JP5205089B2 - Waste electrolyte treatment method - Google Patents
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- JP5205089B2 JP5205089B2 JP2008070027A JP2008070027A JP5205089B2 JP 5205089 B2 JP5205089 B2 JP 5205089B2 JP 2008070027 A JP2008070027 A JP 2008070027A JP 2008070027 A JP2008070027 A JP 2008070027A JP 5205089 B2 JP5205089 B2 JP 5205089B2
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- 239000002699 waste material Substances 0.000 title claims description 90
- 239000003792 electrolyte Substances 0.000 title claims description 50
- 238000000034 method Methods 0.000 title claims description 43
- 229910001385 heavy metal Inorganic materials 0.000 claims description 110
- 239000002351 wastewater Substances 0.000 claims description 89
- 239000008151 electrolyte solution Substances 0.000 claims description 48
- 238000004519 manufacturing process Methods 0.000 claims description 29
- 238000005345 coagulation Methods 0.000 claims description 22
- 230000015271 coagulation Effects 0.000 claims description 22
- 229920000642 polymer Polymers 0.000 claims description 21
- 238000010979 pH adjustment Methods 0.000 claims description 15
- 238000004062 sedimentation Methods 0.000 claims description 15
- 238000001556 precipitation Methods 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 238000003672 processing method Methods 0.000 claims description 4
- 239000000701 coagulant Substances 0.000 claims 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 17
- 239000000126 substance Substances 0.000 description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000002738 chelating agent Substances 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 12
- 238000004065 wastewater treatment Methods 0.000 description 12
- 230000002776 aggregation Effects 0.000 description 11
- 238000003860 storage Methods 0.000 description 11
- 229910052759 nickel Inorganic materials 0.000 description 9
- 238000001914 filtration Methods 0.000 description 7
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 238000005054 agglomeration Methods 0.000 description 6
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 238000004220 aggregation Methods 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 239000003002 pH adjusting agent Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 229920002401 polyacrylamide Polymers 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 229920006318 anionic polymer Polymers 0.000 description 3
- 229910052793 cadmium Inorganic materials 0.000 description 3
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 3
- 229910000480 nickel oxide Inorganic materials 0.000 description 3
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical class [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 2
- 229920006317 cationic polymer Polymers 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005189 flocculation Methods 0.000 description 2
- 230000016615 flocculation Effects 0.000 description 2
- 239000002440 industrial waste Substances 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000004520 agglutination Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 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 description 1
- -1 aluminum hydroxide ions Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical group NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 description 1
- NVIVJPRCKQTWLY-UHFFFAOYSA-N cobalt nickel Chemical compound [Co][Ni][Co] NVIVJPRCKQTWLY-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 239000008394 flocculating agent Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Separation Of Suspended Particles By Flocculating Agents (AREA)
- Secondary Cells (AREA)
Description
本発明は、廃棄電解液の処理方法に関する。 The present invention relates to a method for treating a waste electrolyte.
電池工場の排水には、例えば、電極の製造工程において排出される電極重金属を含む排水（以下、「電極重金属含有排水」ともいう）、電解液の注液工程等において排出される電解液成分を含む排水（以下、「廃棄電解液」ともいう）等があるが、これらの排水は別々に処理を行われている。電極重金属を含む排水は、例えば、酸やアルカリで中和処理された後、凝集沈殿処理法によって処理がされている。一方、廃棄電解液は、産業廃棄物として廃棄処理されることが多いが、環境対策及び廃棄量の削減の観点から、廃棄電解液を処理して不要な成分を除去し、電解液として再利用することが試みられている（例えば、特許文献１及び２）。 The battery factory wastewater includes, for example, wastewater containing electrode heavy metals discharged in the electrode manufacturing process (hereinafter also referred to as “electrode heavy metal-containing wastewater”), electrolyte components discharged in the electrolyte injection process, etc. There is wastewater (hereinafter also referred to as “waste electrolyte”), etc., but these wastewaters are treated separately. For example, the waste water containing the electrode heavy metal is neutralized with an acid or an alkali and then treated by a coagulation sedimentation method. On the other hand, waste electrolyte is often disposed of as industrial waste, but from the viewpoint of environmental measures and reduction of waste, waste electrolyte is treated to remove unnecessary components and reused as electrolyte. Attempts have been made (for example, Patent Documents 1 and 2).
その他に、鉛電池製造過程において排出される鉛含有酸廃液を、アルカリ電池製造過程において排出されるアルカリ性廃液により中和して廃液処理を行うことが提案されている（例えば、特許文献３）。
アルカリ二次電池の製造過程で排出される電極重金属含有排水の処理において、排水をｐＨ調整するためのアルカリ性剤の使用量が増加するという問題があった。一方、廃棄電解液についても、ここ数年、その処理費用が高騰しており、廃棄電解液の処理方法の見直しが求められている。 In the treatment of waste water containing electrode heavy metals discharged in the process of manufacturing an alkaline secondary battery, there is a problem that the amount of alkaline agent used to adjust the pH of the waste water increases. On the other hand, the disposal cost of the waste electrolyte has increased in recent years, and a review of the disposal method of the waste electrolyte has been demanded.
