CN104724795B - A kind of electrochemical treatments system and electrochemical method for handling nickel-containing waste water - Google Patents
A kind of electrochemical treatments system and electrochemical method for handling nickel-containing waste water Download PDFInfo
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- CN104724795B CN104724795B CN201510127982.5A CN201510127982A CN104724795B CN 104724795 B CN104724795 B CN 104724795B CN 201510127982 A CN201510127982 A CN 201510127982A CN 104724795 B CN104724795 B CN 104724795B
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Abstract
The invention discloses a kind of electrochemical treatments system and electrochemical process for treating for handling nickel-containing waste water.Dimensional stable anode is which used as anode, separated between the anode chamber and the cathode chamber using cation-exchange membrane, promote the complex state nickel ion in nickel-containing waste water that solution complexing occurs to discharge free state nickel ion by the oxidation of dimensional stable anode, and enter cathode chamber through cation-exchange membrane and be reduced to elemental nickel.The electrochemical treatments system and method for the present invention can handle complex state nickel ion, and also have certain removal effect to the organic pollution in nickel-containing waste water, and technique is simple, efficient, energy saving, environmental protection.
Description
Technical field
The invention belongs to field of industrial waste water treatment.
Background technology
Industrially produce substantial amounts of nickel-containing waste water, wherein nickel mainly exists in the form of nickel ion, mainly divide free state nickel from
Two kinds of son and complex state nickel ion, wherein complex state nickel ion is mainly Ni2+With various organic acids or organic acid, CN-、
SCN-, the complex compound that is formed of EDTA classes material, ammonia or amine substance.In view of the toxicity of nickel ion to nickel-containing waste water, it is necessary to carry out
It could be discharged after processing.
Existing nickel-containing waste water processing method has the precipitation method, ion-exchange, electrodeposition process etc..Wherein the precipitation method are to add
Enter alkali or carbonate and nickel ion is precipitated as nickel hydroxide or nickelous carbonate, produce a large amount of silt deposits, and want from precipitated product
Reclaim metallic nickel, it is also necessary to cumbersome follow-up process.Ion exchange rule can only handle free state nickel ion, to complex state nickel from
Sub- helpless.And the normal plug ion exchange membrane of other organic pollutions or ion exchange resin in nickel-containing waste water, it has to
Often stop work and clear up.Electrodeposition process is also difficult to handle complex state nickel ion, because the strong complexing of part is made in complex state nickel ion
It is difficult to receive electronics in itself with, nickel ion to be reduced, still more some complex state nickel ions, such as Ni (CN)4-Or Ni (SCN
)4-, anion has been had changed into, negative electrode can not be reached at all under electric field action, to be let alone reduced.In addition, negative electrode
It is upper also often to deposit organic pollution mud, cause cathode efficiency to decline.
Therefore, there is an urgent need to a kind of processing system and place that can handle the nickel-containing waste water containing complex state nickel ion for this area
Reason method.
The content of the invention
The first aspect of the present invention provides a kind of electrochemical treatments system for handling nickel-containing waste water, and it includes：
Diaphragm electrolysis reactor, it includes：Anode chamber and anode disposed within, wherein the anode is dimensional stable anode；
Cathode chamber and negative electrode disposed within；The cation-exchange membrane that anode chamber and cathode chamber are separated；
Catholyte cyclic water tank, it is connected with the entrance and exit circulation of the cathode chamber.
In the preferred embodiment of the first aspect of the present invention, the dimensional stable anode is titanium-based ruthenium-oxide iridium electrode.
The second aspect of the present invention provides a kind of electrochemical method for handling nickel-containing waste water.Wherein described nickel-containing waste water contains
There are free state nickel ion and complex state nickel ion, this method uses the electrochemical treatments system described in the first aspect of the present invention,
And this method comprises the following steps：
The nickel-containing waste water is set to flow into the anode chamber of the diaphragm electrolysis reactor, wherein complex state nickel ion is in the shape
Decomplexing occurs under the oxidation of steady anode to close, discharges free state nickel ion, and together with original free state nickel ion
Enter cathode chamber through the cation-exchange membrane under electric field action, and electro-deposition effect occurs at negative electrode, generate elemental nickel；
The water outlet of anode chamber is directly as the discharge of wastewater after processing or is recirculated back to anode chamber after circular treatment as processing
Discharge of wastewater afterwards.For commercial Application, in order to reduce the volume of anode chamber, it is often necessary to which anode chamber's water outlet is recycled
Anode chamber is gone back to, experience a period of time is just discharged after the nickel ion concentration in waste water drops to discharge standard.
