JPH07106351B2 - Dephosphorization and desalination method and apparatus - Google Patents
Dephosphorization and desalination method and apparatusInfo
- Publication number
- JPH07106351B2 JPH07106351B2 JP12141688A JP12141688A JPH07106351B2 JP H07106351 B2 JPH07106351 B2 JP H07106351B2 JP 12141688 A JP12141688 A JP 12141688A JP 12141688 A JP12141688 A JP 12141688A JP H07106351 B2 JPH07106351 B2 JP H07106351B2
- Authority
- JP
- Japan
- Prior art keywords
- aluminum
- exchange membrane
- chamber
- tank
- electrodialysis
- 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
Links
- 238000000034 method Methods 0.000 title claims description 14
- 238000010612 desalination reaction Methods 0.000 title claims description 11
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 42
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 40
- 239000010842 industrial wastewater Substances 0.000 claims description 33
- 239000012528 membrane Substances 0.000 claims description 30
- 229910052782 aluminium Inorganic materials 0.000 claims description 28
- 238000005341 cation exchange Methods 0.000 claims description 26
- 238000000909 electrodialysis Methods 0.000 claims description 25
- 239000003011 anion exchange membrane Substances 0.000 claims description 24
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 21
- 229910052751 metal Inorganic materials 0.000 claims description 14
- 239000002184 metal Substances 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 14
- 150000003839 salts Chemical class 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 14
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 13
- 238000001556 precipitation Methods 0.000 claims description 13
- 230000002378 acidificating effect Effects 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 claims description 11
- 238000005260 corrosion Methods 0.000 claims description 10
- 230000007797 corrosion Effects 0.000 claims description 10
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 9
- 229910001220 stainless steel Inorganic materials 0.000 claims description 7
- 239000010935 stainless steel Substances 0.000 claims description 7
- 150000001768 cations Chemical class 0.000 claims description 5
- 150000001450 anions Chemical class 0.000 claims description 4
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- -1 aluminum ions Chemical class 0.000 claims description 3
- 230000001112 coagulating effect Effects 0.000 claims description 3
- 238000011033 desalting Methods 0.000 claims description 3
- 238000005868 electrolysis reaction Methods 0.000 claims description 3
- 239000003014 ion exchange membrane Substances 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 230000001376 precipitating effect Effects 0.000 claims description 2
- 239000002351 wastewater Substances 0.000 claims 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 9
- 239000000126 substance Substances 0.000 description 6
- 229910019142 PO4 Inorganic materials 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-L Phosphate ion(2-) Chemical compound OP([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-L 0.000 description 5
- 235000021317 phosphate Nutrition 0.000 description 5
- 235000011121 sodium hydroxide Nutrition 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 4
- 239000010452 phosphate Substances 0.000 description 4
- 239000000701 coagulant Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000005086 pumping Methods 0.000 description 3
- 238000004381 surface treatment Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- BUACSMWVFUNQET-UHFFFAOYSA-H dialuminum;trisulfate;hydrate Chemical compound O.[Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O BUACSMWVFUNQET-UHFFFAOYSA-H 0.000 description 2
- 238000000502 dialysis Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- RPUZVWKKWXPKIP-UHFFFAOYSA-H dialuminum;hydrogen phosphate Chemical compound [Al+3].[Al+3].OP([O-])([O-])=O.OP([O-])([O-])=O.OP([O-])([O-])=O RPUZVWKKWXPKIP-UHFFFAOYSA-H 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000012851 eutrophication Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
Landscapes
- Separation Of Suspended Particles By Flocculating Agents (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明はリン酸塩を溶存した産業廃水の脱リン，脱塩方
法とその装置に関し、特にアルミニウムの電解と、イオ
ン交換膜を利用した電気透析処理により、産業廃水の前
処理、中和に必要な薬剤投入量を低減し、処理設備を簡
素化できることを特徴とする。Description: TECHNICAL FIELD The present invention relates to a method for dephosphorizing and desalting industrial wastewater in which phosphate is dissolved, and an apparatus therefor, and particularly to electrolysis of aluminum and electricity using an ion exchange membrane. The dialysis treatment is characterized in that the amount of chemicals required for pretreatment and neutralization of industrial wastewater can be reduced and the treatment equipment can be simplified.