そこで、本発明は、アルカリ二次電池の製造過程で排出される廃棄電解液の新たな処理方法を提供する。 Accordingly, the present invention provides a new method for treating a waste electrolyte discharged in the process of manufacturing an alkaline secondary battery.
本発明のアルカリ二次電池の廃棄電解液処理方法は、アルカリ二次電池の製造過程で排出される電解液を含む廃棄電解液を、前記アルカリ二次電池の製造過程で排出される電極重金属含有排水の凝集沈殿処理におけるｐＨの調整に使用すること特徴とする。 The method for treating a waste electrolyte of an alkaline secondary battery according to the present invention includes a waste electrolyte containing an electrolyte discharged in the process of manufacturing an alkaline secondary battery, and containing an electrode heavy metal discharged in the process of manufacturing the alkaline secondary battery. It is characterized by being used for pH adjustment in the coagulation sedimentation treatment of waste water.
本発明の廃棄電解液の処理方法によれば、アルカリ二次電池の製造過程で排出される廃棄電解液を、同製造過程で排出される電極重金属含有排水のｐＨ調整に使用することによって処理する。本発明の廃棄電解液の処理方法によれば、例えば、廃棄電解液の処分費用及び電極重金属含有排水処理におけるアルカリ性剤の使用量を削減できる。 According to the disposal method of the waste electrolyte solution of the present invention, the waste electrolyte solution discharged in the manufacturing process of the alkaline secondary battery is used by adjusting the pH of the waste water containing electrode heavy metal discharged in the manufacturing process. . According to the disposal method of the waste electrolyte solution of the present invention, for example, the disposal cost of the waste electrolyte solution and the amount of alkaline agent used in the electrode heavy metal-containing wastewater treatment can be reduced.
［廃棄電解液］
本発明において廃棄電解液とは、アルカリ二次電池の製造過程で排出される電解液成分を含む排水のことをいう。電解液成分を含む排水としては、例えば、二次電池の各電槽に電解液を注液する工程において排出される電解液、電解液注液後の二次電池を純水によって洗浄する工程において排出される電解液成分を含む排水等が挙げられる。アルカリ二次電池の電解液としては、一般的には水酸化カリウムを主成分としたアルカリ電解液が挙げられ、アルカリ二次電池の製造過程で排出される廃棄電解液としては、例えば、水酸化カリウム等を含むアルカリ性の水溶液が挙げられる。
[Disposable electrolyte]
In the present invention, the waste electrolyte solution refers to waste water containing an electrolyte component that is discharged during the production process of an alkaline secondary battery. As the waste water containing the electrolyte component, for example, in the step of washing the electrolyte solution discharged in the step of injecting the electrolyte solution into each battery tank of the secondary battery, the step of washing the secondary battery after the electrolyte solution injection with pure water Examples include waste water containing discharged electrolyte components. Examples of the alkaline secondary battery electrolyte generally include alkaline electrolytes mainly composed of potassium hydroxide. Examples of the waste electrolyte discharged during the alkaline secondary battery manufacturing process include, for example, hydroxide An alkaline aqueous solution containing potassium and the like can be mentioned.
［電極重金属含有排水］
本発明において電極重金属含有排水とは、アルカリ二次電池の製造過程で排出される重金属を含む排水のことをいう。排出される重金属とは、主に、電極の製造工程で排出される重金属であって、例えば、アルカリ二次電池の電極に使用される金属等が挙げられる。アルカリ二次電池としては、例えば、ニッケル・水素電池及びニッケル・カドミウム電池等が挙げられる。ニッケル・水素電池は、正極としてニッケル酸化物、負極として水素吸蔵合金が使用される。ニッケル・カドミウム電池は、正極としてニッケル酸化物、負極としてカドミウムが使用される。ニッケル酸化物としては、例えば、水酸化ニッケル等が挙げられる。水素吸蔵合金としては、例えば、（ＡＢ５型）コバルト・ニッケル合金、ニッケルとランタンとを主成分としてさらにマンガン、アルミニウム及びコバルトを含む合金等が挙げられる。電極重金属含有排水に含まれる重金属としては、例えば、ニッケル、コバルト、亜鉛等がある。電極重金属含有排水は、例えば、その他の製造工程で使用される重金属やその他の金属等を含んでいても良い。
[Electrode heavy metal-containing wastewater]
In the present invention, the electrode heavy metal-containing waste water refers to waste water containing heavy metals discharged in the process of manufacturing an alkaline secondary battery. The discharged heavy metal is mainly a heavy metal discharged in the electrode manufacturing process, and examples thereof include metals used for electrodes of alkaline secondary batteries. Examples of the alkaline secondary battery include a nickel / hydrogen battery and a nickel / cadmium battery. Nickel / hydrogen batteries use nickel oxide as the positive electrode and a hydrogen storage alloy as the negative electrode. Nickel / cadmium batteries use nickel oxide as the positive electrode and cadmium as the negative electrode. Examples of the nickel oxide include nickel hydroxide. Examples of the hydrogen storage alloy include (AB5 type) cobalt-nickel alloy, an alloy containing nickel and lanthanum as main components and further containing manganese, aluminum, and cobalt. Examples of the heavy metal contained in the electrode heavy metal-containing wastewater include nickel, cobalt, and zinc. The electrode heavy metal-containing waste water may contain, for example, heavy metals used in other manufacturing processes, other metals, and the like.
