JPH07299333A - Regeneration of organic acid - Google Patents
Regeneration of organic acidInfo
- Publication number
- JPH07299333A JPH07299333A JP11976394A JP11976394A JPH07299333A JP H07299333 A JPH07299333 A JP H07299333A JP 11976394 A JP11976394 A JP 11976394A JP 11976394 A JP11976394 A JP 11976394A JP H07299333 A JPH07299333 A JP H07299333A
- Authority
- JP
- Japan
- Prior art keywords
- exchange membrane
- chamber
- cation exchange
- organic acid
- acid
- 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.)
- Pending
Links
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は有機酸の再生方法、更に
詳しくは電気透析法により有機酸とその金属塩の混合溶
液より有機酸を分離回収する方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for regenerating an organic acid, and more particularly to a method for separating and recovering an organic acid from a mixed solution of an organic acid and its metal salt by an electrodialysis method.
【０００２】[0002]
【従来の技術】有機酸とその金属塩の混合溶液から電気
透析法により有機酸を分離回収する場合、例えば図３の
ように電気透析槽内に隔膜として、陽イオン交換膜Ｃを
多数配列し、陽イオン交換膜Ｃと陽イオン交換膜Ｃで区
画形成された複数の室の一つ置きの室（脱塩室ａ）に有
機酸例えばギ酸と、その金属塩例えばＮａ塩の混合溶液
を流通させ、残る一つ置きの室（濃縮室ｂ）に濃縮液と
して硫酸を流通させることにより行われていた。2. Description of the Related Art When an organic acid is separated and recovered from a mixed solution of an organic acid and its metal salt by an electrodialysis method, for example, a large number of cation exchange membranes C are arranged as a diaphragm in an electrodialysis tank as shown in FIG. A mixed solution of an organic acid such as formic acid and its metal salt such as Na salt is circulated in the cation exchange membrane C and every other chamber (demineralization chamber a) defined by the cation exchange membrane C. Then, sulfuric acid was made to flow through as a concentrated liquid in the remaining chamber (concentration chamber b).
【０００３】即ち通電すると、脱塩室ａにおいてＮａ塩
が解離してできたＮａイオンは陰極に向かって陽イオン
交換膜Ｃを透過して陽イオン交換膜の陰極側の硫酸が流
通している濃縮室ｂに移動し硫酸ナトリウムを形成し硫
酸と共に除去される。一方、ギ酸が解離してできたＨＣ
ＯＯ- イオンは陽極に引っ張られるが陽イオン交換膜を
透過することができない。さらに濃縮室ｂよりＨ+ イオ
ンが陽イオン交換膜を通過し、脱塩室ａに移動して、脱
塩室ａにてＨＣＯＯＨが形成される。従って脱塩室ａか
ら金属イオンが除去され有機酸だけが回収される。That is, when energized, Na ions formed by dissociation of Na salt in the desalination chamber a permeate the cation exchange membrane C toward the cathode and sulfuric acid on the cathode side of the cation exchange membrane flows. It moves to the concentration chamber b, forms sodium sulfate, and is removed together with sulfuric acid. On the other hand, HC formed by dissociation of formic acid
OO − ions are pulled to the anode but cannot pass through the cation exchange membrane. Further, H + ions pass through the cation exchange membrane from the concentrating chamber b, move to the desalting chamber a, and HCOOH is formed in the desalting chamber a. Therefore, the metal ions are removed from the desalting chamber a and only the organic acid is recovered.
【０００４】[0004]
【発明が解決しようとする課題】しかしながら、上述の
ように陽イオン交換膜を使用した場合、硫酸が流通して
いる濃縮室ｂへ移動した金属イオンが、さらに陰極に向
かって次のイオン交換膜を透過して、陰極側の隣の脱塩
室ａに移動し、脱塩室での有機酸の分離回収率が低下す
る即ち電流効率が悪くなるという欠点があった。However, when the cation exchange membrane is used as described above, the metal ions transferred to the concentrating chamber b in which sulfuric acid is flowing further pass toward the cathode to the next ion exchange membrane. There is a drawback that the organic acid is transmitted to the desalting chamber a adjacent to the cathode side and the separation and recovery rate of the organic acid in the desalting chamber is lowered, that is, the current efficiency is deteriorated.
【０００５】本発明は、有機酸とその金属塩の混合溶液
から有機酸を効率よく電気透析法により分離回収する有
機酸の再生方法を提供することを目的としている。An object of the present invention is to provide a method for regenerating an organic acid, which efficiently separates and recovers the organic acid from a mixed solution of the organic acid and a metal salt thereof by electrodialysis.
