CN104724795A - Electrochemical treatment system and electrochemical treatment method for treating nickel-containing wastewater - Google Patents
Electrochemical treatment system and electrochemical treatment method for treating nickel-containing wastewater Download PDFInfo
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- CN104724795A CN104724795A CN201510127982.5A CN201510127982A CN104724795A CN 104724795 A CN104724795 A CN 104724795A CN 201510127982 A CN201510127982 A CN 201510127982A CN 104724795 A CN104724795 A CN 104724795A
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Abstract
The invention discloses an electrochemical treatment system and electrochemical treatment method for treating nickel-containing wastewater. According to the system, a dimensional stable anode is used as an anode, cathode and anode chambers are separated by a cation exchange membrane, complexing-state nickel ions in the nickel-containing wastewater are subjected to decomplexation to release free-state nickel ions under the oxidization effect of the dimensional stable anode and the free-state nickel ions penetrate through the cation exchange membrane to enter the cathode chamber to be reduced into elementary nickel. The electrochemical treatment system and electrochemical treatment method, disclosed by the invention, can be used for treating complexing-state nickel ions, also can be used for removing organic pollutants in the nickel-containing wastewater to some extent, and are simple in process, efficient, energy-saving and environmentally friendly.
Description
Technical field
The invention belongs to field of industrial waste water treatment.
Background technology
The nickel-containing waste water that industrial generation is a large amount of, wherein nickel mainly exists with nickel ion form, main point free state nickel ion and complex state nickel ion two kinds, wherein complex state nickel ion mainly Ni
2+with various organic acid or organic acid, CN
-, SCN
-, the complex compound that formed of EDTA class material, ammonia or amine substance.In view of the toxicity of nickel ion, could discharge after needing to process nickel-containing waste water.
Existing nickel-containing waste water treatment process has the precipitator method, ion exchange method, electrodip process etc.Wherein the precipitator method add alkali or nickel ion is precipitated as nickel hydroxide or nickelous carbonate by carbonate, produces a large amount of silt deposit, and want, from precipitated product Footwall drift nickel, also to need loaded down with trivial details follow-up flow process.Ion-exchange rule can only process free state nickel ion, to complex state nickel ion helpless.And the normal plug ion exchange membrane of other organic pollutant in nickel-containing waste water or ion exchange resin, cleaning of often stopping work of having to.Electrodip process is also difficult to process complex state nickel ion, because the strong complexing action of part in complex state nickel ion, nickel ion itself is difficult to accept electronics and is reduced, still more some complex state nickel ion, such as Ni (CN)
4-or Ni (SCN)
4-, become negatively charged ion, under electric field action, cannot negative electrode be arrived at all, let alone will be reduced.In addition, negative electrode also often deposits organic pollutants mud, cause cathode efficiency to decline.
Therefore, this area is in the urgent need to a kind for the treatment of system and the treatment process that can process the nickel-containing waste water containing complex state nickel ion.
Summary of the invention
A first aspect of the present invention provides a kind of electrochemical treatment system processing nickel-containing waste water, and it comprises:
Diaphragm electrolysis reactor, it comprises: anolyte compartment and the anode put in the inner, and wherein said anode is dimensional stable anode; Cathode compartment and the negative electrode put in the inner; By the cationic exchange membrane that anolyte compartment and cathode compartment separate;
Catholyte cyclic water tank, it circulates with the entrance and exit of described cathode compartment and is communicated with.
In the preferred embodiment of a first aspect of the present invention, described dimensional stable anode is titanium base ruthenium oxide iridium electrode.
A second aspect of the present invention provides a kind of electrochemical method processing nickel-containing waste water.Wherein said nickel-containing waste water contains free state nickel ion and complex state nickel ion, and the method uses the electrochemical treatment system described in a first aspect of the present invention, and the method comprises the following steps:
Described nickel-containing waste water is made to flow into the anolyte compartment of described diaphragm electrolysis reactor, wherein there is decomplexing conjunction in complex state nickel ion under the oxygenizement of described dimensional stable anode, discharge free state nickel ion, and under electric field action, cathode compartment is entered through described cationic exchange membrane together with original free state nickel ion, and there is galvanic deposit effect at negative electrode place, generate elemental nickel; The water outlet of anolyte compartment directly goes back to anolyte compartment after circular treatment as the discharge of wastewater after process as the discharge of wastewater after process or recirculation.For industrial application, in order to reduce the volume of anolyte compartment, often need that anolyte compartment is gone out water recycle and go back to anolyte compartment, experience for some time after the nickel ion concentration in waste water drops to emission standard, just discharged.