［廃棄電解液の処理方法］
本発明において廃棄電解液の処理とは、廃棄電解液をアルカリ二次電池の製造過程で排出される電極重金属含有排水の凝集沈殿処理におけるｐＨの調整に利用し、廃棄電解液を処分することをいう。本発明の廃棄電解液の処理方法によれば、例えば、既存の重金属含有排水処理設備を使用して廃棄電解液を処理できるため、設備投資や処理コストを低減できる。廃棄電解液を利用したｐＨの調整は、電極重金属含有排水の凝集沈殿処理で行ういずれのｐＨの調整であっても良い。
[Waste electrolyte treatment method]
In the present invention, the treatment of the waste electrolyte solution means that the waste electrolyte solution is used for pH adjustment in the coagulation sedimentation treatment of the electrode heavy metal-containing wastewater discharged in the manufacturing process of the alkaline secondary battery, and the waste electrolyte solution is disposed. Say. According to the disposal method of the waste electrolyte solution of the present invention, for example, the waste electrolyte solution can be treated using existing heavy metal-containing wastewater treatment equipment, so that the equipment investment and the processing cost can be reduced. The pH adjustment using the waste electrolyte may be any pH adjustment performed in the coagulation sedimentation treatment of the electrode heavy metal-containing wastewater.
本発明の廃棄電解液の処理方法は、廃棄電解液を、アルカリ二次電池の製造過程で排出される電極重金属含有排水の凝集沈殿処理におけるｐＨの調整に使用する以外は特に制限されない。また、電極重金属含有排水の凝集沈殿処理は、従来公知の重金属含有排水の凝集沈殿処理と同様に行うことができる。凝集沈殿処理は、例えば、電極重金属含有排水に無機凝集剤を添加する工程を含み、さらに、無機凝集剤を含む電極重金属含有排水に高分子凝集剤及びキレート剤の少なくとも一方を添加する工程等を含むことが好ましい。無機凝集剤を添加することにより重金属を含む難溶性物質（フロック）を形成させ、例えば、その難溶性物質を濾過及び／又は沈殿させること等により電極重金属含有排水中の重金属を回収できる。また、さらに、高分子凝集剤及びキレート剤の少なくとも一方を添加することにより、電極重金属含有排水中の重金属や重金属を含む難溶性物質を凝集させ、電極重金属含有排水中の重金属の回収をより容易にし、回収量を向上できる。 The disposal method of the waste electrolyte solution of the present invention is not particularly limited except that the waste electrolyte solution is used for pH adjustment in the coagulation sedimentation treatment of the electrode heavy metal-containing wastewater discharged in the production process of the alkaline secondary battery. Moreover, the coagulation precipitation process of electrode heavy metal containing wastewater can be performed similarly to the conventionally well-known coagulation precipitation process of heavy metal containing wastewater. The coagulation sedimentation treatment includes, for example, a step of adding an inorganic flocculant to the electrode heavy metal-containing wastewater, and further a step of adding at least one of a polymer flocculant and a chelating agent to the electrode heavy metal-containing wastewater containing the inorganic flocculant. It is preferable to include. By adding an inorganic flocculant, a hardly soluble substance (floc) containing heavy metal is formed, and for example, the heavy metal in the waste water containing electrode heavy metal can be recovered by filtering and / or precipitating the hardly soluble substance. Furthermore, by adding at least one of a polymer flocculant and a chelating agent, heavy metals in the electrode heavy metal-containing wastewater and hardly soluble substances containing heavy metals are aggregated, making it easier to recover heavy metals in the electrode heavy metal-containing wastewater. And the amount recovered can be improved.
廃棄電解液は、無機凝集剤を添加する工程における電極重金属含有排水のｐＨ調整に使用することが好ましい。これにより、電極重金属含有排水中の重金属と無機凝集剤とを反応させ、難溶性物質の形成を促進させることができる。ｐＨの調整は、無機凝集剤の添加と同時に行っても良く、又は添加後に行っても良い。 The waste electrolyte is preferably used for pH adjustment of the electrode heavy metal-containing wastewater in the step of adding the inorganic flocculant. Thereby, the heavy metal in an electrode heavy metal containing waste water and an inorganic flocculant can be made to react, and formation of a hardly soluble substance can be accelerated | stimulated. The pH adjustment may be performed simultaneously with the addition of the inorganic flocculant or after the addition.