従来、産業廃水の脱リン方法としては、産業廃水中に直
接ポリ塩化アルミニウム、硫酸バンド等の凝集剤を加
え、リン酸成分をリン酸アルミニウムとして沈澱させる
凝集沈澱法や、プラス極板にカーボン、マイナス極板に
ステンレス等を用いて水中にイオンが遊離しないように
し、両極板の間に陰イオン交換膜、陽イオン交換膜を配
設することにより産業廃水中に溶存するリン酸成分をも
含む塩類を透析分離し、それぞれを濃縮除去する電気透
析法が用いられてきた、 〔発明が解決しようとする課題〕 金属の表面処理洗浄には、リン酸系の表面処理剤、洗浄
剤が多く使用されており、表面処理洗浄施設を持つ工場
では多量のリン酸成分を溶存する産業廃水を排出してい
るところが多い。Conventionally, as a method for dephosphorizing industrial wastewater, polyaluminum chloride, a coagulant such as a sulfuric acid band is directly added to the industrial wastewater to precipitate a phosphoric acid component as aluminum phosphate, or a carbon plate is added to the positive electrode plate. By using stainless steel etc. for the negative electrode plate to prevent ions from being released in water, and by placing an anion exchange membrane and a cation exchange membrane between both electrode plates, salts containing phosphoric acid components dissolved in industrial wastewater can be removed. An electrodialysis method has been used in which dialysis separation is performed, and each of them is concentrated and removed. [Problems to be solved by the invention] A phosphoric acid-based surface treatment agent and a detergent are often used for surface treatment cleaning of metal. However, many factories that have surface treatment and cleaning facilities discharge industrial wastewater in which a large amount of phosphoric acid components are dissolved.
リン酸成分の排出は、下水を通じて湖沼や内湾等閉鎖水
域の富栄養化の一因となるもので、これを防止するため
に産業廃水中からリン酸成分を除去する必要が生ずる。Discharge of phosphoric acid component contributes to eutrophication of closed water areas such as lakes and bays through sewage, and it is necessary to remove phosphoric acid component from industrial wastewater in order to prevent this.
そこでこれらリン酸成分を除去するために前記した凝集
沈澱法、電気透析法などが用いられる。産業廃水中に含
まれるリン酸化合物をみると、リン酸水素塩の形で溶解
されている場合が多い。このリン酸水素塩の一種である
リン酸水素アルミニウムは水によく溶解されることか
ら、リン酸水素塩を含む状態から硫酸バンド等の凝集剤
を使用して凝集沈澱しようとしても効果がない。そこで
あらかじめリン酸成分を含む産業廃水中に苛性ソーダ等
を加え、リン酸水素塩を構成する水素とアルカリイオン
を置換し、リン酸塩とした後硫酸バンド等の酸性アルミ
ニウム凝集剤を加えると、化学反応により水に溶解した
リン酸アルミニウムが生成され、沈澱等により凝集除去
が可能となる。Therefore, in order to remove these phosphoric acid components, the above-mentioned coagulation-precipitation method, electrodialysis method and the like are used. Looking at the phosphoric acid compounds contained in industrial wastewater, they are often dissolved in the form of hydrogen phosphate. Since aluminum hydrogen phosphate, which is a kind of hydrogen phosphate, is well dissolved in water, there is no effect even if it is attempted to coagulate and precipitate from a state containing hydrogen phosphate using a flocculant such as a sulfuric acid band. Therefore, by adding caustic soda to the industrial wastewater containing the phosphoric acid component in advance, substituting the alkali ions with the hydrogen that constitutes the hydrogen phosphate, and converting it to a phosphate, and then adding an acidic aluminum coagulant such as a sulfuric acid band, the chemical By the reaction, aluminum phosphate dissolved in water is produced, and it becomes possible to remove the aggregate by precipitation or the like.
ところが、リン酸成分を含む産業廃水から、リン酸成分
を効率よく凝集除去しようとする場合、前処理剤として
の苛性ソーダ、凝集剤としての硫酸バンド等が多量に必
要となるが、これらの保存設備を必要量に応じて大きく
する必要があるなどの欠点がある。However, in order to efficiently remove coagulation of phosphoric acid components from industrial wastewater containing phosphoric acid components, a large amount of caustic soda as a pretreatment agent and a sulfuric acid band as a coagulant is required. Has the drawback that it must be increased according to the required amount.
また電気透析法では、産業廃水に溶存している塩類を陽
イオン、陰イオンに分けて濃縮分離除去されるものであ
るが、リン酸塩類は電気透析によつて除去しにくい成分
である。In the electrodialysis method, salts dissolved in industrial wastewater are separated into cations and anions and concentrated and separated, but phosphates are components that are difficult to remove by electrodialysis.
