy is required, and the apparatus is large when continuously degassing. It is economically and industrially disadvantageous. Therefore, in the present invention, a simple method of passing a diffusion liquid through a hollow polymer membrane provided in a vacuum chamber and degassing under reduced pressure is preferably adopted, and by adjusting the degree of vacuum, It can be easily degassed to 2ppm or less as a dissolved oxygen containing dissolved gas. The hollow fiber polymer film provided in such a vacuum chamber is, for example, a fluorine-based polymer film such as polytetrafluoroethylene, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, polysulfone, polyetherimide, silicon, or the like. Oxygen permeable materials are also used.
以下、本発明の代表的な方法について、添付図面にそ
のフローを示す。中空糸状イオン交換膜の多数を集束し
て円筒体内に構成したモジュール1において、該中空糸
状膜の内側にそれぞれ拡散用液２を液槽３より定量ポン
プ４を用いて上部から供給し、また該中空糸状膜の外側
に透析用液５を液槽６より定量ポンプ７を用いて下部か
ら供給して、該膜を介して向流接触させることにより拡
散透析を実施する。本発明は、かかる拡散透析法におい
て拡散用液２を予め真空チャンバー８内に設けた中空糸
状高分子膜９を通過させて後、モジュール1に供給する
ことを特徴とするものである。なお、拡散用液２として
水を供給し、透析用液５として酸を含有する金属塩水溶
液を供給する場合、拡散液10として酸含有の水溶液およ
び透析液11として分離された金属塩水溶液が回収され
る。Hereinafter, the flow of a typical method of the present invention will be shown in the accompanying drawings. In a module 1 in which a large number of hollow fiber ion-exchange membranes are bundled into a cylindrical body, a diffusion liquid 2 is supplied to the inside of the hollow fiber membranes from a liquid tank 3 using a metering pump 4 from above, and Diffusion dialysis 5 is performed by supplying the dialysing liquid 5 from the lower part of the hollow fiber membrane from a liquid tank 6 using a metering pump 7 and bringing it into countercurrent contact through the membrane. The present invention is characterized in that, in the diffusion dialysis method, the diffusion liquid 2 is supplied to the module 1 after passing through the hollow fiber polymer membrane 9 previously provided in the vacuum chamber 8. When water is supplied as the diffusion liquid 2 and an acid-containing metal salt aqueous solution is supplied as the dialysis liquid 5, the acid-containing aqueous solution as the diffusion liquid 10 and the separated metal salt aqueous solution as the dialysis liquid 11 are recovered. To be done.
以上の説明より理解されるように、本発明によれば、
イオン交換膜を介してそれぞれ拡散用液と透析用液を存
在させて拡散透析を行うにあたり、該拡散用液を予め脱
気して供給することにより、例えば拡散用液が水であ
り、透析用液が酸を含有する金属塩水溶液の連続透析に
おいて、酸の回収率及び金属塩分離効率が低下すること
なく、長期にわたり性能を維持することができる。な
お、本発明は主に中空糸状のイオン交換膜を用いた場合
について説明したが、通常のイオン交換膜（平膜）の場
合においても、相応の効果が得られるであろうことが簡
易に理解される。As understood from the above description, according to the present invention,
When performing diffusion dialysis in the presence of a diffusion liquid and a dialysis liquid respectively through an ion exchange membrane, the diffusion liquid is degassed in advance to supply, for example, the diffusion liquid is water, In continuous dialysis of an aqueous metal salt solution in which the solution contains an acid, the performance can be maintained for a long period of time without lowering the acid recovery rate and the metal salt separation efficiency. Although the present invention has mainly been described for the case of using a hollow fiber-shaped ion exchange membrane, it will be easily understood that a corresponding effect will be obtained even in the case of a normal ion exchange membrane (flat membrane). To be done.
以下、本発明の実施例を示すが、本発明はこれらの実
施例に限定されるものではない。Examples of the present invention will be shown below, but the present invention is not limited to these examples.
実施例１ 第１図に示したフローシートにおいて、陰イオン交換
基を有する中空糸状膜、即ち、内径1mm、外径2mmのチュ
ーブ状の陰イオン交換膜を220本束ね、透析有効長400mm
の外筒に封入した拡散透析セルを用いて、透析用液とし
て硫酸マグネシウムの硫酸水溶液また拡散用液としてイ
オン交換水をそれぞれ向流にて供給し、硫酸の回収を行
った。Example 1 In the flow sheet shown in FIG. 1, a hollow fiber membrane having an anion exchange group, that is, 220 tube-shaped anion exchange membranes having an inner diameter of 1 mm and an outer diameter of 2 mm are bundled to form a dialysis effective length of 400 mm.
Using a diffusion dialysis cell enclosed in the outer cylinder of the above, the sulfuric acid aqueous solution of magnesium sulfate as a dialysis solution and ion-exchanged water as a diffusion solution were respectively supplied in countercurrent to recover sulfuric acid.