In the preferred version of a second aspect of the present invention, described catholyte is single nickel salt or nickel chloride solution, and it is only added into when described method just starts in described catholyte cyclic water tank, then stops adding after startup.Preferably, the starting point concentration of described single nickel salt or nickelous chloride is higher, do the higher nickel ion concentration that can maintain the catholyte in cathode compartment when starting like this, be conducive to the current efficiency improving negative electrode, after the free nickel ion from nickel-containing waste water migrates into cathode compartment continuously under electric field action, then can cut off the circulation between cathode compartment and catholyte cyclic water tank, only can maintain normal cathode efficiency by above-mentioned free state nickel ion of moving into.
In a second aspect of the present invention, it is organic acid or organic acid, CN that described complex state nickel ion comprises part
-, SCN
-, ammonia or amine part complex state nickel ion.
Electrochemical treatment system work process of the present invention is as follows:
After nickel-containing waste water enters the anolyte compartment of described diaphragm electrolysis reactor, because dimensional stable anode itself just has higher oxygen evolution potential as anode, can in electrode surface generation oxygenizement, and the nascent oxygen that its surface electrical parses also has strong oxidation, therefore, part in complex state nickel ion can be carried out oxygenolysis, thus discharge free nickel ion, this process can be called as solution complexing.The free nickel ion discharged, together with nickel ion original in waste water, and a part of hydrogen ion that may exist, under electric field action, through cationic exchange membrane, arrive cathode compartment, and reduction reaction is there is on negative electrode, form elemental nickel, complete the recovery of nickel.This cationic exchange membrane only allows free state nickel ion and hydrogen ion to pass through, and do not allow complex state nickel ion to pass through, other organic pollutant is not allowed to pass through yet, organic additive and the degraded products etc. thereof such as such as, in nickel-containing waste water common brightening agent, washing composition, all stopped by this cationic exchange membrane and be retained in anolyte compartment, under the oxygenizement of anode itself and nascent oxygen, be broken down into less innoxious substance.Because these organic pollutants do not enter cathode compartment, therefore avoid them and be deposited on cathode surface formation mud, ensure that the clean of negative electrode and cathode electrodeposition efficiency do not decline.
Do not have particular requirement to the material of cationic exchange membrane in the present invention, general industrial cationic exchange membrane all can use, and these cationic exchange membranes all have enough barrier effects to the organic pollutant in waste water.
Advantage of the present invention is as follows:
1. dimensional stable anode can carry out complexation and decomplexation to complex state nickel ion, therefore, it is possible to effectively process complex state nickel ion, and without the need to adding contact break mixture extraly, the nickel recovery of nickel-containing waste water is improved greatly.Technical process is simpler, efficient, energy saving standard.
2. dimensional stable anode can also other organic pollutant in oxidative degradation nickel-containing waste water.
3. the existence of cationic exchange membrane, prevents organic pollutant to enter cathode compartment, is conducive to cathode surface and keeps clean, maintain higher current efficiency.
4. because the nickel ion of cathode compartment is electrically deposited into elemental nickel and constantly reduces, between anode and cathode there is concentration difference in nickel ion, the existence of cationic exchange membrane also increases this concentration difference, therefore except under normal electric field driven power, the motivating force that the nickel ion also increasing anolyte compartment moves to cathode compartment, thus save traditional electrodialysis or membrane sepn carries out the step of pre-concentration to nickel-containing waste water.
Accompanying drawing explanation
Fig. 1 is the schematic diagram of electrochemical treatment system of the present invention.
Fig. 2 is the schematic diagram of diaphragm electrolysis reactor.