本発明はかかる技術的及び経済的な欠点を補つた脱リ
ン，脱塩方法および装置を提供しようとするもので、特
に苛性ソーダなどの前処理剤が不要となるほか、処理水
の再利用を可能とするものである。The present invention is intended to provide a dephosphorization and desalination method and apparatus that compensates for such technical and economical drawbacks. In particular, a pretreatment agent such as caustic soda is not required and treated water can be reused. It is what
前記課題を解決するため、本発明の脱リン、脱塩方法
は、アルミニュウム（２）にプラス、ステンレス等の耐
触性金属板（３）にマイナス電極をそれぞれ接続し、該
アルミニュウム（２）と耐触性金属板（３）の間に前記
アルミニュウム（２）側より第１の陰イオン交換膜（4
a）、第２の陽イオン交換膜（5b）、第２の陰イオン交
換膜（4b）および第１の陽イオン交換膜（5a）を適宜の
間隔で配設して該各交換膜で分離された陽極室（８）、
電気透析室（10b）、塩濃縮室（９）、電気透析室（10
a）および陰極室（７）を有する処理槽（６）におい
て、前記第１の陽イオン交換膜（5a）を通り陰極室
（７）に吸引された陽イオンによって陰極室（７）に供
給されたリン酸成分を含む産業廃水をアルカリ化すると
ともに、前記第１の陰イオン交換膜（4a）を通り陽極室
（８）に吸引された陰イオンとアルミニュウムの電解に
より生じたアルミニュウムイオンとによって陽極室
（８）に酸性アルミニュウム塩を生成し、さらに該酸性
アルミニュウム塩に硫酸アルミニュウム溶液を混合し、
該混合液と前記アルカリ化されたリン酸成分を含む産業
廃水を混合中和するとともに、生成されたリン酸アルミ
ニュウムを沈殿分離し、該脱リンされた産業廃水を前記
電気透析室（10b）（10a）に供給脱塩するものである。In order to solve the above-mentioned problems, the dephosphorization and desalination method of the present invention is a method in which a positive electrode is connected to an aluminum (2) and a negative electrode is connected to a touch-resistant metal plate (3) such as stainless steel, and the aluminum (2) and The first anion exchange membrane (4) from the aluminum (2) side is placed between the touch-resistant metal plates (3).
a), the second cation exchange membrane (5b), the second anion exchange membrane (4b) and the first cation exchange membrane (5a) are arranged at appropriate intervals and separated by the respective exchange membranes. Anode chamber (8),
Electrodialysis room (10b), salt concentration room (9), electrodialysis room (10
a) and a treatment chamber (6) having a cathode chamber (7) are supplied to the cathode chamber (7) by the cations that have been sucked into the cathode chamber (7) through the first cation exchange membrane (5a). The industrial wastewater containing phosphoric acid component is alkalized, and at the same time, the anion is sucked into the anode chamber (8) through the first anion exchange membrane (4a) and the aluminum ion generated by the electrolysis of aluminum is used as an anode. Generating an acidic aluminum salt in the chamber (8), further mixing the acidic aluminum salt with an aluminum sulfate solution,
The mixed solution and the industrial wastewater containing the alkalized phosphoric acid component are mixed and neutralized, and the produced aluminum phosphate is separated by precipitation, and the dephosphorized industrial wastewater is electrodialysis chamber (10b) ( It is supplied to 10a) for desalting.
前記したアルミニュウム（２）について隔膜（22）で流
出を防止された粉末成形品を用いると後記する理由によ
り効果的である。It is effective to use a powder molded product of the above-mentioned aluminum (2) which is prevented from flowing out by the diaphragm (22) for the reason described later.