In the preferred scheme of the second aspect of the present invention, the catholyte is nickel sulfate or nickel chloride solution, its
Only it is added into when methods described just starts in the catholyte cyclic water tank, then stops adding after startup.Preferably,
The initial concentration of the nickel sulfate or nickel chloride is higher, so does the catholyte that can maintain on startup in cathode chamber
Higher nickel ion concentration, be advantageous to improve the current efficiency of negative electrode, treat that the free nickel ion from nickel-containing waste water is made in electric field
After continuously migrating into cathode chamber under, then the circulation between cathode chamber and catholyte cyclic water tank can be cut off, only
Normal cathode efficiency can be maintained by the above-mentioned free state nickel ion moved into.
In the second aspect of the present invention, the complex state nickel ion is organic acid or organic acid, CN including part-、
SCN-, ammonia or amine part complex state nickel ion.
The electrochemical treatments system work process of the present invention is as follows：
After nickel-containing waste water enters the anode chamber of the diaphragm electrolysis reactor, because dimensional stable anode just has as anode in itself
Higher oxygen evolution potential, oxidation can occur in electrode surface, and the nascent oxygen that the electrolysis of its surface separates out also has
Strong oxidation, therefore, it is possible to which the part in complex state nickel ion is carried out into oxidation Decomposition, so as to discharge free nickel ion,
This process is referred to alternatively as solution complexing.The free nickel ion discharged, together with original nickel ion in waste water, and it may deposit
A part of hydrogen ion, under electric field action, through cation-exchange membrane, reach cathode chamber, and reduced on negative electrode
Reaction, elemental nickel is formed, completes the recovery of nickel.The cation-exchange membrane only allow free state nickel ion and hydrogen ion by,
Without allowing complex state nickel ion by also not allowing other organic pollutions by, for example, light common in nickel-containing waste water
The organic additives such as agent, detergent and its catabolite etc., stopped by the cation-exchange membrane and be retained in anode chamber, in sun
Pole is broken down into smaller innocuous substance in itself and under the oxidation of nascent oxygen.Because these organic pollutions do not enter
Cathode chamber, therefore avoid them and be deposited on cathode surface formation mud, it ensure that cleaning and the negative electrode electro-deposition efficiency of negative electrode
Do not decline.
There is no particular/special requirement, the industrial cation-exchange membrane of in general to the material of cation-exchange membrane in the present invention
Use, and these cation-exchange membranes all there are enough barrier effects to the organic pollution in waste water.
Advantages 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 handle complex state nickel
Ion, without adding extraly contact break mixture so that the nickel recovery of nickel-containing waste water greatly improves.Technological process is simpler,
Efficiently, energy-conservation and environmental protection.
2. other organic pollutions that dimensional stable anode can also be in oxidative degradation nickel-containing waste water.
3. the presence of cation-exchange membrane, preventing organic pollution to enter cathode chamber, be advantageous to cathode surface and keep clear
It is clean, maintain higher current efficiency.
4. reducing because the nickel ion of cathode chamber is electrically deposited into elemental nickel and constantly, nickel ion exists dense between anode and cathode
Degree is poor, and the presence of cation-exchange membrane also increases this concentration difference, therefore except under normal electric field driven power, also increasing
The driving force that the nickel ion of anode chamber migrates to cathode chamber, enters so as to save traditional electrodialysis or UF membrane to nickel-containing waste water
The step of row pre-concentration.
Brief description of the drawings
Fig. 1 is the schematic diagram of the electrochemical treatments system of the present invention.
Fig. 2 is the schematic diagram of diaphragm electrolysis reactor.