真空チャンバーの真空度により、拡散用液における溶
存酸素を第１表に示す濃度に調節して所定の運転を行っ
た。その結果、拡散用液中の硫酸濃度および硫酸の回収
率は第１表の通りであった。比較のため、No.1〜３の条
件における拡散用液は、脱気処理していないイオン交換
水を用いた。The dissolved oxygen in the diffusion liquid was adjusted to the concentration shown in Table 1 by the degree of vacuum in the vacuum chamber, and a predetermined operation was performed. As a result, the concentration of sulfuric acid in the liquid for diffusion and the recovery rate of sulfuric acid are shown in Table 1. For comparison, ion-exchanged water that had not been degassed was used as the diffusion liquid under the conditions of Nos. 1 to 3.
実施例２ 実施例１と同条件で第２表（No.1〜７）に示す塩化第
１鉄の塩酸水溶液から塩酸の回収を行なった。 Example 2 Hydrochloric acid was recovered from the aqueous hydrochloric acid solution of ferrous chloride shown in Table 2 (Nos. 1 to 7) under the same conditions as in Example 1.
その結果、拡散液中の塩酸濃度および塩酸の回収率は
第２表の通りであった。比較のため、No.1〜２の条件に
おける拡散用液は、脱気処理をしてないイオン交換水を
用いた。As a result, the concentration of hydrochloric acid in the diffusion liquid and the recovery rate of hydrochloric acid are shown in Table 2. For comparison, ion-exchanged water that had not been degassed was used as the diffusion liquid under the conditions of Nos. 1 and 2.
第１図は、本発明の方法における代表的なフローシート
である。1は中空糸状膜を中空筒内に設けて構成した拡
散透析装置、２は拡散用液、３はその液槽、４は定量ポ
ンプ、５は透析用液、６はその液槽、７は定量ポンプ、
８は真空チャンバー、９は中空糸膜、10は拡散液、11は
透析液を示す。FIG. 1 is a typical flow sheet in the method of the present invention. 1 is a diffusion dialysis device in which a hollow fiber membrane is provided in a hollow cylinder, 2 is a diffusion liquid, 3 is a liquid tank, 4 is a metering pump, 5 is a dialysis liquid, 6 is the liquid tank, and 7 is a fixed amount. pump,
8 is a vacuum chamber, 9 is a hollow fiber membrane, 10 is a diffusion liquid, and 11 is a dialysate.
Claims (7)
透析用液を存在させて拡散透析を行うにあたり、該拡散
用液中に存在する酸素を5ppm以下となるように予め脱気
して供給することを特徴とする拡散透析法1. When carrying out diffusion dialysis in the presence of a diffusion liquid and a dialysis liquid respectively through an ion exchange membrane, the oxygen present in the diffusion liquid is degassed in advance to 5 ppm or less. Diffusion dialysis method characterized by supplying
の範囲第１項記載の拡散透析法2. The diffusion dialysis method according to claim 1, wherein the ion exchange membrane is a hollow fiber membrane.
記載の拡散透析法3. The diffusion dialysis method according to claim 1, wherein the diffusion liquid is water.
る特許請求の範囲第１項記載の拡散透析法4. The diffusion dialysis method according to claim 1, wherein the dialysis solution is an aqueous metal salt solution containing an acid.
拡散透析法5. The diffusion dialysis method according to claim 4, wherein the acid is recovered.
特許請求の範囲第１項記載の拡散透析法6. The diffusion dialysis method according to claim 1, wherein dissolved oxygen in the diffusion liquid is degassed to 2 ppm or less.
特許請求の範囲第１項または同第６項記載の拡散透析法7. The diffusion dialysis method according to claim 1 or 6, wherein the diffusion liquid is degassed by a continuous vacuum degassing method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62310868A JPH0817917B2 (en) | 1987-12-10 | 1987-12-10 | Diffusion dialysis method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62310868A JPH0817917B2 (en) | 1987-12-10 | 1987-12-10 | Diffusion dialysis method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01151903A JPH01151903A (en) | 1989-06-14 |
| JPH0817917B2 true JPH0817917B2 (en) | 1996-02-28 |
Family
ID=18010356
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62310868A Expired - Lifetime JPH0817917B2 (en) | 1987-12-10 | 1987-12-10 | Diffusion dialysis method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0817917B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102921319B (en) * | 2012-11-09 | 2015-02-25 | 杭州水处理技术研究开发中心有限公司 | Preparation method of hollow fiber diffusion dialysis acid recovery membrane |
| EP3650411A1 (en) * | 2018-11-12 | 2020-05-13 | Lenzing Aktiengesellschaft | Device and method for recovering alkaline solution and device and method for producing regenerated cellulose moulded bodies with such a method |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS50105545A (en) * | 1973-11-15 | 1975-08-20 | ||
| JPS53142382A (en) * | 1977-05-17 | 1978-12-12 | Toray Ind Inc | Controlling device for ultrafiltrating quantity |
-
1987
- 1987-12-10 JP JP62310868A patent/JPH0817917B2/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS50105545A (en) * | 1973-11-15 | 1975-08-20 | ||
| JPS53142382A (en) * | 1977-05-17 | 1978-12-12 | Toray Ind Inc | Controlling device for ultrafiltrating quantity |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH01151903A (en) | 1989-06-14 |
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