【０００６】[0006]
【課題を解決するための手段】この目的を達成するため
に請求項１に記載の有機酸の再生方法では、電気透析槽
内の陽極及び陰極間に隔膜として、陽イオン交換膜と水
素イオン選択透過性イオン交換膜とを配列し、陽イオン
交換膜とその陽極側に配置された水素イオン選択透過性
イオン交換膜との間の室に有機酸とその金属塩の混合溶
液を流通させ、また陽イオン交換膜とその陰極側に配置
された水素イオン選択透過性イオン交換膜又は陽イオン
交換膜との間の室に濃縮液を流通させ、通電し、陽イオ
ン交換膜の陽極側の有機酸とその金属塩の混合溶液を流
通している室から金属イオンを除去して有機酸を回収す
るように構成した。In order to achieve this object, in the method for regenerating an organic acid according to claim 1, a cation exchange membrane and hydrogen ion selection are used as a diaphragm between an anode and a cathode in an electrodialysis cell. A permeable ion exchange membrane is arranged, and a mixed solution of an organic acid and its metal salt is circulated in a chamber between the cation exchange membrane and a hydrogen ion selective permeable ion exchange membrane arranged on the anode side thereof, and The concentrated liquid is passed through the chamber between the cation exchange membrane and the hydrogen ion selective permeable ion exchange membrane or the cation exchange membrane arranged on the cathode side of the cation exchange membrane to energize the organic acid on the anode side of the cation exchange membrane. The organic acid was recovered by removing the metal ions from the chamber in which the mixed solution of the metal salt and the metal salt flows.
【０００７】請求項２に記載の発明では、請求項１に記
載の有機酸の再生方法において、水素イオン選択透過性
イオン交換膜として、イオン交換容量０．５〜４ミリ当
量／ｇ乾燥樹脂、固定イオン濃度１〜１０ミリ当量／ｇ
Ｈ2 Ｏ、膜厚０．１〜１５０μｍ、硫酸０．５モル／リ
ットル溶液中の抵抗５Ω・ｃｍ2 以下を有する陽極側の
陰イオン交換体層と、陰極側の陽イオン交換層との複層
イオン交換膜を使用するように構成した。According to a second aspect of the present invention, in the method for regenerating an organic acid according to the first aspect, the ion exchange capacity is 0.5 to 4 meq / g dry resin as a hydrogen ion selective permeable ion exchange membrane. Fixed ion concentration 1-10 meq / g
H 2 O, a film thickness of 0.1 to 150 μm, a composite of an anion-exchange layer on the anode side and a cation-exchange layer on the cathode side having a resistance of 5 Ω · cm 2 or less in a solution of 0.5 mol / liter of sulfuric acid. It was configured to use a layer ion exchange membrane.
【０００８】図１のように陽イオン交換膜Ｃと水素イオ
ン選択透過性イオン交換膜Ｈは交互に配列しても、ある
いは図２のように例えば陽イオン交換膜Ｃを２個配置し
た後水素イオン選択透過性イオン交換膜Ｈを１個配置す
るように配列するなど、配列の仕方は自由である。As shown in FIG. 1, the cation exchange membranes C and the hydrogen ion-selective permeable ion exchange membranes H may be arranged alternately, or, for example, as shown in FIG. The ion-selective permeable ion-exchange membrane H may be arranged in any desired manner, such as one.
【０００９】有機酸とその金属塩の混合溶液は、陽イオ
ン交換膜とその陽極側の水素イオン選択透過性イオン交
換膜との間の室（脱塩室１又は３）に流通せしめられ
る。一方、濃縮液は陽イオン交換膜とその陰極側の水素
イオン選択透過性イオン交換膜又は陽イオン交換膜との
間の室（濃縮室２又は４、５）に流通せしめられる。A mixed solution of an organic acid and its metal salt is circulated in a chamber (desalting chamber 1 or 3) between the cation exchange membrane and the hydrogen ion selective permeable ion exchange membrane on the anode side. On the other hand, the concentrated liquid is allowed to flow into a chamber (concentration chamber 2 or 4, 5) between the cation exchange membrane and the hydrogen ion selective permeable ion exchange membrane or the cation exchange membrane on the cathode side thereof.
【００１０】陽イオン交換膜としては、例えば強酸性ス
チレンージビニルベンゼン系均一膜を使用でき、このよ
うな陽イオン交換膜としては、例えば旭硝子株式会社製
のセレミオンＣＭＶがある。As the cation exchange membrane, for example, a strongly acidic styrene-divinylbenzene-based uniform membrane can be used, and as such a cation exchange membrane, there is, for example, Selemion CMV manufactured by Asahi Glass Co., Ltd.