Reference implication is as follows in figure：
1- nickel-containing waste water imports；2- electrolysis inlet water tanks (while being anolyte circulation water tank)；3- anode circulation water pumps；
4- diaphragm electrolysis reactors；401- dimensional stable anodes；402- negative electrodes；403- cation-exchange membranes；5- catholyte cyclic water tanks；
6- cathode circulation water pumps；7- anode water tanks；8- backflow water valves；9- draining valves；10- catholyte imports
Embodiment
The present invention is described in further details with accompanying drawing with reference to embodiments, embodiment is only limitted to the explanation present invention,
Rather than limitation of the invention.
Embodiment 1：
By 1L nickel-containing waste waters, (ionic state nickel concentration is 100mg/L, and total nickel concentration is 120mg/L, COD value 56mg/L, is used
Sulfuric acid adjusts pH=4) electrolysis inlet water tank 2, while the nickel sulfate solution by 1L concentration for 20g/L are put into, with sulphur acid for adjusting pH
=4 are put into catholyte cyclic water tank, close draining valve 9, open backflow water valve 8, the dimensional stable anode of diaphragm electrolysis reactor 4
It is positive using the CMB of Japanese ASTOM companies using titanium-based ruthenium-oxide iridium electrode, annode area 15cm*15cm, cation-exchange membrane
Film, negative electrode are stainless steel electrode, area 15cm*15cm, open anode and cathode water circulating pump 3,6, open dc source 404 and open
Close, regulation voltage is 5.0V, and the nickel ion concentration that dissociates after being electrolysed 20h, in the electrolyte of anode region is 0.32mg/L, and total nickel concentration is
0.46mg/L, COD value 22g/L, layer of metal nickel is produced on minus plate, be 99.6% through analyzing nickel purity, nickel recovery is big
In 99.9%, current efficiency is more than 80%.Any organic pollution mud is not almost found on negative electrode.
Comparative example
Waste water and process conditions are substantially the same manner as Example 1, but are not as anode, the graphite electrode using graphite electrode
Dimensional stable anode, then the free nickel ion concentration of water outlet is 0.43mg/L, and total nickel concentration is 15mg/L, illustrates also considerable network
State nickel is closed not to be disposed off.The COD of water outlet is 48mg/L, illustrates that organic pollution still largely remains.
Claims (2)
- A kind of 1. electrochemical method for handling nickel-containing waste water, wherein the nickel-containing waste water contains free state nickel ion and complex state nickel Ion, this method comprise the following steps：Nickel-containing waste water is put into electrolysis inlet water tank, while nickel sulfate solution is put into catholyte with sulfuric acid regulation pH=4 and followed Ring water tank, draining valve to be closed, open backflow water valve, the dimensional stable anode of diaphragm electrolysis reactor uses titanium-based ruthenium-oxide iridium electrode, Barrier film uses cation-exchange membrane, and negative electrode is stainless steel electrode, opens cathode circulation water pump and anode circulation water pump, opens direct current Power switch, regulation voltage are 5.0V, are electrolysed 20h, and wherein complex state nickel ion issues in the oxidation of the dimensional stable anode Raw solution complexing, discharges free state nickel ion, and pass through the sun under electric field action together with original free state nickel ion Amberplex enters cathode chamber, and electro-deposition effect occurs at negative electrode, generates elemental nickel；The water outlet of anode chamber directly as Discharge of wastewater after processing is recirculated back to anode chamber after circular treatment as the discharge of wastewater after processing；The nickel sulfate solution, only it is added into the catholyte cyclic water tank, starts when methods described just starts Then stop adding afterwards.
- 2. electrochemical method according to claim 1, it is organic acid or has wherein the complex state nickel ion includes part Machine acid group, CN-、SCN-, EDTA, the complex state nickel ion of ammonia or amine substance.
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| 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 |
| CN109626519B (en) * | 2019-01-23 | 2019-09-03 | 江苏省环境科学研究院 | A method of chemical nickel waste liquid is recycled using duplex spread-blade electrode |
| CN113463133B (en) * | 2021-06-23 | 2022-09-27 | 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 |
| CN113694692B (en) * | 2021-07-16 | 2022-08-16 | 西安交通大学 | Preparation method of monatomic fluid containing metallic nickel |
| CN113562892B (en) * | 2021-07-22 | 2023-04-18 | 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 |
| CN113636691B (en) * | 2021-07-23 | 2023-04-04 | 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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