また、本発明の脱リン、脱塩装置は、アルミニュウム
（２）にプラス、ステンレス等の耐触性金属板（３）に
マイナスの電極をそれぞれ接続し、該アルミニュウム
（２）と耐触性金属板（３）の間に前記アルミニュウム
（２）側より第１の陰イオン交換膜（4a）、第２の陽イ
オン交換膜（5b）、第２の陰イオン交換膜（4b）および
第１の陽イオン交換膜（5a）を適宜の間隔で配設して該
各交換膜で分離された陽極室（８）、電気透析室（（10
b）、塩濃縮室（９）、電気透析室（10a）および陰極室
（７）を有する処理槽（６）と、陰極室（７）でアルカ
リ化された産業廃水と陽極室（８）で生成された酸性ア
ルミニュウム塩および貯蔵タンク（13）内に貯蔵された
硫酸アルミニュウム溶液を混合してリン酸アルミニュウ
ムを生成する混合槽（11）と、該リン酸アルミニュウム
を凝集沈殿する沈殿槽（12）と、該沈殿槽（12）内の水
素イオン濃度を計測して前記貯蔵タンク（13）内の硫酸
アルミニュウム溶液の前記混合槽（11）への混合量を調
整するpH調整装置（19）と、前記沈殿室（12）から前記
各電気透析室（10b）（10a）への脱リン水供給管路（2
3）とかり構成したものである。In the dephosphorization and desalination apparatus of the present invention, a positive electrode is connected to the aluminum (2) and a negative electrode is connected to the corrosion-resistant metal plate (3) such as stainless steel, and the aluminum (2) and the corrosion-resistant metal are connected. The first anion exchange membrane (4a), the second cation exchange membrane (5b), the second anion exchange membrane (4b) and the first anion exchange membrane (4a) are placed between the plates (3) from the aluminum (2) side. The cation exchange membranes (5a) are arranged at appropriate intervals, and the anode chamber (8) and the electrodialysis chamber ((10
b), a treatment tank (6) having a salt concentrating chamber (9), an electrodialysis chamber (10a) and a cathode chamber (7), and industrial wastewater alkalized in the cathode chamber (7) and an anode chamber (8). A mixing tank (11) for mixing the generated acidic aluminum salt and the aluminum sulfate solution stored in the storage tank (13) to generate aluminum phosphate, and a settling tank (12) for coagulating and precipitating the aluminum phosphate. A pH adjusting device (19) for measuring the hydrogen ion concentration in the precipitation tank (12) and adjusting the mixing amount of the aluminum sulfate solution in the storage tank (13) into the mixing tank (11), Dephosphorized water supply pipe (2) from the precipitation chamber (12) to the electrodialysis chambers (10b) (10a)
3) It is composed of a balance.
さらにpH調整装置（19）は、貯蔵タンク（13）より硫酸
アルミニュウム溶液を汲み上げる汲み上げポンプ（14）
と、沈殿槽（12）における水素イオン濃度を計測するpH
計測装置（15）と、該pH計測装置（15）による計測値に
応じて汲み上げポンプ（14）を駆動する駆動制御回路
（16）とにより構成される。Further, the pH adjusting device (19) is a pump (14) for pumping the aluminum sulfate solution from the storage tank (13).
And pH for measuring hydrogen ion concentration in the settling tank (12)
It is composed of a measuring device (15) and a drive control circuit (16) for driving the pumping pump (14) according to the value measured by the pH measuring device (15).
本発明においては、まずリン酸成分を含む産業廃水
（１）を陰極室（７）でアルカリ化し、リン酸成分中の
リン酸水素塩、リン酸二水素塩のうちの水素をアルカリ
金属と置換し、次に酸性アルミニウム塩及び硫酸アルミ
ニュウム溶液を加えてリン酸アルミニウムを生成し、凝
集沈澱させて、リン酸成分を除去する。In the present invention, first, the industrial wastewater (1) containing a phosphoric acid component is alkalized in the cathode chamber (7) and hydrogen in the phosphoric acid component or hydrogen phosphate in the phosphoric acid component is replaced with an alkali metal. Then, an acidic aluminum salt and an aluminum sulfate solution are added to produce aluminum phosphate, which is coagulated and precipitated to remove the phosphoric acid component.
次に脱リンされた産業廃水（１）にはアルミニウム
（２）で構成されるプラス側極板とステンレス等の耐蝕
性金属板（３）で構成されるマイナス側極板との間で、
プラス側極板に近い側より第１の陰イオン交換膜（4
a）、第２の陽イオン交換膜（5b）、第２の陰イオン交
換膜（4b）、第１の陽イオン交換膜（5a）が適宜の間隔
で配設された処理槽（６）中の第１の陰イオン交換膜
（4a）と第２の陽イオン交換膜（5b）の間および第２の
陰イオン交換膜（4b）と第１の陽イオン交換膜（5a）の
間に形成された電気透析室（10b）および（10a）に注入
され、電気透析により第２の陽イオン交換膜（5b）と第
２の陰イオン交換膜（4b）の間で濃縮脱塩される。Next, in the dephosphorized industrial wastewater (1), between the positive side electrode plate composed of aluminum (2) and the negative side electrode plate composed of a corrosion-resistant metal plate (3) such as stainless steel,
The first anion exchange membrane (4
a), a second cation exchange membrane (5b), a second anion exchange membrane (4b), and a first cation exchange membrane (5a) in a treatment tank (6) arranged at appropriate intervals Between the first anion exchange membrane (4a) and the second cation exchange membrane (5b) and between the second anion exchange membrane (4b) and the first cation exchange membrane (5a) It is injected into the electrodialysis chambers (10b) and (10a) thus prepared, and concentrated and desalted between the second cation exchange membrane (5b) and the second anion exchange membrane (4b) by electrodialysis.
以下図面にもとづき一実施例を説明する。 An embodiment will be described below with reference to the drawings.