【００１１】一方、水素イオン選択透過性イオン交換膜
は、例えば陽極側の陰イオン交換体層と陰極側の陽イオ
ン交換体層との複層イオン交換膜を使用でき、このよう
な水素イオン選択透過性イオン交換膜としては例えば特
開平５ー２２８３４４号に開示されている複層イオン交
換膜を使用できる。On the other hand, as the hydrogen ion selective permeable ion exchange membrane, for example, a multilayer ion exchange membrane having an anion exchange layer on the anode side and a cation exchange layer on the cathode side can be used. As the permeable ion exchange membrane, for example, the multilayer ion exchange membrane disclosed in JP-A-5-228344 can be used.
【００１２】この複層イオン交換膜は陽極側の陰イオン
交換体層と陰極側の陽イオン交換体層との複層イオン交
換膜からなり、陽イオン交換体層はイオン交換容量が好
ましくは０．５〜４．５ミリ当量／ｇ乾燥樹脂、特に
０．８〜３．０ミリ当量／ｇ乾燥樹脂が適切であり、ま
た膜厚が１０〜１０００μｍ、特には１０〜５００μｍ
の厚い膜が使用される。このような陽イオン交換体層と
してはスチレンまたはその誘導体とジビニルベンゼンと
の共重合体を母体とし、スルホン酸基などの強酸性陽イ
オン交換基を有する陽イオン交換膜、または、スルホン
酸基を有するパーフルオロカーボン重合体からなる陽イ
オン交換膜が使用される。The multi-layer ion exchange membrane comprises a multi-layer ion exchange membrane comprising an anion exchange layer on the anode side and a cation exchange layer on the cathode side, and the cation exchange layer preferably has an ion exchange capacity of 0. 0.5 to 4.5 meq / g dry resin, particularly 0.8 to 3.0 meq / g dry resin, and a film thickness of 10 to 1000 μm, especially 10 to 500 μm.
Thick film is used. As such a cation exchange layer, a copolymer of styrene or a derivative thereof and divinylbenzene is used as a matrix, and a cation exchange membrane having a strong acidic cation exchange group such as a sulfonic acid group or a sulfonic acid group is used. A cation exchange membrane consisting of a perfluorocarbon polymer is used.
【００１３】一方、陰イオン交換体層としては、例えば
スチレンまたはクロロメチルスチレンとジビニルベンゼ
ンとの共重合体、ビニルピリジン系重合体、ビニルアニ
リン系重合体、ビニルイミダゾール系重合体、エポキシ
／アミン系重合体、および側鎖の末端に陰イオン交換基
を有しポリマー骨格がパーフルオロポリマーからなる含
フッ素系重合体があり、なかでも陰イオン交換体層とし
ては、繰り返し単位内に一般式ーＸーＡｒーＹー（式中
Ｘ、Ｙは互いに同一または異なる電子供与性の連結基を
表し、好ましくはーＯー、ーＳー、炭素数１〜１３のア
ルキレン基または単結合であり、Ａｒは、On the other hand, examples of the anion exchanger layer include a copolymer of styrene or chloromethylstyrene and divinylbenzene, a vinylpyridine polymer, a vinylaniline polymer, a vinylimidazole polymer, and an epoxy / amine system. There are polymers and fluorine-containing polymers having an anion exchange group at the end of the side chain and a polymer skeleton made of a perfluoropolymer. Among them, the anion exchange layer includes a compound represented by the general formula -X -Ar-Y- (wherein X and Y represent the same or different electron donating linking groups, preferably -O-, -S-, an alkylene group having 1 to 13 carbon atoms or a single bond, Ar Is
【００１４】[0014]
【化１】 [Chemical 1]
【００１５】を表す。Ｒ1 〜Ｒ5 は互いに同一または異
なる炭素数１〜８の炭化水素基であり、ａは０〜４、ｂ
＋ｃは０〜６、ｄ＋ｅは０〜６から選ばれる。）を有す
る芳香族系重合体からなり、その芳香族環に陰イオン交
換基が導入された陰イオン交換体層の使用が好ましい。Represents R 1 to R 5 are the same or different hydrocarbon groups having 1 to 8 carbon atoms, a is 0 to 4, b
+ C is selected from 0 to 6 and d + e is selected from 0 to 6. It is preferable to use an anion exchanger layer comprising an aromatic polymer having a) and having an anion exchange group introduced in its aromatic ring.
【００１６】かかる陰イオン交換体層が、イオン交換基
が導入されたセグメントとイオン交換基が実質的に導入
されていないセグメントからなるブロック共重合体から
なる場合には、得られる複層イオン交換膜の水素イオン
選択透過性が高く、かつ機械的性質に優れているので好
ましい。When such an anion exchanger layer is composed of a block copolymer consisting of a segment into which an ion exchange group is introduced and a segment into which an ion exchange group is not substantially introduced, the resulting multi-layer ion exchange layer is obtained. It is preferable because the membrane has high hydrogen ion selective permeability and excellent mechanical properties.