電極重金属含有排水に対する廃棄電解液の割合（廃棄電解液の添加量／電極重金属含有排水の量）は、電極重金属含有排水及び廃棄電解液のｐＨ、凝集処理に使用する凝集剤（例えば、無機凝集剤、高分子凝集剤、キレート剤等）の種類等によって適宜決定できる。電極重金属含有排水の凝集沈殿処理を効率よく行う観点から、電極重金属含有排水の量に対する廃棄電解液の添加割合は、５ｖｏｌ％以下であることが好ましく、より好ましくは０．５ｖｏｌ％以下であり、さらに好ましくは０．１ｖｏｌ％以下である。 The ratio of the waste electrolyte to the electrode heavy metal-containing wastewater (the amount of waste electrolyte added / the amount of the electrode heavy metal-containing wastewater) is the pH of the electrode heavy metal-containing wastewater and waste electrolyte, and the flocculant used for the agglomeration treatment (for example, inorganic agglomeration). Agent, polymer flocculant, chelating agent, etc.). From the viewpoint of efficiently performing the coagulation sedimentation treatment of the electrode heavy metal-containing wastewater, the addition ratio of the waste electrolyte with respect to the amount of the electrode heavy metal-containing wastewater is preferably 5 vol% or less, more preferably 0.5 vol% or less, More preferably, it is 0.1 vol% or less.
本発明の廃棄電解液の処理方法において、電極重金属含有排水の凝集沈殿処理は、例えば、以下のように行うことができる。 In the method for treating a waste electrolyte solution of the present invention, the coagulation sedimentation treatment of the electrode heavy metal-containing waste water can be performed as follows, for example.
まず、電極重金属含有排水への無機凝集剤の添加、及び、廃棄電解液を用いた電極重金属含有排水のｐＨ調整を行う。これにより、重金属を含む難溶性物質（フロック）を形成させ、後述する重金属を含む凝集物の形成効率を向上できる。 First, the inorganic flocculant is added to the electrode heavy metal-containing wastewater, and the pH of the electrode heavy metal-containing wastewater is adjusted using a waste electrolyte. Thereby, the hardly soluble substance (floc) containing a heavy metal is formed, and the formation efficiency of the aggregate containing the heavy metal mentioned later can be improved.
無機凝集剤としては、例えば、鉄（ＩＩＩ）塩、アルミニウム塩等が挙げられる。鉄（ＩＩＩ）塩としては、例えば、塩化第二鉄、ポリ塩化第二鉄等が挙げられる。アルミニウム塩としては、例えば、ポリ塩化アルミニウム、硫酸アルミニウム（Ａｌ2（ＳＯ4）3・ｎＨ2Ｏ）等が挙げられる。これらの中でも、ニッケルとのフロック形成効率及び水酸化アルミニウムイオンの残留を回避する点から、塩化第二鉄が好ましい。 Examples of the inorganic flocculant include iron (III) salts and aluminum salts. Examples of the iron (III) salt include ferric chloride and polyferric chloride. Examples of the aluminum salt include polyaluminum chloride and aluminum sulfate (Al 2 (SO 4 ) 3 .nH 2 O). Among these, ferric chloride is preferable in terms of floc formation efficiency with nickel and avoidance of aluminum hydroxide ions.
廃棄電解液を用いて調整するｐＨの範囲は、例えば、電極重金属含有排水中に含まれる重金属の種類及び無機凝集剤の種類等によって適正ｐＨ範囲が異なる。例えば、無機凝集剤として塩化第二鉄を使用し、重金属（例えば、ニッケル、亜鉛）を不溶化して除去するためには、ｐＨ８〜１０の範囲が好ましく、ｐＨ９がより好ましい。廃棄電解液に加え、必要に応じて公知のｐＨ調整薬剤を使用してｐＨの調整を行っても良い。酸性剤としては、例えば、塩酸（ＨＣｌ）、硫酸（Ｈ2ＳＯ4）、リン酸（Ｈ3ＰＯ4）等の鉱酸が挙げられ、硫酸が好ましい。アルカリ性剤としては、水酸化ナトリウム（ＮａＯＨ）、水酸化カルシウム（Ｃａ（ＯＨ）2）等が挙げられ、水酸化ナトリウムが好ましい。 The pH range to be adjusted using the waste electrolyte solution varies depending on, for example, the type of heavy metal contained in the electrode heavy metal-containing wastewater and the type of inorganic flocculant. For example, in order to use ferric chloride as an inorganic flocculant and insolubilize and remove heavy metals (for example, nickel and zinc), the range of pH 8 to 10 is preferable, and pH 9 is more preferable. In addition to the waste electrolyte, the pH may be adjusted using a known pH adjusting agent as necessary. Examples of the acid agent include mineral acids such as hydrochloric acid (HCl), sulfuric acid (H 2 SO 4 ), phosphoric acid (H 3 PO 4 ), and sulfuric acid is preferable. Examples of the alkaline agent include sodium hydroxide (NaOH), calcium hydroxide (Ca (OH) 2 ), and sodium hydroxide is preferable.
つぎに、難溶性物質を含む電極重金属含有排水に高分子凝集剤を添加して重金属を含む凝集物を形成させる。重金属を含む凝集物を形成させることによって、電極重金属含有排水中の重金属濃度を低減できる。 Next, a polymer flocculant is added to the electrode heavy metal-containing wastewater containing a hardly soluble substance to form an agglomerate containing heavy metal. By forming an agglomerate containing heavy metal, the concentration of heavy metal in the waste water containing electrode heavy metal can be reduced.