第１図において、（１）は産業廃水で、まず金属表面処
理装置等から排水され、まず生物学的処理法で処理され
た後、排水ポンプ（20）にて過装置（17）、紫外線殺
菌装置（18）を介して浄化され処理槽（６）へと送られ
る。In Fig. 1, (1) is industrial wastewater, which is first discharged from a metal surface treatment device, etc., and first treated by a biological treatment method, and then is treated by a drainage pump (20) with an excess device (17) and ultraviolet sterilization. Purified through the device (18) and sent to the treatment tank (6).
処理槽（６）内にはプラスの電極を接続されたアルミニ
ウム（２）と、マイナスの電極を接続されたステンレス
等の耐蝕性金属板（３）が対向して配設されている。ま
たアルミニウム（２）と耐蝕性金属板（３）との間に
は、前記アルミニュウム（２）側より第１の陰イオン交
換膜（4a）、第２の陽イオン交換膜（5b）、第２の陰イ
オン交換膜（4b）、第１の陽イオン交換膜（5a）が適宜
の間隔で配設され、該各交換膜で分離された陽極室
（８）、電気透析室（10b）、塩濃縮室（９）、電気透
析室（10a）および陰極室（７）を形成している。第１
図においてアルミニウム（２）は産業廃水（１）中への
流失を防止するべく隔膜（22）で保護された粉末成形品
で構成され、中央部にはカーボン等の化学的に安定な物
質で電極の中核が形成されている。In the processing tank (6), an aluminum (2) connected to a positive electrode and a corrosion-resistant metal plate (3) such as stainless steel connected to a negative electrode are arranged to face each other. Further, between the aluminum (2) and the corrosion-resistant metal plate (3), the first anion exchange membrane (4a), the second cation exchange membrane (5b), and the second cation exchange membrane (5b) are arranged from the aluminum (2) side. The anion exchange membrane (4b) and the first cation exchange membrane (5a) are arranged at appropriate intervals, and the anode chamber (8), the electrodialysis chamber (10b) and the salt are separated by the respective exchange membranes. A concentration chamber (9), an electrodialysis chamber (10a) and a cathode chamber (7) are formed. First
In the figure, the aluminum (2) is composed of a powder molded product protected by a diaphragm (22) to prevent it from being washed into the industrial wastewater (1), and the central part is made of a chemically stable substance such as carbon. The core of is formed.
アルミニウム（２）は陽極室（８）において硫酸イオン
等と反応して酸性アルミニウム塩を生成するもので、粉
末成形品を用いると表面積を極めて大きくとれることか
ら、イオン化しやすくなり小さな体積でも酸性アルミニ
ウム塩を速やかに生成できるものである。Aluminum (2) reacts with sulfuric acid ions and the like in the anode chamber (8) to form an acidic aluminum salt. When a powder molded product is used, the surface area can be made extremely large, so that it is easy to ionize and acidic aluminum can be produced even in a small volume. The salt can be quickly produced.
陰極室（７）には第１の陽イオン交換膜（5a）、第２の
陰イオン交換膜（4b）の間に形成される電気透析室（10
a）に注入される産業廃水（１）より第１の陽イオン交
換膜（5a）を介してナトリウム等の陽イオンを透過し、
アルカリ化される。該アルカリ化された陰極室（７）内
の水に過装置（17）、紫外線殺菌装置（18）等で浄化
されてなおリン酸塩等を含む産業廃水（１）が加えら
れ、産業廃水（１）をアルカリ化する。（11）は混合槽
で、アルカリ化されたリン酸塩等を多く含む産業廃水
（１）と、陽極室（８）において生成された酸性アルミ
ニウム塩およびpH調整装置を構成する貯蔵タンク（13）
内の硫酸アルミニウム溶液を混合し中和する。この時水
に溶解しないリン酸アルミニウムが生成され、沈澱槽
（12）において、凝集沈澱する。硫酸アルミニウム液貯
蔵タンク（13）内の硫酸アルミニウム溶液はpH調整装置
を構成する汲み上げポンプ（14）によつて陽極室（８）
に汲み上げられ一緒に混合槽（11）に投入することは、
陽極室（８）に新たに水を混入しなくてすむものである
が、汲み上げポンプ（14）から直接混合槽（11｝へ投入
されてもよいものである。The cathode chamber (7) has an electrodialysis chamber (10) formed between the first cation exchange membrane (5a) and the second anion exchange membrane (4b).