【００１７】かかるブロック共重合体としては、ポリフ
ェニレンオキシド／ポリエーテルスルホンブロック共重
合体，ポリフェニレンスルフィド／ポリエーテルスルホ
ンブロック共重合体、ポリアリールエーテルスルホン／
ポリエーテルスルホンブロック共重合体、ポリアリール
エーテルアリレート／ポリアリレートブロック共重合
体、またはポリアリールエーテルスルホン／ポリチオエ
ーテルスルホンブロック共重合体が例示される。なかで
も好ましいブロック重合体として、Examples of the block copolymer include polyphenylene oxide / polyether sulfone block copolymer, polyphenylene sulfide / polyether sulfone block copolymer, polyaryl ether sulfone /
Examples include polyether sulfone block copolymers, polyaryl ether arylate / polyarylate block copolymers, or polyaryl ether sulfone / polythioether sulfone block copolymers. Among them, as a preferable block polymer,
【００１８】[0018]
【化２】 [Chemical 2]
【００１９】等が挙げられる。化２においてｍ、ｎはそ
れぞれ２〜２００、ｍ／ｎは０．１〜１００である。And the like. In Chemical formula 2, m and n are 2 to 200, respectively, and m / n is 0.1 to 100.
【００２０】複層イオン交換膜における陰イオン交換体
層はイオン交換容量が０．５〜４ミリ当量／ｇ乾燥樹
脂、好ましくは０．８〜３．５ミリ当量／ｇ乾燥樹脂、
特には１．０〜３．０ミリ当量／ｇ乾燥樹脂の高いイオ
ン交換容量にもかかわらず固定イオン濃度が１〜１０ミ
リ当量／ｇＨ2 Ｏ、好ましくは２〜６ミリ当量／ｇＨ2
Ｏを有し、膜厚は０．１〜１５０μｍ、好ましくは１〜
５０μｍ、特には１〜２５μｍとすることができる。ま
た硫酸０．５モル／リットル溶液中の抵抗は５Ω・ｃｍ
2 以下である。得られた複層イオン交換膜の有する水素
イオン選択透過性は、水素イオン／金属陽イオンの透過
速度比が２０以上、場合により３０以上と極めて高い値
を有する。The anion exchanger layer in the multilayer ion exchange membrane has an ion exchange capacity of 0.5 to 4 meq / g dry resin, preferably 0.8 to 3.5 meq / g dry resin,
Especially 1.0 to 3.0 meq / g high fixed ion concentration in spite ion exchange capacity of dry resin is 1 to 10 meq / gH 2 O, preferably 2 to 6 meq / gH 2
O and has a film thickness of 0.1 to 150 μm, preferably 1 to
It can be 50 μm, especially 1 to 25 μm. The resistance in a solution of sulfuric acid 0.5 mol / liter is 5 Ω · cm.
2 or less. The hydrogen ion / selective permeability of the obtained multilayer ion-exchange membrane has an extremely high value of a hydrogen ion / metal cation permeation rate ratio of 20 or more, and in some cases 30 or more.
【００２１】本発明方法で再生される有機酸としては、
例えばギ酸、酢酸、クエン酸、シュウ酸、酒石酸、安息
香酸などのカルボン酸の他に、スルホン酸、スルフィン
酸などの官能基をもつ有機酸がある。また金属塩として
は例えばナトリウム塩、アルミニウム塩、銅塩、カリウ
ム塩、鉄塩、亜鉛塩、クロム塩などがある。有機酸は、
例えば、１〜１００ｇ／リットルで含有され、また金属
塩は、好ましくは１〜５０ｇ／リットルで含有される混
合液が良好に処理され、有機酸が効率よく再生される。The organic acid regenerated by the method of the present invention includes:
For example, in addition to carboxylic acids such as formic acid, acetic acid, citric acid, oxalic acid, tartaric acid and benzoic acid, there are organic acids having a functional group such as sulfonic acid and sulfinic acid. Examples of the metal salt include sodium salt, aluminum salt, copper salt, potassium salt, iron salt, zinc salt and chromium salt. The organic acid is
For example, the mixed solution containing 1 to 100 g / liter and the metal salt preferably containing 1 to 50 g / liter is well treated, and the organic acid is efficiently regenerated.