高分子凝集剤としては、例えば、アニオン系高分子凝集剤、カチオン系高分子凝集剤、ノニオン系高分子凝集剤等が挙げられる。アニオン系高分子凝集剤及びノニオン系高分子凝集剤としては、ポリアクリルアミドが主体のものが挙げられる。カチオン系高分子凝集剤としては、ポリアクリル酸エステル系のものが挙げられる。また、高分子凝集剤との併用又は高分子凝集剤に替えてキレート剤を使用しても良い。キレート剤としては、例えば、液体キレート剤が挙げられる。液体キレート剤としては、例えば、ジチオカルバミン酸基及びチオール基の双方の基またはいずれかの基を有する化合物を含むキレート剤が挙げられる。キレート剤は市販品のものを使用しても良く、例えば、東ソー（株）製のＴＸ−１０（商品名）、ミヨシ油脂（株）製のエポフロックＬ−１（商品名）等が挙げられる。高分子凝集剤及びキレート剤の添加割合は、例えば、重金属の濃度によって適宜決定できる。 Examples of the polymer flocculant include an anionic polymer flocculant, a cationic polymer flocculant, and a nonionic polymer flocculant. Examples of the anionic polymer flocculant and nonionic polymer flocculant include those mainly composed of polyacrylamide. Examples of the cationic polymer flocculant include polyacrylate esters. A chelating agent may be used in combination with the polymer flocculant or in place of the polymer flocculant. Examples of chelating agents include liquid chelating agents. Examples of the liquid chelating agent include a chelating agent containing a compound having both or one of a dithiocarbamic acid group and a thiol group. As the chelating agent, commercially available products may be used, and examples thereof include TX-10 (trade name) manufactured by Tosoh Corporation, and Epofloc L-1 (trade name) manufactured by Miyoshi Oil & Fats. The addition ratio of the polymer flocculant and the chelating agent can be appropriately determined depending on, for example, the concentration of heavy metal.
なお、上記例では、無機凝集剤と高分子凝集剤及び／又はキレート剤とを併用した凝集沈殿処理を例にとり説明したが、これに限定されずその他の方法でも良く、例えば、無機凝集剤、高分子凝集剤及びキレート剤のいずれかを用いた凝集沈殿処理であっても良い。 In the above example, the aggregation precipitation treatment using an inorganic flocculant and a polymer flocculant and / or a chelating agent is described as an example. However, the present invention is not limited to this, and other methods may be used, for example, an inorganic flocculant, It may be a coagulation precipitation treatment using either a polymer flocculant or a chelating agent.
［電極重金属含有排水の処理方法］
その他の態様として、本発明は電極重金属含有排水の処理方法に関する。本発明の電極重金属含有排水処理方法は、アルカリ二次電池の製造過程で排出される電極重金属含有排水の処理方法であって、前記電極重金属含有排水の凝集沈殿工程を含み、前記凝集沈殿工程において、前記電極重金属含有排水のｐＨ調整にアルカリ二次電池の製造過程で排出される廃棄電解液を使用することを特徴とする。本発明の電極重金属含有排水の処理方法によれば、アルカリ二次電池の製造過程で排出される廃棄電解液を、電極重金属含有排水のｐＨ調整に使用するため、例えば、アルカリ性剤の使用量を削減できる。電極重金属含有排水の処理方法における電極重金属含有排水の凝集沈殿工程は、例えば、上述と同様に行うことができる。
[Treatment of waste water containing electrode heavy metals]
As another aspect, the present invention relates to a method for treating waste water containing electrode heavy metals. The electrode heavy metal-containing wastewater treatment method of the present invention is a method for treating electrode heavy metal-containing wastewater discharged during the production process of an alkaline secondary battery, and includes a coagulation-precipitation step of the electrode heavy metal-containing wastewater, The waste electrolyte solution discharged in the manufacturing process of the alkaline secondary battery is used for pH adjustment of the electrode heavy metal-containing wastewater. According to the electrode heavy metal-containing wastewater treatment method of the present invention, the waste electrolyte discharged during the production process of the alkaline secondary battery is used for pH adjustment of the electrode heavy metal-containing wastewater. Can be reduced. The aggregation precipitation process of the electrode heavy metal-containing wastewater in the method for treating electrode heavy metal-containing wastewater can be performed, for example, in the same manner as described above.