Permeation of cations such as sodium from the industrial wastewater (1) injected into a) through the first cation exchange membrane (5a),
Be alkalized. Industrial wastewater (1) that has been purified by a filter device (17), an ultraviolet sterilizer (18), etc. and still contains phosphate etc. is added to the water in the alkalized cathode chamber (7), and the industrial wastewater ( Alkaline 1). A mixing tank (11) is an industrial wastewater (1) containing a large amount of alkalized phosphate, etc., an acidic aluminum salt produced in the anode chamber (8) and a storage tank (13) constituting a pH adjusting device.
The aluminum sulfate solution in the mixture is mixed and neutralized. At this time, aluminum phosphate that is insoluble in water is produced and coagulates and precipitates in the precipitation tank (12). The aluminum sulphate solution in the aluminum sulphate solution storage tank (13) is supplied to the anode chamber (8) by a pump (14) which constitutes a pH adjusting device.
It is pumped to and put into the mixing tank (11) together.
Although it is not necessary to newly mix water in the anode chamber (8), it may be directly fed into the mixing tank (11) from the pumping pump (14).
以上のようにして沈澱槽（12）において脱リンされた産
業廃水ではあるがまたリン酸成分以外の塩が残るため再
び処理槽（６）内の第１の陽イオン交換膜（5a）と第２
の陰イオン交換膜（4b）の間および第２の陽イオン交換
膜（5b）と第１の陰イオン交換膜（4a）の間に形成され
た電気透析室（10a）および（10b）へと脱リン水供給管
路（23）を介して送られ、第２の陰イオン交換膜（4b）
と第２の陽イオン交換膜（5b）で形成された塩濃縮室
（９）へ陽イオン、陰イオンが集められリン酸成分のな
い塩として濃縮される。したがつて処理槽（６）、混合
槽（11）、沈澱槽（12）を循環する産業廃水（１）内の
塩濃度は一定に保たれる。また電気透析室（10a）（10
b）で脱塩された産業廃水（１）は不純物が含まれない
もので、再利用される。Although it is the industrial wastewater dephosphorized in the settling tank (12) as described above, since salts other than the phosphoric acid component remain, the first cation exchange membrane (5a) and the first cation exchange membrane (5a) in the processing tank (6) are reused. Two
To the electrodialysis chambers (10a) and (10b) formed between the anion exchange membrane (4b) and between the second cation exchange membrane (5b) and the first anion exchange membrane (4a). The second anion exchange membrane (4b) sent through the dephosphorized water supply pipe (23)
Then, cations and anions are collected in a salt concentrating chamber (9) formed by the second cation exchange membrane (5b) and concentrated as a salt having no phosphoric acid component. Therefore, the salt concentration in the industrial wastewater (1) circulating in the treatment tank (6), the mixing tank (11) and the precipitation tank (12) is kept constant. The electrodialysis room (10a) (10
The industrial wastewater (1) desalted in b) contains no impurities and is reused.
なお、（15）はpH調整装置（19）を構成するpH計測装置
で沈澱槽（12）内が中和されているかを確認し、アルカ
リ性であることを確認してpH調整装置を構成する駆動制
御回路（16）を制御し汲み上げポンプ（14）を介して貯
蔵タンク（13）内の硫酸アルミニウム溶液を混合槽（1
1）へ調整投入するものである。In addition, (15) is a drive for configuring the pH adjusting device by confirming that the inside of the precipitation tank (12) is neutralized by the pH measuring device that constitutes the pH adjusting device (19) and confirming that it is alkaline. The aluminum sulfate solution in the storage tank (13) is mixed through the pump (14) by controlling the control circuit (16) to mix tank (1
It is to adjust and put into 1).
本発明の脱リン，脱塩方法および装置によれば、産業廃
水（１）よりリン酸成分を効率よく凝集除去するために
必要な苛性ソーダ等のアルカリ物質が不要となるほか、
苛性ソーダ投入設備も不要となる。またリン酸アルミニ
ウムを生成するために必要な硫酸アルミニウム溶液の約
半量を産業廃水（１）中の酸性イオンと電解アルミニュ
ウムから生成した酸性アルミニュウム塩でまかなうこと
ができ、薬剤の費用を少くでき、さらにこれら薬剤を投
入する容器の大きさを小さくできるなどの効果がある。
さらに電気透析処理によつて脱塩された産業廃水は再利
用が可能であり、脱リン，脱塩処理にかかる薬剤等の消
耗品費、設備費、水の再利用により大幅に処理費用を低
減できる効果が得られるものである。According to the dephosphorization and desalination method and apparatus of the present invention, the alkaline substance such as caustic soda required for efficiently coagulating and removing the phosphoric acid component from the industrial wastewater (1) is not required, and
No caustic soda charging equipment is required. Also, about half of the aluminum sulfate solution required to produce aluminum phosphate can be covered by acidic ions in industrial wastewater (1) and acidic aluminum salts produced from electrolytic aluminum, reducing the cost of the drug, and This has the effect of reducing the size of the container into which these chemicals are charged.