【００２２】図１のように電気透析槽内の陽極及び陰極
間に隔膜として、陽イオン交換膜Ｃと水素イオン選択透
過性イオン交換膜Ｈとを交互に配列する。水素イオン選
択透過性イオン交換膜Ｈは陰イオン交換体層が陽極に面
するように配置する。陽イオン交換膜Ｃと水素イオン選
択透過性イオン交換膜Ｈとの配列は、図２のように複数
個の陽イオン交換膜Ｃを配置した後水素イオン選択透過
性イオン交換膜Ｈを配置するように配列してもよい。As shown in FIG. 1, a cation exchange membrane C and a hydrogen ion selective permeable ion exchange membrane H are alternately arranged as a diaphragm between the anode and the cathode in the electrodialysis tank. The hydrogen ion selective permeable ion exchange membrane H is arranged so that the anion exchanger layer faces the anode. The cation exchange membrane C and the hydrogen ion selective permeable ion exchange membrane H are arranged such that a plurality of cation exchange membranes C are arranged and then the hydrogen ion selective permeable ion exchange membrane H is arranged as shown in FIG. You may arrange in.
【００２３】陽イオン交換膜の陽極側の水素イオン選択
透過性イオン交換膜との間の室（脱塩室１）に有機酸と
その金属塩の混合溶液を流通させ、また陽イオン交換膜
の陰極側の室（濃縮室２）に濃縮液として酸溶液を流通
させ、通電すると、金属塩が解離してできた金属イオン
は陰極に向かって陽イオン交換膜を透過して陽イオン交
換膜の陰極側の酸溶液が流通している室（濃縮室２）に
移動し塩を形成して酸溶液と共に除去される。水素イオ
ン選択透過性イオン交換膜Ｈは水素イオンだけを選択的
に透過し、金属イオンを透過しないので金属イオンが陰
極に引かれても水素イオン選択透過性イオン交換膜Ｈを
透過して陰極側の隣の脱塩室１に移動することはない。
一方、有機酸が解離してできた陰イオンは陽極に引っ張
られるが陽イオン交換膜を透過することができない。さ
らに濃縮室２よりＨ+ イオンが陽イオン交換膜を通過
し、脱塩室１に移動して脱塩室１にて有機酸が形成され
る。従って脱塩室１から金属イオンが除去され有機酸が
回収される。A mixed solution of an organic acid and its metal salt is circulated in a chamber (desalting chamber 1) between the cation exchange membrane and the hydrogen ion selective permeable ion exchange membrane on the anode side. When an acid solution is circulated as a concentrate in the chamber on the cathode side (concentration chamber 2) and electricity is applied, metal ions produced by dissociation of the metal salt pass through the cation exchange membrane toward the cathode and pass through the cation exchange membrane. The acid solution on the cathode side moves to a chamber (concentration chamber 2) in which the acid solution flows, forms a salt, and is removed together with the acid solution. Since the hydrogen ion selectively permeable ion exchange membrane H selectively permeates only hydrogen ions and does not permeate metal ions, even if metal ions are attracted to the cathode, the hydrogen ion selectively permeable ion exchange membrane H permeates the cathode side. It does not move to the desalination room 1 next to the.
On the other hand, anions formed by dissociation of the organic acid are pulled by the anode but cannot pass through the cation exchange membrane. Further, H + ions pass through the cation exchange membrane from the concentrating chamber 2 and move to the desalting chamber 1 to form an organic acid in the desalting chamber 1. Therefore, the metal ions are removed from the desalting chamber 1 and the organic acid is recovered.
【００２４】濃縮室に流通せしめられる濃縮液として
は、陽イオン交換膜を透過してきた金属イオンと塩を形
成するものであればよく、例えば硫酸、塩酸、硝酸など
が使用できる。The concentrated liquid to be circulated in the concentrating chamber may be any liquid as long as it forms a salt with the metal ions that have permeated the cation exchange membrane, and for example, sulfuric acid, hydrochloric acid, nitric acid or the like can be used.
【００２５】[0025]
【００２６】＜実施例１＞<Example 1>
【００２７】図１のように陽極と陰極の間に、特開平５
ー２２８３４４号に開示されている水素イオン選択透過
性イオン交換膜Ｈと、陽イオン交換膜Ｃ（旭硝子株式会
社製のセレミオンＣＭＶ）の２枚からなるセルを１ユニ
ットとして配列し、有効面積が０．１ｍ2 とした電気透
析槽で、陽イオン交換膜Ｃの陽極側の室（脱塩室）１に
ギ酸２０ｇ／リットルとナトリウム２ｇ／リットルの混
合溶液を流通させ、陽イオン交換膜Ｃの陰極側の室（濃
縮室）２に硫酸５ｇ／リットルの溶液を流通させ、ユニ
ットセル当たり０．５Ｖの定電圧で通電したところ、陽
イオン交換膜Ｃの陽極側の室１からギ酸が、陰極側の室
２から、硫酸ナトリウムと硫酸の混液が得られた。この
ときの、ナトリウムの電流効率は２８％であり、陽イオ
ン交換膜Ｃの陽極側の室１の溶液に残ったナトリウム
は、０．１ｇ／リットルであり、陽イオン交換膜Ｃの陰
極側の室２の溶液のナトリウム濃度は１．７ｇ／リット
ルであった。As shown in FIG. 1, there is a gap between the anode and the cathode.