In figure, Reference numeral implication is as follows:
The import of 1-nickel-containing waste water; 2-electrolysis inlet chest (being simultaneously anolyte circulation water tank); 3-anode circulation water pump; 4-diaphragm electrolysis reactor; 401-dimensional stable anode; 402-negative electrode; 403-cationic exchange membrane; 5-catholyte cyclic water tank; 6-cathode circulation water pump; 7-anode water tank; 8-refluxes water valve; 9-water discharge valve; The import of 10-catholyte
Embodiment
Be described in further details the present invention below in conjunction with embodiment and accompanying drawing, embodiment is only limitted to the present invention is described, but not limitation of the invention.
Embodiment 1:
By 1L nickel-containing waste water, (ionic state nickel concentration is 100mg/L, total nickel concentration is 120mg/L, COD value is 56mg/L, pH=4 is regulated with sulfuric acid) put into electrolysis inlet chest 2, be the nickel sulfate solution of 20g/L by the concentration of 1L simultaneously, pH=4 is regulated to put into catholyte cyclic water tank with sulfuric acid, close water discharge valve 9, open backflow water valve 8, the dimensional stable anode of diaphragm electrolysis reactor 4 adopts titanium base ruthenium oxide iridium electrode, annode area is 15cm*15cm, cationic exchange membrane adopts the CMB anode membrane of Japanese ASTOM company, negative electrode is stainless steel electrode, area is 15cm*15cm, open anode and cathode water circulating pump 3, 6, open direct supply 404 switch, regulating voltage is 5.0V, after electrolysis 20h, in the electrolytic solution of positive column, free nickel ion concentration is 0.32mg/L, total nickel concentration is 0.46mg/L, COD value is 22g/L, negative plate produces layer of metal nickel, nickel purity is 99.6% by analysis, nickel recovery is greater than 99.9%, current efficiency is greater than 80%.Negative electrode does not almost find any organic pollutant mud.
Comparative example
Waste water and processing condition substantially the same manner as Example 1, but adopt Graphite Electrodes as anode, this Graphite Electrodes is not dimensional stable anode, then the free nickel ion concentration of water outlet is 0.43mg/L, total nickel concentration is 15mg/L, illustrates that considerable complex state nickel is not processed in addition.The COD of water outlet is 48mg/L, illustrates that organic pollutant still remains in a large number.
Claims (5)
1. process an electrochemical treatment system for nickel-containing waste water, it comprises:
Diaphragm electrolysis reactor, it comprises: anolyte compartment and the anode put in the inner, and wherein said anode is dimensional stable anode; Cathode compartment and the negative electrode put in the inner; By the cationic exchange membrane that anolyte compartment and cathode compartment separate;
Catholyte cyclic water tank, it circulates with the entrance and exit of described cathode compartment and is communicated with.
2. electrochemical treatment system according to claim 1, wherein said dimensional stable anode refer on the metallic matrixes such as Ti, Zr, Ta, Nb, to deposit one deck micron or submicron order be selected from SnO
2, IrO
2, RuO
2, PbO
2in one or more metal oxide films and the stabilized electrodes be prepared into.
3. one kind processes the electrochemical method of nickel-containing waste water.Wherein said nickel-containing waste water contains free state nickel ion and complex state nickel ion, and the method uses the electrochemical treatment system described in claim 1, and the method comprises the following steps:
Described nickel-containing waste water is made to flow into the anolyte compartment of described diaphragm electrolysis reactor, wherein there is decomplexing conjunction in complex state nickel ion under the oxygenizement of described dimensional stable anode, discharge free state nickel ion, and under electric field action, cathode compartment is entered through described cationic exchange membrane together with original free state nickel ion, and there is galvanic deposit effect at negative electrode place, generate elemental nickel; The water outlet of anolyte compartment directly goes back to anolyte compartment after circular treatment as the discharge of wastewater after process as the discharge of wastewater after process or recirculation.
4. electrochemical method according to claim 3, wherein said catholyte is single nickel salt or nickel chloride solution, and it is only added into when described method just starts in described catholyte cyclic water tank, then stops adding after startup.