Furthermore, the industrial wastewater desalted by electrodialysis can be reused, and the cost of consumables such as chemicals for dephosphorization and desalination, equipment costs, and water reuse can be greatly reduced. The effect that can be obtained is obtained.
第１図は本発明にかかる脱リン，脱塩装置の説明図を示
す。 （１）……産業廃水、（２）……アルミニウム粉末、
（３）……耐蝕性金属板、（４）……陰イオン交換膜、
（５）……陽イオン交換膜、（６）……処理槽、（７）
……陰極室、（８）……陽極室、（９）……塩濃縮室、
（10a）（10b）……電気透析室、（11）……混合槽、
（12）……沈澱槽、（13）……硫酸アルミニウム液貯蔵
タンク、（14）……汲み上げポンプ、（15）……pH計測
装置、（16）……駆動回路、（22）……隔膜。FIG. 1 shows an explanatory view of a dephosphorization / desalination apparatus according to the present invention. (1) …… Industrial wastewater, (2) …… Aluminum powder,
(3) …… Corrosion resistant metal plate, (4) …… Anion exchange membrane,
(5) …… Cation exchange membrane, (6) …… Treatment tank, (7)
…… Cathode chamber, (8) …… Anode chamber, (9) …… Salt concentrating chamber,
(10a) (10b) …… Electrodialysis room, (11) …… Mixing tank,
(12) …… Precipitation tank, (13) …… Aluminum sulfate storage tank, (14) …… Pump pump, (15) …… pH measuring device, (16) …… Drive circuit, (22) …… Separator .
Claims (4)
耐触性金属板にマイナス電極をそれぞれ接続し、該アル
ミニュウムと耐触性金属板の間に前記アルミニュウム側
より第１の陰イオン交換膜、第２の陽イオン交換膜、第
２の陰イオン交換膜および第１の陽イオン交換膜を適宜
の間隔で配設して該各交換膜で分離された陽極室、電気
透析室、塩濃縮室、電気透析室および陰極室を有する処
理槽において、前記第１の陽イオン交換膜を通り陰極室
に吸引された陽イオンによって陰極室に供給されたリン
酸成分を含む産業廃水をアルカリ化するとともに、前記
第１の陰イオン交換膜を通り陽極室に吸引された陰イオ
ンとアルミニュウムの電解により生じたアルミニュウム
イオンとによって陽極室に酸性アルミニュウム塩を生成
し、さらに該酸性アルミニュウム塩に硫酸アルミニュウ
ム溶液を混合し、該混合液と前記アルカリ化されたリン
酸成分を含む産業廃水を混合中和するとともに、生成さ
れたリン酸アルミニュウムを沈殿分離し、該脱リンされ
た産業廃水を前記電気透析室に供給脱塩することを特徴
とする脱リン、脱塩方法。1. A positive electrode is connected to aluminum and a negative electrode is connected to a corrosion-resistant metal plate such as stainless steel, and a first anion exchange membrane and a second cation exchange membrane are provided between the aluminum and the corrosion-resistant metal plate from the aluminum side. An ion exchange membrane, a second anion exchange membrane, and a first cation exchange membrane are arranged at appropriate intervals, and an anode chamber, an electrodialysis chamber, a salt concentration chamber, and an electrodialysis chamber are separated by the respective exchange membranes. In a treatment tank having a cathode chamber, the industrial wastewater containing a phosphoric acid component supplied to the cathode chamber is alkalized by the cations that have been sucked into the cathode chamber through the first cation exchange membrane, and the first Of the anion that has been sucked into the anode chamber through the anion exchange membrane and the aluminum ions generated by the electrolysis of aluminum to produce an acidic aluminum salt in the anode chamber, The aluminum sulfate solution is mixed with the luminium salt, and the mixed solution and the industrial wastewater containing the alkalized phosphoric acid component are mixed and neutralized, and the produced aluminum phosphate is separated by precipitation to remove the dephosphorized industry. A method for dephosphorization and desalination, which comprises supplying wastewater to the electrodialysis chamber for desalting.
末成形品である請求項１記載の脱リン、脱塩方法。2. The dephosphorization and desalination method according to claim 1, which is a powder molded product in which aluminum is prevented from flowing out by a diaphragm.