No. 228344, a hydrogen ion selective permeable ion exchange membrane H and a cation exchange membrane C (Selemion CMV manufactured by Asahi Glass Co., Ltd.) are arranged as one unit cell, and the effective area is 0. in electrodialysis cell which was .1m 2, was passed through a mixed solution of formic acid 20 g / l of sodium 2 g / liter in the chamber (depletion chamber) 1 on the anode side of the cation exchange membrane C, the cathode of the cation exchange membrane C A solution of 5 g / liter of sulfuric acid was circulated through the side chamber (concentration chamber) 2 and energized at a constant voltage of 0.5 V per unit cell. As a result, formic acid was discharged from the chamber 1 on the anode side of the cation exchange membrane C to the cathode side. A mixed solution of sodium sulfate and sulfuric acid was obtained from the chamber 2. At this time, the current efficiency of sodium was 28%, the amount of sodium remaining in the solution in the chamber 1 on the anode side of the cation exchange membrane C was 0.1 g / liter, and the amount of sodium on the cathode side of the cation exchange membrane C was The sodium concentration of the solution in chamber 2 was 1.7 g / liter.
【００２８】＜実施例２＞<Example 2>
【００２９】実施例１と同じ膜を使い、図２のように陽
極側から水素イオン選択透過性イオン交換膜Ｈと２枚の
陽イオン交換膜Ｃの計３枚からなるセルを１ユニットと
して配列した電気透析槽で、水素イオン選択透過性イオ
ン交換膜Ｈの陰極側の室（脱塩室）３にギ酸４０ｇ／リ
ットルとナトリウム４ｇ／リットルの混合溶液を流通さ
せ、陽イオン交換膜Ｃと陽イオン交換膜Ｃの間の室（第
一濃縮室）４に硫酸１０ｇ／リットルの溶液を流通さ
せ、水素イオン選択透過性イオン交換膜Ｈの陽極側の室
（第二濃縮室）５に硫酸７０ｇ／リットルの溶液を流通
させ、ユニットセル当たり０．５Ｖの定電圧で通電し
た。Using the same membrane as in Example 1, as shown in FIG. 2, a cell composed of a total of three hydrogen ion selective permeable ion exchange membranes H and two cation exchange membranes C from the anode side is arranged as one unit. In the prepared electrodialysis tank, a mixed solution of 40 g / liter of formic acid and 4 g / liter of sodium was passed through the cathode-side chamber (desalination chamber) 3 of the ion-selective permeable ion exchange membrane H, and the cation-exchange membrane C and cation were exchanged. A solution of sulfuric acid 10 g / liter was circulated in a chamber (first concentrating chamber) 4 between the ion exchange membranes C, and 70 g of sulfuric acid was placed in an anode side chamber (second concentrating chamber) 5 of the hydrogen ion selective permeable ion exchange membrane H. / Liter of the solution was circulated, and electricity was applied at a constant voltage of 0.5 V per unit cell.
【００３０】その結果、水素イオン選択透過性イオン交
換膜Ｈの陽極側の室３からギ酸が、陽イオン交換膜Ｃと
陽イオン交換膜Ｃの間の室４、及び水素イオン選択透過
性イオン交換膜Ｈの陽極側の室５から、硫酸ナトリウム
と硫酸の混液が得られた。水素イオン選択透過性イオン
交換膜Ｈの陰極側の室３の溶液に残ったナトリウムは
０．１ｇ／リットルであり、陽イオン交換膜Ｃと陽イオ
ン交換膜Ｃの間の室４の溶液のナトリウム濃度は３．８
ｇ／リットル、水素イオン選択透過性イオン交換膜Ｈの
陽極側の室５の溶液のナトリウム濃度は１５ｇ／リット
ルであった。このときの、水素イオン選択透過性イオン
交換膜Ｈの陰極側の室３の溶液からのナトリウム脱塩電
流効率は２７％であった。As a result, formic acid from the anode-side chamber 3 of the hydrogen ion-selective permeable ion exchange membrane H, the chamber 4 between the cation exchange membrane C and the cation-exchange membrane C, and the hydrogen ion-selective permeable ion exchange. From the chamber 5 on the anode side of the membrane H, a mixed solution of sodium sulfate and sulfuric acid was obtained. The amount of sodium remaining in the solution in the chamber 3 on the cathode side of the hydrogen ion selective permeable ion exchange membrane H was 0.1 g / liter, and the sodium in the solution in the chamber 4 between the cation exchange membrane C and the cation exchange membrane C was sodium. Concentration is 3.8
The sodium concentration of the solution in the chamber 5 on the anode side of the hydrogen ion selective permeable ion exchange membrane H was 15 g / l. At this time, the sodium desalination current efficiency from the solution in the chamber 3 on the cathode side of the hydrogen ion selective permeable ion exchange membrane H was 27%.