5. electrochemical method according to claim 3, it is organic acid or organic acid, CN that wherein said complex state nickel ion comprises part
-, SCN
-, EDTA, ammonia or amine substance complex state nickel ion.
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|---|---|---|---|
| CN201510127982.5A CN104724795B (en) | 2015-03-23 | 2015-03-23 | A kind of electrochemical treatments system and electrochemical method for handling nickel-containing waste water |
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| CN201510127982.5A CN104724795B (en) | 2015-03-23 | 2015-03-23 | A kind of electrochemical treatments system and electrochemical method for handling nickel-containing waste water |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109437446A (en) * | 2018-10-19 | 2019-03-08 | 浙江海拓环境技术有限公司 | A kind of zinc nickel alloy electroplating waste water treatment process |
| CN109553224A (en) * | 2018-12-07 | 2019-04-02 | 杭州水处理技术研究开发中心有限公司 | A kind of chemical nickle-plating wastewater processing equipment and its method |
| CN109626519A (en) * | 2019-01-23 | 2019-04-16 | 江苏省环境科学研究院 | A method of chemical nickel waste liquid is recycled using duplex spread-blade electrode |
| CN113463133A (en) * | 2021-06-23 | 2021-10-01 | 华中师范大学 | Electrochemical device, application thereof and method for recycling metal in industrial wastewater |
| CN113562892A (en) * | 2021-07-22 | 2021-10-29 | 生态环境部华南环境科学研究所 | Method for efficiently separating, concentrating and recycling nickel in chemical nickel plating waste liquid |
| CN113636691A (en) * | 2021-07-23 | 2021-11-12 | 生态环境部华南环境科学研究所 | Method for recycling nickel and phosphorus resources in chemical nickel plating waste liquid |
| CN113694692A (en) * | 2021-07-16 | 2021-11-26 | 西安交通大学 | Preparation method of monatomic fluid containing metallic nickel |
| CN115611371A (en) * | 2021-07-14 | 2023-01-17 | 江苏省环科院环境科技有限责任公司 | Electrode and preparation method and application thereof |
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| CN1278564A (en) * | 1999-04-07 | 2001-01-03 | 希普雷公司 | Method and system for recovering and removing copper from fluid |
| CN202272954U (en) * | 2011-09-02 | 2012-06-13 | 广州市天承化工有限公司 | System for acid chloride etching liquid cycle regeneration and metallic copper recycling |
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| CN1278564A (en) * | 1999-04-07 | 2001-01-03 | 希普雷公司 | Method and system for recovering and removing copper from fluid |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109437446A (en) * | 2018-10-19 | 2019-03-08 | 浙江海拓环境技术有限公司 | A kind of zinc nickel alloy electroplating waste water treatment process |
| CN109553224A (en) * | 2018-12-07 | 2019-04-02 | 杭州水处理技术研究开发中心有限公司 | A kind of chemical nickle-plating wastewater processing equipment and its method |
| CN109626519A (en) * | 2019-01-23 | 2019-04-16 | 江苏省环境科学研究院 | A method of chemical nickel waste liquid is recycled using duplex spread-blade electrode |
| CN113463133A (en) * | 2021-06-23 | 2021-10-01 | 华中师范大学 | Electrochemical device, application thereof and method for recycling metal in industrial wastewater |
| CN115611371A (en) * | 2021-07-14 | 2023-01-17 | 江苏省环科院环境科技有限责任公司 | Electrode and preparation method and application thereof |
| CN113694692A (en) * | 2021-07-16 | 2021-11-26 | 西安交通大学 | Preparation method of monatomic fluid containing metallic nickel |
| CN113562892A (en) * | 2021-07-22 | 2021-10-29 | 生态环境部华南环境科学研究所 | Method for efficiently separating, concentrating and recycling nickel in chemical nickel plating waste liquid |
| CN113636691A (en) * | 2021-07-23 | 2021-11-12 | 生态环境部华南环境科学研究所 | Method for recycling nickel and phosphorus resources in chemical nickel plating waste liquid |
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