［排水処理装置］
その他の態様として、本発明は排水処理装置に関する。本発明の排水処理装置は、本発明の電極重金属含有排水の処理方法を行うための排水処理装置であって、アルカリ二次電池の製造過程で排出される電極重金属含有排水を回収する原排水槽と、電極重金属含有排水の凝集沈殿処理を行う処理槽とを含み、前記処理槽が、アルカリ二次電池の製造過程で排出される廃棄電解液添加手段を備えることを特徴とする。本発明の排水処理装置によれば、廃棄電解液添加手段を有する処理槽を備えるため、廃棄電解液を電極重金属含有排水の凝集沈殿処理におけるｐＨの調整に使用できる。このため、例えば、廃棄電解液と電極重金属含有排水とを同時に処理することができ、廃棄電解液の処分費用を大幅に削減することができる。なお、本発明の排水処理装置は、本発明の廃棄電解液の処理方法に使用しても良い。
[Wastewater treatment equipment]
As another aspect, the present invention relates to a wastewater treatment apparatus. The wastewater treatment apparatus of the present invention is a wastewater treatment apparatus for performing the electrode heavy metal-containing wastewater treatment method of the present invention, and is a raw drainage tank that collects electrode heavy metal-containing wastewater discharged in the manufacturing process of alkaline secondary batteries. And a treatment tank for performing a coagulation-precipitation treatment of the electrode heavy metal-containing wastewater, wherein the treatment tank is provided with a waste electrolyte addition means that is discharged during the manufacturing process of the alkaline secondary battery. According to the wastewater treatment apparatus of the present invention, since the treatment tank having the waste electrolyte solution adding means is provided, the waste electrolyte solution can be used for pH adjustment in the coagulation precipitation treatment of electrode heavy metal-containing wastewater. For this reason, for example, waste electrolyte solution and electrode heavy metal containing waste water can be processed simultaneously, and the disposal cost of waste electrolyte solution can be reduced significantly. In addition, you may use the waste water treatment apparatus of this invention for the processing method of the waste electrolyte solution of this invention.
処理槽は、廃棄電解液添加手段を有し、電極重金属含有排水の凝集沈殿処理を行い、電極重金属含有排水に含まれる重金属の凝集物を形成させるための槽である。処理槽は、少なくとも１つの槽を備えていれば良く、槽を２つ以上備えていても良いし、また、１つの槽が実質的に区画されて２つ以上の反応区画に分割されて２つ以上の槽が形成されたものであっても良い。処理槽は、例えば、無機凝集剤を混合する混和槽と、ｐＨを調整して難溶性物質を形成させる反応槽と、高分子凝集剤を混合して凝集反応を行う凝集槽との３つに分かれていても良いし、混和槽と反応凝集槽との２つに分かれていても良い。これらの場合、廃棄電解液添加手段は、混和槽に形成されていることが好ましい。 The treatment tank is a tank that has a waste electrolyte solution addition means, performs a coagulation sedimentation treatment of the electrode heavy metal-containing wastewater, and forms heavy metal aggregates contained in the electrode heavy metal-containing wastewater. The treatment tank only needs to include at least one tank, and may include two or more tanks. In addition, one tank is substantially partitioned and divided into two or more reaction sections. Two or more tanks may be formed. For example, there are three treatment tanks: a mixing tank for mixing an inorganic flocculant, a reaction tank for adjusting a pH to form a hardly soluble substance, and a flocculant tank for mixing a polymer flocculant to perform an agglutination reaction. You may divide | segment, and you may divide into two, a mixing tank and a reaction coagulation tank. In these cases, the waste electrolyte solution adding means is preferably formed in the mixing tank.
廃棄電解液添加手段は、処理槽に廃棄電解液を添加するための手段であって、例えば、廃棄電解液貯槽と廃棄電解液を送るポンプとにより構成される。 The waste electrolyte solution adding means is a means for adding the waste electrolyte solution to the treatment tank, and includes, for example, a waste electrolyte solution storage tank and a pump for sending the waste electrolyte solution.
本発明の排水処理装置は、凝集槽で形成された凝集物の沈殿を行う沈殿槽及び凝集物を含む排水の濾過を行う濾過装置等をさらに備えていても良い。沈殿槽としては、例えば、クラリファイヤー、シックナー等の固液分離装置等が挙げられる。濾過装置は、例えば、濾材を含み、濾材により凝集物を含む排水を濾過して凝集物を捕集できる。 The waste water treatment apparatus of the present invention may further include a sedimentation tank for precipitating the aggregate formed in the aggregation tank, a filtration apparatus for filtering waste water containing the aggregate, and the like. As a sedimentation tank, solid-liquid separation apparatuses, such as a clarifier and a thickener, etc. are mentioned, for example. The filtration device includes, for example, a filter medium, and can collect the aggregate by filtering waste water containing the aggregate with the filter medium.
つぎに、本発明の廃棄電解液の処理方法の例について図面に基づき説明する。但し、本発明は以下の例に制限されない。 Next, an example of the processing method of the waste electrolyte solution of the present invention will be described with reference to the drawings. However, the present invention is not limited to the following examples.