【００３１】＜実施例３＞<Example 3>
【００３２】実施例１と同じ電気透析槽（図１）を用い
て、陽イオン交換膜Ｃの陽極側の室１にクエン酸４０ｇ
／リットルとアルミニウム４ｇ／リットルの混合溶液を
流通させ、陽イオン交換膜Ｃの陰極側の室２に硫酸７ｇ
／リットルの溶液を流通させ、ユニットセル当たり０．
５Ｖの定電圧で通電したところ、陽イオン交換膜Ｃの陽
極側の室１の溶液からクエン酸が、陰極側の室２から硫
酸アルミニウムと硫酸の混液が得られた。陽イオン交換
膜Ｃの陽極側の室１の溶液に残ったアルミニウムは、
０．２ｇ／リットルであり、陽イオン交換膜Ｃの陰極側
の室２の溶液のアルミニウム濃度は３．５ｇ／リットル
であった。このときの水素イオン選択透過性イオン交換
膜Ｈの陰極側の室１の溶液からのアルミニウム脱塩電流
効率は３７％であった。Using the same electrodialysis cell as in Example 1 (FIG. 1), 40 g of citric acid was placed in the chamber 1 on the anode side of the cation exchange membrane C.
/ G and aluminum 4g / l mixed solution was circulated, and 7g of sulfuric acid was placed in the chamber 2 on the cathode side of the cation exchange membrane C.
Per liter of the solution is passed through, and a unit cell of 0.
When electricity was applied at a constant voltage of 5 V, citric acid was obtained from the solution in the chamber 1 on the anode side of the cation exchange membrane C, and a mixed solution of aluminum sulfate and sulfuric acid was obtained from the chamber 2 on the cathode side. The aluminum remaining in the solution in the chamber 1 on the anode side of the cation exchange membrane C is
It was 0.2 g / liter, and the aluminum concentration of the solution in the chamber 2 on the cathode side of the cation exchange membrane C was 3.5 g / liter. At this time, the aluminum desalination current efficiency from the solution in the chamber 1 on the cathode side of the hydrogen ion selective permeable ion exchange membrane H was 37%.
【００３３】[0033]
【発明の効果】隔膜として陽イオン交換膜と水素イオン
選択透過性イオン交換膜とを用いることにより、有機酸
とその金属塩の混合溶液から有機酸を効率よく分離回収
することができる。By using a cation exchange membrane and a hydrogen ion selective permeable ion exchange membrane as the diaphragm, the organic acid can be efficiently separated and recovered from the mixed solution of the organic acid and its metal salt.
【図１】本発明を実施する電気透析槽の一例を示す図。FIG. 1 is a diagram showing an example of an electrodialysis tank for carrying out the present invention.
【図２】本発明を実施する別の電気透析槽を示す図。FIG. 2 is a diagram showing another electrodialysis tank for carrying out the present invention.
【図３】従来の電気透析槽の一例を示す図。FIG. 3 is a diagram showing an example of a conventional electrodialysis tank.
１ 室（脱塩室） ２ 室（濃縮室） ３ 室（脱塩室） ４ 室（第一濃縮室） ５ 室（第二濃縮室） 1 room (desalination room) 2 rooms (concentration room) 3 rooms (desalination room) 4 rooms (first concentration room) 5 rooms (second concentration room)
Claims (2)
て、陽イオン交換膜と水素イオン選択透過性イオン交換
膜とを配列し、陽イオン交換膜とその陽極側に配置され
た水素イオン選択透過性イオン交換膜との間の室に有機
酸とその金属塩の混合溶液を流通させ、また陽イオン交
換膜とその陰極側に配置された水素イオン選択透過性イ
オン交換膜又は陽イオン交換膜との間の室に濃縮液を流
通させて、通電し、陽イオン交換膜の陽極側の有機酸と
その金属塩の混合溶液を流通している室から金属イオン
を除去して有機酸を回収する有機酸の再生方法。1. A cation exchange membrane and a hydrogen ion selective permeable ion exchange membrane are arranged as a diaphragm between an anode and a cathode in an electrodialysis tank, and a cation exchange membrane and hydrogen ions arranged on the anode side thereof are arranged. A mixed solution of an organic acid and its metal salt is circulated in a chamber between the permselective ion exchange membrane and a cation exchange membrane or a cation exchange membrane which is disposed on the cathode side of the cation exchange membrane. The concentrated liquid is circulated in the chamber between the membranes and energized to remove the metal ions from the chamber in which the mixed solution of the organic acid and its metal salt on the anode side of the cation exchange membrane is circulated to remove the organic acid. A method of regenerating an organic acid to be recovered.