耐触性金属板にマイナスの電極をそれぞれ接続し、該ア
ルミニュウムと耐触性金属板の間に前記アルミニュウム
側より第１の陰イオン交換膜、第２の陽イオン交換膜、
第２の陰イオン交換膜および第１の陽イオン交換膜を適
宜の間隔で配設して該各交換膜で分離された陽極室、電
気透析室、塩濃縮室、電気透析室及び陰極室を有する処
理槽と、陰極室でアルカリ化された産業廃水と陽極室で
生成された酸性アルミニュウム塩および貯蔵タンク内に
貯蔵された硫酸アルミニュウム溶液を混合してリン酸ア
ルミニュウムを生成する混合槽と、該リン酸アルミニュ
ウムを凝集沈殿する沈殿槽と、該沈殿槽内の水素イオン
濃度を計測して前記貯蔵タンク内の硫酸アルミニュウム
溶液の前記混合槽への混合量を調整するpH調整装置と、
前記沈殿槽から前記各電気透析室への脱リン水供給管路
とより構成されたことを特徴とする脱リン、脱塩装置。3. A positive electrode is connected to aluminum and a negative electrode is connected to a corrosion-resistant metal plate such as stainless steel, and a first anion exchange membrane and a second electrode are provided between the aluminum and the corrosion-resistant metal plate from the aluminum side. Cation exchange membrane,
The second anion exchange membrane and the first cation exchange membrane are arranged at appropriate intervals, and the anode chamber, the electrodialysis chamber, the salt concentration chamber, the electrodialysis chamber, and the cathode chamber separated by the respective exchange membranes are provided. A treatment tank having, a mixing tank for mixing the industrial wastewater alkalized in the cathode chamber and the acidic aluminum salt generated in the anode chamber and the aluminum sulfate solution stored in the storage tank to generate aluminum phosphate, and A precipitation tank for coagulating and precipitating aluminum phosphate, a pH adjusting device for measuring the hydrogen ion concentration in the precipitation tank and adjusting the mixing amount of the aluminum sulfate solution in the storage tank to the mixing tank,
A dephosphorization / desalination apparatus comprising a dephosphorization water supply pipe line from the settling tank to each of the electrodialysis chambers.
ニュウム溶液を汲み上げる汲み上げポンプと、沈殿槽に
おける水素イオン濃度を計測するpH計測装置と、該pH計
測装置による計測値に応じて前記した汲み上げポンプを
駆動する駆動制御回路とにより構成された請求項３記載
の脱リン、脱塩装置。4. A pH adjusting device for drawing up an aluminum sulfate solution from a storage tank, a pH measuring device for measuring the hydrogen ion concentration in a precipitation tank, and the above-mentioned drawing pump according to the value measured by the pH measuring device. The dephosphorization and desalination apparatus according to claim 3, which is configured by a drive control circuit for driving the.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12141688A JPH07106351B2 (en) | 1988-05-18 | 1988-05-18 | Dephosphorization and desalination method and apparatus |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12141688A JPH07106351B2 (en) | 1988-05-18 | 1988-05-18 | Dephosphorization and desalination method and apparatus |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01293185A JPH01293185A (en) | 1989-11-27 |
| JPH07106351B2 true JPH07106351B2 (en) | 1995-11-15 |
Family
ID=14810621
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12141688A Expired - Lifetime JPH07106351B2 (en) | 1988-05-18 | 1988-05-18 | Dephosphorization and desalination method and apparatus |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH07106351B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2025135533A1 (en) * | 2023-12-18 | 2025-06-26 | 포스코홀딩스 주식회사 | Electrodialysis device and electrodialysis process |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106587452A (en) * | 2016-12-30 | 2017-04-26 | 云南省环境科学研究院(中国昆明高原湖泊国际研究中心) | Method for treating arsenic-containing wastewater by ionic membrane electrolysis |
| CN107673539B (en) * | 2017-11-17 | 2021-07-09 | 云南省环境科学研究院(中国昆明高原湖泊国际研究中心) | Acidic wastewater treatment equipment and treatment method |
| CN113582403A (en) * | 2021-09-06 | 2021-11-02 | 瓮福（集团）有限责任公司 | Method for removing easily-scaling components in phosphorus chemical industry acidic wastewater by membrane separation technology |
| CN115020757B (en) * | 2022-06-09 | 2024-08-20 | 四川发展兴欣钒能源科技有限公司 | Method for removing organic matters in strong acid vanadium solution based on electrodialysis |
-
1988
- 1988-05-18 JP JP12141688A patent/JPH07106351B2/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2025135533A1 (en) * | 2023-12-18 | 2025-06-26 | 포스코홀딩스 주식회사 | Electrodialysis device and electrodialysis process |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH01293185A (en) | 1989-11-27 |
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