図１は、本発明の廃棄電解液の処理方法の一実施形態を示す概略構成図であり、原排水槽１０、混和槽１１、反応槽１２及び凝集槽１３を有する処理装置１を用いて廃棄電解液の処理を行う例である。
FIG. 1 is a schematic configuration diagram showing an embodiment of a method for treating a waste electrolyte solution according to the present invention, which is discarded using a treatment apparatus 1 having a
図１に示すように、電極重金属含有排水が流れる方向に沿って、原排水槽１０、混和槽１１、反応槽１２及び凝集槽１３が形成されており、原排水槽１０と混和槽１１とはパイプＰ１によって連結されている。混和槽１１は無機凝集剤槽２２及び廃棄電解液貯槽２１、反応槽１２はｐＨ調整薬剤貯槽２４、凝集槽１３は高分子凝集剤槽２３をそれぞれ有する。混和槽１１と無機凝集剤槽２２及び廃棄電解液貯槽２１とをつなぐパイプ、反応槽１２とｐＨ調整薬剤貯槽２４とをつなぐパイプ、凝集槽１３と高分子凝集剤槽２３とをつなぐパイプのそれぞれにはポンプが形成されていても良く、このポンプを駆動することによって添加量を調整できる。また、混和槽１１、反応槽１２は、それぞれｐＨセンサ（図示せず）を有していても良い。
As shown in FIG. 1, a
まず、アルカリ二次電池の製造過程で排出される電極重金属含有排水を原排水槽１０に回収する。原排水槽１０における電極重金属含有排水の重金属濃度は、一般的には５０００ｍｇ／Ｌ以下である。原排水槽１０における電極重金属含有排水のｐＨは、一般的には８未満である。
First, electrode heavy metal-containing wastewater discharged in the process of manufacturing an alkaline secondary battery is collected in the
つぎに、原排水槽１０からパイプＰ１を通じて混和槽１１に電極重金属含有排水を導入する。ここで、無機凝集剤槽２２から無機凝集剤が、廃電解液貯槽２１から廃電解液が添加される。この廃棄電解液の添加により、電極重金属含有排水のｐＨが後述するｐＨ付近に調整されうる。
Next, electrode heavy metal-containing wastewater is introduced from the
無機凝集剤は、例えば、塩化第二鉄等の上述のものが使用できる。その添加量は、電極重金属含有排水中の重金属の種類や濃度等に応じて適宜設定できる。 As the inorganic flocculant, for example, those described above such as ferric chloride can be used. The amount added can be appropriately set according to the type and concentration of the heavy metal in the electrode heavy metal-containing waste water.
廃棄電解液の添加量は、例えば、電極重金属含有排水のｐＨ等に応じて適宜設定できる。凝集槽１３における重金属を含む凝集物の形成効率の観点から電極重金属含有排水に対する廃棄電解液の添加割合（廃棄電解液／重金属含有排水）が５ｖｏｌ％以下であることが好ましい。また、凝集槽１３において添加する高分子凝集剤としてポリアクリルアミドを使用する場合、電極重金属含有排水に対する廃棄電解液の添加量は０．５ｖｏｌ％以下が好ましく、重金属とポリアクリルアミドとの凝集効率の観点から、０．１ｖｏｌ％以下がより好ましい。
The amount of waste electrolyte added can be appropriately set according to, for example, the pH of the electrode heavy metal-containing waste water. From the viewpoint of the formation efficiency of agglomerates containing heavy metals in the
つぎに、無機凝集剤が添加された電極重金属含有排水を反応槽１２に導入する。ここで、ｐＨ調整薬剤貯槽２４から必要に応じてｐＨ調整薬剤を添加して電極重金属含有排水のｐＨを調整して重金属を含む難溶性物質を形成させる。
Next, the electrode heavy metal-containing wastewater to which the inorganic flocculant is added is introduced into the
調整後のｐＨは、例えば、無機凝集剤、重金属の種類等によって適宜決定できる。無機凝集剤として塩化第二鉄を使用する場合、調整後のｐＨが、例えば、ｐＨ８〜１０が好ましく、より好ましくはｐＨ９付近である。 The pH after the adjustment can be appropriately determined depending on, for example, the inorganic flocculant and the type of heavy metal. When ferric chloride is used as the inorganic flocculant, the adjusted pH is preferably, for example, pH 8 to 10, more preferably around pH 9.
つぎに、難溶性物質を含む電極重金属含有排水を凝集槽１３に導入する。ここで、高分子凝集剤槽２３から高分子凝集剤を添加し、重金属を含む凝集物を形成させる。高分子凝集剤としては前述のものが使用できる。
Next, electrode heavy metal-containing wastewater containing a hardly soluble substance is introduced into the
凝集槽１３で形成された凝集物は、凝集槽１３において沈殿させて凝集物を含む固相と液相とに分離しても良いし、凝集物を含む排水を沈殿槽（図示せず）に導入し、凝集物を沈殿させて凝集物を含む固相と液相とに分離しても良い。また、凝集物を含む排水を濾過設備（図示せず）に導入し、濾過処理を行っても良い。
The agglomerate formed in the
なお、上記例では、混和槽、反応槽及び凝集槽の３つに分かれた処理槽を用いて処理を行う場合を例にとり説明したが、これに限定されず、１つ又は２つの処理槽で上記すべての処理を行っても良い。また、上記例では無機凝集剤の添加後にｐＨを調整しているが、これについても限定されることはない。 In the above example, the case where the treatment is performed using the three treatment tanks, that is, the mixing tank, the reaction tank, and the aggregation tank, has been described as an example. However, the present invention is not limited thereto, and one or two treatment tanks are used. You may perform all the said processes. In the above example, the pH is adjusted after the addition of the inorganic flocculant, but this is not limited.