て、イオン交換容量０．５〜４ミリ当量／ｇ乾燥樹脂、
固定イオン濃度１〜１０ミリ当量／ｇＨ2 Ｏ、膜厚０．
１〜１５０μｍ、硫酸０．５モル／リットル溶液中の抵
抗５Ω・ｃｍ2 以下を有する陽極側の陰イオン交換体層
と、陰極側の陽イオン交換層との複層イオン交換膜を使
用する請求項１に記載の有機酸の再生方法。2. A hydrogen ion selective permeable ion exchange membrane, which has an ion exchange capacity of 0.5 to 4 meq / g dry resin,
Fixed ion concentration 1-10 meq / gH 2 O, film thickness 0.
A multi-layer ion exchange membrane comprising an anion exchange layer on the anode side and a cation exchange layer on the cathode side having a resistance of 5 Ω · cm 2 or less in a solution of 1 to 150 μm and 0.5 mol / liter of sulfuric acid. Item 2. A method for regenerating an organic acid according to Item 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11976394A JPH07299333A (en) | 1994-05-10 | 1994-05-10 | Regeneration of organic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11976394A JPH07299333A (en) | 1994-05-10 | 1994-05-10 | Regeneration of organic acid |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH07299333A true JPH07299333A (en) | 1995-11-14 |
Family
ID=14769582
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11976394A Pending JPH07299333A (en) | 1994-05-10 | 1994-05-10 | Regeneration of organic acid |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH07299333A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09216848A (en) * | 1996-01-10 | 1997-08-19 | Hoechst Ag | Production of pure glycolic acid |
| KR20020088230A (en) * | 2001-05-18 | 2002-11-27 | 광주과학기술원 | Production methods of organics from organic salts by ion substitution reaction using ion-exchange membranes |
| WO2009090105A1 (en) * | 2008-01-18 | 2009-07-23 | Eni S.P.A. | Process for the treatment of the aqueous stream coming from the fischer-tropsch reaction |
| JP2012149001A (en) * | 2011-01-18 | 2012-08-09 | Kurita Water Ind Ltd | Recovery device of oxalate ion from indium oxalate aqueous solution and recovery method of oxalate ion from indium oxalate aqueous solution |
| JP2016183088A (en) * | 2015-03-27 | 2016-10-20 | セントラルフィルター工業株式会社 | Generator for chlorine dioxide-containing sterile water |
| CN112439321A (en) * | 2019-08-29 | 2021-03-05 | 大禹环服（北京）科技有限公司 | Electrodialysis method for removing heat-stable amine salt |
| WO2022211128A1 (en) * | 2021-04-01 | 2022-10-06 | 出光興産株式会社 | Method for producing lithium compound and apparatus for producing lithium compound |
-
1994
- 1994-05-10 JP JP11976394A patent/JPH07299333A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09216848A (en) * | 1996-01-10 | 1997-08-19 | Hoechst Ag | Production of pure glycolic acid |
| KR20020088230A (en) * | 2001-05-18 | 2002-11-27 | 광주과학기술원 | Production methods of organics from organic salts by ion substitution reaction using ion-exchange membranes |
| WO2009090105A1 (en) * | 2008-01-18 | 2009-07-23 | Eni S.P.A. | Process for the treatment of the aqueous stream coming from the fischer-tropsch reaction |
| CN101952206A (en) * | 2008-01-18 | 2011-01-19 | 艾尼股份公司 | Process for the treatment of the aqueous stream coming from the fischer-tropsch reaction |
| JP2012149001A (en) * | 2011-01-18 | 2012-08-09 | Kurita Water Ind Ltd | Recovery device of oxalate ion from indium oxalate aqueous solution and recovery method of oxalate ion from indium oxalate aqueous solution |
| JP2016183088A (en) * | 2015-03-27 | 2016-10-20 | セントラルフィルター工業株式会社 | Generator for chlorine dioxide-containing sterile water |
| CN112439321A (en) * | 2019-08-29 | 2021-03-05 | 大禹环服（北京）科技有限公司 | Electrodialysis method for removing heat-stable amine salt |
| WO2022211128A1 (en) * | 2021-04-01 | 2022-10-06 | 出光興産株式会社 | Method for producing lithium compound and apparatus for producing lithium compound |
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