ニッケル・水素電池の製造過程において排出されるＣｏ、Ｎｉ及びＺｎを含む電極重金属含有排水（重金属濃度４３００ｍｇ／Ｌ）に、塩化第二鉄１０００ｍｇ／Ｌを添加し、同製造過程で排出される廃棄電解液（ｐＨ１３〜１４程度）を用いてｐＨを９に調整した。廃棄電解液は水酸化カリウムを含み、その添加量は電極重金属含有排水に対して０．１ｖｏｌ％、０．５ｖｏｌ％の２通りとした。つぎに、アニオン系高分子凝集剤（ポリアクリルアミド）を５ｍｇ／Ｌ添加した後、重金属を含む凝集物を生成させた。そして、凝集物を含む排水を濾過して凝集物の分離除去を行った。
1000 mg / L of ferric chloride is added to waste water containing heavy metals (heavy metal concentration: 4300 mg / L) containing Co, Ni and Zn discharged during the manufacturing process of nickel-hydrogen batteries, and the waste discharged during the manufacturing process The pH was adjusted to 9 using an electrolytic solution (about
その結果、重金属を含む凝集物が形成された。したがって、廃棄電解液を電極重金属含有排水のｐＨ調整に使用することによって、従来産業廃棄物として廃棄されていた廃棄電解液及び凝集物等の廃棄物の削減と、ｐＨ調整薬剤等の使用量の低減が図られた。すなわち、廃棄電解液を有効利用することにより廃棄物を削減でき、加えてＮａＯＨ等のｐＨ調整薬剤の使用量を低減できた。特に、廃棄電解液の添加量が０．１ｖｏｌ％の実施例では、凝集物等の廃棄物の削減と、ｐＨ調整薬剤等の使用量の低減が顕著であった。したがって、本発明の処理方法によれば、廃棄電解液を電極重金属含有排水の凝集沈殿処理におけるｐＨの調整に使用することから、これまで別々に行っていた廃棄電解液の処理と重金属含有排水の処理とを同時に、また、簡便に行うことができ、凝集物等の廃棄物の削減と、ｐＨ調整薬剤等の使用量の低減ができる。 As a result, aggregates containing heavy metals were formed. Therefore, by using the waste electrolyte for pH adjustment of waste water containing electrode heavy metals, waste electrolyte such as waste electrolyte and agglomerate, which has been conventionally discarded as industrial waste, and the amount of use of pH adjustment chemicals, etc. Reduction was achieved. That is, waste can be reduced by effectively using the waste electrolyte, and the amount of pH adjusting agent such as NaOH can be reduced. In particular, in the example in which the amount of waste electrolyte added was 0.1 vol%, the reduction of waste such as aggregates and the reduction of the amount of use of pH adjusting chemicals were significant. Therefore, according to the treatment method of the present invention, the waste electrolyte solution is used for pH adjustment in the coagulation sedimentation treatment of electrode heavy metal-containing wastewater. The treatment can be performed at the same time and easily, and the waste such as aggregates can be reduced and the amount of the pH adjusting agent used can be reduced.
本発明の廃棄電解液の処理方法は、例えば、アルカリ二次電池の製造過程で排出される廃棄電解液及び重金属含有排水の処理に有用である。 The disposal method of the waste electrolyte solution of the present invention is useful for, for example, the treatment of waste electrolyte solution and heavy metal-containing wastewater discharged in the process of manufacturing an alkaline secondary battery.
１・・・処理装置
１０・・・原排水槽
１１・・・混和槽
１２・・・反応槽
１３・・・凝集槽
２１・・・廃棄電解液貯層
２２・・・無機凝集剤槽
２３・・・高分子凝集剤槽
２４・・・ｐＨ調整薬剤貯槽
Ｐ１、Ｐ２・・・パイプ
DESCRIPTION OF SYMBOLS 1 ...
Claims (7)
アルカリ二次電池の製造過程で排出される電解液を含む廃棄電解液を、前記アルカリ二次電池の製造過程で排出される電極重金属含有排水の凝集沈殿処理におけるｐＨの調整に使用することを特徴とする、廃棄電解液の処理方法。 A method for treating a waste electrolyte of an alkaline secondary battery,
A waste electrolyte containing an electrolyte discharged in the process of manufacturing an alkaline secondary battery is used for pH adjustment in the coagulation-precipitation treatment of electrode heavy metal-containing wastewater discharged in the process of manufacturing the alkaline secondary battery. And a method for treating a waste electrolyte.
前記電極重金属含有排水の凝集沈殿工程を含み、
前記凝集沈殿工程において、前記電極重金属含有排水のｐＨ調整にアルカリ二次電池の製造過程で排出される廃棄電解液を使用することを特徴とする電極重金属含有排水の処理方法。 A method for treating drainage containing heavy metal electrodes discharged during the manufacturing process of alkaline secondary batteries,
A coagulation sedimentation step of the electrode heavy metal-containing wastewater,
In the coagulation sedimentation step, a waste electrolytic solution discharged in the process of manufacturing an alkaline secondary battery is used for pH adjustment of the electrode heavy metal-containing wastewater.
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